CN101243563B - Electrochemical apparatus and barrier layer protected substrate - Google Patents

Electrochemical apparatus and barrier layer protected substrate Download PDF

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Publication number
CN101243563B
CN101243563B CN2006800296432A CN200680029643A CN101243563B CN 101243563 B CN101243563 B CN 101243563B CN 2006800296432 A CN2006800296432 A CN 2006800296432A CN 200680029643 A CN200680029643 A CN 200680029643A CN 101243563 B CN101243563 B CN 101243563B
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electro
substrate
electrochemical apparatus
chemical activity
barrier layer
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CN101243563A (en
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S·W·斯奈德
B·J·纽德克尔
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Saplast Research LLC
Phonex Corp
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Infinite Power Solutions Inc
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Priority claimed from US11/374,282 external-priority patent/US20080003496A1/en
Priority claimed from US11/209,536 external-priority patent/US8021778B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to apparatus, compositions and methods of fabricating high performance thin-film batteries on metallic substrates, polymeric substrates, or doped or undoped silicon substrates by fabricating an appropriate barrier layer composed, for example, of barrier sublayers between the substrate and the battery part of the present invention thereby separating these two parts chemically during the entire battery fabrication process as well as during any operation and storage of the electrochemical apparatus during its entire lifetime. In a preferred embodiment of the present invention thin-film batteries fabricated onto a thin, flexible stainless steel foil substrate using an appropriate barrier layer that is composed of barrier sublayers have uncompromised electrochemical performance compared to thin-film batteries fabricated onto ceramic substrates when using a 700 DEG C. post-deposition anneal process for a LiCoO2 positive cathode.

Description

Electrochemical apparatus and barrier layer protected substrate
Related application
The application be submitted on June 15th, 2005, the part subsequent application of No. the 60/690697th, unaliened U.S. Provisional Patent Application sequence still, and require the preference of this application according to 35U.S.C. § 120; No. the 11/209536th, the U. S. application sequence that the application relates on August 23rd, 2005 and submits to, and require the preference of this application according to 35U.S.C. § 120; These two parts of applications all are incorporated into this by reference.
Invention field
The present invention relates to equipment, composition and the manufacturing field of lithium base solid film secondary battery and primary cell group, described battery pack has capacity density (capacity density), energy density and the power density of raising, and preferably has form factor and crystal LiCoO flexibly 2, LiNiO 2, LiMn 2O 4Negative electrode and derived material.
Background of invention
Following paragraph is described the demand and the progress of subject technology in the hull cell group field.
Can by on given substrate for example in the following order the battery pack component of vacuum moulding machine layering make the hull cell group: positive negative electrode (positive cathode) collector electrode, positive negative electrode, negative anode (negativeanode) collector electrode, dielectric substrate (separate layer), negative anode and encapsulated layer.Can adopt lamination process to replace depositing operation step (for example referring to United States Patent (USP) 6916679, people's such as Wang 143J.Electrochem.Soc.3203-13 (1996) or United States Patent (USP) 5561004).Two ends of hull cell group can randomly not only comprise the extension of the positivity and the negativity current collection layer utmost point, can also deposit the terminal contacts that electrically contacts with corresponding collector electrode.Positive cathode material may be abundant inadequately in the degree of crystallinity of depositional phase, thereby show inadequate electrochemical properties (for example referring to people such as above-mentioned Wang document).Therefore, can be in battery pack manufacturing process make positive negative electrode generation crystallization (for example referring to people's such as above-mentioned Wang document by post-depositional high temperature (annealing) technology, perhaps people such as Bates, " Thin-Film LithiumBatteries ", New Trends in Electrochemical Technology:Energy StorageSystems for Electronics (T.Osaka ﹠amp; M.Datta compiles, Gordon and Breach, 2000)).The annealing process that carries out at once after positive cathodic deposition may be selected to cause restriction to the material that is used for substrate and positive negative electrode current collection layer, thereby has limited capacity density, energy density and the power density of hull cell group on unit volume and Unit Weight meaning.Below further describe the influence of substrate to these three amounts.
The volume and weight density of capacity, energy and the power of lithium base solid film secondary battery (rechargeable) and primary cell group (not rechargeable) intrinsic (promptly not having substrate and encapsulated layer) is by the volume and weight density decision of capacitance, energy and the power of positive cathode material.Consider capacity, the energy of whole (non-film-type) and hull cell group, the volume and weight density and the recyclability of power, for the situation of secondary battery, crystal LiMn in addition 2O 4, crystal LiMnO 2With crystal LiNiO 2Derivative, crystal LiCoO 2It is a kind of example of alternative positive cathode material.Have been found that, when using other transition metal (formation derivative) for example Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, La, Hf, Ta, W and Re and the major element that is selected from the 1st, 2,13,14,15,16 and 17 families mixing to these main original positive cathode materials, can change LiCoO 2, LiMn 2O 4, LiMnO 2And LiNiO 2Character, but say on the whole, even there is improvement also very little.
According to United States Patent (USP) 6280875, the inertia of the primary titanium oxide on the Ti substrate still is not enough to prevent between Ti substrate and the battery pack component adverse reaction takes place.Because the selection of baseplate material is limited to the material that can form primary oxide on surface in the annealing steps of positive negative electrode, so this approach is subjected to serious restriction.Except the present invention, successfully will not comprise the substrate of the metal substrate of the compliant foil that can not form primary oxide on surface as yet as the hull cell group.(comprise compliant foil by for example the high temperature cathode material directly being deposited to metal substrate, except that Zr) on, then in 700 ℃ of high temperature for example, annealing 1 hour in air, make the solid film secondary battery, may cause the adverse reaction that positive negative electrode and baseplate material take place to reach the degree that makes that positive negative electrode is ineffective.And pure Ti and Zr substrate are also relatively more expensive.
The hull cell group of prior art is not disclosed between substrate and the battery pack uses effective barrier layer, thereby and provides potential opposite observations.The objective of the invention is, the barrier layer that utilizes the present invention to have subgrade overcomes some difficult problem of prior art hull cell group.
Summary of the invention
Relate to the demand that produces in some shortcoming that proposed background technology and the related industries by following example various aspects of the present invention in greater detail and execution mode.
The quantity of device continues to increase sharply on the portable and plate, and available physical size may dwindle simultaneously.The battery pack that drives these devices should keep synchronous with the demand of the device of serving, and size reduction for example transmits identical power simultaneously as much as possible.It is thin more that battery pack becomes, and it is can applicable field just big more.A kind of power device of enabling is the thin film solid state group.When bottom surface (footprint) is limiting factor and capacity requirement still when " height ", assembling and stack of cells Battery pack are very important as much as possible in free space (bottom surface * highly).
Battery pack with peak capacity, voltage, electric current, power and rechargeable cycle life has for example been utilized the most positive at present cathode material LiCo 2, LiMn 2O 4, LiMnO 2, LiNiO 2And derived material.
When these material vacuum moulding machines are become film, be preferably included in high temperature these materials are deposited post growth annealing, to improve their degree of crystallinity, this is directly related with the whole electrochemical properties that form them.Make the electrochemical apparatus of using this hull cell group become thinner, should make this electrochemical apparatus be mainly inertia, the inactive part of electrochemistry becomes thinner.A kind of approach is that battery pack is structured on thin metal foil substrate rather than the big and thick ceramic substrate.Compare with the ceramic substrate of same bottom area, metal forming is more soft, thinner, and more cheap.And metal forming is easier of to obtain, to make to save when making more costs than large tracts of land.
But, the same with other positive cathode materials, LiCoO 2Be strong oxidizer, have very big, the therefore reactive very large lithium ion of mobility.Make the LiCoO of deposition 2Under the required high temperature anneal temperature of membrane crystallization, kickback takes place in itself and most of metal and alloy and chemical compound lot (except the inert ceramic material of limited quantity).In other cases, the material that exists of not wishing from substrate can diffuse into LiCoO in high-temperature annealing process 2In, pollute positive negative electrode, thereby change its electrochemical properties unfriendly.If keep annealing temperature low to being enough to prevent reaction or undesirable diffusion, then positive negative electrode may complete crystallization, for the rechargeable battery group, its capacity, energy, electric current and power-performance and useful life, (cycle-index) can be affected.
The positive cathode material of high power its crystalline state can show its completely, desirable electrochemical properties.Because these materials can for example use with its form of film in the present invention, so use a kind of gas phase membrane deposition process of routine that it is deposited usually, described deposition process is the vapour deposition, cathodic arc deposition etc. of the auxiliary electron beam evaporation of chemical vapour deposition (CVD), spray pyrolysis, the ion strengthened of sputtering sedimentation (RF, pulsed D C or AC), electron beam evaporation, chemical vapour deposition (CVD), plasma, electron beam guiding for example.The issuable positive cathodic coating in the depositional phase of these gas phase process can not show the suitable electrochemical properties made from the powder of, sufficient crystallising corresponding by it (for example using in cell phone and the gamma camera battery pack in the integral battery door group) of positive negative electrode.Therefore, can be by the relatively poor electrochemical properties of these positive negative electrodes of film process deposition owing to the degree of crystallinity that in the depositional phase, lacks desirability.
Yet, by at higher temperature, be generally 200-900 ℃, more preferably at 500-850 ℃, more preferably under 650-800 ℃, deposit after annealing, can improve degree of crystallinity.The atmosphere of using in these annealing steps is generally air, O 2, N 2, Ar, He, H 2, H 2O, CO 2, vacuum (P＜1 holder), or the mixing of these atmosphere.In order to reach enough crystallization degrees and to improve electrochemical properties thus, when annealing temperature being brought down below about 650 ℃, should preferably prolong annealing time.Exponential activation can take place along with temperature in crystalline rate, therefore can reduce and significantly reduce with annealing temperature.If annealing temperature is reduced to too low, then the hot activation energy that complete crystallization process needs takes place to overcome in the energy shortage that is applied by annealing temperature.For example, the degree of crystallinity that in air, produced in 15 minutes in 900 ℃ of annealing and the LiCoO of magnetron sputtering 2Film is annealed 1 hour with identical in 12 hours degree of crystallinity of 600 ℃ of annealing in air in 700 ℃ in air.In air in 400 ℃ annealing 24 hours after, the LiCoO of magnetron sputter deposition 2The electrochemical properties of cathodic coating may be still very poor, and annealing did not improve after 72 hours under this temperature.Therefore, the LiCoO that makes by gas phase process 2Cathodic coating may deposit after annealing about 30 minutes to 2 hours in 700 ℃ in air.But this higher annealing temperature may cause occurring the problem of chemical compatibility, is disadvantageous to the manufacture process of hull cell group probably thereby make this annealing steps, and has increased cost and reduced manufacturing output.
The selection of the serious restricting substrate material of condition meeting of deposition after annealing.Not only require substrate should preferably can bear high temperature anneal temperature (T＞500 ℃), also require substrate preferably chemically inert under the condition of annealing atmosphere, battery pack work and storage for all battery pack membrane materials that it contacted.Equally, in the manufacture process of electrochemical apparatus and subsequently work and storage process, substrate should preferably not be the source that possible diffuse into the impurity in the battery pack membrane material.These impurity can be poisoned the battery pack membrane material, and reduce, have a strong impact on or even destroy battery performance and useful life.Some selection of substrate may be limited to for example chemically inert high-temperature ceramic materials, for example Al 2O 3, MgO, NaCl, SiC and quartz glass.Proved that use Zr and these two kinds of metals of Ti are very limited as the successful property of metal substrate.Electrochemical apparatus of the present invention does not also require that substrate is Zr or Ti.
Though verified above-mentioned ceramic material can bear the high temperature of hull cell group manufacture process and chemical reaction can not take place, and is to use them to come cost to make the hull cell group effectively and also has significant disadvantage.The thickness of ceramic material generally is at least 5 mils (approximating 125 microns), is fragility, inflexible (rigidity), and expensive with given bottom area average specific.In addition, their pure area is limited.It is thin more that ceramic substrate becomes, can safety operation and can not to damage the maximum area of ceramic substrate more little.For example, the Al that 12 inches * 12 inches, thickness are 1/4 inch 2O 3Plate commercial be to obtain easily.But, be the Al of 10 mils (approximating 250 microns) through the thickness after thinning and the polishing 2O 3Ceramic substrate allows to area with reasonable productive rate manufacturing and narrows down to and be about 4 inches * 4 inches.Can need provide according to the client through 4 inches * 8 inches ceramic thin plate of polishing (＜20 mils or＜500 microns), but be not to be to come conventional stock with extensive manufacturing hull cell group acceptable price.
Because it is unpractical (though thickness being discussed less than 100 microns mica substrate in the United States Patent (USP) 6632563) as the baseplate material of hull cell group that ceramic material, uses ceramic material in the frangible character of thickness during less than about 100 microns.A kind of character of mica is, even thickness also is unusual fragility and frangible considerably beyond 100 microns.But the ceramic substrate of used thickness above 100 microns may cause the quality of the inactive substrate of electrochemical properties and volume to account for more than 90% of whole battery group weight and volume, and this is disadvantageous.
Because all these point out that the paper tinsel that can use non-pottery is as the hull cell group substrate.Under the situation of non-ceramic substrate, comprise for example situation of metal and polymeric substrates, can think that the silicon of silicon and doping mediates.
The paper tinsel that uses non-pottery for example has as the advantage of hull cell group substrate, makes baseplate material can bear processing conditions, comprises temperature conditions, and for example contacts with some battery pack layer with potential reaction.Ceramic substrate with respect to given bottom surface, the foil substrate of non-pottery can be thinner, more flexible, price is lower, obtain with large scale more easily, and can reduce the integral thickness of battery pack and electrochemical apparatus, reduce the inactive quality of electrochemistry and the volume of whole battery group simultaneously, thereby increase capacity density, energy density and the power density of battery pack.The paper tinsel of non-pottery for example can be that the coiled material of 0.5-5 mil (approximating the 12-125 micron) obtains with thickness, and width can reach some rice, and length can reach several meters.Compare with batch manufacture process of general use at present, the substrate that provides with the long paper material can carry out the reel-to-reel manufacturing with much lower cost.Compare with the hull cell group of making on thick hard substrate, the hull cell group of making on thin flexible base, board can not damaged battery performance, has played certain effect in some application facet of facilitating hull cell group technology.
By making substrate thinner inactive quality of electrochemistry and the volume that reduces battery pack that obviously become, can improve capacity density, energy density and power density on battery pack unit mass and the volume.For example, a kind of given volume of using possibility specific battery group is 0.1 centimetre of 2 cm x, 2 cm x.Do not meet at present conventional button battery or gluey rolling (jelly roll) (spiral twines or be prismatic) battery pack that this physical size requires.On the contrary, the thin film solid state group can meet this volume requirement, and reason is that even make on 0.05 centimetre ceramic substrate, whole battery group comprises that optional protectiveness is sealed or the thickness of cover (referring to give a definition) is also much thin than 0.1 centimetre.Be when making the hull cell group of same capability on the foil substrate of 2 mils (approximating 50 microns, promptly 0.005 centimetre), can further in this volume range, pile up maximum 20 battery pack at the thickness of identical floor space.The actual quantity of battery pack is by the thickness of for example each battery cell (comprise its substrate, its optional protectiveness seal or cover) decision.Use thin non-ceramic foil substrate to substitute thick ceramic substrate, capacity density, energy density and power density are significantly improved.
For example, can make the hull cell group by sequential aggradation single battery group component layer on mutual top layer.As mentioned above, the example of Zui Jia positive negative electrode comprises (but being not limited to) LiCoO 2, LiMn 2O 4, LiMnO 2, LiNiO 2And derivative.Electrochemical apparatus of the present invention does not need Li xV 2O yNegative electrode, wherein 0＜x≤100 and 0＜y≤5.Can under temperature, align negative electrode and deposit post growth annealing, make its complete crystallization, thereby obtain its electrochemical properties completely far above 500 ℃.Because breaking reaction can take place when contacting with the positive negative electrode of high temperature in some known solid-state lithium electrolyte under these hot conditionss, so can before deposit electrolyte layer, deposit positive negative electrode and anneal.
It is generally acknowledged that positive cathode material is the semiconductor of difference at least in some scopes of the state of charge of the battery pack course of work.In order to make battery pack make maximum power and be delivered in the external circuit, can go up the positive cathode layer of deposition at the negative electrode current collection layer (CCC) of metal backing contact.Described CCC should experience the high temperature cathode annealing process equally, and does not react with positive negative electrode when carrying out high annealing.Therefore, can use noble metal, for example gold or its alloy, perhaps equivalent.
Above summarized content is pointed out, in order to improve the performance of battery pack, can deposit the second layer of positive cathode material as battery pack at once after deposition CCC.Therefore, at next manufacturing step (electrolyte deposition) before, positive cathode layer deposits after annealing can make it finish crystallization.Because high temperature cathode material and substrate are very approaching, may just separate each other by thin CCC (0.1-1 micron), so, when being the metal forming (for example stainless steel) of high-temperature stable for it, observing positive negative electrode and substrate strong, harmful counterdiffusion mutually and reaction take place not using ceramic substrate.For example, there are three main causes to cause metal CCC itself can not block the phase counterdiffusion.At first, the CCC film is thin (0.1-1 micron) relatively, can only be as a thin empty diffusion impervious layer.Secondly, CCC shows grainiess.Crystal boundary may become the common location of ion and electrons spread and conduction, so, think that CCC is from being permeable to ion and electronics from adjacent positive cathode layer and adjacent metal foil substrate in essence.Therefore, in the negative electrode annealing steps, foil substrate material and cathodic coating material can counterdiffusion.The 3rd, the direct and metal forming substrate formation alloy of metal CCC, thus influence its current collection character.
The thickness of CCC is by for example cost, weight, volume and adherence decision, and when manufacturing thickness surpassed about 2 microns CCC, it was unpractical technically that these factors may all can become, particularly when using expensive noble metal for example golden.Obviously thicker CCC film (approximately greater than 5 microns) can be avoided the phase counterdiffusion probably, and this depends on for example temperature and relevant residence time of annealing steps.But using so, thick CCC can for example increase material cost and make adherence become unreliable potentially.
Use the metal forming substrate to replace ceramic substrate not only to reduce the cost of the hull cell group of on ceramic substrate, making, also use the new technology of hull cell group and brought great chance for exploitation.Compare with ceramic wafer, obtain easily thickness on the market less than 75 microns metal forming, some can obtain material even be as thin as 4 microns.These paper tinsels flexible more much higher than ceramic substrate, the ratio that accounts for the structure of battery pack, nonactive weight is littler, and, the most important thing is, significantly reduced the integral thickness of the hull cell group device of finishing.What need emphatically point out is, integral thickness is minimized and the flexibility that improves battery pack is very important for most of hull cell groups are used.Thinner hull cell group device can adapt to application new, that physical size is littler.Consist of possibility (being smart card etc.) with hull cell now with the impracticable application of button battery battery pack in the past.The flexibility that foil substrate increases further for example allows to be configured to new, nonplanar shape.
And average with the unit bottom area, the cost of thin metal foil generally is lower than pottery, and forms much bigger size, for example becomes coiled material to provide.Flexible owing to having, substrate area is big, has the possibility of exploitation reel-to-reel manufacture method, so the further manufacturing cost that reduces.
The hull cell group of making on ceramic substrate with prior art specific energy mutually provides the hull cell group of unaffected or augmented performance to can be used in the new application of exploitation.Consider from this aspect, the present invention can be included in the barrier layer of deposition counterdiffusion on the metal forming substrate, wherein, under (for example at 100 ℃ to scope) under high deposition after annealing temperature and the low deposition after annealing temperature and all working and condition of storage at electrochemical apparatus up to the substrate fusing point, described barrier layer chemically separates the substrate portion of battery pack (being the electro-chemical activity battery) part with electrochemical apparatus, itself does not become the source of impurity simultaneously.This execution mode on the one hand of the present invention as shown in fig. 1.
In battery pack manufacturing process and under battery pack work and condition of storage, the barrier layer can for example prevent that any pollutant from diffusing into the battery pack from substrate, and stops ion disengaging battery pack to diffuse in the substrate.This barrier layer at any time can not show grainiess.That is, it is amorphous or glassy state in the depositional phase, and keeps this state in whole annealing and battery pack manufacturing process and under battery pack work and condition of storage.There is not grainiess can avoid harmful the crystal boundary diffusion or the conduction of ion and electronics in the barrier layer.As indicated above, crystal boundary is that impurity and pollutant are along its current path.When meeting some condition in these conditions, the hull cell group that metal substrate (flexible and thin, perhaps flexible lower and thicker) go up to be made can show with chemical inertness, but thick and firmly, the suitable character of hull cell group made on the heavier and expensive ceramic substrate.
Some potential material that is suitable for diffusion impervious layer may be the material of ionic conduction difference, for example is boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide and any multiple compound thereof.In these compounds, electrical insulating material can further prevent contingent reaction between substrate and the battery pack layer, and reason is, if these chemical reactions comprise ion and electron diffusion, then block electrons is exactly a kind of method of blocking these chemical reactions.But, also can use electric conducting material, as long as ZrN for example is any ion of their non-conducting substrates or battery pack layer material.In some cases, can use metal, alloy and/or semimetal as the sufficient barrier layer of function, this depends on the annealing temperature used and the baseplate material of use in battery pack manufacturing process.Described diffusion impervious layer can for example be single-phase or heterogeneous, crystal, glassy state, amorphous, perhaps their any mixture, but often use glassy state and amorphous structure, reason is not have crystal boundary in these two kinds of structures, can not become the position that increases disadvantageous ion and electrical conductivity generation.
Because some material has been blocked the conduction of different kinds of ions, so they also can be used for the hull cell group that some does not contain lithium, for example electroactive ion is the battery pack of beryllium, sodium, magnesium, potassium, calcium, boron and aluminium for example.The thickness of described diffusion impervious layer can be for example 0.01 micron-1 millimeter.
Though be used for the barrier layer of hull cell group of the present invention and/or stop that the notion of subgrade and principle are the metal substrate exploitation at first, but can be on polymeric substrates and doping and unadulterated silicon substrate sedimentary facies with barrier material, the relevant hull cell group of these polymeric substrates and silicon substrate is used and has been attracted commercial interest equally.The temperature of deposition after annealing can for example be lower than the silicon substrate of use or the fusing point of polymeric substrates, and does not consider the barrier layer that applies, thereby avoids making the substrate fusing.
An embodiment of the invention for example relate to the method that goes up the solid-state thin-film battery group of making flexible, high power capacity at thin foil substrate (for example metal substrate).For the purposes of the present invention, electrochemical apparatus is defined as the equipment (referring to Fig. 1) that comprises at least one electro-chemical activity battery (for example hull cell group), related substrate (for example metal substrate) and the suitable diffusion impervious layer between electro-chemical activity battery and substrate (forming) by a plurality of subgrades that stop.In addition, described electrochemical apparatus can comprise that protectiveness is sealed or the protectiveness cover, below will further discuss.
The success of some execution mode of the present invention is suitable owing to having used between substrate and hull cell group, chemically inert diffusion impervious layer and stop subgrade, these barrier layers and stop that subgrade can isolate these two parts of electrochemical apparatus effectively.Diffusion impervious layer preferably can bear the high temperature anneal temperature that applies when making hull cell group part on substrate on this part, the barrier layer all is chemically inert to substrate and hull cell group part, not impurity source (at least for hull cell group part and Yan Bushi), and finish under work after making and the condition of storage and the hull cell group partly can be separated with the substrate chemistry at electrochemical apparatus.In addition, in battery pack manufacturing process and under all battery pack work and condition of storage, the barrier layer can prevent that preferably any pollutant from attempting from substrate diffuses into hull cell group part, and stops the Li ion to break away from the hull cell group partly to diffuse in the substrate.Extra benefit is, the atmosphere influence that applies in the post anneal can also be avoided depositing by protective substrate in the barrier layer in the course of processing, and the influence of avoiding any hull cell group component of having existed in the fabrication stage at uncompleted electrochemical apparatus.
Making a plurality of diffusion impervious layers of subgrade that stop can finely tune the physical property (engineering properties (specifically being not have pin hole, flexible and adherence), electrical property, magnetic property, acoustic properties, thermal property and optical property) and the chemical property of diffusion impervious layer, thereby with respect to the electrochemical apparatus made from the diffusion impervious layer that may include only the given material of individual layer, improve the Performance And Reliability of described electrochemical apparatus, described given material for example is Si 3N 4Or Ti 84B 16(on thermodynamic significance, this material is the TiB of equivalent almost 2And the two-phase system of β-B (compound), referring to Binary Alloy Phase Diagrams, the 2nd edition (T.B.Massalski, H.Okamoto, P.R.Subramanian and L.Kacprzak compile, ASMInternational 1990), the document is incorporated into this by reference) or TiO 2-Ba 0.5Sr 0.5TiO 3Composite materials (material described in the United States Patent (USP) 6444336 for example, this patent by with reference to being incorporated into this).In the simplest form, diffusion impervious layer of the present invention can comprise that thin (about 1000 dusts) with extra raising adherence character stop subgrade, Ti for example, and thicker (1 micron) stops for example Si of subgrade 3N 4
The sublayer material that stops that is used for diffusion impervious layer of the present invention can include but not limited to amorphous Si 3N 4, SiC, ZrN and TiC etc. film.Since these exemplary compound have ion barrier character, amorphous structure and to the battery pack of substrate and electrochemical apparatus partly for chemically inert, so they can be effective as the barrier layer.The feature of these barrier layer chemical substance brilliances is up under 700 ℃ the high temperature for example, in long period of 2 hours for example, at preferred LiCoO 2Keep their capabilities in the crystallization deposition post anneal in amorphous state and the diffusion barrier properties of depositional phase.Therefore, kept good electric chemical property with the hull cell group of the equivalent construction of on ceramic substrate, making in the hull cell group of making on the metal forming, but also had flexible, thinner and more cheap advantage with these barrier layers.
An embodiment of the invention for example also relate in the subsequent manufacturing processes of hull cell group, on substrate, make suitable barrier layer, in battery pack manufacturing process and under battery pack work subsequently and condition of storage, the barrier layer is from chemically isolated substrate and battery pack part.Except metal substrate, can also use polymeric substrates and doping and unadulterated silicon substrate.
A purpose of an embodiment of the invention provides for example a kind of electrochemical apparatus, described electrochemical apparatus has metal substrate, polymeric substrates or doping or unadulterated silicon substrate, and the battery pack (electro-chemical activity battery) that only is positioned at described substrate one side.
Another purpose of an embodiment of the invention provides for example a kind of electrochemical apparatus, described electrochemical apparatus has metal substrate, polymeric substrates or doping or unadulterated silicon substrate, and two battery pack (two electro-chemical activity batteries) that are each positioned at described substrate one side.
Another purpose of an embodiment of the invention provides for example a kind of method of making electrochemical apparatus, described electrochemical apparatus has metal substrate, polymeric substrates or doping or unadulterated silicon substrate, and the battery pack (electro-chemical activity battery) that only is positioned at described substrate one side.
Another purpose of an embodiment of the invention provides for example a kind of method of making electrochemical apparatus, described electrochemical apparatus has metal substrate, polymeric substrates or doping or unadulterated silicon substrate, and two battery pack (two electro-chemical activity batteries) that are each positioned at described substrate one side.
Brief Description Of Drawings
Fig. 1 illustrates by the barrier layer the schematic diagram of the electro-chemical activity battery of substrate portion and electrochemical apparatus part from the execution mode of chemically isolating, and described barrier layer comprises a plurality of subgrades that stop.
Fig. 2 illustrates the barrier layer that stops subgrade that comprises different area provides the example application of the execution mode that electricity isolates between the positivity of electro-chemical activity battery and negativity part schematic diagram.
Fig. 3 a illustrates and comprises that conductivity stops the barrier layer of subgrade, thereby by make fully the negativity part realizes the example application of the execution mode that electricity is isolated between the positivity of electro-chemical activity battery and negativity part schematic diagram at the electrolyte top.
Fig. 3 b illustrates the barrier layer that the conductivity that is included on the metal substrate stops subgrade, thereby by make fully the negativity part realizes another example application of the execution mode that electricity is isolated between the positivity of battery pack and negativity part schematic diagram at the electrolyte top.
Fig. 3 c illustrates the barrier layer that the conductivity that is included on the metal substrate stops subgrade, thereby by make fully the positivity part realizes the example application of the execution mode that electricity is isolated between the positivity of battery pack and negativity part schematic diagram at the electrolyte top.
Fig. 4 a illustrates and comprises that conductivity stops the barrier layer of subgrade, by make the negativity part fully at the electrolyte top, does not realize the schematic diagram of the example application of the execution mode that electricity is isolated between the positivity of electro-chemical activity battery and negativity part.
Fig. 4 b illustrates and comprises that conductivity stops the barrier layer of subgrade, by make the negativity part fully at the electrolyte top, does not realize the schematic diagram of another example application of the execution mode that electricity is isolated between the positivity of electro-chemical activity battery and negativity part.
Fig. 4 c illustrates and comprises that conductivity stops the barrier layer of subgrade, by make the negativity part fully at the electrolyte top, do not realize between the positivity of electro-chemical activity battery and negativity part that electricity isolates, the schematic diagram of negative simultaneously anode and another example application that stops the execution mode that subgrade directly contacts.
Fig. 5 illustrates the X diffracting spectrum (XRD) of an execution mode, in this execution mode, has by two on stainless steel foil type 430 substrates of 50 micron thickness and stops subgrade (5000
Figure 2006800296432_5
Al 2O 3With 6000
Figure 2006800296432_6
Co 3O 4) the electric insulation barrier layer formed, be attached with 300 on the barrier layer
Figure 2006800296432_7
Adhesion layer, have 3000 on the adhesion layer
Figure 2006800296432_8
The Au cathode current collector, make the LiCoO that 1.6 micron thickness are arranged on the cathode current collector 2Positive cathodic coating.
Fig. 6 illustrates the X diffracting spectrum (XRD) of an execution mode, in this execution mode, has on the silicon substrate of 300 micron thickness by two subgrades (5000
Figure 2006800296432_9
Si 3N 4With 5000
Figure 2006800296432_10
SiO 2) barrier layer formed, have 300 on the barrier layer
Figure 2006800296432_11
Adhesion layer, have 3000 on the adhesion layer
Figure 2006800296432_12
The Au cathode current collector, make the LiCoO that 1.6 micron thickness are arranged on the cathode current collector 2Positive cathodic coating.
Fig. 7 a illustrates the schematic diagram of execution mode of a kind of anode construction of " conventional structure ", and wherein negative anode does not directly contact with the barrier layer.
Fig. 7 b illustrates the schematic diagram of execution mode of a kind of anode construction of " conventional structure ", and wherein negative anode stops that with at least one subgrade directly contacts.
Fig. 8 illustrates the schematic diagram of execution mode of a kind of anode construction of " conventional structure ", and wherein negative anode stops that with the conductivity ZrN that also plays the anode collector effect subgrade directly contacts.
Fig. 9 illustrates the schematic diagram of a kind of execution mode of battery pack structure, wherein, is chemically inert situation at substrate for negative anode, and negative anode directly contacts with substrate.In this embodiment, if the conductivity of substrate enough big (for example being stainless steel), then substrate plays the effect of negative anode collector and negative terminal.
Figure 10 illustrates the schematic diagram that uses the moisture overcoat to protect the execution mode of the influence of moisture that the dielectric substrate of moisture-sensitive is avoided existing in the surrounding environment, in this embodiment, an opening is arranged in the protectiveness encapsulated layer of manufacturing, for the contact negative terminal.
Detailed Description Of The Invention
Be to be understood that to the invention is not restricted to the ad hoc approach described in the literary composition, draft etc., but can change. The term that uses in the literary composition is just in order to describe the specific embodiment, and do not attempt to limit the scope of the invention, and scope of the present invention is only determined by claims.
The singulative that uses in specification and claims " one ", " a kind of " and " this " comprise plural form, unless clearly represent other implications in the context.
All patents of listing and other publications all are incorporated into this in full by the reference mode, and purpose is to describe and disclose method, equipment and the composition that can be used in combination with the present invention in these patents and the publication. Provide these patents and publication only to be because the content that their disclose early than submission date of the application. Should not think that the inventor admits by utilizing formerly invention or having no right to expect these contents for any other reason.
Unless other explanation is arranged, otherwise all technical terms that use in the literary composition have all and well known to a person skilled in the art identical meanings. Although can use any known method, device and material in enforcement of the present invention or the test, describe some exemplary method for optimizing, device and material in the literary composition.
For example, thus can make the hull cell group in a batch mode by depositing in order single battery group component layer. Selected after the baseplate material, carried out other preliminary treatment in the time of can and needing by cleaning and be prepared. , gross thickness that subgrade forms by stopping is that the barrier layer of 0.5-5 micron is the key of successfully making the hull cell group on metal and polymer foil and silicon. The annealing temperature for positive cathodic coating and cathode current collector should be born in the barrier layer, keeps chemical inertness, and does not become the impurity source.
In addition, under battery pack manufacturing and all battery pack work and condition of storage, the barrier layer should prevent that any pollutant from entering the positive negative electrode from substrate, and stops ion and atom from positive negative electrode and cathode current collector to diffuse in the substrate. The barrier layer can be deposited on the clean substrate, normally covers the even flawless film of whole substrate. Can deposit next battery pack layer in a batch mode in order then, distinguish the border of each layer of hull cell group with shadow mask. The battery pack layer can Design and manufacture becomes, and the effect of isolated crystal boundary diffusion is eliminated the positive negative electrode (LiCoO for example of subsequent deposition2) and the cathode current collector of its below and the reaction between the substrate (for example being respectively au cathode colelctor electrode and flexible stainless steel foil substrate). Hereinafter be given in the exemplary manner of the embodiment of deposited barrier layer (comprise and stop subgrade) on the substrate of making the hull cell group.
1. substrate is selected and preparation
At first select baseplate material. Can make the hull cell group in the various metal formings with different surfaces fineness and sheet. Can use stainless thin foil as substrate. But, also can use other more expensive and thicker materials or the lower material of fusing point, include, but are not limited to Ti and Ti alloy, Al and Al alloy, Cu and Cu alloy and Ni and Ni alloy etc. In addition, the user can for example kind, surface roughness, homogeneity (homogeneity) and the purity of steel alloy be determined the best Fabrication parameter of concrete device according to the preferred physical properties of paper tinsel. Electrochemical apparatus of the present invention does not require that substrate is the Al that is coated with metal or semimetal (comprising V, Mn, Mg, Fe, Ge, Cr, Ni, Zn and Co). And electrochemical apparatus of the present invention does not require that substrate is pure polymide.
For example selected after the stainless steel foil material, generally it has been cleaned to remove oil, particulate and other surface contaminants that the chemistry that may affect barrier layer and substrate or machinery are adhered. Consider from this respect, can use any clean method that abundant clean surface can be provided, for example any suitable those wet chemistry cleans or plasma cleaning method. Can choose wantonly as required the further preliminary treatment of foil substrate through cleaning. For example, in order to alleviate the natural stress of metal forming, can before deposited barrier layer, carry out high temperature (for example 500 ℃) annealing steps, as long as annealing temperature keeps below the fusing point of metal forming.
Although basically irrelevant with foil material and thickness thereof, can further reduce in the mode of film successively or regulate thermal stress and mechanical stress by some annealing steps. For example, can carry out preannealing to the paper tinsel through cleaning according to mentioned above, regulate uncoated metal forming. In addition, other annealing steps can comprise any combination of for example deposition rear barrier layer annealing, the rear negative electrode current collection layer annealing of deposition or post-depositional layer of annealing before the negative electrode recrystallization annealing temperature. The plasma treatment step that can add before or after these steps is (referring to for example D.M.Mattox, Handbook of Physical VaporDeposition (PVD) Processing (physical vapour deposition (PVD) (PVD) is processed handbook), Society ofVacuum Coaters, Albuquerque, New Mexico 660ff and 692ff (NoyesPublications 1998)). Can prepare silicon substrate and polymeric substrates similarly.
2. barrier deposition
When making the hull cell group, can be on substrate deposited barrier layer, thereby in battery pack manufacturing process and under subsequently battery pack work and condition of storage, with substrate and battery pack part chemical isolation.
In general, in the space that ion or the electronics of potential reaction thing is limited in reactant separately or be stopped in the reactant interface, so that when preferably not having the phase counterdiffusion between these potential reaction things, can prevent between the potential reaction thing chemical reaction taking place. Except diffusion stops character, select to be used for should be taken into account following 3 points when barrier layer and composition thereof stop the material of subgrade: (a) should bear and align the annealing temperature that cathodic coating and cathode current collector apply, (b) should keep chemical inertness, (c) should not become the source of impurity.
For example can the depositing electrically conductive material, ZrN for example, this material has the character of sufficient prevention ions diffusion, can on chemical sense the battery pack in substrate and the electrochemical apparatus partly be isolated. In this case, electric conductivity stops that subgrade can also be used as colelctor electrode. Because ZrN is being stable when contacting with negative anode material (specifically being lithium metal), so it can be used as the negative electrode current collection layer utmost point and/or anode collector.
Although only use the certain material (Si of electrical insulating property and barrier metal ion for example of individual layer3N 4) to make up the barrier layer be feasible in principle, but have been found that, the barrier layer that is made up of the suitable subgrade that surpasses can obtain higher manufacturing productive rate, and the hull cell group length of life in appointment obtains higher battery performance reliability thus, each subgrade in the described barrier layer its objective is barrier layer character is finely tuned for the barrier layer provides different specific natures. Therefore, the present invention pays close attention to by the manufacturing on the barrier layer that forms above a subgrade and provides, and preferably this equipment can with the chemically isolation of battery pack part of substrate and electrochemical apparatus, can be made simultaneously reliably in this barrier layer.
2.1 make the barrier layer that comprises that insulation stops subgrade
The barrier layer can Direct precipitation on substrate. Can design and make the barrier layer that stops that by a plurality of subgrade forms, wherein at least one stops that subgrade is amorphous or glassy state, to avoid the crystal boundary diffusion of ion and electronics, this crystal boundary diffusion phenomena are minimized, thereby in battery pack manufacturing process and under the work and condition of storage of battery pack subsequently, reduce unwanted material and diffuse into battery pack layer and the phenomenon from wherein diffusing out. Preferably to prevent the chemical reaction between battery pack component and the substrate or this chemical reaction is minimized.
Stop that respectively subgrade can be selected from the material that for example has following character, that is, can stop from LiCoO2The ion of cathode layer (lithium ion, cobalt ions and oxonium ion) diffusion, spread from the atom of colelctor electrode and ion (gold, platinum, nickel, copper etc.) diffusion and from ion and the atom (major element of iron, chromium, nickel, other heavy metals and selected stainless steel kind) of stainless steel substrate, but, for example a needs use substrate, colelctor electrode and/or positive negative electrode just enough as the electrically insulating material of inertia. Substrate portion and the chemically isolation of battery pack part considering in making the electrochemical apparatus process and under the work of electrochemical apparatus subsequently and condition of storage, will make electrochemical apparatus, can think select by can blocks ions and the subgrade of electronics to form the barrier layer be preferred method.
The boride of binary, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide, and the polysiloxanes of the organic polymer of diamond, diamond-like carbon, high-temperature stable and high-temperature stable is except providing electrical insulation property that general ion barrier character can also be provided. Therefore, can use these materials as stopping sublayer material. Except the binary compound of preferred these materials of use, stop that subgrade can be formed by any multi-element compounds of for example these materials, such as but not limited to oxygen-nitride, carbon-boride, carbon-oxygen-nitride, silico-carbo-nitride and oxygen-fluoride. Electrochemical apparatus of the present invention does not require that the barrier layer is pure oxide.
Can select one or more suitable membrane deposition methods to deposit above-mentioned binary and the polynary sublayer material that stops, described deposition process comprises chemical vapour deposition (CVD) that sputter (RF-magnetron, AC magnetron, DC and DC pulsed magnetron, diode RF or DC or AC), electron beam evaporation, heat (resistive (resistive)) evaporation, plasma strengthen, ion beam assisted depositing, cathodic arc deposition, electrochemical deposition, spray pyrolysis etc. Si for example3N 4Stop that subgrade can make in such a way: use preferably at the RF magnetron sputtering system, use Ar-N2The pure silicon target of sputter in the reactive plasma environments. SiC and TiC stop that the subgrade film is undertaken by the target of identical corresponding composition in inertia Ar plasma environment normally that the RF magnetron sputtering forms, and the derivative (SiC:N and TiC:N) that its nitrogen mixes can be at reactive Ar-N2Use the RF magnetic controlled tube sputtering apparatus respectively by SiC and TiC target deposition in the plasma environment.
By the independent N that contains is provided2、O 2、N 2O、BF 3、C 2F 6、B 2H 6、CH 4、SiH 4Deng the sputter gas mixture, perhaps also contain for example sputter gas mixture of argon of inert carrier gas, and/or provide element from sputtering target, oxygen-nitride of form optimizing, carbon-boride, carbon-oxygen-nitride, silico-carbo-nitride, oxygen-fluoride etc. For example, silicon-carbon titanium nitride (or titanium carbonitride silicon) Ti3SiC 2: the thin film deposition of N can be passed through at Ar-N2In the plasma atmosphere, the single sputtering target that use is made of the TiC that replaces and SiC zone (gross area ratio is 3: 1) or use two independently sputtering target (one is TiC, another is SiC) realize that their mode of operation means that to fix time all be 3: 1 (dual-target sputtering deposition) so that the TiC/SiC ratio of the mixed material layer that deposits at the same substrate area is in office. Before continuing battery pack manufacturing process, can carry out deposit post-treatment to the substrate that has been coated with the barrier layer, perhaps do not carry out deposit post-treatment.
An example that stops sublayer material can be Si3N 4，SiN xO y(3x+2y=4), the perhaps Si of graded oxidation thing3N 4, reach stoichiometry on its surface, all be almost SiO on two surface when perhaps needing2 In addition, the SiC of doping nitrogen or the nitrogen that do not mix or TiC can be as the materials that stops subgrade.
Some specific derivatives of these materials are used for the barrier layer but do not have other suitable when stopping subgrade, these specific derivatives may not be most preferred as the ion barrier layer, because these derivatives allow some ions diffusion in manufacture process or in battery pack work with between the storage life, only show simultaneously the insulating property (properties) of going on business, for example non-stoichiometric ZrO2, non-stoichiometric YSZ (zirconia that yttrium is stable) and non-stoichiometric LiI (lithium iodide). Different from their stoichiometric analog, non-stoichiometry is the main cause that these material conductions allow oxygen and lithium ion diffusion simultaneously.
For example, in order to finely tune some character on barrier layer, for example the cohesive, mechanically flexible of raising and substrate and/or battery pack part, with the stability of adjacent layer, pin hole, resistive and chemical inertness do not appear, can use to comprise the suitable barrier layer that stops subgrade. For example, the barrier layer at stainless steel 430 substrate tops can stopping that subgrade is stacking and consist of by following sequence: 500
Figure 2006800296432_13
SiO2(for increasing with adherence in conjunction with the stainless steel substrate of oxide)/2000Si3N 4(be electric insulation, and be the material that can stop lithium ion, cobalt ions, oxonium ion, iron ion, chromium ion and gold atom diffusion)/1000
Figure 2006800296432_15
SiC:N (layer that strongly stops the diffusion of lithium ion, cobalt ions, oxonium ion, iron ion, chromium ion and gold atom)/2000
Figure 2006800296432_16
Si3N 4(be electric insulation, and be the material that stops lithium ion, cobalt ions, oxonium ion, iron ion, chromium ion and gold atom diffusion)/500
Figure 2006800296432_17
SiO2(promoting the layer bonding with collector layer) can deposit 300 on it
Figure 2006800296432_18
Cobalt colelctor electrode adhesion layer and 300
Figure 2006800296432_19
Golden colelctor electrode.
In some cases, insulation stops that subgrade not only can contact with positive negative electrode and/or cathode current collector, can also contact with negative anode and/or anode collector. Under any circumstance, stop subgrade can be for example all be chemically inert to all material of its contact preferably. This feature may limit for example pure Al2O 3Or SiO2The purposes of barrier layer when contacting with the negative anode of lithium metal forms Li otherwise adverse reaction can take place lithium metal2O、LiAlO 2With Li-Al alloy or Li2O、Li 2SiO 3With the Li-Si alloy.
2.2 make and comprise that at least one electric conductivity stops the barrier layer of subgrade
If for example electric conductivity stops that subgrade satisfies following preferred attribute, then electric conductivity stop subgrade also be same effectively: 1) prevent that ions diffusion from entering the battery pack layer or diffuse out from it, 2) in manufacture process and under subsequently all battery pack work and condition of storage, with substrate or the reaction of battery pack layer. Described battery pack layer can for example comprise also that electrical insulating property stops subgrade. These electrical insulating property subgrades and electric conductivity subgrade can for example not be all to have identical shaped or area size. Therefore, these stop that the barrier layer that the hybrid stack-ups of subgrade forms can be electric conductivity in the zone that some and substrate portion or battery pack partly contact for example, and in the zone that other and substrate portion or battery pack partly contact, the barrier layer shows electrical insulation property.
Be used for electric conductivity and stop that the material of subgrade can for example be selected from boride, carbide, silicide, nitride, phosphide and the oxide of electric conductivity binary, and the arbitrarily electric conductivity multi-element compounds that is selected from them, such as but not limited to oxygen-nitride, carbon-boride, carbon-oxygen-nitride, silico-carbo-nitride and oxygen-fluoride. Can also use through particular design and become the polymer of high-temperature stable of electric conductivity and the polysiloxanes of high-temperature stable. In 2.1 parts above, provide to be used for electrical insulating property and to stop the material selective listing of subgrade, and be incorporated into this. Can be formed by diverse composition and stop subgrade, for example can be by the following stacking barrier layer that forms of subgrade, 5000 of stopping
Figure 2006800296432_20
ZrN/4000
Figure 2006800296432_21
Si3N 4/3000 WC/1000
Figure 2006800296432_23
MoSi2, the wherein each subgrade that stops can for example have different area size.
The result is, for example Si3N 4Stop that subgrade can extend beyond for example whole bottom area of metal substrate, and ZrN stops the zone of a subgrade covered substrate below cathode current collector, and WC and MoSi2Stop that subgrade for example covers at least the whole zone of anode collector below and further extends in the zone of ZrN. Since area size, the Si of insertion3N 4Stop that subgrade can for example stop subgrade and electric conductivity WC/MoSi at electric conductivity ZrN2Stopping provides electricity to completely cut off between the subgrade, thereby partly and between the negativity part provides electricity isolated (referring to Fig. 2) in the positivity of battery pack.
In this embodiment, can stop subgrade by standard deposition method depositing electrically conductive on substrate, for example ZrN, TiN, WC, MoSi2、TiB 2Or NiP, described standard deposition method comprises chemical vapour deposition (CVD) that sputtering sedimentation (RF-magnetron, DC and DC pulsed magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, heat (resistive) evaporation, plasma strengthen, ion beam assisted depositing, cathodic arc deposition, electrochemical deposition, spray pyrolysis etc. For example, ZrN stops that subgrade can carry out the DC magnetron sputter deposition by the ZrN sputtering target and make in inertia Ar atmosphere, perhaps at reactive Ar-N2Carrying out equally the DC magnetron sputter deposition by metallic Z r target in the atmosphere makes.
In addition, preferred but be not limited under the temperature that makes the required deposition after annealing of positive negative electrode crystallization is medium for example 200-500 ℃ situation, can select some metal (for example Au, Pt, Ir, Os, Ag, Pd), semimetal (for example graphitic carbon, Si) and alloy (for example based on Au, Pt, Ir, Os, Ag, Pd, C and Si alloy) to stop subgrade as electric conductivity. Before proceeding battery pack manufacturing process, can stop that subgrade carries out further heat treatment to electric conductivity, perhaps do not heat-treat.
If manufacture at the battery pack anode and have the suitably form of electrically contacting property, then electric conductivity stops that subgrade can have extra advantage, namely omitted independently cathode current collector, unless for example select by with the thin layer of better electric conductivity and inertia for example gold be coated with electric conductivity and stop that thereby subgrade stops that to electric conductivity the electrical property of subgrade is optimized. No matter whether be coated with this better conductive layer, electric conductivity stops that the method for subgrade can comprise makes anode collector and negative anode and electric conductivity stop subgrade isolation simultaneously, and positive negative electrode and/or its cathode current collector and electric conductivity stop that subgrade electrically contacts. For example can realize this isolation by following steps:
1) extends dielectric substrate, so that negative anode and anode collector thereof all are positioned at the top of the dielectric substrate of electric insulation fully, in this case, the dielectric substrate part that is effective as negative anode and anode collector thereof stops subgrade (referring to Fig. 3 a and 3b). If the concrete Fabrication parameter of positive negative electrode can not cause reacting with the dielectric substrate that has existed, then can be positioned at according to the similar approach manufacturing positive negative electrode and the cathode current collector thereof at the top of dielectric substrate fully, and negative anode is positioned at the below (referring to Fig. 3 c) of dielectric substrate.
2) at negative anode and/or anode collector and when not exclusively being positioned at the top of dielectric substrate, then they can contact with the barrier layer, thereby stop that with one subgrade and/or metal substrate contact at least.In this case, one or more subgrades that stop can be conductivity, and at least one stops that subgrade should be (referring to Fig. 4 a and the 4b) of insulation.Under any circumstance, all stop that subgrade all should be chemically inert to all material of its contact.Can for example preferably forbid when contacting, using Pt like this with the negative anode of lithium metal 2Si stops subgrade, and formation Li not so can cause reacting xSi (0＜x≤4.4=and Li yPt (0＜y≤2=(referring to Fig. 4 c).
2.3 barrier layer and substrate
Provide a reason on barrier layer to be, for example in the manufacture process of battery pack part (process temperature can up to the fusing point of substrate), then under all working and condition of storage of electrochemical apparatus, between the substrate portion of the electrochemical apparatus of embodiment of the present invention and battery pack part, provide chemical isolation.Principle same as described above can be applied at least three kinds of substrate kinds of the present invention, these kinds can comprise metal substrate, polymeric substrates and doping or unadulterated silicon substrate.
Can be directly on above-mentioned three kinds of substrates deposition electrical insulating property or conductivity stop subgrade.Certainly, should observe intrinsic physics and chemical restriction condition that various substrates have, and correspondingly regulate the deposition parameter that respectively stops subgrade.For example, can carry out sputtering sedimentation under the high deposition rate condition, the depositing temperature that high deposition rate makes the substrate surface place produce surpasses the polymeric substrates fusing point.Therefore, should preferably limit deposition parameter, thereby observe the fusing point of substrate.In another example, can use and have only 10 microns extremely thin Si substrate.In this case, need correspondingly to regulate to stop the stress of subgrade in its deposition process, ignore any deposition after annealing at this moment, adapting to the engineering properties of frangible Si substrate, thereby be unlikely to follow-up it to be broken before stopping subgrade and/or battery pack layer in that deposition is any.According to may using of all three kinds of substrates, and the make the barrier layer thereon basic principle of (comprising that it stops subgrade), can provide example more specifically, these examples are not limitation of the scope of the invention.
3. the manufacturing of battery pack
Made the barrier layer on substrate of the present invention after, the subsequent fabrication steps of electrochemical apparatus depends on whether will make the second electro-chemical activity battery to finish " two-sided " electrochemical apparatus on second side of substrate, below will further discuss.Electrochemical apparatus of the present invention does not require that the first electro-chemical activity battery is a solar battery group.
But for the situation of " single face " electrochemical apparatus, wherein the first electro-chemical activity battery of only making on first side of substrate before the component layer of making the first electro-chemical activity battery, is chosen wantonly on second side of substrate and is deposited the second layer.The purpose of making the second layer is a protective substrate in manufacturing, work and the storage process at electrochemical apparatus, in order to avoid be subjected to the influence of chemistry and mechanical factor in the surrounding environment.In addition; by realizing the second layer; can in manufacturing, work and/or the storage process of electrochemical apparatus, protect the first electro-chemical activity battery in order to avoid be subjected to influence from the chemical pollutant of surrounding environment; these pollutants can be second (or be called protect), and the side enters substrate and diffuses through substrate, thereby may arrive the first electro-chemical activity battery and harmful reaction takes place with it.Protection that provides except substrate itself and the protection that provides by the barrier layer between substrate and the described first electro-chemical activity battery; this protection to the first electro-chemical activity battery is a kind of extra safeguard measure, and the situation in whole zone that may not cover first electro-chemical activity battery below for wherein barrier layer is all the more so.The useful life that can cause prolonging electrochemical apparatus to the protection of the substrate and the first electro-chemical activity battery.
The second layer can be by comprising the made that is selected from following compound: metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide, perhaps for example by being selected from any multi-element compounds manufacturing that following material is formed: boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide perhaps for example are the polysiloxanes manufacturings of the organic polymer and the high-temperature stable of high-temperature stable.Specifically, in manufacturing, work and/or the storage process of electrochemical apparatus, can used thickness be 500
Figure 2006800296432_24
-5 microns thin metal layer enters protective substrate by what stop pollutant on second side.And, with ceramic analog for example TiC compare, can use the metal level of nickel for example or titanium, because metal level can deposit at faster speed and cost is lower.
The barrier effect of the second layer for example comprises the prevention second layer and pollutant generation chemical reaction, it is air-breathing that this is called chemistry in the literature, corrode inhibition or sacrifice layer is provided, this barrier effect is not limited to be finished by metal level, can also finish by for example following material: low oxide or low price nitride (the insufficient or inadequate membrane material of nitrogenize of oxidation, for example can easily make by sputtering sedimentation), perhaps can be in the manufacturing of electrochemical apparatus, in work and/or the storage process by with surrounding environment in the oxygen that exists, moisture or carbon dioxide pollution thing reaction and be converted into the nitride or the carbide of oxide or carbonate.
By selecting mainly is that the material that chemical reaction provides protection or protection mainly is provided by chemical reaction does not take place, and can finely tune the second layer on substrate second side.Then, but can further finely tune by selecting to belong to a kind of material that under certain ambient environmental conditions, has higher or less reactive in back.For example, Al 4C 3Change into Al 2O 3The time temperature and partial pressure of oxygen change into SiO far below SiC 2The time temperature and partial pressure of oxygen.Similarly, the nitride that the enthalpy of formation is very little (Co for example 2Temperature when N) changing into corresponding oxide and the partial pressure of oxygen nitride more negative (Si for example far below the enthalpy of formation 3N 4Temperature and partial pressure of oxygen when and ZrN) changing into corresponding oxide.
Fundamentally, be that producer by electrochemical apparatus decides when making the second layer on second side of substrate, with respect to the cost that increases and optimum parameters, mainly being that material is selected and the manufacturing thickness of the second layer increases function to substrate and the protection of the first electro-chemical activity battery with respect to the particular ambient environmental condition that exists at the specific period, also mainly is that material is selected and the function of second layer manufacturing thickness.
Can use shadow mask to make up single battery group component layer according to batch manufacture method utilization order physics and/or chemical vapour deposition (CVD) step, make the hull cell group.Can make the electro-chemical activity battery according to any structure in some structures.Feature can comprise following:
(i) employed positive cathode construction
A. (the first deposition cathode before deposition anode of the positive negative electrode between barrier layer and negative anode; " conventional structure "), negative anode (the first deposition anode before deposition cathode between barrier layer and positive negative electrode; " inversion structures ")
B. align the deposition post growth annealing that negative electrode applies
(ii) employed anode construction
A. negative anode layer contacts with the barrier layer or does not contact with the barrier layer
B. the anode collector layer contacts with the barrier layer or does not contact with the barrier layer
(iii) employed barrier layer type
A. the electrical insulating property subgrade is to the conductivity subgrade
B. other subgrades in the area size of given subgrade and the given barrier layer compare
C. combined insulation subgrade and conductivity subgrade in order in the barrier layer
(iv) substrate electrically contacts or does not electrically contact with the electro-chemical activity battery (partly contact with its positivity or partly contact with its negativity no matter be) with the electro-chemical activity battery
(v) making manufacturing electro-chemical activity battery (two-sided electrochemical apparatus) on electro-chemical activity battery (single face electrochemical apparatus) or two sides on the side of substrate at substrate
(vi) employed protectiveness is sealed or the design of protectiveness cover
A. seal cover
B. seal or cover in have opening with touch terminal to seal or cover in do not have opening
C. in the open area, use the moisture overcoat or do not use the moisture overcoat
(vii) collector electrode and terminal
3.1 cathode construction
3.1.1 the positive negative electrode between barrier layer and negative anode was equivalent to before the negative anode of deposition earlier the positive negative electrode of deposition and may aligns the situation that negative electrode deposits after annealing: " conventional structure "
According to the electrical property on barrier layer, can before the positive negative electrode of deposition, make cathode current collector earlier.That is, if be insulating properties in the zone that will make positive negative electrode based on the barrier layer of its subgrade, then can the deposition cathode collector electrode, produce essential electrically contacting from anode to positive negative electrode.But,, then can choose the extra inert metal layer (" conduction promoting layer ") of deposition between barrier layer and positive negative electrode wantonly, to strengthen the current collection character on barrier layer if be conductivity in the zone that will deposit positive negative electrode based on the barrier layer of its subgrade.
Can deposit the conduction promoting layer on positive negative electrode, cathode current collector and barrier layer by selecting any method in many deposition processs, described deposition process comprises chemical vapour deposition (CVD) that sputter (RF-magnetron, DC and DC pulsed magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, heat (resistive) evaporation, plasma strengthen, ion beam assisted depositing, cathodic arc deposition, electrochemical deposition, spray pyrolysis etc.
Deposited after the positive negative electrode, can deposit the after annealing step, thereby improved physics, chemistry and the electrochemical properties of positive negative electrode.The most frequently used deposition after annealing carried out in air about 30 minutes to 2 hours at 700 ℃ usually, finished positive cathode material (LiCoO 2, LiMn 2O 4, LiMnO 2, LiNiO 2And derivative) crystallization.
The parameter of the composition of given derivative and the deposition after annealing step that applies can be pointed out the selection to barrier material.For example, for pure LiCoO 2And 700 ℃ in air annealing 2 hours, an optional combination is: 3000
Figure 2006800296432_25
The au cathode collector electrode, by 300
Figure 2006800296432_26
The cobalt adhesion layer be attached to the barrier layer of electrical insulating property, the barrier layer comprises that two stop subgrade: 5000
Figure 2006800296432_27
Al 2O 3With 6000
Figure 2006800296432_28
Co 3O 4, the barrier layer is on 50 microns stainless steel 430 paper tinsels.The X diffracting spectrum (XRD) of this structure after 700 ℃ of annealing as shown in Figure 5.LiCoO 2The crystallite size of (101) crystal grain of positive negative electrode shows as about 560
Figure 2006800296432_29
, its meticulous lattice parameter (a of while Six sides=2.8146 (4)
Figure 2006800296432_30
c Six sides=14.0732 (8)
Figure 2006800296432_31
) meet theoretical value (for example, ICDD77-1370:a Six sides=2.815 (1)
Figure 2006800296432_32
c Six sides=14.05 (1)
Figure 2006800296432_33
).This explanation crystal LiCoO 2Positive cathodic coating may not can and its any material (comprising substrate) reaction on every side, reaches simultaneously to show the suitable crystallization parameters that best electrochemical behavior needs in the electro-chemical activity battery.
Equally, 3000 Au/300
Figure 2006800296432_35
Make pure LiCoO on the cathode current collector of Co 2Positive negative electrode, described cathode current collector is attached to by two and stops subgrade (5000
Figure 2006800296432_36
Si 3N 4With 5000
Figure 2006800296432_37
SiO 2) on the barrier layer formed, described barrier layer afterwards, 700 ℃ of annealing 2 hours in air, can obtain good crystal LiCoO on the unadulterated silicon substrate of 300 micron thickness 2Positive negative electrode (a Six sides=2.8151 (4)
Figure 2006800296432_38
c Six sides=14.066 (7)
Figure 2006800296432_39
The crystallite dimension of sample on (101) plane is 1100 ), with theoretical lattice parameter very near (for example, ICDD 77-1370:a Six sides=2.815 (1)
Figure 2006800296432_41
c Six sides=14.05 (1)
Figure 2006800296432_42
).Owing to form good crystal, have the stoichiometric LiCoO of layer structure and theoretical crystallography lattice parameter 2Positive cathodic coating can not react with the material (comprising silicon substrate) around it, as shown in Figure 6.With the LiCoO that on stainless steel 430 foil substrates, makes in the example above 2Positive cathodic coating is similar, theoretical crystallography lattice parameter (a Six sides=2.8151 (4)
Figure 2006800296432_43
c Six sides=14.066 (7)
Figure 2006800296432_44
) LiCoO on the Si substrate is described 2Positive cathodic coating can show some preferred electrochemical properties.
3.1.2 the negative anode between barrier layer and positive negative electrode can provide near the negative anode of deposition and may deposit the performance of the situation of after annealing to negative anode earlier before the positive negative electrode of deposition: " inversion structures "
The example of " inversion structures " of an embodiment of the invention as shown in Figure 3, in this case, substrate can be a metal substrate.According to the electrical property on barrier layer, can before the negative anode of deposition, make anode collector earlier.That is, if the barrier layer is an insulating properties based on its subgrade and in the zone that will make negative anode, then can the deposition anode collector electrode, produce essential electrically contacting from negative terminal to negative anode.But,, then can choose the extra inert metal layer (" conduction promoting layer ") of deposition between barrier layer and negative anode wantonly, thereby strengthen the current collection character on barrier layer if the barrier layer is a conductivity based on its subgrade and in the zone that will deposit negative anode.
Can deposit the conduction promoting layer on negative anode, anode current collection layer and barrier layer by selecting any method in many deposition processs, described deposition process comprises chemical vapour deposition (CVD) that sputter (RF-magnetron, DC and DC pulsed magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, heat (resistive) evaporation, plasma strengthen, ion beam assisted depositing, cathodic arc deposition, electrochemical deposition, spray pyrolysis etc.
Negative anode can be selected from lithium metal, lithium-ion anode and so-called no lithium anode (referring to for example United States Patent (USP) 6168884, this patent is incorporated into this by reference in its entirety).Deposited after the negative anode, can deposit the after annealing step, thereby improved physics, chemistry and the electrochemical properties of negative anode.Preferably can be to all lithium-ion anode (Li for example 4Ti 5O 12) carry out this annealing steps, but can not carry out this annealing steps to lithium metal, and no lithium anode is carried out this annealing steps also is not preferred.
The parameter of the actual composition of negative anode and the deposition after annealing step that applies can be pointed out the selection to barrier material.For example, for the negative anode of lithium metal, be positioned at 5000 on the silicon substrate Si 3N 4The subgrade that stops the negative anode of described silicon substrate and described lithium metal is separated, can provide the barrier layer character that needs, by response path 12Li+Si 3N 4=4Li 3The positive reaction enthalpy of N+3Si has been realized the chemical inertness between barrier layer and lithium metal.
In exemplary inversion structures, positive negative electrode can be deposited on the dielectric substrate.Therefore, the temperature that aligns the deposition after annealing step that negative electrode may carry out is restricted, and reason is for example preferably will avoid the chemical reaction between dielectric substrate and the positive negative electrode, and avoid the reaction between negative anode and the dielectric substrate.
3.2 anode construction
The exemplary embodiment of " inversion structures " has above been described.
When making the execution mode of the negative anode that is positioned at the dielectric substrate top fully, between negative anode and barrier layer, can for example there be direct chemistry to react to each other.
When being positioned to fabrication portion the execution mode of negative anode at dielectric substrate top, preferred " conventional structure " (referring to the 3.1.1) that adopt.To there being the situation of anode collector, can prevent that negative anode overhanging part above the dielectric substrate edge from touching the barrier layer (referring to Fig. 7 a).When not having abundant anode collector of constructing to exist, the extension of negative anode may touch barrier layer (referring to Fig. 7 b).In above-mentioned any situation, all the preferred negative anode be chemically inert to the subgrade that stops of barrier layer and the direct contact of this negative anode, because the thickness of anode collector layer is limited and because the crystal boundary form makes the anode current collection layer possibly can't provide sufficient chemical isolation between negative anode and barrier layer.In this case, the selection of negative anode material has determined to stop the selection of sublayer material.Consider from this respect, if negative anode is lithium metal anode and this anode and Co 3O 4Stop the subgrade contact, then can not use Co 3O 4Stop subgrade.Otherwise, lithium metal meeting and Co 3O 4Stop the subgrade reaction, it is decomposed into Li 2The solid solution of O, CoO and Li (Co) and Co (Li).
If negative anode and/or its anode collector contact with the barrier layer, following two kinds of situations of needs assessment then: 1) whether negative anode and/or its anode collector stop that subgrade contact, 2 with insulating properties) bear anode and/or whether its anode collector stops that with conductivity subgrade contacts.Under first kind of situation, when using lithium metal anode, then make to stop that subgrade is to negative anode and/or its anode collector (Si for example 3N 4) be that chemical inertness is just enough.For second kind of situation, is the chemical inertness except the conductivity that requires to contact stops subgrade to negative anode and/or its anode collector, also need to use the more complicated subgrade that stops to design (referring to the example among Fig. 4 a-4c) to conductive board (for example metal substrate, and doping and unadulterated silicon substrate).For insulating properties polymeric substrates and second kind of situation, use noncontinuity conductivity to stop that subgrade is just enough, make the positivity part of battery pack and negativity part can not stop that subgrade is short-circuited by this conductivity.
For the negative anode of lithium metal stop the subgrade contact with ZrN and the positivity of battery pack partly not sharing this ZrN stops subgrade, stop for example Si of subgrade but the positivity of battery pack partly is positioned at insulating properties 3N 4On execution mode, for example using, the ZrN of 1 micron thickness stops that subgrade is fairly simple and effective.An advantage of the execution mode in back is that ZrN stops that subgrade can also be as the anode collector layer (referring to Fig. 8) of the negative anode of lithium metal.
Anode collector can comprise inert metal, inert alloy or inertia nitride, therefore can not tend to react with the barrier layer or with negative anode.Anode collector should preferably not stop that with conductivity subgrade electrically contacts, and positive negative electrode and/or cathode current collector and this conductivity stop that subgrade electrically contacts.Not so battery pack can be in short-circuit condition.
3.3 be in the substrate of electric contact state with the electro-chemical activity battery
In the execution mode that reaction does not take place between substrate and positive negative electrode or negative anode, substrate and these electrodes can directly electrically contact or electrically contact indirectly by collector electrode.But, for conductive board (for example metal substrate, doping and unadulterated silicon wafer or metallized polymeric substrates), only allow a kind of electrode and substrate in these electrodes to electrically contact, reason is, otherwise can makes the electro-chemical activity battery short circuit or cause strong electric leakage.The advantage of this exemplary method is, can make conductive board become a terminal (referring to Fig. 9) in the electrochemical apparatus two ends easily.
3.4 two-sided electrochemical apparatus
The present invention includes electrochemical apparatus and all have the execution mode of at least one electro-chemical activity battery in each side of substrate.The manufacture process of execution mode comprises: use can be before the manufacture process of carrying out next battery assembly layer to two devices that the side deposits simultaneously of substrate, the given electro-chemical activity battery component layer (for example positive negative electrode) of deposition on two sides of substrate, form each electro-chemical activity battery, described next battery assembly layer also can be deposited on two sides of substrate simultaneously.
Can carry out the order manufacture process to the battery assembly layer according to the mode identical with the single face electrochemical apparatus.Because of before the next layer of deposition on two sides of substrate, finishing the result of this example operation of on these two sides, carrying out, can not deposit substrate on the layer of another side of after annealing and not deposit post growth annealing.
Another kind of example operation can be, before the manufacturing of the second electro-chemical activity battery is finished on top, substrate second side, perhaps finish before further electro-chemical activity battery makes, finish the manufacturing of the first electro-chemical activity battery earlier on the top, first side of substrate on the top, first or second side of substrate.When available precipitation equipment does not allow to carry out double-sided deposition simultaneously, can use this operation.For example, before deposition cathode collector electrode on second side of substrate and positive cathode layer, on first side of substrate, finish deposition earlier, comprise that the deposition cathode collector electrode deposits positive cathode layer then.After these steps, on first side of substrate, continue to make electro-chemical activity battery (manufacturing sequence is dielectric substrate-anode collector-anode) before, can deposit the after annealing step simultaneously the electro-chemical activity battery that finish on this substrate top.Then, before two sides of sealing substrate with the thermally sensitive polymeric laminated product simultaneously, perhaps can simultaneously or carry out in order before the thin film encapsulation step identical manufacturing sequence being carried out in second side of substrate.
According to the physical condition that may align the deposition after annealing that negative electrode and/or negative anode carry out, the third operation can also be arranged, that is, beginning was finished earlier the manufacturing of the first electro-chemical activity battery on first side of substrate before making the second electro-chemical activity battery on second side of substrate.
3.5 protectiveness is sealed or the design of protectiveness cover
For the purposes of the present invention, " protectiveness cover " is defined as a kind of protectiveness shell, for example can holds the packing or the air-tightness metal can of electrochemical apparatus, in some embodiments can complete closed and/or hold described equipment fully." protectiveness is sealed " is defined as the protective layer of the one or more given independent electro-chemical activity battery of for example a kind of " covering " electrochemical apparatus or described electrochemical apparatus.For example, cover layer is attached to and can or be attached to any suitable substrate regions of electrochemical apparatus with the available substrate regions of next-door neighbour's electro-chemical activity battery.
Make before electrochemical apparatus of the present invention works in the environment around, preferably to its protect with avoid in given surrounding environment, existing, may or make the influence of any reactive chemical of its deterioration with electrochemical apparatus generation adverse reaction.For example, if surrounding environment is an air, then preferably electrochemical apparatus of the present invention is protected in order to avoid be subjected to for example O of moisture and other reactive chemicals 2Or CO 2Influence (referring to for example United States Patent (USP) 6916679, it is incorporated into this in full).Can protect in order to avoid be subjected to the influence of outside chemical factor electrochemical apparatus of the present invention, for example place the air-tightness metal can that has the electric connection device, place the stainless cylinder of steel of laser fusion welding, place vacuum-packed metal or glass tube or container.But the size of these protectiveness covers can increase the useless volume and the useless quality of electrochemical apparatus too much, can its assembly (except the positive negative electrode of conveying capacity) be minimized with respect to their thickness.This minimized strategy is specially adapted to the thickness of the useless assembly of electrochemical apparatus; for example substrate and any protectiveness cover or also have protectiveness to seal; their existence always can reduce power density, energy density and the capacity density of electro-chemical activity battery, thereby reduces power density, energy density and the capacity density of electrochemical device.
For above-mentioned reasons, protectiveness encapsulated layer or protective cowl layer should be preferably thin as much as possible, still can protect electrochemical apparatus in order to avoid the influence of the various chemical substances that are subjected to existing in the surrounding environment of electrochemical apparatus work simultaneously.The protection of these chemical substances is included in useful life of electrochemical apparatus to the protection of associated temperature and with time range that described chemical substance contacts in protection.But, set up the parameters optimization of electrochemical apparatus at manufacturing cost and performance, be the unique problem that will consider of electrochemical apparatus producer.Consider that from this respect for the electrochemical apparatus of only working several days after making, its protectiveness is sealed or the protectiveness cover can be used for that the protectiveness of the electrochemical apparatus in several years of work is sealed or the protectiveness cover is more cheap and simpler than design.
Protectiveness is sealed the terminal that all should allow to touch from the outside electrochemical apparatus with the protectiveness cover.This outside contact for example can be by adopting a kind of realization the in following three kinds of main engineering designs.The first, substrate and/or protectiveness are sealed can be used as and are carried out the directly terminal (referring to for example Fig. 3 b, substrate 300 is as anode) of outside contact.The second, thus terminal can be positioned at the below at the air-tightness edge that protectiveness seals and further extend to the outside that described protectiveness seals and contacts (referring to for example Fig. 4 a, layer 430 and 480).Similarly, thus air-tightness outlet that terminal can be by the protectiveness cover or opening and the outside that further extends to described protectiveness cover contact (referring to for example prismatic Li ion integral battery door group technology).The 3rd; can protectiveness seal or the protectiveness cover in opening is provided; allow directly to touch the terminal of electrochemical apparatus inside, but only sensitiveness part (for example dielectric substrate of moisture-sensitive) and surrounding environment (for example containing wetly air) are isolated by thickness or its adjacent collector electrode of terminal from the outside.
For increase the service life (a useful performance parameter representing electrochemical apparatus of the present invention), particularly under near the situation the opening of described the third design is positioned at the dielectric substrate zone, can guarantee that dielectric substrate obtains extra protection by for example moisture overcoat (as shown in Figure 10).
3.6 collector electrode and terminal
The relatively poor electrode material of conductivity is LiCoO for example 2Positive negative electrode or Li 4Ti 5O 12The contact (collector electrode) that negative anode may need to conduct the good inertia back side is Au or Ni for example, thereby the resistance that makes described electrode keeps lower, and makes the ions diffusion path in the electrode minimize (this realizes) when the z of electronics and Ion paths parameter (thickness) keeps minimizing.All used this principle in most of battery pack, promptly electrode is preferably configured as plane or slim (z parameter),, compares length (x parameter) and width (y parameter) maximization with thickness (z parameter) that is.Some electrodes aspect electronics and ions all be good electric conductor, so do not need collector electrode.But they may be reactive aspect chemical property, and for example metal Li bears anode, so preferably will they and other battery pack parts (for example negative terminal) be isolated by suitable inertia " bridge " (situation for the negative anode of metal Li for example is Ni).This " bridge " can contact with electrode reactive, good conductive in a corner or an edge, on the contrary, for the situation of the relatively poor electrode of conductivity, then is to come in contact on the whole area overleaf.Described bridge is as the inert media between reactive electrode and the terminal thereof, and current collection character is provided, and therefore also can be called " collector electrode ".
In one embodiment, the terminal of electrochemical apparatus of the present invention is the collector electrode that extends, and therefore can be made by the same material that contacts with electrode.But the collector electrode that uses in the hull cell group can be extremely thin, and be fine and close on mechanical sense, thereby cause that (for example adopting mechanical system (clamping), soft soldering or spot welding) can't form permanent electric contact preferably when the outside is in contact with it.People are preferably by improving the contact property of collector electrode to the good material of the terminal interpolation conduction thicker and/or porous of collector electrode, the zone of described interpolation material is called " terminal ", can realize machinery, external electric contact soft soldering or spot welding at the terminal place.Consider from this respect, (thickness is about the 5-15 micron successfully to have utilized the silver of silk screen printing and silver alloy, quite a lot of permeability) as terminal, print by certain mode, make negative electrode or anode collector can reach good electrical contact with it, simultaneously, at the random time point of manufacturing, work or storage process, the material of silk screen printing can not produce chemical contamination to electro-chemical activity battery or battery pack.
Embodiments of the present invention and implementation procedure are described with reference to the drawings.
Fig. 1 illustrates an execution mode of electrochemical apparatus.Substrate portion 100 is chemically isolated by barrier layer 110 and battery pack part 120, and barrier layer 110 is by stopping that subgrade 111-114 forms.Battery assembly layer 121-125 is provided.Battery pack anode 126 and battery pack negative terminal 127 also are provided.
Fig. 2 illustrates an execution mode on barrier layer 210, and barrier layer 210 comprises the following exemplary subgrade that stops: 1000
Figure 2006800296432_46
MoSi 2211,3000
Figure 2006800296432_47
WC 212,4000
Figure 2006800296432_48
Si 3N 4213, and 5000
Figure 2006800296432_49
ZrN 214.As shown in the figure, the area size of these subgrades can have nothing in common with each other, but they still are implemented in the positivity part (214,220,230 and 240) and the partly preferred electricity isolation between (260,270 and 280) of negativity of electro-chemical activity battery.Cathode current collector, anode and positive negative electrode are used 220,230 and 240 expressions respectively.The positivity part of electro-chemical activity battery can comprise positive negative electrode, cathode current collector and anode at least.Cathode current collector can be separately as anode.Negative anode, anode collector and negative terminal are used 260,270 and 280 expressions respectively.The negativity part of electro-chemical activity battery can comprise negative anode, anode collector and negative terminal at least.The anode collector that extends can also be used as: (1) negative terminal, (2) anode, (3) anode current collection layer utmost point, anode and negative terminal.Dielectric substrate 250 is for example isolated the positivity part of electro-chemical activity battery with negativity part electricity.Under this particular case, can protect so that touch the 290 pairs of electro-chemical activity batteries of sealing of negative terminal 280 with having opening 291.Can on substrate 200, make this electro-chemical activity battery of sealing, thereby form electrochemical apparatus together.
Fig. 3 a illustrates an execution mode on barrier layer 310, barrier layer 310 comprises that first stops that subgrade 311 and second stops subgrade 312, for the negativity at dielectric substrate 350 tops partly realizes the positivity part of electro-chemical activity battery and the execution mode that the electricity between the negativity part is isolated by making fully, the barrier layer can be a conductivity.The positivity part for example comprises that second stops subgrade 312, cathode current collector 320, anode 330 and positive negative electrode 340.What provide first stops when subgrade 311 is conductivity, and the positivity part can also comprise that first stops subgrade 311.Be conductivity (for example substrate is a metal) and have the execution mode that conductivity first stops subgrade 311 that described substrate also can become the part of positivity part for substrate 300.The negativity part can comprise negative anode 360, anode collector 370 and negative terminal 380.In this particular example, can protect so that touch the 390 pairs of electro-chemical activity batteries of sealing of negative terminal 380 with having opening 391.
Fig. 3 b illustrates an execution mode on barrier layer 310, barrier layer 310 comprises that first stops that subgrade 311 and second stops subgrade 312, for the negativity at dielectric substrate 350 tops partly realizes the positivity part of electro-chemical activity battery and the execution mode that the electricity between the negativity part is isolated by making fully, the barrier layer can be a conductivity, and cathode current collector 320, anode 330 and positive negative electrode 340 stop that by second subgrade 312 electrically contacts with metal substrate 300.In this structure, metal substrate 300 can be used as anode.Positivity comprises that partly metal substrate 300, the second stops subgrade 312, cathode current collector 320, anode 330 and positive negative electrode 340.Stop that for first subgrade 311 is execution modes of conductivity, the positivity part can also comprise that first stops subgrade 311.The negativity part can comprise negative anode 360, anode collector 370 and negative terminal 380.In this particular example, can protect so that touch the 390 pairs of electro-chemical activity batteries of sealing of negative terminal 380 with having opening 391.
Fig. 3 c illustrates an example embodiment on barrier layer 310, barrier layer 310 comprises that first stops that subgrade 311 and second stops subgrade 312, for the positivity at dielectric substrate 350 tops partly realizes the positivity part of electro-chemical activity battery and the situation that the electricity between the negativity part is isolated by making fully, the barrier layer can be a conductivity, and anode collector 370, negative terminal 380 and negative anode stop that by second subgrade 312 and metal substrate 300 electrically contact.In this structure, substrate 300 also can be used as anode.Positivity partly comprises cathode current collector 320, anode 330 and positive negative electrode 340.The negativity part can comprise that metal substrate 300, the second stops subgrade 312, negative anode 360, anode collector 370 and negative terminal 380.Stop that first subgrade 311 also is under the situation of conductivity, the negativity part can also comprise that this first stops subgrade 311.In this particular example, can protect so that touch the 390 pairs of electro-chemical activity batteries of sealing of anode 330 with having opening 391.
Fig. 4 a illustrates and comprises the execution mode that conductivity stops the barrier layer 410 of subgrade, at this moment can't partly and between the negativity part realize electric the isolation in the positivity of electro-chemical activity battery by making complete negativity part at dielectric substrate 450 tops.Second of electrical insulating property stops that subgrade 412 can be for example partly isolate the positivity part and the negativity of electro-chemical activity battery with dielectric substrate 450.The positivity part can comprise cathode current collector 420, anode 430 and positive negative electrode.If the 3rd stops that subgrade 413 is a conductivity, then this subgrade also becomes the part of positivity part.First stop subgrade 411 can be electrical insulating property also can be conductivity.Under latter event, the part that it can become the negativity part for example makes substrate 400 also become the part of negativity part.In addition, the negativity part can comprise negative anode 460, anode collector 470 and negative terminal 480.In this structure, metal substrate also can be used as negative terminal.At last, protect with sealing 490 pairs of electro-chemical activity batteries.
Fig. 4 b illustrates and comprises that conductivity stops another execution mode on the barrier layer 410 of subgrade, at this moment can't partly and between the negativity part realize electric the isolation in the positivity of electro-chemical activity battery by making complete negativity part at dielectric substrate 450 tops.Second of electrical insulating property stops that subgrade 412 can be for example partly isolate the positivity part and the negativity of electro-chemical activity battery with dielectric substrate 450.The positivity part can comprise cathode current collector 420, anode 430 and positive negative electrode 440.If the 3rd stops that subgrade 413 is a conductivity, then it also becomes the part of positivity part.First stop subgrade 411 can be electrical insulating property also can be conductivity.Under latter event, it can become the part of negativity part, makes substrate 400 also become the part of negativity part simultaneously.In addition, the negativity part can comprise negative anode 460, anode collector 470 and negative terminal 480.In this structure, metal substrate also can be used as negative terminal.At last, protect with sealing 490 pairs of electro-chemical activity batteries.
Fig. 4 c illustrates and comprises that conductivity stops in another execution mode on barrier layer 410 of subgrade, at this moment can't realize between the positivity part of electro-chemical activity battery and negativity part that by making fully in the negativity part at dielectric substrate 450 tops electricity isolates.Negative anode 460 can for example stop that with the 3rd subgrade 413 directly contacts, and therefore, the preferred the 3rd stops that 413 pairs of negative anodes 460 of subgrade are chemically inert.In this embodiment, the 3rd stops that subgrade 413 can be an electrical insulating property, and it partly and between the negativity part provides electricity to isolate with dielectric substrate 450 in the positivity of electro-chemical activity battery.The positivity part can comprise cathode current collector 420, anode 430 and positive negative electrode 440.If second stops that subgrade 412 is a conductivity, then it also becomes the part of positivity part, also makes metal substrate 400 become the part of positivity part simultaneously.First stop subgrade 411 can be electrical insulating property also can be conductivity.Under latter event, it can become the part of positivity part, but condition is second to stop that subgrade 412 also is the part of positivity part.The negativity part can comprise negative anode 460, anode collector 470 and negative terminal 480.In this structure, metal substrate can be used as negative terminal.At last, protect with sealing 490 pairs of electro-chemical activity batteries.
Fig. 5 illustrates the X diffracting spectrum (XRD) of following structure: have by two on stainless steel foil 430 substrates of 50 micron thickness and stop subgrade (5000 Al 2O 3With 6000 Co 3O 4) barrier layer formed, be attached with 300 on the barrier layer
Figure 2006800296432_52
The cobalt adhesion layer, have 3000 on this adhesion layer
Figure 2006800296432_53
The au cathode collector electrode, on this cathode current collector, make the LiCoO that 1.6 micron thickness are arranged 2Positive cathodic coating.LiCoO 2Positive negative electrode is at 700 ℃ of deposition after annealings that carry out 2 hours in air, deposition after annealing step in similar calorifics mode to substrate, the barrier layer of below and stop that subgrade, cathode current collector adhesion layer and cathode current collector exert an influence.Crystal LiCoO 2Meticulous lattice parameter (a of positive cathodic coating Six sides=2.8146 (4)
Figure 2006800296432_54
c Six sides=14.0732 (8)
Figure 2006800296432_55
) very near theoretical value (for example, ICDD 77-1370:a Six sides=2.815 (1)
Figure 2006800296432_56
c Six sides=14.05 (1)
Figure 2006800296432_57
), crystalline LiCoO is described 2Positive negative electrode is (by the degree of crystallinity on (101) plane of Scherrer equation estimation: 560
Figure 2006800296432_58
) film do not react with any material (comprising substrate) around it." Au " expression au cathode collector electrode.The overlap peak of " Au+S " expression au cathode collector electrode and stainless steel 430 substrate foil.
Fig. 6 illustrates the X diffracting spectrum (XRD) of following structure: stop subgrade (5000 at the unadulterated silicon substrate of 300 micron thickness by two
Figure 2006800296432_59
Si 3N 4With 5000
Figure 2006800296432_60
SiO 2) barrier layer formed, on this barrier layer, have 300 The cobalt adhesion layer is positioned on this adhesion layer and has 3000
Figure 2006800296432_62
The au cathode collector electrode, on this cathode current collector, make the LiCoO that 1.6 micron thickness are arranged 2Positive cathodic coating.LiCoO 2Positive negative electrode is at 700 ℃ of deposition after annealings that carry out 2 hours in air, deposition after annealing step in similar calorifics mode to substrate, the barrier layer of below and stop that subgrade, cathode current collector adhesion layer and cathode current collector exert an influence.Crystalline LiCoO 2Meticulous lattice parameter (a of positive cathodic coating Six sides=2.8151 (4) c SixSide=14.066 (6)
Figure 2006800296432_64
) near the theoretical value that provides in the document (ICDD 77-1370:a Six sides=2.815 (1)
Figure 2006800296432_65
c Six sides=14.05 (1)
Figure 2006800296432_66
), crystalline LiCoO is described 2Positive negative electrode is (by the degree of crystallinity on (101) plane of Scherrer equation estimation: 1100
Figure 2006800296432_67
) film do not react with any material (comprising substrate) around it." Au " expression au cathode collector electrode.Eliminated the peak of monocrystalline silicon substrate by the θ-2 θ geometry of diffractometer.
Fig. 7 a illustrates a kind of execution mode of anode construction, and wherein negative anode 760 does not directly contact with barrier layer 710, does not therefore directly contact with its any subgrade 711,712 that stops yet.First stop subgrade 711 can be electrical insulating property also can be conductivity, second stops that subgrade 712 should be an electrical insulating property, is short-circuited to avoid the electro-chemical activity battery, and then avoids electrochemical apparatus to be short-circuited.In such structure, negative anode 760 does not contact the barrier layer, can not determine the selection to the chemical composition that stops subgrade 711,712.The positivity of electrochemical cell part can comprise cathode current collector 720, anode 730, and by dielectric substrate 750 and with the partially isolated positive negative electrode 740 of negativity; Negativity partly comprises negative anode 760, anode collector 770, and negative terminal 780.At last, protect with sealing 790 pairs of electro-chemical activity batteries.
Fig. 7 b illustrates a kind of execution mode of anode construction, and wherein negative anode 760 directly contacts with barrier layer 710, therefore stops that with it subgrade 712 directly contacts.First stop subgrade 711 can be electrical insulating property also can be conductivity, second stops preferably electrical insulating property of subgrade 712, is short-circuited to avoid the electro-chemical activity battery, and then avoids electrochemical apparatus to be short-circuited.In such structure, negative anode 760 contacts barrier layers, thereby determines the selection to the chemical composition that stops subgrade 712 of its contact at least.The positivity of electrochemical cell part can comprise for example cathode current collector layer 720, anode 730, and by dielectric substrate 750 and with the partially isolated positive negative electrode 740 of negativity; Negativity partly comprises negative anode 760, anode collector 770, and negative terminal 780.At last, protect with 790 pairs of electro-chemical activity batteries of encapsulated layer.
Fig. 8 illustrates a kind of execution mode of anode construction, and wherein negative anode 860 stops that with conductivity ZrN subgrade 811 directly contacts, subgrade 811 be shown in electrochemical apparatus first stop subgrade, it can also be as anode collector.Anode collector and stop subgrade 811 in addition to the negative anode 860 of reactivity for example lithium metal also be chemically inert, if select negative anode 860 like this.Because the particular geometries of selecting in the electrochemical apparatus execution mode shown in this figure that stops subgrade 811, make second to stop preferably electrical insulating property of subgrade 812, for example be Si 3N 4The positivity of electrochemical cell part can comprise cathode current collector 820, anode 830, and by dielectric substrate 850 and with the partially isolated positive negative electrode 840 of negativity; The negativity part can comprise metal substrate 800, and ZrN stops subgrade, anode collector 811, negative anode 860 and negative terminal 870.At last, protect with sealing 880 pairs of electro-chemical activity batteries.
Fig. 9 illustrates a kind of execution mode of particular battery structure, and wherein negative anode 960 directly contacts with substrate 900, and at this moment substrate is chemically inert to negative anode 960.In this case, similar with the situation of stainless steel substrate if the conductivity of substrate is enough strong, then substrate can be used as negative anode collector and negative terminal.The positivity of electro-chemical activity battery part can comprise for example cathode current collector 920, anode 930, and positive negative electrode 940, and if conductivity comprises that also second stops subgrade 912.But first stops preferably electrical insulating property of subgrade 911, partly is short-circuited to negativity to avoid electrochemical apparatus.The negativity part can comprise for example metal substrate 900 and negative anode 960.
Figure 10 illustrates a kind of execution mode of particular battery structure; wherein moisture overcoat 1092 is protected the influence of the moisture that the dielectric substrate 1050 of moisture-sensitive is avoided existing in the surrounding environment; in this embodiment; the protectiveness of making is sealed 1090 and is had opening 1091, so that touch negative terminal 1080.The thickness of the negative terminal 1080 and the anode current collection layer utmost point 1070 and/or moisture barrier ability may be not enough to protect for a long time the dielectric substrate 1050 of below.This schematic diagram is the modified model to the electrochemical apparatus shown in Fig. 3 a.Substrate 1000 can be electrical insulating property can be conductivity also, stop that subgrade 1011 and 1012 also is so, these two subgrades are formed barrier layers 1010.Other assemblies of electrochemical apparatus shown in Figure 10 are cathode current collector 1020, anode 1030, positive negative electrode 1040 and negative anode 1060.
Though the present invention has been carried out concrete displaying and explanation with reference to the various execution modes that provide above, but should be appreciated that those skilled in the art can be in that various execution modes carry out on the various forms and the variation aspect the details to these under the condition that does not deviate from the principle of the invention and scope.

Claims (117)

1. electrochemical apparatus, it comprises:
A) substrate is selected from metal, polymer or doping or unadulterated silicon materials, and described substrate has first side;
B) be positioned at the first electro-chemical activity battery on described first side, it has negativity part and positivity part, and described these parts also comprise one or more terminals;
C) be positioned at first barrier layer on described first side, this barrier layer chemically isolates described first electro-chemical activity battery and described substrate;
D) wherein, described first barrier layer further comprises a plurality of subgrades.
2. electrochemical apparatus as claimed in claim 1 is characterized in that, described equipment also comprises a plurality of electro-chemical activity batteries on described first side that is positioned at described substrate.
3. electrochemical apparatus as claimed in claim 1 is characterized in that, it is chemically inert material that described first barrier layer comprises for described first electro-chemical activity battery and described substrate; Make on described substrate in the described first electro-chemical activity cell process and under the work and condition of storage of described electrochemical apparatus, first barrier layer is suitable for stoping the diffusion to described first electro-chemical activity battery and the generation of described substrate.
4. electrochemical apparatus as claimed in claim 1 is characterized in that, described subgrade is selected from conductivity, electrical insulating property or semi-conductive material, wherein:
A) the described positivity of described first electro-chemical activity battery part or not does not electrically contact with the described negativity of the described first electro-chemical activity battery;
B) the described positivity part of the described first electro-chemical activity battery comprises positive negative electrode, cathode current collector and anode at least;
C) the described negativity part of the described first electro-chemical activity battery comprises negative anode, anode collector and negative terminal at least.
5. electrochemical apparatus as claimed in claim 4 is characterized in that described cathode current collector comprises described anode.
6. electrochemical apparatus as claimed in claim 4 is characterized in that described anode collector comprises described negative terminal.
7. electrochemical apparatus as claimed in claim 4 is characterized in that, described anode collector comprises described negative anode.
8. electrochemical apparatus as claimed in claim 4 is characterized in that, described anode collector comprises described negative anode and described negative terminal.
9. electrochemical apparatus as claimed in claim 1 is characterized in that described subgrade all is of similar shape and area size.
10. electrochemical apparatus as claimed in claim 1 is characterized in that, at least one subgrade has different shapes and area size with another subgrade in the described subgrade in the described subgrade.
11. electrochemical apparatus as claimed in claim 1 is characterized in that, described first barrier layer only part covers described substrate, makes the part of positivity at least of the described first electro-chemical activity battery chemically isolate with described substrate.
12. electrochemical apparatus as claimed in claim 1 is characterized in that, described first barrier layer only part covers described substrate, makes the part of negativity at least of the described first electro-chemical activity battery chemically isolate with described substrate.
13. electrochemical apparatus as claimed in claim 1 is characterized in that, the thickness on described first barrier layer is 0.01 micron-1 millimeter.
14. electrochemical apparatus as claimed in claim 1 is characterized in that, the thickness on described first barrier layer is the 0.1-100 micron.
15. electrochemical apparatus as claimed in claim 1 is characterized in that, the thickness on described first barrier layer is the 0.5-5 micron.
16. electrochemical apparatus as claimed in claim 1 is characterized in that, the thickness of described substrate is 0.1 micron-1 centimetre.
17. electrochemical apparatus as claimed in claim 1 is characterized in that, the thickness of described substrate is 1 micron-1 millimeter.
18. electrochemical apparatus as claimed in claim 1 is characterized in that, the thickness of described substrate is the 10-100 micron.
19. electrochemical apparatus as claimed in claim 1 is characterized in that, described subgrade comprises and is selected from following material:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
20. electrochemical apparatus as claimed in claim 1 is characterized in that, at least one described subgrade comprises single-phase crystal, nanocrystal, amorphous or vitreous material, perhaps their multiphase mixture or compound.
21. electrochemical apparatus as claimed in claim 1 is characterized in that, described at least one subgrade comprises single-phase amorphous or vitreous material.
22. electrochemical apparatus as claimed in claim 1 is characterized in that, the described first electro-chemical activity battery comprises and is selected from following battery pack: lithium anodes battery pack, lithium-ion anode battery pack and do not have the lithium anode battery pack.
23. electrochemical apparatus as claimed in claim 22 is characterized in that, the described first electro-chemical activity battery comprises that the thickness of the positive negative electrode of described film is less than 200 microns by the positive negative electrode of film of CVD (Chemical Vapor Deposition) method deposition.
24. electrochemical apparatus as claimed in claim 22 is characterized in that, the described first electro-chemical activity battery comprises that by the positive negative electrode of the film of antivacuum deposition, the thickness of the positive negative electrode of described film is less than 200 microns.
25. electrochemical apparatus as claimed in claim 23 is characterized in that, the positive negative electrode of described film comprises size and is at least
Figure FSB00000445580300031
Monocrystalline.
26. electrochemical apparatus as claimed in claim 24 is characterized in that, the positive negative electrode of described film comprises size and is at least
Figure FSB00000445580300032
Monocrystalline.
27. electrochemical apparatus as claimed in claim 1 is characterized in that, the described first electro-chemical activity battery comprises that thickness is less than 100 microns film solid electrolyte.
28. electrochemical apparatus as claimed in claim 1, it is characterized in that, the described first electro-chemical activity battery comprises that film bears anode, and described negative anode is selected from lithium metal, lithium-ion anode or does not form the metal of intermetallic compound with lithium, and the thickness of the negative anode of described film is less than 200 microns.
29. electrochemical apparatus as claimed in claim 1; it is characterized in that; the described first electro-chemical activity battery comprises that also protectiveness seals, described protectiveness seal be suitable at least machinery and chemical aspect protect the described first electro-chemical activity battery to avoid the influence of surrounding environment.
30. electrochemical apparatus as claimed in claim 1 is characterized in that, described equipment also comprises the protectiveness cover, and described protectiveness cover can protect described electrochemical apparatus to avoid the influence of surrounding environment aspect mechanical and chemical at least.
31. electrochemical apparatus as claimed in claim 29 is characterized in that, described sealing has at least one opening so that at least one terminal of direct and the described first electro-chemical activity battery electrically contacts.
32. electrochemical apparatus as claimed in claim 30 is characterized in that, described protectiveness cover has at least one opening so that at least one terminal of direct and described first electrochemical apparatus electrically contacts.
33. electrochemical apparatus as claimed in claim 31 is characterized in that, described electro-chemical activity battery further comprises electrolyte, and described one or more terminals are isolated by moisture overcoat and described electrolyte.
34. electrochemical apparatus as claimed in claim 32 is characterized in that, described electro-chemical activity battery further comprises electrolyte, and described one or more terminals are isolated by moisture overcoat and described electrolyte.
35. electrochemical apparatus as claimed in claim 33 is characterized in that, described moisture overcoat comprises the material with moisture barrier character, is selected from:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
36. electrochemical apparatus as claimed in claim 33 is characterized in that, described moisture overcoat comprises single-phase crystal, nanocrystal, amorphous or vitreous material, perhaps their multiphase mixture or compound.
37. electrochemical apparatus as claimed in claim 34 is characterized in that, described moisture overcoat comprises the material with moisture barrier character, is selected from:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
38. electrochemical apparatus as claimed in claim 34 is characterized in that, described moisture overcoat comprises single-phase crystal, nanocrystal, amorphous or vitreous material, perhaps their multiphase mixture or compound.
39. electrochemical apparatus as claimed in claim 1 is characterized in that, described equipment further comprises the second layer that is positioned on described substrate second side.
40. electrochemical apparatus as claimed in claim 39 is characterized in that, the described second layer comprises and is selected from following material:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
41. an electrochemical apparatus, it comprises:
A) metal, polymer or doping or unadulterated silicon substrate, it has first side and second side;
B) be positioned at the first electro-chemical activity battery on described first side, it further comprises positivity part and negativity part, and described these parts further comprise one or more terminals;
C) be positioned at first barrier layer on described first side, this barrier layer chemically isolates the described first electro-chemical activity battery with described metal, polymer or doping or unadulterated silicon substrate;
D) be positioned at the second electro-chemical activity battery on described second side, it further comprises positivity part and negativity part, and described these parts further comprise one or more terminals;
E) be positioned at second barrier layer on described second side, this barrier layer chemically isolates described second electro-chemical activity battery and described substrate;
F) wherein, described first barrier layer comprises a plurality of subgrades;
G) wherein, described second barrier layer comprises a plurality of subgrades.
42. electrochemical apparatus as claimed in claim 41 is characterized in that, described equipment further comprises a plurality of electro-chemical activity batteries on described first side that is positioned at described substrate.
43. electrochemical apparatus as claimed in claim 41 is characterized in that, described equipment further comprises a plurality of electro-chemical activity batteries on described second side that is positioned at described substrate.
44. electrochemical apparatus as claimed in claim 41 is characterized in that, the described barrier layer that is positioned on two sides of described substrate is suitable for described electro-chemical activity battery and described substrate are chemically isolated, and the barrier layer further comprises following situation:
(a) described first barrier layer comprises for the first electro-chemical activity battery on first side of described substrate and is chemically inert material for described substrate;
(b) described second barrier layer comprises for the second electro-chemical activity battery on second side of described substrate and is chemically inert material for described substrate;
(c) described first barrier layer further has the character that diffusion takes place for chemical element in the first electro-chemical activity battery on first side that stops described substrate;
(d) described second barrier layer further has the character that diffusion takes place for chemical element in the second electro-chemical activity battery on second side that stops described substrate.
45. electrochemical apparatus as claimed in claim 41 is characterized in that:
A) described subgrade is selected from conductivity, electrical insulating property or semi-conductive material;
B) partly do not electrically contact in the positivity of two the above electro-chemical activity batteries of side of described substrate part with the negativity of electro-chemical activity battery;
C) positivity of described electro-chemical activity battery part comprises positive negative electrode, cathode current collector and anode at least;
D) negativity of described electro-chemical activity battery part comprises negative anode, anode collector and negative terminal at least.
46. electrochemical apparatus as claimed in claim 45 is characterized in that, described cathode current collector comprises described anode.
47. electrochemical apparatus as claimed in claim 45 is characterized in that, described anode collector comprises described negative terminal.
48. electrochemical apparatus as claimed in claim 45 is characterized in that, described anode collector comprises described negative anode.
49. electrochemical apparatus as claimed in claim 45 is characterized in that, described anode collector comprises described negative anode and described negative terminal.
50. electrochemical apparatus as claimed in claim 41 is characterized in that, described subgrade all is of similar shape and area size.
51. electrochemical apparatus as claimed in claim 41 is characterized in that, at least one subgrade in the described subgrade have with described a plurality of subgrades in different shape and the area size of another subgrade.
52. electrochemical apparatus as claimed in claim 41 is characterized in that, at least one described barrier layer only part covers described substrate, and the described at least positivity part of described electro-chemical activity battery is chemically isolated with described substrate.
53. electrochemical apparatus as claimed in claim 41 is characterized in that, at least one described barrier layer only part covers described substrate, and the described at least negativity part of described electro-chemical activity battery is chemically isolated with described substrate.
54. electrochemical apparatus as claimed in claim 41 is characterized in that, the thickness that is positioned at the described barrier layer on two sides of described substrate is 0.01 micron-1 millimeter.
55. electrochemical apparatus as claimed in claim 41 is characterized in that, the thickness that is positioned at the described barrier layer on two sides of described substrate is the 0.1-100 micron.
56. electrochemical apparatus as claimed in claim 41 is characterized in that, the thickness that is positioned at the described barrier layer on two sides of described substrate is the 0.5-5 micron.
57. electrochemical apparatus as claimed in claim 41 is characterized in that, the thickness of described substrate is 0.1 micron-1 centimetre.
58. electrochemical apparatus as claimed in claim 41 is characterized in that, the thickness of described substrate is 1 micron-1 millimeter.
59. electrochemical apparatus as claimed in claim 41 is characterized in that, the thickness of described substrate is the 10-100 micron.
60. electrochemical apparatus as claimed in claim 41 is characterized in that, at least one described subgrade comprises and is selected from following material:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
61. electrochemical apparatus as claimed in claim 41 is characterized in that, at least one described subgrade comprises single-phase crystal, nanocrystal, amorphous or vitreous material, perhaps their any multiphase mixture or compound.
62. electrochemical apparatus as claimed in claim 41 is characterized in that, at least one described subgrade comprises single-phase amorphous or vitreous material.
63. electrochemical apparatus as claimed in claim 41 is characterized in that, is positioned at described electro-chemical activity battery on two sides of described substrate and comprises and be selected from following battery pack: lithium anodes battery pack, lithium-ion anode battery pack and do not have the lithium anode battery pack.
64. electrochemical apparatus as claimed in claim 41 is characterized in that, described electro-chemical activity battery comprises that by the positive negative electrode of the film of CVD (Chemical Vapor Deposition) method or antivacuum deposition, the thickness of the positive negative electrode of described film is less than 200 microns.
65., it is characterized in that the positive negative electrode of described film comprises size and is at least as the described electrochemical apparatus of claim 64
Figure FSB00000445580300071
Monocrystalline.
66. electrochemical apparatus as claimed in claim 41 is characterized in that, described electro-chemical activity battery comprises that further thickness is less than 100 microns film solid electrolyte.
67. electrochemical apparatus as claimed in claim 41, it is characterized in that, described electro-chemical activity battery comprises that film bears anode, and negative anode is selected from lithium metal, lithium-ion anode or does not form the metal of intermetallic compound with lithium, and the thickness of the negative anode of described film is less than 200 microns.
68. electrochemical apparatus as claimed in claim 41; it is characterized in that; each electro-chemical activity battery of described electrochemical apparatus comprises that all protectiveness is sealed or the protectiveness cover, described seal or cover be suitable at least machinery and chemical aspect protect described electro-chemical activity battery or described electrochemical apparatus in order to avoid be subjected to the influence of surrounding environment.
69. as the described electrochemical apparatus of claim 68, it is characterized in that, described seal or described cover has at least one opening so as directly and at least one terminal of each described electro-chemical activity battery electrically contact.
70., it is characterized in that described electro-chemical activity battery further comprises electrolyte as the described electrochemical apparatus of claim 69, described terminal contacts from the outside by the opening in described the sealing, terminal is isolated by moisture overcoat and described electrolyte.
71., it is characterized in that described moisture overcoat comprises the material with moisture barrier character, is selected from as the described electrochemical apparatus of claim 70:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
72., it is characterized in that described moisture overcoat comprises single-phase crystal, nanocrystal, amorphous or vitreous material as the described electrochemical apparatus of claim 70, perhaps their any multiphase mixture or compound.
73. a method of making electrochemical apparatus, it comprises:
(a) provide the substrate of metal, polymer or silicon with first side;
(b) deposition first barrier layer on described first side;
(c) make the first electro-chemical activity battery that comprises positivity part and negativity part, described these parts further comprise one or more terminals, described battery is positioned on first side at top, described first barrier layer, and described barrier layer chemically isolates described first electro-chemical activity battery and described substrate;
(d) make described first barrier layer by a plurality of chemically different subgrades.
74., it is characterized in that this method further is included on first side of described substrate a plurality of electro-chemical activity batteries are provided as the described method of claim 73.
75., it is characterized in that this method further comprises as the described method of claim 73:
A) from conductivity, electrical insulating property or semi-conductive material, select described subgrade;
B) stop the positivity part of the described first electro-chemical activity battery partly to electrically contact with negativity;
C) on the positivity part of the described first electro-chemical activity battery, provide positive negative electrode, cathode current collector and anode;
D) on the negativity part of the described first electro-chemical activity battery, provide negative anode, anode collector and negative terminal.
76., it is characterized in that this method further comprises provides described cathode current collector as described anode as the described method of claim 75.
77., it is characterized in that this method further comprises provides described anode collector as described negative terminal as the described method of claim 75.
78., it is characterized in that this method further comprises provides described anode collector as described negative anode as the described method of claim 75.
79., it is characterized in that this method further comprises provides described anode collector as described negative anode and described negative terminal as the described method of claim 75.
80., it is characterized in that this method further comprises providing to have identical shaped and a plurality of subgrades area size as the described method of claim 73.
81., it is characterized in that this method comprises that further another subgrade that provides at least one and the described a plurality of subgrade has the subgrade of difformity and area size as the described method of claim 73.
82., it is characterized in that this method further comprises with described first barrier layer and only partly covers described substrate, makes the part of positivity at least of the described first electro-chemical activity battery chemically isolate with described substrate as the described method of claim 73.
83., it is characterized in that this method further comprises provides described first barrier layer that only partly covers described substrate as the described method of claim 73, make the part of negativity at least of the described first electro-chemical activity battery chemically isolate with described substrate.
84., it is characterized in that this method further comprises with being selected from the described subgrade of following made as the described method of claim 73:
A) metal, semimetal, alloy, bromide, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide, the perhaps polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
85., it is characterized in that this method further comprises by the material of single-phase crystal, nanocrystal, amorphous or glassy state or their any multiphase mixture or compound makes described subgrade as the described method of claim 73.
86., it is characterized in that this method further comprises by the described subgrade of the made of single-phase amorphous or glassy state as the described method of claim 73.
87. as the described method of claim 73, it is characterized in that, this method further comprises is by the following method making positive negative electrode on described first electrochemical cell: at 100 ℃ of original positions of carrying out to the temperature range that is up to described substrate fusing point or the temperature course of offing normal, make described positive negative electrode comprise size and be at least
Figure FSB00000445580300091
Crystal.
88. as the described method of claim 73; it is characterized in that; this method further comprises by providing protectiveness to seal or the method for protectiveness cover; protect described first electro-chemical activity battery or described electrochemical apparatus respectively, thus at least machinery and chemical aspect avoid the influence of surrounding environment.
89., it is characterized in that this method further comprises making to have that at least one opening is described to be sealed or described cover, makes it possible to directly electrically contact with described one or more terminals of the described first electro-chemical activity battery as the described method of claim 88.
90., it is characterized in that this method further is included in the described electro-chemical activity battery electrolyte is provided as the described method of claim 89, and described electrolyte and described one or more terminal isolated by the moisture overcoat.
91., it is characterized in that this method further comprises by the described moisture overcoat of the made with moisture barrier character, is used for the material of moisture overcoat from following group selection as the described method of claim 90:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
92. as the described method of claim 90, it is characterized in that, this method further comprises by being selected from the described moisture overcoat of following made: the material of single-phase crystal, nanocrystal, amorphous or glassy state, perhaps their any multiphase mixture or compound.
93. as the described method of claim 73, it is characterized in that, this method deposits the second layer before further being included in and making the described first electro-chemical activity battery on second side of described substrate, purpose is the described first electro-chemical activity battery on described substrate of chemoproection and substrate first side, in order to avoid be subjected to the influence of surrounding environment; And chemically protect the described first electro-chemical activity battery from the diffusion of the pollutant of surrounding environment by prevention.
94., it is characterized in that this method further comprises by being selected from the described second layer of following made as the described method of claim 93:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
95. as the described method of claim 93, it is characterized in that, this method comprises that further heat alleviates described first barrier layer and the second layer in the following manner: at 100 ℃ of temperature courses that carry out original position or off normal to the temperature range that is up to described substrate fusing point, described temperature course of offing normal applies described temperature course after further being included in and having deposited described first barrier layer and the second layer.
96. a method of making electrochemical apparatus may further comprise the steps:
(a) provide metal, polymer or the doping with first side and second side or the substrate of undoped silicon;
(b) deposition first barrier layer on described first side;
(c) deposition second barrier layer on described second side;
(d) make the first electro-chemical activity battery on first side at top, described first barrier layer, described first barrier layer chemically isolates the first electro-chemical activity battery and substrate;
(e) make the second electro-chemical activity battery on second side at top, described second barrier layer, described second barrier layer chemically isolates the second electro-chemical activity battery and substrate;
(f) form described first barrier layer by a plurality of chemically different subgrades;
(g) form described second barrier layer by a plurality of chemically different subgrades.
97., it is characterized in that this method further is included on first side of described substrate a plurality of described electro-chemical activity batteries are provided as the described method of claim 96.
98., it is characterized in that this method further is included on second side of described substrate a plurality of described electro-chemical activity batteries are provided as the described method of claim 96.
99., it is characterized in that this method further comprises as the described method of claim 96:
A) from conductivity, electrical insulating property or semi-conductive material, select described subgrade;
B) avoid making the positivity part that is positioned at the electro-chemical activity battery on two sides of described substrate partly to electrically contact with negativity;
C) on the positivity part of described electro-chemical activity battery, provide positive negative electrode, cathode current collector and anode;
D) on the negativity part of described electro-chemical activity battery, provide negative anode, anode collector and negative terminal.
100., it is characterized in that this method further comprises provides described cathode current collector as described anode as the described method of claim 99.
101., it is characterized in that this method further comprises provides described anode collector as described negative terminal as the described method of claim 99.
102., it is characterized in that this method further comprises provides described anode collector as described negative anode as the described method of claim 99.
103., it is characterized in that this method further comprises provides described anode collector as described negative anode and described negative terminal as the described method of claim 99.
104., it is characterized in that this method further comprises providing to have identical shaped and subgrade area size as the described method of claim 96.
105., it is characterized in that this method comprises that further another subgrade that provides at least one and the described a plurality of subgrade has the subgrade of difformity and area size as the described method of claim 96.
106., it is characterized in that this method further comprises with at least one described barrier layer and only partly covers described substrate, makes the part of positivity at least of described electro-chemical activity battery chemically isolate with described substrate as the described method of claim 96.
107., it is characterized in that this method further comprises with at least one described barrier layer and only partly covers described substrate, makes the part of negativity at least of described electro-chemical activity battery chemically isolate with described substrate as the described method of claim 96.
108., it is characterized in that this method further comprises by being selected from following material makes described subgrade as the described method of claim 96 on two sides of described substrate:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
109., it is characterized in that this method further comprises the material by single-phase crystal, nanocrystal, amorphous or glassy state as the described method of claim 96, perhaps their any multiphase mixture or compound are made described subgrade.
110., it is characterized in that this method further comprises by the described subgrade of the made of single-phase amorphous or glassy state as the described method of claim 96.
111. as the described method of claim 96, it is characterized in that, this method comprises that further heat alleviates described first barrier layer and second barrier layer in the following manner: at 100 ℃ of temperature courses that carry out original position or off normal to the temperature range that is up to the substrate fusing point, described temperature course of offing normal applies after having deposited described first barrier layer and second barrier layer.
112. as the described method of claim 96, it is characterized in that, this method further comprises the positive negative electrode of making described electrochemical cell in the following manner: at 100 ℃ of temperature courses that carry out original position or off normal to the temperature range that is up to the substrate fusing point, comprise size and be at least thereby provide
Figure FSB00000445580300121
The positive negative electrode of crystal.
113. as the described method of claim 96; it is characterized in that; this method comprises that further manufacturing has respectively that protectiveness is sealed or the electro-chemical activity battery or the electrochemical apparatus of protectiveness cover, at least machinery and chemical aspect protect described electro-chemical activity battery or electrochemical apparatus to avoid the influence of surrounding environment.
114., it is characterized in that this method comprises that further manufacturing respectively has sealing of at least one opening or cover as the described method of claim 113, thereby can directly electrically contact with at least one terminal in a plurality of terminals of each electro-chemical activity battery.
115., it is characterized in that this method further is included in the described electro-chemical activity battery electrolyte is provided as the described method of claim 114, and described electrolyte and described terminal isolated by the moisture overcoat.
116., it is characterized in that this method further comprises the described moisture overcoat of the made of the wetly barrier properties of apparatus as the described method of claim 115, described moisture overcoat comprises and is selected from following material:
A) metal, semimetal, alloy, boride, carbide, diamond, diamond-like carbon, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, iodide;
B) any multi-element compounds of forming by boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide; Or
C) polysiloxanes of the organic polymer of high-temperature stable and high-temperature stable.
117. as the described method of claim 115, it is characterized in that, this method further comprises with being selected from the described moisture overcoat of following made: the material of single-phase crystal, nanocrystal, amorphous or glassy state, perhaps their any multiphase mixture or compound.
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4948510B2 (en) * 2008-12-02 2012-06-06 トヨタ自動車株式会社 All solid battery
JP6100248B2 (en) * 2011-06-17 2017-03-22 アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ Maskless manufacturing of thin film batteries
US9812706B2 (en) 2012-12-28 2017-11-07 Industrial Technology Research Institute Protected active metal electrode and device with the electrode
US9318774B2 (en) * 2013-06-28 2016-04-19 Google Inc. Substrate for solid-state battery
US9748582B2 (en) * 2014-03-31 2017-08-29 X Development Llc Forming an interconnection for solid-state batteries
KR102496474B1 (en) * 2015-06-03 2023-02-06 삼성전자주식회사 Secondary battery structure/system and methods of manufacturing and operating the same
CN105449168B (en) * 2015-11-19 2018-01-19 中国航空工业集团公司北京航空材料研究院 The preparation method of Metal Substrate solid film lithium battery anode with interface-modifying layer
EP3759752A1 (en) * 2018-02-26 2021-01-06 Graphenix Development, Inc. Anodes for lithium-based energy storage devices
KR20210012045A (en) * 2018-06-21 2021-02-02 어플라이드 머티어리얼스, 인코포레이티드 Diffusion barrier films enabling stability of lithium
CN109560286A (en) * 2018-09-28 2019-04-02 桑顿新能源科技有限公司 A kind of lithium ion battery improving high temperature short-circuit capability

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5338624A (en) * 1993-02-08 1994-08-16 Globe-Union Inc. Thermal management of rechargeable batteries
CN1415124A (en) * 1999-11-01 2003-04-30 波利普拉斯电池有限公司 Layered arrangements of lithium cells
US6906436B2 (en) * 2003-01-02 2005-06-14 Cymbet Corporation Solid state activity-activated battery device and method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3708474B2 (en) * 2001-10-22 2005-10-19 松下電器産業株式会社 Semiconductor device
JP4043296B2 (en) * 2002-06-13 2008-02-06 松下電器産業株式会社 All solid battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5338624A (en) * 1993-02-08 1994-08-16 Globe-Union Inc. Thermal management of rechargeable batteries
CN1415124A (en) * 1999-11-01 2003-04-30 波利普拉斯电池有限公司 Layered arrangements of lithium cells
US6906436B2 (en) * 2003-01-02 2005-06-14 Cymbet Corporation Solid state activity-activated battery device and method

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