WO2000060682A1 - Thin lithium film battery - Google Patents

Thin lithium film battery Download PDF

Info

Publication number
WO2000060682A1
WO2000060682A1 PCT/US2000/008576 US0008576W WO0060682A1 WO 2000060682 A1 WO2000060682 A1 WO 2000060682A1 US 0008576 W US0008576 W US 0008576W WO 0060682 A1 WO0060682 A1 WO 0060682A1
Authority
WO
WIPO (PCT)
Prior art keywords
cathode
collector
anode
thin film
electrolyte
Prior art date
Application number
PCT/US2000/008576
Other languages
French (fr)
Inventor
Lonnie G. Johnson
Original Assignee
Excellatron Solid State, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Excellatron Solid State, Llc filed Critical Excellatron Solid State, Llc
Priority to AU39315/00A priority Critical patent/AU763305B2/en
Priority to EP00918517A priority patent/EP1177589A4/en
Priority to CA002368425A priority patent/CA2368425A1/en
Priority to MXPA01010004A priority patent/MXPA01010004A/en
Priority to NZ514966A priority patent/NZ514966A/en
Publication of WO2000060682A1 publication Critical patent/WO2000060682A1/en

Links

Classifications

    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

Definitions

  • This invention relates generally to thin film batteries, and more particularly to thin film, rechargeable lithium ion batteries.
  • canister type batteries today includes toxic materials such as cadmium, mercury, lead and acid electrolytes. These chemicals are presently facing governmental regulations or bans as manufacturing materials, thus limiting their use as battery components. Another limitation associated with them is that the amount of energy stored and delivered by these batteries is directly related to their size and weight. Large batteries, such as those found in automobiles, produce large amounts of current but have very low energy densities (Watts hours per liter) and specific energies (Watt hours per gram) . As such, they require lengthy recharge times which render them impractical for many uses. To address the need for higher energy densities and specific energies, the battery industry has been moving towards lithium based batteries. The major focus of the battery industry has been on liquid and polymer electrolyte systems.
  • Thin film lithium batteries have been produced which have a stacked configuration of films commencing with an inert ceramic substrate upon which a cathode current collector and cathode is mounted. A solid state electrolyte is deposited upon the cathode, an anode in turn deposited upon the electrolyte, and an anode current collector mounted upon the anode. Typically, a protective coating is applied over the entire cell.
  • Lithium batteries of this type are describe in detail in U.S. Patent Nos . 5,569,520 and 5,597,660, the disclosures of which are specifically incorporated herein. These lithiated cathode material of these batteries have a (003) alignment of the lithium cells, as shown in Fig. 1, which creates a high internal cell resistance resulting in large capacity losses .
  • This orientation is preferred as it provides for high lithium ion diffusion through the cathode since the lithium planes are aligned parallel to the direction of current flow. It is believed that the preferred orientation is formed because the extreme heating during annealing creates a large volume strain energy oriented generally parallel to the underlying rigid substrate surface. As the crystals form they naturally grow in the direction of the least energy strain, as such the annealing process and its resulting volume strain energy promotes crystal growth in a direction generally normal to the underlying substrate surface, which also is -.4 -
  • cathode collectors have been made of cobalt overlaid with a layer of gold or platinum. During the annealing process the cobalt becomes a transition ion passing which is pulled through the gold or platinum and into the cathode material, thereby leaving the gold or platinum layer as the collector .
  • a thin film lithium battery comprises an aluminum cathode collector, a crystallized lithium intercalation compound cathode deposited upon the aluminum cathode collector, an anode, an electrolyte disposed between the lithium intercalation compound cathode and the anode, and an anode collector coupled to the anode.
  • Fig. 1 is an illustration of a lithium intercalation compound oriented along the (003) plane.
  • Fig. 2 is an illustration of a lithium intercalation compound oriented along the preferred (101) plane.
  • Fig. 3 is a plan view of a thin film lithium battery illustrating principles of the invention in a preferred embodiment .
  • Fig. 4 is a cross-sectional view of the thin film lithium battery of Fig. 3 taken along plane 4-4.
  • Fig. 6 is a photocopy of a photograph showing the aluminum cathode collector and lithiated cathode of the thin film lithium battery of Fig. 3.
  • DETAILED DESCRIPTION With reference next to the drawings, there is shown in a rechargeable, thin film lithium battery cell 10 embodying principles of the invention in a preferred form.
  • the battery cell 10 has an aluminum cathode current collector 11 sandwiched between two cathodes 12.
  • the cathodes 12 are made of a lithium intercalation compound, preferably a metal oxide such as LiNi0 2 , V 2 0 5 , Li x Mn 2 0 4 , LiCo0 2 or TiS 2 .
  • Each cathode 12 has a solid state electrolyte 13 formed thereon.
  • the electrolyte 13 is preferable made of lithium phosphorus oxynitride, Li-PO y N-.
  • each electrolyte 13 has an anode 14 deposited thereon.
  • the anode 14 is preferably made of silicon-tin oxynitride, SiTON, when used in lithium ion batteries, or other suitable materials such as lithium metal, zinc nitride or tin nitride.
  • an anode current collector 16 preferably made of copper or nickel, contacts both anodes 14 to substantially encase the cathode collector 11, cathode 12, electrolyte 13 and anode 14.
  • a solderable contact 16 may be mounted in electrical contact with the cathode current collector 11.
  • the battery cell 10 is preferably manufactured in the following manner.
  • a web of approximately 4 micron thick aluminum foil is passed through a plasma treatment station to remove any oil residue from the foil.
  • the aluminum foil is passed through a cathode Leybold chamber equipped with two large cryopumps and a series of rf or dc magnetron sputtering or diode sputtering cathodes positioned around a rotating drum in a substantially pure oxygen atmosphere.
  • the sputtering cathodes deposit an approximately 3 micron thick cathode onto one side of the foil.
  • the aluminum foil is then flips so that the magnetrons deposit a 3 micron thick cathode on the opposite side of the foil.
  • the coated foil is next removed from the coating chamber and segmented into pieces that are clamped onto aluminum frames . These frames act as both means for handling the material during processing and means for providing accurate mask registration during deposition of the materials.
  • the coated foil is then sintered for approximately eight hours at a temperature of approximately 600 " C to crystalize the cathode material.
  • the electrolyte 13 is then deposited upon the cathodes 12 by the sputtering of lithium orthophosphate, Li 5 P0 4 , in a nitrogen atmosphere to produce a lithium phosphorus oxynitride layer.
  • each anode 14 is applied to the corresponding electrolyte 13 by sputtering.
  • the anode current collector 16 is then deposited onto the anode by the sputtering of copper or nickel.
  • crystallized lithium material deposited upon the aluminum collector and annealed at 600 'C has the preferred (101) crystal growth plane orientation shown in Fig. 2. This orientation is believed to be achieved by minimizing the volume strain energy and maximizing the surface energy during crystal growth through the difference in the thermal expansion coefficient between the aluminum cathode collector and the lithium intercalation compound cathode.
  • the thermal expansion coefficient of the aluminum cathode collector is 13.3 x IO ' VF while the thermal expansion coefficient of the cathode material (LiCo0 2 ) is 4.5 x 10 "6 /'F.
  • the difference in the coefficients results in intension or compression strain in the lattice of the lithium intercalation material.
  • the aluminum has almost no structural strength at this temperature and therefore is very limited in its ability to apply the required strain energy to the cathode material deposited thereon. As best shown in Figs. 3 and 4, the end of the cathode collector is exposed so that the battery cell may be - 10 -
  • the just describe battery cell is fabricated with a surface area of approximately ten (10) square centimeters, a weight of approximately 5.4 x 10_ 2 grams, and a thickness of approximately 14 microns. This configuration shows a capacity of 82.4 milliamp hours. Using 82.4 millamps as the 1C charge or discharge rate, these cells show a degradation of less than 20% at discharge rates of over 10C, i.e. 824.0 milliamps.
  • the energy density of the cell is approximately 293 Watt hours per kilogram based on the combined masses of the cathode, electrolyte, current collectors and anode. It should be noted that the cell does not have an initial substrate which was previously required in the production of thin film lithium batteries. This advantageously reduces the weight and thickness as compared to those thin film lithium batteries of the prior art which utilized other heavier and thicker substrates.
  • Fig. 5 shows a comparison of the inventive lithium ion battery (MLI Li-Ion) and inventive lithium metal battery MLI (Li Metal) with a lithium polymer battery (Li Poly) , liquid lithium ion battery (LLI) , nickel metal hydride battery (NiMH) and nickel cadmium battery (NiCd) .
  • the table of Fig. 5 illustrates that the inventive batteries deliver a substantial increase in energy (Whr/kg) , a dramatic increase in power (W/kg) , a dramatic increase in the energy for a given volume size (Whr/1) and a dramatic increase in the number of times the battery may be cycled through charges and discharges .
  • the decrease in the size and weight of the cells allows batteries to be manufactured smaller and lighter without decreasing their capacity and power output, as compared to batteries of the prior art.
  • the number of cells in a battery may be increased to achieve a greater capacity without increasing the battery same size and weight as compared with previous manufactured thin film lithium battery cells that utilize an underlying substrate.
  • the aluminum foil may be pre- annealed prior to the deposition of the cathode material so limit deformation of the aluminum foil.
  • an insulator 18, such as parylene, may be used to fill any spaces between these components and the anode current collector 16.
  • the aluminum foil need not be pure aluminum. Certain aluminum alloys may also be utilized, hence the term aluminum used herein also refers to aluminum alloys. Also, the aluminum foil may include a thin coating of cobalt or titanium deposited by conventional sputtering methods.

Abstract

A rechargeable, thin film lithium battery cell (10) is provided having an aluminum cathode current collector (11) sandwiched between two crystallized cathodes (12). Each cathode has an electrolyte (13) deposited thereon which is overlaid with a lithium anode (14). An anode current collector (15) contacts the anode and substantially encases the cathode collector, cathode, electrolyte and anode.

Description

THIN LITHIUM FILM BATTERY
TECHNICAL FIELD
This invention relates generally to thin film batteries, and more particularly to thin film, rechargeable lithium ion batteries.
BACKGROUND OF THE INVENTION
Conventional, canister type batteries today includes toxic materials such as cadmium, mercury, lead and acid electrolytes. These chemicals are presently facing governmental regulations or bans as manufacturing materials, thus limiting their use as battery components. Another limitation associated with them is that the amount of energy stored and delivered by these batteries is directly related to their size and weight. Large batteries, such as those found in automobiles, produce large amounts of current but have very low energy densities (Watts hours per liter) and specific energies (Watt hours per gram) . As such, they require lengthy recharge times which render them impractical for many uses. To address the need for higher energy densities and specific energies, the battery industry has been moving towards lithium based batteries. The major focus of the battery industry has been on liquid and polymer electrolyte systems. However, these systems have inherent safety problems because of the volatile nature of the electrolyte solvents. These types of batteries have a relatively high ratio of inert material components, such as the current collector, separator, and substrate, relative to the active energy storage materials used for the anode and cathode. In addition, their relatively high internal impedance results in low rate capability (watts/kilogram) which renders them impractical for many applications.
Thin film lithium batteries have been produced which have a stacked configuration of films commencing with an inert ceramic substrate upon which a cathode current collector and cathode is mounted. A solid state electrolyte is deposited upon the cathode, an anode in turn deposited upon the electrolyte, and an anode current collector mounted upon the anode. Typically, a protective coating is applied over the entire cell. Lithium batteries of this type are describe in detail in U.S. Patent Nos . 5,569,520 and 5,597,660, the disclosures of which are specifically incorporated herein. These lithiated cathode material of these batteries have a (003) alignment of the lithium cells, as shown in Fig. 1, which creates a high internal cell resistance resulting in large capacity losses .
Recently, it has been discovered that the annealing of lithiated cathode materials on a substrate under proper conditions results in batteries having significantly enhanced performances, for the annealing causes the lithiated material to crystalize. This crystallized material has a hexagonal layered structure in which alternating planes containing Li and Co ions are separated by close packed oxygen layers. It has been discovered that LiCo02 films deposited onto an alumina substrate by magnetron sputtering and crystallized by annealing at 700 *C exhibit a high degree of preferred orientation or texturing with the layers of the oxygen, cobalt and lithium are oriented generally normal to the substrate, i.e. the (101) plane as shown in Fig. 2. This orientation is preferred as it provides for high lithium ion diffusion through the cathode since the lithium planes are aligned parallel to the direction of current flow. It is believed that the preferred orientation is formed because the extreme heating during annealing creates a large volume strain energy oriented generally parallel to the underlying rigid substrate surface. As the crystals form they naturally grow in the direction of the least energy strain, as such the annealing process and its resulting volume strain energy promotes crystal growth in a direction generally normal to the underlying substrate surface, which also is -.4 -
the preferred orientation for ion diffusion through the crystal .
However, the limitations of these batteries have been the thickness and weight of their substrates upon which the layers of active material are laid upon. Because of the size of the substrate, these batteries have -not been competitive with other formulations in terms of energy density and specific energy. High energy density cells have not been successfully constructed. The supporting substrates 'have been made of relatively thick sheets of alumina, sapphire, silica glass and various other types of ceramic material. The current collector and substrate of these batteries typically constitute nearly 70% of the total weight and an even larger percentage of the volume, thus only a small amount of the of the battery weight and volume is attributed to the active materials. This ratio of active material to the overall weight and volume of the battery limits their use.
With an annealing temperature below 600 'C the lithium material has no significant change in the microstructure, and thus the lithium orientation remains amorphous, as taught in Characterization of Thin-Film Rechargeable Lithium Batteries With Lithium Cobalt Oxide Cathodes, in the Journal of The Electrochemical Society, Vol. 143, No 10, by B.Wang, J.B. Bates, F.X. Hart, B.C. Sales, R.A. Zuhr and J.D. Robertson. This amorphous state restricts lithium ion diffusion through the layers of oxygen and cobalt, and therefore creates a high internal cell resistance resulting in large capacity losses.
Hence, in order to anneal the lithiated cathode material to the most efficient orientation it was believed that the cathode had to be bonded to a rigid substrate and heated to nearly 700 °C for an extended period of time. Because of .such extreme heating, it was believed that only certain metals with high melting points could be used as the cathode collector. A problem associated with these metals has been there inability to bond with the substrate material, as these metals "de-wet" thereby forming small pools upon the substrate surface. As such, cathode collectors have been made of cobalt overlaid with a layer of gold or platinum. During the annealing process the cobalt becomes a transition ion passing which is pulled through the gold or platinum and into the cathode material, thereby leaving the gold or platinum layer as the collector .
It was believed that a lightweight, low melting point metal, such as aluminum, could not survive the annealing process and therefore could not be used as a current collector in thin film lithium batteries having crystallized cathodes. This was a common belief even though such metals would be chemically compatible for use with lithium cathodes.
It thus is seen that a need remains for a high performance rechargeable, thin film lithium battery which is smaller and lighter than those of the prior art. Accordingly, it is to the provision of such that the present invention is primarily directed.
SUMMARY OF THE INVENTION
In a preferred form of the invention, a thin film lithium battery comprises an aluminum cathode collector, a crystallized lithium intercalation compound cathode deposited upon the aluminum cathode collector, an anode, an electrolyte disposed between the lithium intercalation compound cathode and the anode, and an anode collector coupled to the anode.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an illustration of a lithium intercalation compound oriented along the (003) plane.
Fig. 2 is an illustration of a lithium intercalation compound oriented along the preferred (101) plane.
Fig. 3 is a plan view of a thin film lithium battery illustrating principles of the invention in a preferred embodiment .
Fig. 4 is a cross-sectional view of the thin film lithium battery of Fig. 3 taken along plane 4-4.
Fig. 6 is a photocopy of a photograph showing the aluminum cathode collector and lithiated cathode of the thin film lithium battery of Fig. 3. DETAILED DESCRIPTION With reference next to the drawings, there is shown in a rechargeable, thin film lithium battery cell 10 embodying principles of the invention in a preferred form. The battery cell 10 has an aluminum cathode current collector 11 sandwiched between two cathodes 12. The cathodes 12 are made of a lithium intercalation compound, preferably a metal oxide such as LiNi02, V205, LixMn204, LiCo02 or TiS2. Each cathode 12 has a solid state electrolyte 13 formed thereon. The electrolyte 13 is preferable made of lithium phosphorus oxynitride, Li-POyN-. In turn, each electrolyte 13 has an anode 14 deposited thereon. The anode 14 is preferably made of silicon-tin oxynitride, SiTON, when used in lithium ion batteries, or other suitable materials such as lithium metal, zinc nitride or tin nitride. Finally, an anode current collector 16, preferably made of copper or nickel, contacts both anodes 14 to substantially encase the cathode collector 11, cathode 12, electrolyte 13 and anode 14. A solderable contact 16 may be mounted in electrical contact with the cathode current collector 11.
The battery cell 10 is preferably manufactured in the following manner. A web of approximately 4 micron thick aluminum foil is passed through a plasma treatment station to remove any oil residue from the foil. The aluminum foil is passed through a cathode Leybold chamber equipped with two large cryopumps and a series of rf or dc magnetron sputtering or diode sputtering cathodes positioned around a rotating drum in a substantially pure oxygen atmosphere. The sputtering cathodes deposit an approximately 3 micron thick cathode onto one side of the foil. The aluminum foil is then flips so that the magnetrons deposit a 3 micron thick cathode on the opposite side of the foil.
The coated foil is next removed from the coating chamber and segmented into pieces that are clamped onto aluminum frames . These frames act as both means for handling the material during processing and means for providing accurate mask registration during deposition of the materials. The coated foil is then sintered for approximately eight hours at a temperature of approximately 600 " C to crystalize the cathode material.
The electrolyte 13 is then deposited upon the cathodes 12 by the sputtering of lithium orthophosphate, Li5P04, in a nitrogen atmosphere to produce a lithium phosphorus oxynitride layer. Similarly, each anode 14 is applied to the corresponding electrolyte 13 by sputtering. The anode current collector 16 is then deposited onto the anode by the sputtering of copper or nickel.
It has been found that crystallized lithium material deposited upon the aluminum collector and annealed at 600 'C has the preferred (101) crystal growth plane orientation shown in Fig. 2. This orientation is believed to be achieved by minimizing the volume strain energy and maximizing the surface energy during crystal growth through the difference in the thermal expansion coefficient between the aluminum cathode collector and the lithium intercalation compound cathode. The thermal expansion coefficient of the aluminum cathode collector is 13.3 x IO'VF while the thermal expansion coefficient of the cathode material (LiCo02) is 4.5 x 10"6/'F. The difference in the coefficients results in intension or compression strain in the lattice of the lithium intercalation material. It is this volumetric stress energy between the aluminum and the cathode which causes the re-orientation of the lithiated material from an amorphous condition to the crystalline (101) plane. The alignment of the lithiated material is illustrated in Fig. 6 which shows the lithiated cathode 12 aligned generally normal to the underlying aluminum collector 11, illustrated by the streaking of the cathode. This effective annealing at a temperature of 600 'C on an aluminum film greatly improves the efficiencies in the manufacturing of the battery. Successful annealing on an aluminum substrate is remarkable because the annealing temperature of 600 'C is very close to the aluminum melting temperature of 648 *C. The aluminum has almost no structural strength at this temperature and therefore is very limited in its ability to apply the required strain energy to the cathode material deposited thereon. As best shown in Figs. 3 and 4, the end of the cathode collector is exposed so that the battery cell may be - 10 -
conventionally connected to other similar cells in either an electrical series or in parallel circuit.
The just describe battery cell is fabricated with a surface area of approximately ten (10) square centimeters, a weight of approximately 5.4 x 10_2 grams, and a thickness of approximately 14 microns. This configuration shows a capacity of 82.4 milliamp hours. Using 82.4 millamps as the 1C charge or discharge rate, these cells show a degradation of less than 20% at discharge rates of over 10C, i.e. 824.0 milliamps. The energy density of the cell is approximately 293 Watt hours per kilogram based on the combined masses of the cathode, electrolyte, current collectors and anode. It should be noted that the cell does not have an initial substrate which was previously required in the production of thin film lithium batteries. This advantageously reduces the weight and thickness as compared to those thin film lithium batteries of the prior art which utilized other heavier and thicker substrates.
Fig. 5, shows a comparison of the inventive lithium ion battery (MLI Li-Ion) and inventive lithium metal battery MLI (Li Metal) with a lithium polymer battery (Li Poly) , liquid lithium ion battery (LLI) , nickel metal hydride battery (NiMH) and nickel cadmium battery (NiCd) . The table of Fig. 5 illustrates that the inventive batteries deliver a substantial increase in energy (Whr/kg) , a dramatic increase in power (W/kg) , a dramatic increase in the energy for a given volume size (Whr/1) and a dramatic increase in the number of times the battery may be cycled through charges and discharges . The decrease in the size and weight of the cells allows batteries to be manufactured smaller and lighter without decreasing their capacity and power output, as compared to batteries of the prior art. Alternatively, because of the reduced thickness of the cells, the number of cells in a battery may be increased to achieve a greater capacity without increasing the battery same size and weight as compared with previous manufactured thin film lithium battery cells that utilize an underlying substrate.
It is believed that the aluminum foil may be pre- annealed prior to the deposition of the cathode material so limit deformation of the aluminum foil. It should be understood that an insulator 18, such as parylene, may be used to fill any spaces between these components and the anode current collector 16.
It should be understood that the aluminum foil need not be pure aluminum. Certain aluminum alloys may also be utilized, hence the term aluminum used herein also refers to aluminum alloys. Also, the aluminum foil may include a thin coating of cobalt or titanium deposited by conventional sputtering methods.
It thus is seen that a high rate capability battery is now provide which is lighter and smaller than those of the prior art. It should of course be understood that many modifications may be made to the specific preferred embodiment described herein without departure from the spirit and scope of the invention as set forth in the following claims.

Claims

1. A thin film lithium battery comprising: an aluminum cathode collector; a crystallized lithium intercalation compound cathode deposited upon said aluminum cathode collector; an anode ; an electrolyte disposed between said lithium intercalation compound cathode and said anode; and an anode collector coupled to said anode.
2. The thin film lithium battery of claim 1 wherein said aluminum cathode collector has a cobalt coating.
3. The thin film lithium battery of claim 1 wherein said aluminum cathode collector has a titanium coating.
4. The thin film lithium battery of claim 1 wherein said cathode comprises two layers disposed upon opposite sides of said cathode collector.
5. The thin film lithium battery of claim 4 wherein said electrolyte comprises two layers sandwiching said cathode layers.
6. The thin film lithium battery of claim 5 wherein said anode comprises two layers sandwiching said electrolyte layers.
7. The thin film lithium battery of claim 6 wherein said anode collector comprises two layers sandwiching said electrolyte layers .
8. A thin film lithium battery comprising: an aluminum cathode collector; a lithium intercalation compound cathode sandwiching said collector,-' an electrolyte overlaying said cathode; an anode overlaying said electrolyte; and an anode collector coupled to said anode.
9. The thin film lithium battery of claim 8 wherein said cathode comprises two layers disposed upon opposite sides of said cathode collector.
10. The thin film lithium battery of claim 9 wherein said electrolyte comprises two layers sandwiching said cathode layers.
11. The thin film lithium battery of claim 10 wherein said anode comprises two layers sandwiching said electrolyte layers.
12. The thin film lithium battery of claim 11 wherein said anode collector comprises two layers sandwiching said electrolyte layers .
13. The thin film lithium battery of claim 8 wherein said cathode is a crystallized lithium intercalation compound.
14. A method of producing a thin film lithium battery comprising the steps of: providing an aluminum cathode collector; depositing a lithium intercalation compound cathode upon the aluminum cathode collector; annealing the collector and cathode at a select temperature for a select period of time to enable the surface strain between the collector and the cathode to orient the crystallization of the cathode; mounting an electrolyte upon the crystallized cathode; mounting an anode upon the electrolyte; and mounting an anode collector upon the anode.
15. The method of producing a thin film battery of claim
14 wherein the lithium intercalation compound cathode is deposited upon opposite sides of the aluminum cathode collector.
16. The method of producing a thin film battery of claim
15 wherein the electrolyte, the anode and the anode collector sandwich the aluminum collector and cathode.
PCT/US2000/008576 1999-04-02 2000-03-31 Thin lithium film battery WO2000060682A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU39315/00A AU763305B2 (en) 1999-04-02 2000-03-31 Thin lithium film battery
EP00918517A EP1177589A4 (en) 1999-04-02 2000-03-31 Thin lithium film battery
CA002368425A CA2368425A1 (en) 1999-04-02 2000-03-31 Thin lithium film battery
MXPA01010004A MXPA01010004A (en) 1999-04-02 2000-03-31 Thin lithium film battery.
NZ514966A NZ514966A (en) 1999-04-02 2000-03-31 Thin lithium film battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/286,112 1999-04-02
US09/286,112 US6242129B1 (en) 1999-04-02 1999-04-02 Thin lithium film battery

Publications (1)

Publication Number Publication Date
WO2000060682A1 true WO2000060682A1 (en) 2000-10-12

Family

ID=23097131

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/008576 WO2000060682A1 (en) 1999-04-02 2000-03-31 Thin lithium film battery

Country Status (9)

Country Link
US (1) US6242129B1 (en)
EP (1) EP1177589A4 (en)
CN (1) CN100365851C (en)
AU (1) AU763305B2 (en)
CA (1) CA2368425A1 (en)
MX (1) MXPA01010004A (en)
NZ (1) NZ514966A (en)
WO (1) WO2000060682A1 (en)
ZA (1) ZA200108166B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6916679B2 (en) 2002-08-09 2005-07-12 Infinite Power Solutions, Inc. Methods of and device for encapsulation and termination of electronic devices
US9334557B2 (en) 2007-12-21 2016-05-10 Sapurast Research Llc Method for sputter targets for electrolyte films
US9532453B2 (en) 2009-09-01 2016-12-27 Sapurast Research Llc Printed circuit board with integrated thin film battery
US9634296B2 (en) 2002-08-09 2017-04-25 Sapurast Research Llc Thin film battery on an integrated circuit or circuit board and method thereof
US9786873B2 (en) 2008-01-11 2017-10-10 Sapurast Research Llc Thin film encapsulation for thin film batteries and other devices
US9793523B2 (en) 2002-08-09 2017-10-17 Sapurast Research Llc Electrochemical apparatus with barrier layer protected substrate
WO2019035745A1 (en) 2017-08-14 2019-02-21 Thinika, Llc Solid-state thin film hybrid electrochemical cell
US10680277B2 (en) 2010-06-07 2020-06-09 Sapurast Research Llc Rechargeable, high-density electrochemical device

Families Citing this family (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6982132B1 (en) * 1997-10-15 2006-01-03 Trustees Of Tufts College Rechargeable thin film battery and method for making the same
JP4854112B2 (en) * 1998-05-20 2012-01-18 株式会社Ｋｒｉ Lithium ion battery and control method thereof
JP4423699B2 (en) * 1999-05-27 2010-03-03 ソニー株式会社 Semiconductor laser device and manufacturing method thereof
US6344366B1 (en) * 1999-09-15 2002-02-05 Lockheed Martin Energy Research Corporation Fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing
US6887511B1 (en) * 1999-10-22 2005-05-03 Sanyo Electric Co., Ltd. Method for preparing electrode material for lithium battery
US6517968B2 (en) * 2001-06-11 2003-02-11 Excellatron Solid State, Llc Thin lithium film battery
US6677076B2 (en) * 2002-01-15 2004-01-13 Quallion Llc Electric storage battery construction and method of manufacture
US6670071B2 (en) * 2002-01-15 2003-12-30 Quallion Llc Electric storage battery construction and method of manufacture
US6884327B2 (en) 2002-03-16 2005-04-26 Tao Pan Mode size converter for a planar waveguide
US7378356B2 (en) * 2002-03-16 2008-05-27 Springworks, Llc Biased pulse DC reactive sputtering of oxide films
US20030175142A1 (en) * 2002-03-16 2003-09-18 Vassiliki Milonopoulou Rare-earth pre-alloyed PVD targets for dielectric planar applications
US8431264B2 (en) 2002-08-09 2013-04-30 Infinite Power Solutions, Inc. Hybrid thin-film battery
US8394522B2 (en) 2002-08-09 2013-03-12 Infinite Power Solutions, Inc. Robust metal film encapsulation
US8236443B2 (en) 2002-08-09 2012-08-07 Infinite Power Solutions, Inc. Metal film encapsulation
US8021778B2 (en) 2002-08-09 2011-09-20 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US8404376B2 (en) 2002-08-09 2013-03-26 Infinite Power Solutions, Inc. Metal film encapsulation
US8445130B2 (en) 2002-08-09 2013-05-21 Infinite Power Solutions, Inc. Hybrid thin-film battery
WO2004021532A1 (en) 2002-08-27 2004-03-11 Symmorphix, Inc. Optically coupling into highly uniform waveguides
US20060035147A1 (en) * 2003-01-15 2006-02-16 Quallion Llc Battery
CN1756856B (en) * 2003-02-27 2011-10-12 希莫菲克斯公司 Dielectric barrier layer films
US7238628B2 (en) * 2003-05-23 2007-07-03 Symmorphix, Inc. Energy conversion and storage films and devices by physical vapor deposition of titanium and titanium oxides and sub-oxides
US8728285B2 (en) 2003-05-23 2014-05-20 Demaray, Llc Transparent conductive oxides
US8080329B1 (en) 2004-03-25 2011-12-20 Quallion Llc Uniformly wound battery
JP4302591B2 (en) * 2004-08-20 2009-07-29 浜松ホトニクス株式会社 Droplet formation condition determination method, droplet volume measurement method, particle number measurement method, and droplet formation apparatus
JP5095412B2 (en) 2004-12-08 2012-12-12 シモーフィックス，インコーポレーテッド LiCoO2 deposition
US7959769B2 (en) 2004-12-08 2011-06-14 Infinite Power Solutions, Inc. Deposition of LiCoO2
US7846579B2 (en) * 2005-03-25 2010-12-07 Victor Krasnov Thin film battery with protective packaging
US8679674B2 (en) * 2005-03-25 2014-03-25 Front Edge Technology, Inc. Battery with protective packaging
US7838133B2 (en) 2005-09-02 2010-11-23 Springworks, Llc Deposition of perovskite and other compound ceramic films for dielectric applications
CN101523571A (en) 2006-09-29 2009-09-02 无穷动力解决方案股份有限公司 Masking of and material constraint for depositing battery layers on flexible substrates
US8197781B2 (en) 2006-11-07 2012-06-12 Infinite Power Solutions, Inc. Sputtering target of Li3PO4 and method for producing same
US7862927B2 (en) * 2007-03-02 2011-01-04 Front Edge Technology Thin film battery and manufacturing method
US8870974B2 (en) * 2008-02-18 2014-10-28 Front Edge Technology, Inc. Thin film battery fabrication using laser shaping
US7862627B2 (en) * 2007-04-27 2011-01-04 Front Edge Technology, Inc. Thin film battery substrate cutting and fabrication process
US20120196189A1 (en) 2007-06-29 2012-08-02 Johnson Ip Holding, Llc Amorphous ionically conductive metal oxides and sol gel method of preparation
US9034525B2 (en) * 2008-06-27 2015-05-19 Johnson Ip Holding, Llc Ionically-conductive amorphous lithium lanthanum zirconium oxide
US8211496B2 (en) * 2007-06-29 2012-07-03 Johnson Ip Holding, Llc Amorphous lithium lanthanum titanate thin films manufacturing method
US20090092903A1 (en) * 2007-08-29 2009-04-09 Johnson Lonnie G Low Cost Solid State Rechargeable Battery and Method of Manufacturing Same
US8628645B2 (en) * 2007-09-04 2014-01-14 Front Edge Technology, Inc. Manufacturing method for thin film battery
US20090136839A1 (en) * 2007-11-28 2009-05-28 Front Edge Technology, Inc. Thin film battery comprising stacked battery cells and method
US8268488B2 (en) 2007-12-21 2012-09-18 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
EP2266183B1 (en) 2008-04-02 2018-12-12 Sapurast Research LLC Passive over/under voltage control and protection for energy storage devices associated with energy harvesting
JP5417757B2 (en) * 2008-07-16 2014-02-19 ソニー株式会社 Method for producing positive electrode of thin film battery and method for producing thin film battery
US8906523B2 (en) 2008-08-11 2014-12-09 Infinite Power Solutions, Inc. Energy device with integral collector surface for electromagnetic energy harvesting and method thereof
CN102150185B (en) 2008-09-12 2014-05-28 无穷动力解决方案股份有限公司 Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof
WO2010042594A1 (en) 2008-10-08 2010-04-15 Infinite Power Solutions, Inc. Environmentally-powered wireless sensor module
US8502494B2 (en) * 2009-08-28 2013-08-06 Front Edge Technology, Inc. Battery charging apparatus and method
US8865340B2 (en) 2011-10-20 2014-10-21 Front Edge Technology Inc. Thin film battery packaging formed by localized heating
US9887429B2 (en) 2011-12-21 2018-02-06 Front Edge Technology Inc. Laminated lithium battery
US8864954B2 (en) 2011-12-23 2014-10-21 Front Edge Technology Inc. Sputtering lithium-containing material with multiple targets
KR20150016210A (en) 2012-03-01 2015-02-11 엑셀라트론 솔리드 스테이트 엘엘씨 High Capacity Solid State Composite Cathode, Solid State Composite Separator, Solid-State Rechargeable Lithium Battery and Methods of Making Same
US9257695B2 (en) 2012-03-29 2016-02-09 Front Edge Technology, Inc. Localized heat treatment of battery component films
US9077000B2 (en) 2012-03-29 2015-07-07 Front Edge Technology, Inc. Thin film battery and localized heat treatment
RU2488196C1 (en) * 2012-06-04 2013-07-20 федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский университет "МЭИ" (ФГБОУ ВПО "НИУ МЭИ") Manufacturing method of cathode of lithium current source
US9548511B2 (en) 2012-07-18 2017-01-17 Nthdegree Technologies Worldwide Inc. Diatomaceous energy storage devices
EP2875515B1 (en) 2012-07-18 2017-08-23 Printed Energy Pty Ltd Diatomaceous energy storage devices
US10396365B2 (en) 2012-07-18 2019-08-27 Printed Energy Pty Ltd Diatomaceous energy storage devices
US9159964B2 (en) 2012-09-25 2015-10-13 Front Edge Technology, Inc. Solid state battery having mismatched battery cells
US8753724B2 (en) 2012-09-26 2014-06-17 Front Edge Technology Inc. Plasma deposition on a partially formed battery through a mesh screen
US9793525B2 (en) 2012-10-09 2017-10-17 Johnson Battery Technologies, Inc. Solid-state battery electrodes
US9397341B2 (en) 2012-10-10 2016-07-19 Nthdegree Technologies Worldwide Inc. Printed energy storage device
US9520598B2 (en) 2012-10-10 2016-12-13 Nthdegree Technologies Worldwide Inc. Printed energy storage device
US9356320B2 (en) 2012-10-15 2016-05-31 Front Edge Technology Inc. Lithium battery having low leakage anode
KR102071269B1 (en) * 2013-07-17 2020-01-30 엔티에이치 디그리 테크놀로지스 월드와이드 인코포레이티드 Printed silver oxide batteries
US9917284B2 (en) * 2014-02-07 2018-03-13 Virideon, Inc System and method for a non-hazmat shippable portable power device
US10008739B2 (en) 2015-02-23 2018-06-26 Front Edge Technology, Inc. Solid-state lithium battery with electrolyte
EP3394918A1 (en) 2015-12-21 2018-10-31 Johnson IP Holding, LLC Solid-state batteries, separators, electrodes, and methods of fabrication
US10218044B2 (en) 2016-01-22 2019-02-26 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092464A (en) * 1976-07-19 1978-05-30 P. R. Mallory & Co. Inc. Flexible cells and batteries formed therefrom
US5569520A (en) * 1994-01-12 1996-10-29 Martin Marietta Energy Systems, Inc. Rechargeable lithium battery for use in applications requiring a low to high power output
US6001139A (en) * 1995-03-06 1999-12-14 Fuji Photo Film Co., Ltd. Nonaqueous secondary battery having multiple-layered negative electrode

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3237078A (en) 1963-03-14 1966-02-22 Mallory & Co Inc P R Rechargeable batteries and regulated charging means therefor
US3393355A (en) 1965-08-09 1968-07-16 Mallory & Co Inc P R Semiconductor charge control through thermal isolation of semiconductor and cell
US4303877A (en) 1978-05-05 1981-12-01 Brown, Boveri & Cie Aktiengesellschaft Circuit for protecting storage cells
SE451924B (en) 1982-10-12 1987-11-02 Ericsson Telefon Ab L M REGULATOR FOR REGULATING A CHARGING CURRENT TO A SINGLE CELL IN A BATTERY OF CELLS
JPS59226472A (en) * 1983-06-06 1984-12-19 Hitachi Ltd Thin film lithium battery
US4719401A (en) 1985-12-04 1988-01-12 Powerplex Technologies, Inc. Zener diode looping element for protecting a battery cell
US4654281A (en) 1986-03-24 1987-03-31 W. R. Grace & Co. Composite cathodic electrode
US5270635A (en) 1989-04-11 1993-12-14 Solid State Chargers, Inc. Universal battery charger
US5110696A (en) * 1990-11-09 1992-05-05 Bell Communications Research Rechargeable lithiated thin film intercalation electrode battery
JP3231801B2 (en) 1991-02-08 2001-11-26 本田技研工業株式会社 Battery charger
EP0570590B1 (en) * 1991-12-06 1997-03-26 Yuasa Corporation Thin battery and monolithic thin battery
US5291116A (en) 1992-01-27 1994-03-01 Batonex, Inc. Apparatus for charging alkaline zinc-manganese dioxide cells
DE69330799T2 (en) 1992-04-03 2002-05-29 Jeol Ltd Power supply with storage capacitor
US5338625A (en) 1992-07-29 1994-08-16 Martin Marietta Energy Systems, Inc. Thin film battery and method for making same
US5362581A (en) 1993-04-01 1994-11-08 W. R. Grace & Co.-Conn. Battery separator
US5336573A (en) 1993-07-20 1994-08-09 W. R. Grace & Co.-Conn. Battery separator
US5314765A (en) 1993-10-14 1994-05-24 Martin Marietta Energy Systems, Inc. Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method
US5821733A (en) 1994-02-22 1998-10-13 Packard Bell Nec Multiple cell and serially connected rechargeable batteries and charging system
US5561004A (en) 1994-02-25 1996-10-01 Bates; John B. Packaging material for thin film lithium batteries
US5654084A (en) 1994-07-22 1997-08-05 Martin Marietta Energy Systems, Inc. Protective coatings for sensitive materials
US5445906A (en) 1994-08-03 1995-08-29 Martin Marietta Energy Systems, Inc. Method and system for constructing a rechargeable battery and battery structures formed with the method
FR2729009B1 (en) 1994-12-28 1997-01-31 Accumulateurs Fixes BIFUNCTIONAL ELECTRODE FOR ELECTROCHEMICAL GENERATOR OR SUPERCAPACITOR AND ITS MANUFACTURING PROCESS
AU1056997A (en) * 1995-11-24 1997-06-11 Ovonic Battery Company, Inc. A solid state battery having a disordered hydrogenated carbon negative electrode
US5778515A (en) 1997-04-11 1998-07-14 Valence Technology, Inc. Methods of fabricating electrochemical cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092464A (en) * 1976-07-19 1978-05-30 P. R. Mallory & Co. Inc. Flexible cells and batteries formed therefrom
US5569520A (en) * 1994-01-12 1996-10-29 Martin Marietta Energy Systems, Inc. Rechargeable lithium battery for use in applications requiring a low to high power output
US6001139A (en) * 1995-03-06 1999-12-14 Fuji Photo Film Co., Ltd. Nonaqueous secondary battery having multiple-layered negative electrode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FRAGNAUD ET. AL.: "Characterization of sprayed and sputter deposited liCoO2 thin films for rechargeable microbatteries.", J. OF POWER SOURCES, vol. 63, December 1996 (1996-12-01), pages 187 - 191, XP002928376 *
See also references of EP1177589A4 *
WANG ET. AL.: "Characterization of Thin-Film Rechargeable Lithium Batteris with Lithium Cobalt Oxide Cathodes.", J. ELECTROCHEM. SOC., vol. 143, no. 10, October 1996 (1996-10-01), pages 3203 - 3213, XP002928377 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6916679B2 (en) 2002-08-09 2005-07-12 Infinite Power Solutions, Inc. Methods of and device for encapsulation and termination of electronic devices
US9634296B2 (en) 2002-08-09 2017-04-25 Sapurast Research Llc Thin film battery on an integrated circuit or circuit board and method thereof
US9793523B2 (en) 2002-08-09 2017-10-17 Sapurast Research Llc Electrochemical apparatus with barrier layer protected substrate
US9334557B2 (en) 2007-12-21 2016-05-10 Sapurast Research Llc Method for sputter targets for electrolyte films
US9786873B2 (en) 2008-01-11 2017-10-10 Sapurast Research Llc Thin film encapsulation for thin film batteries and other devices
US9532453B2 (en) 2009-09-01 2016-12-27 Sapurast Research Llc Printed circuit board with integrated thin film battery
US10680277B2 (en) 2010-06-07 2020-06-09 Sapurast Research Llc Rechargeable, high-density electrochemical device
WO2019035745A1 (en) 2017-08-14 2019-02-21 Thinika, Llc Solid-state thin film hybrid electrochemical cell

Also Published As

Publication number Publication date
CN100365851C (en) 2008-01-30
CA2368425A1 (en) 2000-10-12
CN1695261A (en) 2005-11-09
AU763305B2 (en) 2003-07-17
EP1177589A1 (en) 2002-02-06
ZA200108166B (en) 2002-10-04
MXPA01010004A (en) 2003-07-14
EP1177589A4 (en) 2002-09-25
AU3931500A (en) 2000-10-23
US6242129B1 (en) 2001-06-05
NZ514966A (en) 2003-02-28

Similar Documents

Publication Publication Date Title
US6242129B1 (en) Thin lithium film battery
US6517968B2 (en) Thin lithium film battery
US6398824B1 (en) Method for manufacturing a thin-film lithium battery by direct deposition of battery components on opposite sides of a current collector
US7186479B2 (en) Thin film battery and method of manufacture
US6835493B2 (en) Thin film battery
US6413285B1 (en) Layered arrangements of lithium electrodes
US6168884B1 (en) Battery with an in-situ activation plated lithium anode
US6649033B2 (en) Method for producing electrode for lithium secondary battery
EP1207566B1 (en) Anode thin film for lithium secondary battery
CN100570929C (en) The battery of anode and this anode of employing
US20030160589A1 (en) Rechargeable battery having permeable anode current collector
JP4144335B2 (en) Negative electrode and secondary battery using the same
US7482095B2 (en) Anode and battery using the same

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 00807076.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref document number: 2368425

Country of ref document: CA

Ref document number: 2368425

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/010004

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2001/08166

Country of ref document: ZA

Ref document number: 200108166

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 514966

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 2000918517

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 39315/00

Country of ref document: AU

WWP Wipo information: published in national office

Ref document number: 2000918517

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWG Wipo information: grant in national office

Ref document number: 39315/00

Country of ref document: AU

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Ref document number: 2000918517

Country of ref document: EP