WO2001078172A2 - Electrochemical energy storage device of high specific power and electrodes for said device - Google Patents
Electrochemical energy storage device of high specific power and electrodes for said device Download PDFInfo
- Publication number
- WO2001078172A2 WO2001078172A2 PCT/RU2001/000147 RU0100147W WO0178172A2 WO 2001078172 A2 WO2001078172 A2 WO 2001078172A2 RU 0100147 W RU0100147 W RU 0100147W WO 0178172 A2 WO0178172 A2 WO 0178172A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alloy
- electrolytic
- energy storage
- limits
- electrode
- Prior art date
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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
-
- 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
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- 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
-
- 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
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
- H01M4/0461—Electrochemical alloying
-
- 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
- H01M4/049—Manufacturing of an active layer by chemical means
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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
Definitions
- the claimed invention relates to electrical engineering, and in particular to production of rechargeable electrochemical energy storage devices (accumulators, electrochemical capacitors) of high specific power, designed for using them in various branches of engineering, such as automotive industry, electrical tools, communication equipment, special electrical transport (workshop battery-operated trucks, loaders, invalid wheeled vehicles), in toys etc.
- rechargeable electrochemical energy storage devices accumulators, electrochemical capacitors
- branch of engineering such as automotive industry, electrical tools, communication equipment, special electrical transport (workshop battery-operated trucks, loaders, invalid wheeled vehicles), in toys etc.
- Electrochemical double-layer capacitors (N.S.Lidorenko. Reports Acad. Sci.
- E sp max C-U 2 / 2m , (1) where E sp - specific energy per mass unit, C - capacitance of the capacitor,
- Increase in operation voltage of electrochemical double-layer capacitors is achieved e.g. by going over to anhydrous organic electrolytes with decomposition voltage over 3 V. However, in this case internal resistance R, grows, i.e. power decreases.
- the stored specific energy of an accumulator can be calculated by the following formula:
- E sp max qo - U / m (3) where q 0 - full charge of the accumulator at discharging by very small current. At increase in discharge current the charge decreases, accumulator voltage decreases both at the first moment and during discharging, at first slowly, then rapidly. Usually a quick voltage drop cannot be tolerated at operation of an accumulator because of unfavourable effect on service life.
- I/m i.e. high current values per mass unit of the accumulator. It is just this reason that explains design peculiarity of high-power accumulator electrodes: very small thickness of both current-carrying collectors and active material.
- one electrode (usually negative one) operates on the principle of double-layer capacitor, the other (usually positive one) - on the principle of accumulator, therewith aqueous solution of electrolyte is used in the capacitors.
- hybrid electrochemical capacitors Due to the above circumstances, hybrid electrochemical capacitors have discharge characteristic similar to that of capacitors and their specific energy and power are determined with formulae (1) - (2).
- Hybrid electrochemical capacitors occupy an intermediate position between electrochemical double-layer capacitors and accumulators, they have high specific power (P sp ma « 3,5 W/g) and energy (E sp ma « 10 J/g), they are much cheaper than double-layer capacitors with organic electrolyte, they are fire- and explosion-proof.
- Service life of a hybrid electrochemical capacitor is determined by the positive electrode and, since the discharging charge is usually several times less than its full charge, the number of recharge cycles may be as high as 50-100 thousand cycles.
- Positive and negative electrodes for electrochemical energy storage device of high specific power are known each of which is made in the form of backing carrying on one or both sides active element interacting with aqueous alkaline electrolyte of the electrochemical energy storage device in the process of redox reactions of charge/ discharge (RU, Cl, 2121728).
- the backing is made out of electron-conductive but not ion-conductive material that is chemically and electrochemically non-active in the working electrolyte of the electrochemical energy storage device and functions in the electrode simultaneously as a carrying base and as a current lead to the active element.
- the active element is structurally formed on the backing by means of applying a coating of a material of initial composition including basic metals out of a certain group or their alloy, or an alloy of at least one metal out of this group with one or several metals- modifiers out of the group: copper, lanthanum or lanthanides, molybdenum, tungsten, manganese, vanadium, titanium, tin, lead, bismuth, gallium; pore-forming metals out of the group: aluminium, zinc, alkali and alkali-earth metals or their combinations with further chemical and/or electrochemical treatment of the coating in solutions of acids, salts or alkalis.
- a coating of a material of initial composition including basic metals out of a certain group or their alloy, or an alloy of at least one metal out of this group with one or several metals- modifiers out of the group: copper, lanthanum or lanthanides, molybdenum, tungsten, manganese, vanadium, titanium, tin, lead,
- Group of basic metals for positive electrodes iron, nickel, cobalt, silver; for negative electrode: iron, nickel, cobalt, cadmium.
- Group of basic metals for positive electrodes iron, nickel, cobalt, silver; for negative electrode: iron, nickel, cobalt, cadmium.
- electrodes of an electrochemical energy storage device in which the active material of the active element (thin oxide and/or hydroxide film) is located on the developed surface of the current-carrying collector (a highly-porous layer of coating on the backing) realizes the traditional principle of mutual arrangement of the main phases participating in current-producing reactions of electrode in the electrochemical energy storage device, namely "electron conductor (collector) - active material (oxides, hydroxides) - electrolyte". Due to extremely small thickness of oxide and/or hydroxide film of active material electrochemical reactions of charge-discharge proceed with a high rate which determines high operating characteristics of the electrochemical energy storage device.
- Electrodes of which the described traditional concept of mutual arrangement of main phases involved in current producing reactions comprising at least one negative and one positive electrodes submerged in aqueous alkaline electrolyte and divided by a separator - a layer of an ion-conductive but not electron-conductive material.
- Each of the electrodes comprises an active element interacting with electrolyte - electron-conductive coating applied on the backing, on the developed surface of which a thin oxide and/or hydroxide active material film is formed taking part in charge-discharge redox reactions of the electrode at operation of the energy storage device.
- the positive and negative electrodes differ by their basic metals being part of coating applied on the backing.
- these are metals of the group: iron, nickel, cobalt, silver, or their alloys
- negative electrode - metals of the group iron, nickel, cobalt, cadmium or their alloys (RU, Cl, 2121728).
- Discharge characteristic of the electrochemical energy storage device by its shape lies between discharge characteristics of a capacitor and an accumulator, but more close to the latter (Example 5, Fig. 6).
- I 0.5 A
- the electrochemical energy storage device discharges during about 2.5 seconds at average voltage of about 1 V, then voltage quickly drops.
- U av 1 V.
- the problem being solved with the present invention is how to enhance the service life period (increase in number of recharge cycles) and exclude the ecological harmful cadmium as structural material without decreasing the specific power and energy.
- Essence of the claimed invention is as follows:
- the active element is made of an electron-conductive electrolytic alloy having composition M( / . x .
- the electrolytic alloy can be obtained by means of mutual electrochemical cathode co-deposition of a metal belonging to said M group of metals and the oxides and/or hydroxides of the M-group.
- the current supply can be carried out directly to the active element; in the case when active element is formed as an electrolytic deposit on one or both sides of a conductive backing which is made of material that is chemically and electrochemically stable in the electrolyte of the electrochemical energy storage device, then the current supply can be carried out through the backing.
- the active element is made of an electron-conductive electrolytic alloy having composition M (/ _ x . y) O x U y , where M is a metal of the group: iron, nickel, cobalt, or an alloy on the basis of one of the metals of this group, x is atomic fraction of absorbed oxygen in the electrolytic alloy being within the limits of
- y is atomic fraction of absorbed hydrogen in the electrolytic alloy being within the limits of 0.01 to 0.4, the said electrolytic alloy functions simultaneously as current- carrying collector and as active material which is participating in the processes of redox charge-discharge reactions; atomic fraction y of absorbed hydrogen in the electrolytic alloy can lie preferably within the limits of 0.05 to 0.4.
- the electrolytic alloy can be obtained by means of mutual electrochemical cathode co-deposition of a metal belonging to the said M group of metals and the oxides and/or hydroxides of the M-group.
- the current supply can be carried out directly to the active element; in the case when the active element is formed as an electrolytic deposit on one or both sides of a conductive backing which is made of material that is chemically and electrochemically stable in the electrolyte of the electrochemical energy storage device, then the current supply can be carried out through the backing.
- an electrochemical energy storage device of high specific power comprising at least one negative and one positive electrode which are submerged in an aqueous alkaline electrolyte and divided by a separator - a layer of ion-conductive but non electron-conductive material, each of the electrodes containing an active element interacting with the electrolyte in the process of redox charge-discharge reactions - the active element of each of the electrodes is made of an electron-conductive electrolytic alloy that has the composition M (/ _ x .
- M for positive electrode is nickel or nickel-based alloy
- M for negative electrode is a metal out of the group: iron, nickel, cobalt or an alloy on the basis of one of the metals of this group
- x is atomic fraction of absorbed oxygen in the electrolytic alloy being within the limits of 0.01 to 0.4
- y is atomic fraction of absorbed hydrogen in the electrolytic alloy being within the limits of 0.01 to 0.4.
- the said electrolytic alloy functions simultaneously as current-carrying collector and as the active material participating in the processes of redox charge-discharge reactions.
- For the positive electrode atomic fraction x of absorbed oxygen in the electrolytic alloy can lie preferably within the limits of 0.05 to 0.4 while for the negative electrode atomic fraction y of absorbed hydrogen in the electrolytic alloy lies preferably within the limits of 0.05 to 0.4.
- an electrochemical energy storage device of high specific power comprising at least one negative and one positive electrode which are submerged in an aqueous alkaline electrolyte and divided by a separator - a layer of ion-conductive but non electron-conductive material, each of the electrodes containing active element interacting with the electrolyte in the process of the redox charge-discharge reactions - the active element of the negative electrode is made of an electron-conductive electrolytic alloy that has the composition My . x .
- M is a metal out of the group: iron, nickel, cobalt or an alloy on the basis of one of the metals of this group
- x is atomic fraction of absorbed oxygen in the electrolytic alloy being within the limits of 0.01 to 0.4
- y is atomic fraction of absorbed hydrogen in the electrolytic alloy being within the limits of 0.01 to 0.4.
- the said electrolytic alloy functions simultaneously as current-carrying collector and as the active material participating in the processes of redox charge-discharge reactions.
- the atomic fraction y of absorbed hydrogen in the electrolytic alloy lies preferably within the limits of 0.05 to 0.4.
- an electrochemical energy storage device of high specific power comprising at least one negative and one positive electrode which are submerged in an aqueous alkaline electrolyte and divided by a separator - a layer of ion-conductive but non electron-conductive material, each of the electrodes containing an active element interacting with the electrolyte in the process of redox charge-discharge reactions - the active element of the positive electrode is made of an electron-conductive electrolytic alloy that has the composition M . x .
- x is atomic fraction of absorbed oxygen in the electrolytic alloy being within the limits of 0.01 to 0.4
- y is atomic fraction of absorbed hydrogen in the electrolytic alloy being within the limits of 0.01 to 0.4.
- the said electrolytic alloy functions simultaneously as current-carrying collector and as the active material participating in the processes of redox charge-discharge reactions.
- the atomic fraction x of absorbed oxygen in the electrolytic alloy lies preferably within the limits of 0.05 to 0.4
- the shared inventive concept that unites the embodiments of the present invention is the realization of a new principle of mutual arrangement of the main phases participating in the current producing reactions of the electrodes. While in all conventional electrodes the active material lies on the collector surface thus realizing the common principle of mutual arrangement of phases: "electron conductor (collector) - active material (oxides, hydroxides) - electrolyte", in the present invention the active material is inside the metal collector being a part of its crystal structure and forms with it a single phase - the phase of "active element". To the applicant's knowledge there is no technical concepts identical to the claimed ones. It allows, according to the applicant's opinion, to draw a conclusion that the invention corresponds to the "novelty" criterion (N).
- Electrodes that permit to accomplish, in the framework of the claimed embodiments, the set task of enhancement of service life (increase in number of recharge cycles) without decrease (even with increase) in specific power and energy.
- absence of contact resistance "collector - active material" in the electrodes and low resistance of active material permit to increase specific power
- impossibility of flaking and peeling off of active material from the collector and impossibility of loss of electronic contact between them permit to increase substantially durability of the electrodes at cyclic load
- combination of functions of current collector and of active material in electrolytic alloy makes it possible to reduce mass of electrodes and consequently to increase specific energy and power of the electrochemical energy storage device.
- reaction (6) hydroxide-ion and electrolyte water participate, i.e. the reaction proceeds under conditions when nickel hydroxide is in contact with electrolyte. It may appear that if Ni(OH) 2 molecules are arranged inside the metal phase of the active element then the proceeding of reaction (6) is impossible. However, as experience shows and as the explanatory examples given below indicate, it is not the case, reaction (6) proceeds, and with rather high rate, even under these conditions. In order to explaine this it is practical to re-write reaction (6) in a little different form taking into account possible presence of absorbed hydrogen H ab in the matrix of the active element: OH OH
- electrolytic alloys of iron can absorb up to 3%at. of hydrogen, nickel - up to 0.4%at, cobalt - up to 1.6%at. It can be easily calculated that a 30 Dm thick galvanic deposit (mass 25 mg/cm ) containing 5%at. of hydrogen can accumulate a charge according to reaction (9) of about 2,5 C/cm which exceeds by several times the specific charge of e.g. electrode of carbon materials operating by double-layer mechanism (see
- 0.05 ⁇ x ⁇ 0.4 for negative electrode electrolytic nickel, iron, cobalt or electrolytic alloys on the basis of these metals, in which atomic fraction of absorbed hydrogen y is within the limits of 0.01 ⁇ y ⁇ 0.4, preferably within the limits of 0.05 ⁇ y ⁇ 0.4.
- the most preferable material for active element of a positive electrode is electrolytic nickel or electrolytic alloys on its basis containing rather large number of (M-OH)-groups in the structure but not too large, in which case electrolytic deposits could be too brittle and with low conductivity.
- negative electrode In the region of potentials where negative electrode operates the following metals and alloys on their basis are stable in alkaline aqueous solutions: iron, nickel, cobalt, cadmium, zirconium. Bismuth and titanium are stable at a lesser extent. Cadmium is to be excluded on ecological grounds and zirconium - on economical grounds. Therefore, preferable materials for negative electrode are electrolytic iron, nickel, cobalt and electrolytic alloys on the basis of one of these metals, containing large enough amount of absorbed hydrogen however not so large as to obtain too brittle electrolytic deposits having too low conductivity. .
- the offered electrodes of electrolytic alloys can be used in electrochemical energy storage devices either together (the third embodiment of the invention) or in different combinations with known electrodes (the fourth and fifth embodiments of the invention).
- the negative electrode according to the second embodiment in accordance with the fourth embodiment of the invention can be used with a known positive electrode, e.g. with positive electrode of prototype, and the positive electrode according to the first embodiment in accordance with the fifth embodiment of the invention can be used with a known negative electrode, e.g. made of a carbon material.
- the claimed electrochemical energy storage device of high specific power according to the third embodiment of the claimed invention in the realization variant being discussed ( Figure 1) comprises negative electrode 1 and positive electrode 2 manufactured according to the first and second embodiments of the claimed invention.
- Electrodes 1 and 2 are submersed in aqueous alkaline electrolyte (not shown in Fig. 1). Electrodes 1 and 2 are set apart by a separator 3 - a layer of ion-conductive but non electron-conductive material. As separator e.g. a layer of porous polymer impregnated with electrolyte can be used.
- Negative 1 and positive 2 electrodes comprise active elements 4 and 5 interacting with electrolyte in the process of redox reaction of charging/discharging.
- Active elements 4 and 5 are made of a conductive electrolytic alloy (deposit) which simultaneously functions as current-carrying collector and as active material taking part in processes of charging/discharging redox reactions in electrodes 1 and 2 respectively.
- Active element 4 of negative electrode 1 is made of an electron-conductive electrolytic alloy (deposit) of composition My . x . y ) O x H y , where M is metal of the following group: iron, nickel, cobalt, or an alloy on the basis of one of the metals of this group with content of the main component at least 40% mass.
- M is metal of the following group: iron, nickel, cobalt, or an alloy on the basis of one of the metals of this group with content of the main component at least 40% mass.
- x is atomic fraction of absorbed oxygen in the electrolytic alloy being within limits of 0.01 ⁇ x ⁇ 0.4
- y is atomic fraction of absorbed hydrogen in the electrolytic alloy being within limits of 0.01 ⁇ x ⁇ 0.4, preferably within limits of 0.05 ⁇ y ⁇ 0.4.
- Active element 5 of positive electrode 2 is made of an electron-conductive electrolytic alloy (deposit) of composition M( / . x .
- x is atomic fraction of absorbed oxygen in the electrolytic alloy being within limits of 0.01 ⁇ x ⁇ 0.4, preferably within the limits of 0.05 ⁇ x ⁇ 0.4
- y is atomic fraction of absorbed hydrogen in the electrolytic alloy being within limits of 0.01 ⁇ x ⁇ 0.4.
- the said limits of absorbed oxygen content are caused by the fact that at lesser oxygen content specific charge of charging/discharging is too small and does not provide competitiveness of the negative electrode while at larger content the deposit becomes brittle and its cycling stability falls.
- the said electrolytic alloys are obtained by mutual electrochemical cathode co-deposition of metals belonging to the said groups M, their oxides and/or hydroxides.
- the active elements 4 and 5 of electrodes 1 and 2 are formed as electrolytic deposits on respective conductive backings 6 and 7, through which in the present design current supply to the active elements 4 and 5 is carried out.
- the backings 6 and 7 are made of a material chemically and electrochemically stable in the working electrolyte of the electrochemical energy storage device.
- the active elements 4 and 5 of the electrodes 1 and 2 can be formed as independent constructive elements as electrolytic deposits mechanically, chemically or electrochemically separated from respective conductive backings on which they have been deposited.
- the active elements 4 and 5 are used without backings and current supply in electrodes 1, 2 is carried out directly to the active elements 4 and 5.
- Electrochemical energy storage device differs from the above considered electrochemical energy storage device according to the third embodiment of the claimed invention by that, that as positive electrode any known and used for such purposes positive electrode is employed provided that it is stable in aqueous alkaline electrolyte, e.g. positive electrode made of carbon, nickel, cobalt or silver.
- positive electrode described in prototype can be used as a positive electrode.
- Electrochemical energy storage device differs from the electrochemical energy storage device according to the third embodiment of the claimed invention by that, that as negative electrode any known and used for such purposes negative electrode is employed provided that it is stable in aqueous alkaline electrolyte, e.g. a negative electrode made of carbon, nickel, cobalt or iron.
- a negative electrode made of carbon, nickel, cobalt or iron e.g. carbon electrode used in hybrid capacitors can be employed as negative electrode.
- the electrochemical energy storage devices made in the way considered above are characterized with improved specific characteristics and increased service life which is defined by permissible number of charge/discharge cycles. Improvement of properties is caused with that a new principle of mutual arrangement of main phases participating in current producing reactions is realized in the electrodes which differs from the prototype and consists in that active material (oxides and/or hydroxides) is arranged within a metal collector (being a part of its crystal structure) and forms with it a unified phase - the phase of "active element".
- the elucidatory examples 1 to 7 relate to negative electrodes according to the second embodiment of the claimed invention. Conditions of production (electrolyte composition, electrolysis conditions) and properties of negative electrodes according to examples 1 to 7 are presented in Table 1 in the end of the description. Conditions and methods of measurement are similar for all the elucidatory examples 1 - 7 and presented in example 1.
- Nio,67 ⁇ o, ⁇ 3 Ho,2 - was defined by gas analysis of the deposit. Specific charge of the electrode was defined by discharge curves at galvanostatic discharge of the electrode in
- Example 2 The negative electrode is obtained as in example 1 but in a different electrolyte and under different conditions of electrochemical deposition (see Table 1). Composition of the obtained electrolytic sediment is Nio ,63 Oo , ⁇ 5 Ho, 22 , mass is 17 mg/cm 2 , specific charge is 165 C/g which is higher than in example 1.
- Example 3 The negative electrode is obtained (see Table 1) by electrodeposition of nickel-cobalt alloy on polished titanium backing with following mechanical separation of the deposit from the backing (galvanoplastic method). Cobalt chloride was added to the electrolyte. Composition of the obtained electrolytic deposit is Nio, 52 C ⁇ o, ⁇ oOo, ⁇ Ho ,23. mass is 17 mg/cm 2 , specific charge is 170 C/cm .
- the deposit separated from the backing is plastic and can be used as an electrode without any additional collector.
- Example 4 The negative electrode is obtained (see Table 1) by electrodeposition of nickel-iron alloy on polished titanium backing with following mechanical separation of the deposit from the backing. Ferrous iron sulphate was added to the electrolyte. Composition of the obtained electrolytic deposit is Nio, 53 Feo, ⁇ 3 Oo, ⁇ Ho,2 ⁇ , mass is 24 mg/cm 2 , specific charge is 133 C/g.
- the electrolytic deposit separated from the backing is strong, plastic and can be used as an electrode without any additional collector.
- Example 5 The negative electrode is obtained (see Table 1) by electrodeposition of cobalt-nickel alloy on polished titanium backing with following mechanical separation of the deposit from the backing. Composition of the obtained electrolytic deposit is
- the electrolytic deposit separated from the backing is strong, plastic and can be used for forming of a cylindrical electrode, e.g. by winding on a cylindrical mandrel 0 5 mm.
- Example 6 The negative electrode is obtained (see Table 1) by electrodeposition of nickel-iron alloy on polished titanium backing with following mechanical separation of the deposit from the backing. Composition of the obtained electrolytic deposit is
- Feo ⁇ 7Nio, ⁇ 6 Oo, ⁇ 2 Ho,25. mass is 31 mg/cm 2 , specific charge is 129 C/g.
- the deposit separated from the backing is strong, plastic and can be used as an electrode without any additional collector.
- Example 7 The negative electrode is obtained (see Table 1) by electrodeposition of nickel-palladium alloy on a backing of rolled nickel foil 25 ⁇ m thick. Composition of the obtained electrolytic deposit is Nio, 6 o Pdo,o 3 ⁇ o,i 6 Ho, 2 ⁇ , mass is 17 mg/cm 2 , specific charge is 176 C/g.
- the presented examples 1 to 7 prove possibility of practical realization of the second embodiment of the claimed invention in respect to negative electrodes.
- the content of absorbed hydrogen in electrolytic alloys (deposits) varied between 18% and 25% at.
- Additional experiments related to determination of limits of permissible content of absorbed hydrogen in electrolytic alloys (deposits) used in negative electrodes have shown that at increase in absorbed hydrogen content up to 40% at. the charge released while discharging has increased as well as the specific energy however the electrolytic alloy (deposit) has become brittle and could only be used on a backing, e.g. on nickel foil or mesh.
- the hydrogen content must be lower, e.g. similar to hydrogen content in the above discussed examples 1 to 7.
- the lower limit for absorbed hydrogen content in electrolytic deposit for a negative electrode must not be below 1% at. because at this point the specific charge falls down to values that make the electrode useless for practical applications.
- Example 8 The positive electrode is obtained by electrochemical deposition
- Electrodeposition of nickel on a backing of nickel foil 25 ⁇ m thick under conditions given in Table 2.
- Composition of obtained electrolytic alloy (deposit) is Nio ,65 Oo , ⁇ 8 Ho , i 7 , mass is 25 mg/cm", specific charge is 88 C/g.
- Fig. 2 there is presented a cyclic voltammagram of the electrode according to the eighth example in 30 % KOH solution.
- the electrode area is 4 cm 2
- reference electrode is a mercury oxide electrode
- sweep rate is 10 mV/s.
- the holding time was 50 seconds.
- Fig. 3 there is presented a cyclic voltammagram of the same electrode but in the potential region of positive electrode operation. Sweep rate is 10 mV/s. At the charging potential +0.52 V the holding time was 50 seconds.
- Example 9 The positive electrode is obtained (see Table 2) by electrodeposition of a nickel-cobalt alloy on a backing of nickel foil 25 ⁇ m thick. Composition of the obtained electrolytic deposit is Nio, 55 Coo,iOo,i9Ho,i6 , mass is 25 mg/cm , specific charge is 96 C/g. in Fig. 4 there is presented a cyclic voltammagram of the electrode according to the ninth example in the potential region of positive electrode operation. The electrode area is 4 cm , sweep rate is 10 mV/s. At the charging potential +0.55 V the holding time was 50 seconds. Comparison of voltammagrams in Fig. 3 and in Fig. 4 shows that by alloying it is possible to increase the specific charge of the positive electrode. Example 10.
- the positive electrode is obtained (see Table 2) by electrodeposition of a nickel-zinc-cobalt alloy on a polished titanium backing with following mechanical separation of the deposit from the backing (galvanoplastic method).
- Composition of the obtained electrolytic deposit is Nio, 52 Coo,o9 Zno,o2 ⁇ o,2oHo,i 7 , mass is 36 mg/cm , specific charge is 119 C/cm 2 .
- the presented examples 8 to 10 prove feasibility of practical realization of the first embodiment of the claimed invention in respect to positive electrodes. In these examples content of absorbed oxygen in electrolytic alloys (deposits) varied from 18% to
- the proposed negative and positive electrodes presented in examples 1 to 7 (see Table 1) and in examples 8 to 10 (see Table 2) can be used in the following three variants of electrochemical energy storage devices: with both proposed electrodes - positive and negative ones which corresponds to the third embodiment of the claimed invention; with proposed negative electrode and a known positive electrode, e.g. an electrode of the prototype, which corresponds to the fourth embodiment of the claimed invention; with proposed positive electrode and a known negative electrode, e.g. a carbon one, which corresponds to the fifth embodiment of the claimed invention.
- Example 15 is a reference example, it relates to an electrochemical energy storage device in which a known negative electrode of carbon material and a known positive electrode made in accordance with the prototype are used.
- the properties of electrochemical energy storage devices according to examples 11-15 are presented in Table 3 given in the end of the description. Measurement conditions in examples 11-15 are similar and presented in example 11.
- Example 11 The model of electrochemical energy storage device according to the third embodiment of the claimed invention is assembled of the negative electrode described in example 6 and the positive electrode described in example 10 divided by separator of 0.05 mm thick polypropylene paper wetted with electrolyte - 30% KOH solution.
- the model of electrochemical energy storage device was charged by current of 0.4 A up to voltage of 1.5 V, then held during 5 minutes at constant voltage of 1.5 V. Discharge curves were recorded at three constant values of the current 0.04 A, 0.4 A and 1.6 A at temperature 20°C. Change of voltage in time was plotted with a high-speed recorder. Discharging continued until attainment of voltage 0.7 V. Charge of discharging was defined by multiplying the discharge current by the discharge time while average voltage was defined by numerical integration of the "voltage - time" curve. Mass of the model was determined by using of scale.
- Fig. 5 there are presented discharge curves of the present model of electrochemical energy storage device. These curves have a shape intermediate between discharge curves of accumulators and those of capacitors. At small values of discharge current they are more close to discharge curves of an accumulator, at larger values -more close to discharge curves of a capacitor.
- Durability test of the present model of electrochemical energy storage device under cyclic loads is illustrated by the curve in Fig. 6 which represents how discharging charge depends on number of charge/discharge cycles.
- the test has shown that service life exceeds 43,000 cycles during which no change in discharging charge has been registered - such was the number of cycles during the tests up to the moment of applying the patent.
- Charging while cycling was carried out with a current of 0.4 A until attainment of voltage 1.5 V, then the voltage was held constant during one minute.
- Discharging was carried out with a current of 0.4 A until attainment of voltage 1.1 V (50% of total charge), then the cycle was repeated.
- Charge of discharging was determined by multiplying current (0,4 A) by discharge time in seconds.
- Example 12 The model of electrochemical energy storage device according to the third embodiment of the claimed invention is made in the same manner as in example 11 but with other negative and positive electrodes according to examples 3 and 9 respectively (see Table 3). Use of these electrodes results in some dissimilarities in characteristics of specific energy and power of this electrochemical energy storage device as compared with the electrochemical energy storage device in example 11 (see table 3).
- Example 13 The model of electrochemical energy storage device according to the fourth embodiment of the claimed invention is assembled with negative electrode made according to example 6 and with positive electrode made as in the prototype. In comparison with the prototype the model of this electrochemical energy storage device has essential advantages in specific energy and power, moreover, it does not contain ecologically harmful cadmium. However, the model of this electrochemical storage device
- Example 14 The model of electrochemical energy storage device according to the fifth embodiment of the claimed invention is assembled with negative electrode of 0.35 mm thick carbon fabric and positive electrode according to example 10. A 4 - 6 ⁇ m thick nickel layer was deposited on one side of carbon fabric by method of cyclotron spraying, after that the carbon fabric was spot welded at nine points to 25 ⁇ m thick nickel foil used as collector. The rest of manufacturing conditions and procedure of measurements were as in example 11. As it is seen from Table 3, the model of such electrochemical energy storage device is substantially inferior to the models of electrochemical energy storage devices presented in examples 11 and 12 where both electrodes are made according to the claimed proposal, as well as to the model of electrochemical energy storage device presented in example 13 where the negative electrode is made according to the claimed proposal and the positive one is made as in the prototype. By specific power at high current densities the model of such an electrochemical energy storage device as in example 14 is close to the model of electrochemical energy storage device as per example 13 but is inferior to the models of electrochemical energy storage devices as per examples 11 and 12 (see Table 3).
- Example 15 The model of electrochemical energy storage device is assembled with both electrodes of known types. As positive electrode an electrode was used made as in example 13 according to the prototype while the negative electrode was made on the basis of carbon fabric as in example 14. The rest of manufacturing and measurement conditions were as in example 1 1. As it is seen from the data given in Table 3 the model of this electrochemical energy storage device is inferior to all the previous examples 1 1 to
- the claimed embodiments of the invention present a substantial practical interest, opening up a new, never used before, direction in designing electrochemical energy storage devices of high specific power based on the employment of active elements in electrodes made out of electron-conductive electrolytic alloys (deposits) with excessive content of absorbed oxygen and hydrogen providing proceeding of charge-discharge redox reactions, the electrolytic alloy (deposit) functioning at the same time as current-carrying collector and as active material.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/240,686 US6844111B2 (en) | 2000-04-10 | 2001-04-09 | Electrochemical energy storage device of high specific power and electrodes for said device |
DE10196060T DE10196060T1 (en) | 2000-04-10 | 2001-04-09 | Electrochemical energy storage with high specific power and electrodes for energy storage |
AU2001250708A AU2001250708A1 (en) | 2000-04-10 | 2001-04-09 | Electrochemical energy storage device of high specific power and electrodes for said device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2000108992 | 2000-04-10 | ||
RU2000108992/09A RU2170468C1 (en) | 2000-04-10 | 2000-04-10 | Electrochemical energy storage of high specific power and its plate |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001078172A2 true WO2001078172A2 (en) | 2001-10-18 |
WO2001078172A3 WO2001078172A3 (en) | 2002-07-25 |
Family
ID=20233156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/RU2001/000147 WO2001078172A2 (en) | 2000-04-10 | 2001-04-09 | Electrochemical energy storage device of high specific power and electrodes for said device |
Country Status (5)
Country | Link |
---|---|
US (1) | US6844111B2 (en) |
AU (1) | AU2001250708A1 (en) |
DE (1) | DE10196060T1 (en) |
RU (1) | RU2170468C1 (en) |
WO (1) | WO2001078172A2 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AUPR194400A0 (en) * | 2000-12-06 | 2001-01-04 | Energy Storage Systems Pty Ltd | An energy storage device |
CA2576752A1 (en) * | 2007-02-02 | 2008-08-02 | Hydro-Quebec | Amorpheous fe100-a-bpamb foil, method for its preparation and use |
US20110149473A1 (en) * | 2009-12-21 | 2011-06-23 | Eilertsen Thor E | Energy storage in edlcs by utilizing a dielectric layer |
RU2012125242A (en) * | 2012-06-18 | 2013-12-27 | Игорь Витальевич Бузмаков | ECONOMIC ELECTROCHEMICAL ELEMENT |
MX2015009647A (en) | 2013-02-06 | 2016-04-25 | Encell Technology Inc | Process for forming a battery containing an iron electrode. |
AU2014214904B2 (en) * | 2013-02-06 | 2018-05-10 | Encell Technology, Inc. | Battery comprising a coated iron anode and improved performance |
US10868338B2 (en) | 2013-02-06 | 2020-12-15 | Encell Technology, Inc. | Nickel-iron battery with high power |
US10847843B2 (en) | 2013-02-06 | 2020-11-24 | Encell Technology, Inc. | Electrolyte for a nickel-iron battery |
US10854926B2 (en) | 2013-02-06 | 2020-12-01 | Encell Technology, Inc. | Nickel-iron battery with high cycle life |
US10804573B2 (en) | 2013-02-06 | 2020-10-13 | Encell Technology, Inc. | Electrolyte for battery containing an iron electrode |
WO2014124123A1 (en) | 2013-02-06 | 2014-08-14 | Encell Technology, Inc. | Nickel iron battery employing untreated polyolefin separator with a surfactant in the electrolyte |
US9450233B2 (en) | 2013-02-06 | 2016-09-20 | Encell Technology, Inc. | Battery comprising a coated iron anode |
RU2605911C2 (en) * | 2014-02-07 | 2016-12-27 | Алексей Иванович Беляков | Electrochemical energy storage device |
CN112805839A (en) * | 2018-03-12 | 2021-05-14 | 奥米加能源系统有限责任公司 | Solid state energy harvester of transition metal suboxide |
WO2021097051A1 (en) | 2019-11-13 | 2021-05-20 | Omega Energy Systems, Llc | Three-electrode solid-state energy harvester of transition metal suboxides |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5654113A (en) * | 1995-06-07 | 1997-08-05 | Comsat Corporation | Protonated cathode battery |
-
2000
- 2000-04-10 RU RU2000108992/09A patent/RU2170468C1/en not_active IP Right Cessation
-
2001
- 2001-04-09 US US10/240,686 patent/US6844111B2/en not_active Expired - Fee Related
- 2001-04-09 DE DE10196060T patent/DE10196060T1/en not_active Ceased
- 2001-04-09 WO PCT/RU2001/000147 patent/WO2001078172A2/en active Application Filing
- 2001-04-09 AU AU2001250708A patent/AU2001250708A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5654113A (en) * | 1995-06-07 | 1997-08-05 | Comsat Corporation | Protonated cathode battery |
Non-Patent Citations (2)
Title |
---|
YARTYS V. A. ET AL: "Hydrogen ordering and H-induced phase transformations in Zr-based intermetallic hydrides" JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 293-295, 20 December 1999 (1999-12-20), pages 74-87, XP001058492 ISSN: 0925-8388 * |
ZAVALIY I Y: "Effect of oxygen content on hydrogen storage capacity of Zr based ETA phases" JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 291, no. 1-2, 27 September 1999 (1999-09-27), pages 102-109, XP001058493 ISSN: 0925-8388 * |
Also Published As
Publication number | Publication date |
---|---|
AU2001250708A1 (en) | 2001-10-23 |
US6844111B2 (en) | 2005-01-18 |
US20030113629A1 (en) | 2003-06-19 |
DE10196060T1 (en) | 2003-05-22 |
RU2170468C1 (en) | 2001-07-10 |
WO2001078172A3 (en) | 2002-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6844111B2 (en) | Electrochemical energy storage device of high specific power and electrodes for said device | |
Besenhard | Handbook of battery materials | |
US6512667B2 (en) | Supercapacitors and method for fabricating the same | |
JP6288655B2 (en) | Reversible fuel cell storage battery | |
US9666381B2 (en) | Asymmetrical supercapacitor with alkaline electrolyte comprising a three-dimensional negative electrode and method for producing same | |
JP2020047571A (en) | Zinc ion secondary battery including aqueous electrolyte | |
JP2001313066A (en) | Alkaline storage battery | |
CN113314770B (en) | Alkaline secondary battery and preparation method thereof | |
JP6911494B2 (en) | How to activate a nickel metal hydride battery | |
WO2017087907A1 (en) | Transition metal depositi0n and oxidation on symmetric metal oxide electrodes for storage application | |
RU2671942C1 (en) | Anode material and accumulator | |
US6678147B2 (en) | Electrochemical capacitor with electrode material for energy storage | |
JP2743416B2 (en) | Zinc plate for rechargeable batteries | |
JP5557385B2 (en) | Energy storage device with proton as insertion species | |
US10547046B2 (en) | High energy/power density nickel oxide/hydroxide materials and nickel cobalt oxide/hydroxide materials and production thereof | |
JP7156258B2 (en) | Aqueous battery | |
CN109686588B (en) | Super capacitor battery based on seawater electrolyte | |
JP6984298B2 (en) | Manufacturing method of nickel metal hydride battery | |
Sharma et al. | Safety and Environmental Impacts of Zn Batteries | |
Ji et al. | Effects of surface treatment on electrochemical properties of AB3. 8-type hydrogen storage alloy in alkaline electrolyte | |
JP6904298B2 (en) | Alkaline storage battery and its manufacturing method | |
JPH05121073A (en) | Nickel-metal hydride storage battery | |
CN209016215U (en) | Rechargeable battery | |
JP5769028B2 (en) | Nickel metal hydride storage battery | |
JP4552238B2 (en) | Method for producing hydrogen storage alloy electrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AT AU BA BG BR BY CA CH CN CZ DE DK EE ES FI GB HR HU ID IL IN IS JP KR LK LT LU LV MX NO NZ PL PT RO SE SG SI SK TR UA US VN YU ZA |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
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) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 10240686 Country of ref document: US |
|
RET | De translation (de og part 6b) |
Ref document number: 10196060 Country of ref document: DE Date of ref document: 20030522 Kind code of ref document: P |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10196060 Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: JP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8607 |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8607 |