WO1989004066A1 - Cathode de pile rechargeable composee de dioxyde cobaltique de sodium en phase p2 - Google Patents

Cathode de pile rechargeable composee de dioxyde cobaltique de sodium en phase p2 Download PDF

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Publication number
WO1989004066A1
WO1989004066A1 PCT/US1988/002377 US8802377W WO8904066A1 WO 1989004066 A1 WO1989004066 A1 WO 1989004066A1 US 8802377 W US8802377 W US 8802377W WO 8904066 A1 WO8904066 A1 WO 8904066A1
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Prior art keywords
sodium
battery according
battery
cobalt dioxide
electrolyte
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PCT/US1988/002377
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English (en)
Inventor
Lawrence Wayne Schacklette
Linda Barberi Townsend
Taiguang Richard Jow
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Allied-Signal Inc.
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Publication of WO1989004066A1 publication Critical patent/WO1989004066A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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

  • This invention relates to positive battery electrodes composed of sodium cobalt dioxide. More particularly, this invention relates to such electrodes in which the cobalt dioxide is in the P2 phase and to batteries comprising such electrodes.
  • Negative electrodes for non-aqueous batteries composed of alkali metal alloys are known.
  • U.S. Patent No. 4,002,492 discloses electrochemical cells having an anode consisting essentially of lithium aluminum alloys that contain lithium in amounts between about 63 and 92 percent by weight and the balance essentially aluminum.
  • Anodes composed of lithium and aluminum are also disclosed in Rao, et al. , J. Electrochem. Soc. 124, 1490 (1977), and Besenhard, J. Electroanal. Chem. , 94, 77 (1978).
  • Conjugated backbone polymers e.g., polyacetylene, polyphenylene, polyacenes, polythiophene, poly(phenylene vinylene) , poly(alkoxyphenylene vinylene), poly(furylene vinylene), poly(thienylene vinylene), polyazulene, poly(phenylene sulfide) , poly(phenylene oxide) , polythianthrene, pol (phenylquinoline) , polyaniline, polythiophene, and polypyrrole, have been suggested for use in a variety of applications based upon their characteristic of becoming conductive when oxidized or reduced either chemically or electrochemically.
  • Such electrodes can, for example, be reversibly complexed with alkali metal or tetraaIky1ammonium cations during battery cycling, most commonly with insertion of cations into a polymer anode (the negative battery electrode) occurring during charging. The more such cations are inserted, the more conductive the electrode becomes and the more cathodic the potential of the anode becomes.
  • Various studies have been made on sodium cobalt dioxide and the electrochemical intercalation of sodium. Illustrative of these studies are those described in J. Molenda et al. , "Transport Properties of Na ⁇ Co ⁇ 2 »y , n Solid State Ionics, 12 pp. 473-477 (1984); Claude Fouassier, et al.
  • U.S. Patent Nos. 4,668,586 and 4,695,521 are directed .to anodes and to batteries containing the anodes.
  • the anodes comprise a mixture of a conjugated backbone polymer and another electroactive material selected from the group consisting of metals which alloy with alkali metals such as aluminum and lead, and alkali metal cation insertion materials such as transition metal chalcogenides.
  • U.S. Patent Nos. 4,668,596 and 4,695,521 also describe cathodes comprised of sodium cobalt dioxide.
  • L. . Shacklette and T. R. Jow "Rechargeable Electrodes From Sodium Cobalt Bronzes," Electrochemical Soc. Abstract No. 64, Honolulu, Oct.
  • This invention relates to a novel cathode comprising sodium cobalt dioxide ( a ⁇ Co ⁇ 2, where x is preferably greater than about 0.4) where the cobalt dioxide is in the P2 phase.
  • the present invention also provides a battery incorporating the anode of this invention, which battery comprises:
  • an electrolyte comprising an organic solvent and one or more alkali metal salts, preferably at least one of which is a sodium salt;
  • an anode comprising one or more anode active materials selected from the group consisting of sodium metal, conjugated backbone polymers capable of inserting sodium metal cations, conjugated backbone copolymers capable of inserting sodium metal cations, blends of said conjugated backbone polymers or copolymers with one or more non-conjugated backbone polymers, metals capable of alloying with the sodium metal cations in said electrolyte and a sodium metal cation insertion materials capable of inserting sodium metal cations in said electrolyte; said sodium metal cations being introduced into said anode as a metal alloy or as an inserted ion in said cation inserting material, polymers or copolymers during the charging of said battery.
  • anode active materials selected from the group consisting of sodium metal, conjugated backbone polymers capable of inserting sodium metal cations, conjugated backbone copolymers capable of inserting sodium metal cations, blends of said conjugated backbone polymers or copolymers with one or more non
  • batteries having cathodes comprised of sodium cobalt dioxide in the P2 phase exhibit better cycle life and better energy efficiencies as compared to batteries in which the cathode is sodium cobalt dioxide in other phases, as for example, the 03, 0'3, P3 and P'3 phases.
  • the battery of this invention includes cobalt dioxide (Na ⁇ C ⁇ 2) in the P2 phase and, preferably where x is greater than about 4 and more preferably where x is from about 4 to about 1, and most preferably from about 0.5 to about 1.
  • the P2 phase sodium cobalt dioxide used in the practice of this invention may contain only intercalated sodium cations, _ or may be cointercalated by other alkali metal cations such as Li + , K + , Rb + , Cs + to form compositions such as Na ⁇ KyCo0 2 , or Na ⁇ Rb Co0 2 where x+y_ ⁇ l.
  • cobalt dioxide (Na ⁇ Co0 2 ) may exist in various phases.
  • phase of the cobalt dioxide has a significant impact on operational characteristics such as _ reversibility, cyclyability and capacity (i.e., the maximum excursion of x) of batteries in which cobalt dioxide is the cathode material.
  • _ reversibility i.e., the maximum excursion of x
  • cyclyability and capacity i.e., the maximum excursion of x
  • the cycle life and energy efficiency of the battery is enhanced where the cathode material is orginally prepared from cobalt dioxide in the P2 phase.
  • Cobalt dioxide in the P2 phase and methods for its production are well known in the art and will not be described herein in great detail. Illustrative of useful procedures are those described in J. Molenda, C. e Delmos, P. Dordor, and A. Stoklosa, Solid State Ionics, 12, p. 473 (1984); and A. Stoklosa, J. Molenda and D. Than, Solid State Ionics, 15, p. 211 (1985) which are incorporated herein by reference.
  • Sodium cobalt dioxide in the P2 phase (Na ⁇ Co ⁇ 2) with specific values of x greater than about 4 can be prepared in accordance with the following:
  • cobalt dioxide in the P2 phase can be prepared by carrying out the reaction at a temperature within the range of from 400°C to 600°C to produce sodium cobalt dioxide (Na ⁇ Co ⁇ 2, where x is greater than about 4, preferably from about 4 to about 1 in the 03, 0'3, P3 or P'3 phase, followed by heating at a temperature greater than 650°C for an extended period of time, i.e. 12h.
  • the cathode may also include other optional materials known to those of skill in the battery art. These materials will not be described in great detail.
  • the cathode may include such other substituents as conductivity aids as for example, carbon black and doped electrically conductive conjugated backbone polymers such as oxidized polyacetylene, poly(p-phenylene) , polyaniline, polypyrrole, polyacenes, poly(phenylene vinylene), polyazulene, polynaphthalene, poly(phenylene sulfide), poly(phenylene oxide), polyphenothiazine, polythiophene, polythianthrene, and substituted versions thereof; and other sodium cation insertion materials such as Na ⁇ ⁇ iS2, Na x S2Cl2, a ⁇ 03_y, Na ⁇ V Q s r 0# 5 S 2 r Na ⁇ MoS3, (amorphous) and a ⁇ TaS2, wherein 0 ⁇ x ⁇
  • substituents include binders such as halocarbons and elastomeric hydrocarbons prepared by polymerization of alkenes having two or more double bonds that are either conjugated or non-conjugated, alone or with one or more other copolymerizable ethylenic monomers such as isobutylene, ethyelene-propylene-butadiene copolymers, polybutadiene, pol (butadiene-co-styrene) , polyethylene, propylene-trifluoroethylene copoly er and poly(tetra- fluoroethylene) ; mechanical supports; current collectors and the like.
  • the cathode includes one or more binders and one or more conductivity aids.
  • the preferred binders are poly(tetrafluoroethylene) and ethylene-propylene- butadiene copolymers.
  • the amount of cobalt dioxide in the cathode can vary widely, depending on a number of factors as for example, the desired energy density, the desired rate of charge and discharge, the cell design, (whether prismatic, round or flat), and the like. In general, the amount of cobalt dioxide should be at least 50 percent by weight of the positive electrode.
  • the amount of cobalt dioxide in the cathode may vary from about 60 to about 100 percent by weight, the amount of binder is from about 10 to about 8 percent by weight, and the amount of conductivity aid is from about 6 to about 12 percent by weight based on the total weight of cobalt dioxide, binders and conductivity aids in the cathode.
  • the amount of cobalt dioxide is from about 85 to about 92 percent by weight, the amount of binders is from about 2 to about 7 percent by weight, and the amount of conductivity aid is from about 6 to about 8 percent by weight on the aforementioned basis.
  • the cathode is composed of an intimate mixture of compressed powders.
  • the cathode is _ _ generally fabricated by mixing a slurry of powdered sodium cobalt dioxide in a solution or dispersion of an elastomer or a halocarbon dissolved or dispersed in a chemically compatible solvent; casting the slurry in a mold or spray coating the slurry on a substrate and removing the solvent; and compressing the composite for improved cohesiveness and uniformity.
  • the battery of this invention includes an electrolyte comprising an organic solvent and a salt.
  • the organic solvents which may be 0 included in the electrolyte of the batteries of the present invention may vary widely and can be organic solvents normally used in batteries.
  • these solvents should be electrochemically inert to oxidation and reduction during use while simultaneously being 5 capable of dissolving the desired alkali metal salt and providing ionic conductivity equal to or in excess of 10 " "* S/cm.
  • organic solvents examples include propylene carbonate, ethylene carbonate, sulfolane, methyl sulfolane, dimethyl sulfolane, 3- 0 methyl-2-oxazolidone, alkene sultones, e.g., propane sultone, butane sulbone (the use of sultones as electrolyte compositions is the subject of a related, commonly assigned U.S. Patent 4,528,254, and the use of sultones for coatings on polymer anodes is the subject 5 of a related, commonly assigned U.S. Patent No.
  • DMSO dimethyl sulfoxide
  • THF tetrahydrofuran
  • 2-MTHF 2-methyltetrahydrofuran
  • DME 1,2-dimethoxyethane
  • Q dimethoxymethane diglymes, gly es, methyltetrahydro- furfuryl ether, anisole, nitriles, (e.g., proprio- nitrile, butyronitrile, acetonitrile, benzonitrile) , dichloromethane, tetraethylsulfamide, aromatic hydrocarbons, e.g., toluene, benzene, organo phosphorus compounds, e.g., hexa ethylene phosphoramide, and 5 trimethyl phosphate.
  • Mixtures of such available organic solvents may also be used, such as mixtures of sulfolane
  • organic solvents chosen for use in any particular situation will, of course, depend upon many factors such as the precise electrolyte composition used and the voltage range desired, as well as the choice of an anode and other components of the battery used.
  • ether-type solvents such as tetrahydrofuran, dimethoxyethane, diglyme, 2-methyltetrahydrofuran, methyltetrahydrofurfuryl ether and mixtures thereof are employed because these solvents are generally not reactive with conjugated backbone polymers, when in their neutral or reduced forms.
  • the electrolyte includes an alkali-metal compound which is ionizable during the operation of the cell into an anionic and a cationic species.
  • the alkali-metal cations of such electrolytes may, depending on the nature of the anode active material, plate out in the zero valent state, insert into the conjugated backbone polymer or inorganic material, or form a metal alloy with anode active metals during the operation of the battery. For example, upon operation of a cell using a conjugated backbone polymer as all or part of the negative electrode, the polymer becomes doped with a cationic dopant species to a conductive n-type material.
  • ionizable compounds for forming anionic and cationic species may be suitably be employed, either individually or in combination, provided that at least a portion of the compounds will ionize into a sodium carbon.
  • ionizable compounds for forming anionic and cationic species may be suitably be employed, either individually or in combination, provided that at least a portion of the compounds will ionize into a sodium carbon.
  • Illustrative of such materials are the salts of alkali metals with anions such as for example, halides, PFg “ , CIO4 “” , AlCl ⁇ “ , FeCl 4 " , SO3CF3 " , BF 4 ⁇ , BCI4 " , N0 3 " ,
  • anode is a composite comprised of one or more conjugated backbone polymers and one or more electroactive materials selected from the group consisting of metals which alloy with alkali metals and alkali metals cation inserting materials, salts for use in the electrolyte of the preferred battery of this invention are of the formula:
  • Na sodium
  • A is a species which is anionic in the electrolyte and stable under operational conditions.
  • Suitable anionic species include I “ , Br “ , Cl ⁇ “ , C10 4 ⁇ , PFg “ , AsFg “ , S0 3 CF 3 ⁇ , BF 4 ⁇ , BC1 4 ⁇ , AlCl “ , SbFg “ alkylborates, arylborates and alkylarylborates such as B(CH ) 4 ⁇ , B(C H5) ⁇ , and their fluorinated derivatives and the like (the use of such borate salts with conjugated polymers being the subject of commonly assigned U.S. Patent No. 4,522,901 which is incorporated herein by reference).
  • Preferred anions are arylborates, alkylarylborates, PFg" * , C10 4 ", halide ions, S0 3 CF 3 ⁇ , and BF 4 ⁇ , with PFg " being the anionic species of choice.
  • Molten salts may also be employed as the electro ⁇ lyte of the battery of the invention.
  • conjugated polymers as anodes in room-temperature molten salt batteries is described in the commonly-assigned U.S. Pat. No. 4,463,071, which is incorporated herein by reference. Since in many cases the polymers, alloys, and other ion inserting materials of this invention are stable at elevated temperature, intermediate temperature molten salts (M.P. ⁇ 200°C) such as NaAlCl 4 or KA1C1 4 , are also suitable for use.
  • M.P. ⁇ 200°C such as NaAlCl 4 or KA1C1 4
  • the battery of this invention includes an anode.
  • the anode active material may vary widely and will usually be an alkali metal or an alkali metal insertion material.
  • the anode for use in the practice of this invention comprises one or more anode active materials selected from the group consisting of sodium metal, alloys of sodium and one or more metallic or non metallic materials, conjugated backbone copolymers and polymers capable of inserting sodium metal cations in the electrolyte and blends of said conjugated backbone polymers or copolymers and one or more non conjugated backbone polymers or copolymers, inserting materials capable of inserting sodium cations in the electrolyte.
  • the sodium cations are plated as sodium metal, or are introduced into the anode as an alloy or as an inserted cation in the cation inserted material, polymers or copolymers.
  • useful anodes are those described in U.S. Patent No. 4,695,521 and U.S. Patent No. 4,668,596.
  • Useful alloys include those formed with alkali metals especially sodium metals and one or more other metals which are capable of being de-alloyed and re- alloyed by electrochemical oxidation and reduction, respectively, in the presence of alkali metal salt electrolytes.
  • alkali metal alloying metals are lead, tin, bismuth, antimony, tellurium, silicon, thallium, selenium, gold, arsenic, cesium, indium, gallium, cadmium, mercury, and alloys of these or other metals, such as PbSn or Wood's Metal (Bi- Pb-Sn-Cd) and the like.
  • alkali metal alloying metals for use in the practice of this invention are those which readily alloy with sodium metal such as antimony, bismuth, selenium, gallium, tellerium, indium, cadium, lead, tin and alloys thereof; and most preferred are tin, lead, bismuth and/or antimony.
  • the mole ratios of the components of the alloy can vary widely, depending on permissible ratios based on allowed interactions between the components and the desired capacity of the anode.
  • sodium is the electroactive material in the anode
  • the greater the mole percent of sodium in the anode the greater the capacity of the anode; and conversely, the lower the mole ratio of sodium in the anode, the lower the capacity.
  • higher capacities are desirable, higher amounts of sodium in the alloy are desirable.
  • Sodium as compared to lithium is readily adaptable to provide such high capacity or alloys such as Na 5 Pb2, Na 5Pb 4 , NasSn2, and Na ⁇ 5Sn , which have higher sodium content.
  • the mole ratio of sodium to other components in the alloy is about equal to or greater than about 0.5 to about 1.
  • the upper amount of sodium in the alloy is the greatest amount of sodium which can be alloyed with the other component or components before pure metallic, unalloyed sodium is formed.
  • the mole ratio of sodium to the other components .in the alloy will usually vary from about 1 to about 1, to about 5 to about 1, and in the most preferred embodiments will vary from about 4 to about 1, to about 1 to about 1.
  • the method of manufacturing the alloy is not critical and can vary widely. Conventional alloying procedures are readily adaptable for use in the practice of this invention.
  • such alloys can be formed electrochemically by plating sodium onto a substrate of the other components as described in more detail in N.N. Tomashova, I.G. Kieseleva and B.N. Kabanov, Electrochemical, Vol, 8, p. 11.2 (1972) which is incorporated herein by reference.
  • Sodium alloys can also be prepared metallurgically by melting appropriate amounts of sodium and other components in an inert atmosphere as described in more detail in R. Kremann and P.V. Reininghaus, Z. Metallischen, Vol. 12, p. 273 (1920) which is hereby incorporated by reference.
  • Useful cation inserting polymers may be any of the variety of conjugated backbone polymers known to those of skill in the art for use as negative electrodes in batteries. Such polymers are preferably conductive in their reduced form and capable of reversibly inserting cations.
  • conjugated backbone polymers polyacetylene, poly(phenylene vinylene) and poly(p- phenylene) are preferred, and polyacetylene and poly(p- phenylene) are particularly preferred.
  • conjugated backbone polymers are known compounds which can be prepared by conventional means.
  • high quality polyacetylene a preferred conjugated backbone polymer
  • forms of high quality poly(p-phenylene) can be prepared by the method of Kovacic described in detail in J. Am. Chem. Soc. 85, 454-458 (1963), incorporated herein by reference.
  • poly(phenylene vinylene), another preferred conjugated backbone polymer can be prepared by the procedure described in U.S. Patent No. 3,404,132 of R.A. Wesslinq et al.
  • the anode may include other optional materials known to those of skill in the battery art. These materials are known to those of skill in the art and will not be described herein in great detail. In brief, by way of illustrative examples, the anode may include such other substituents as binders and conductivity aids, listed below for use in the cathode, mechanical supports, and the like. However, in the preferred embodiments, the combination of polymer plus other electroactive materials is in the major proportion.
  • the preferred anodes of this invention comprise an elastomer or halocarbon binder and one or more anode active materials selected from the group consisting of sodium metal alloy, and conjugated backbone polymers and copolymers.
  • the more preferred anodes comprises a combination of an elastomer binder with a conjugated backbone polymer and a sodium alloy.
  • the particular elastomer, conjugated backbone polymer and alloying metal chosen for use in any particular situation may vary widely. However, in the preferred embodiments of the invention, the conjugated backbone polymer and sodium alloys are selected such that the range of electroactivity of the polymer encompasses or closely matches that of the alloy.
  • the elastomer is preferably chosen such that it is chemically unreactive toward the other components throughout their range of electroactivity in the battery.
  • the secondary battery of this invention can be charged and discharged in accordance with the procedure described in U.S. Pat. Nos. 4,321,114 and 4,602,492. Such procedures are well known to those of skill in the art and will not be described herein in any great detail.
  • Sodium cobalt oxide of composition Na Q ⁇ - 7 Co ⁇ 2 was prepared in the P3(beta) phase by reacting a2 ⁇ 2 and C ⁇ 3 ⁇ 4 in 1:1 molar proportion in pelletized form at 550°C for 16h in flowing dry oxygen.
  • X-ray diffraction spectra taken on this powder confirmed that the oxide was in the P3 (or beta) phase.
  • Scanning Electron Micrographs (SEM) taken on this powder revealed a globular morphology with a primary particle size in the range 0.1 to 0.4 microns.
  • the preferred anodes of this invention comprise an elastomer or halocarbon binder and one or more anode active materials selected from the group consisting of sodium metal alloy, and conjugated backbone polymers and copolymers.
  • the more preferred anodes comprises a combination of an elastomer binder with a conjugated backbone polymer and a sodium alloy.
  • the particular elastomer, conjugated backbone polymer and alloying metal chosen for use in any particular situation may vary widely. However, in the preferred embodiments of the invention, the conjugated backbone polymer and sodium alloys are selected such that the range of electroactivity of the polymer encompasses or closely matches that of the alloy.
  • the elastomer is preferably chosen such that it is chemically unreactive toward the other components throughout their range of electroactivity in the battery.
  • the secondary- battery of this invention can be charged and discharged in accordance with the procedure -described in U.S. Pat. Nos. 4,321,114 and 4,602,492. Such procedures are well known to those of skill in the art and will not be described herein in any great detail.
  • Sodium cobalt oxide of composition was prepared in the P3(beta) phase by reacting Na2 ⁇ 2 and C03O4 in 1:1 molar proportion in pelletized form at 550°C for 16h in flowing dry oxygen. X-ray diffraction spectra taken on this powder confirmed that the oxide was in the P3 (or beta) phase. Scanning Electron Micrographs (SEM) taken on this powder revealed a globular morphology with a primary particle size in the range 0.1 to 0.4 microns. COMPARATIVE EXAMPLE II A cell was assembled using Na Q 7Co0 2 (P3) prepared according to Comparative Example I as a positive electrode.
  • This electrode was fabricated from 82 percent by weight Na Q
  • the cell was further comprised of a sodium metal negative electrode and an electrolyte of 1M NaPFg in dimethoxyethane (DME).
  • DME dimethoxyethane
  • the cell was cycled at a low rate equivalent to 0.2 mA/cm 2 .
  • the charge weighted average voltage differed by 0.06V (2.77 and 2.71V) which demonstrated some reduced energy efficiency.
  • EXAMPLE I Sodium cobalt oxide of composition Nag 7Co ⁇ 2 was prepared in the P2(gamma) phase by reacting Na 2 C ⁇ 3 and C03O4 in 1:1 molar ratio in pelletized from at 750°C for 16h in flowing dry oxygen. X-ray diffraction spectra taken on powder samples of this form confirmed that the oxide was in th-i P2 or (gamma) phase. SEM taken on the powder revealed particles having a plate-like morphology with particle size in the range 1 to 10 microns. EXAMPLE II
  • a cell was assembled using ag ⁇ g 7 Co ⁇ 2.P2) prepared according to Example 2 as a positive electrode.
  • This electrode was fabricated from 82 w/o ag ⁇ 7 Co ⁇ 2»- 10 w/o carbon black, and 8 w/o teflon.
  • the cell was further comprised of a sodium metal negative electrode an in electrolyte of 1M NaPFg in DME.
  • the cell was cycled at a low rate equivalent to 0.2 mA/cm 2 .
  • the charge weighted average voltage for charge and discharge was nearly identical (2.69 and 2.68V respectively) demonstrating high energy efficiency.
  • a cathode-limited cell was assembled using Na 0.67 CoO 2 (p3 ⁇ prepared according to Comparative Example I as cathode and polyphenylene (90 w/o) and polypropylene (10 w/o) as anode.
  • the cell further contained a sodium reference and an electrolyte of 1M NaPFg in DME.
  • the cell was charged and discharged over the voltage range 3.30 to 1.5V at a rate equivalent to 2 mA/cm 2 until cycle number 170 and then at 1 mA/cm 2 until cycle number 225.
  • the projected cycle life to a capacity equivalent to 50 percent by weight of the starting capacity was calculated to be 239 at 2 mA/cm 2 and 340 at 1 mA/cm 2 .
  • a cathode-limited cell was assembled using Nag Co ⁇ 2 (P2) prepared according to Example II as cathode and a composite electrode comprised of 75 w/o Na 3.75 p fc > ' 18 w/o polyphenylene, and 7 w/o polypropylene as anode.
  • the cell also contained a sodium reference electrode and was filled with an electrolyte of 1 M NaPFg in DME.
  • the cell was charged and discharged in the voltage range 3.3 to 1.5V at a constant current equivalent to 2 mA/cm 2 with respect to cathode area for about 290 cycles.
  • the cell was also cycled in 1 mA/cm" for a few cycles around cycle numbers 1, 155, and 290.
  • the projected cycle life to a capacity equivalent to 50 percent by weight of the starting capacity was calculated to be 367 cycles at 2 mA/cm 2 or 997 cycles at 1 mA/cm" 6 .

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Abstract

La présente invention se rapporte à une cathode destinée à être utilisée dans des piles, et à des piles renfermant cette cathode, laquelle comprend du dioxyde cobaltique de sodium dans la phase P2.
PCT/US1988/002377 1987-10-23 1988-07-13 Cathode de pile rechargeable composee de dioxyde cobaltique de sodium en phase p2 WO1989004066A1 (fr)

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US11284787A 1987-10-23 1987-10-23
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EP0317351B1 (fr) * 1987-11-20 1993-04-14 Showa Denko Kabushiki Kaisha Batterie secondaire

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JP5874328B2 (ja) * 2010-11-29 2016-03-02 住友化学株式会社 電極合剤ペースト、電極および非水電解質二次電池
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AU2424488A (en) 1989-05-23
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