CA1288472C - Cathode material for use in lithium electrochemical cell and lithium electrochemical cell including said cathode material - Google Patents

Cathode material for use in lithium electrochemical cell and lithium electrochemical cell including said cathode material

Info

Publication number
CA1288472C
CA1288472C CA000565443A CA565443A CA1288472C CA 1288472 C CA1288472 C CA 1288472C CA 000565443 A CA000565443 A CA 000565443A CA 565443 A CA565443 A CA 565443A CA 1288472 C CA1288472 C CA 1288472C
Authority
CA
Canada
Prior art keywords
moo3
v9mo6o40
cathode
weight percent
electrochemical cell
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
CA000565443A
Other languages
French (fr)
Inventor
Michelle C. Uchiyama
Steven M. Slane
Mark Salomon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
United States Department of the Army
Original Assignee
United States Department of the Army
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 United States Department of the Army filed Critical United States Department of the Army
Application granted granted Critical
Publication of CA1288472C publication Critical patent/CA1288472C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0409Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0471Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

ABSTRACT A cathode is provided for use in a lithium electro-chemical cell wherein the cathode includes a mix of a mixed metal-oxide prepared from V2O5 and MoO3, conductive diluent, and aqueous based binder and wherein the mix is rolled onto a nickel screen and sintered under vacuum at about 280°C.

Description

~ ~8847~J

~ his invention relates in qeneral to a ca~hode material for use in a lithium electrochemical cell and to a lithium electrochemical cell including tlle cathode material, and in particular, to the use of a mixed metal oxide prepared from V205 and MoO3 as the cathode active material for use in a lithium electrochemical cell and to a l.ithium electEochemical cell incl~ding a mixed metal oxide prepared froln V205 and MoO3 as the cathode active material.

The demand for improved energy storage devices has increased steadily with the advent of new techniques utili~in~
batteries as power sources. A particularly large application is batteries for man-portable electronic equipment, where expense, reliability, lightweight, durability and high energy density are critical features. For applications with large loads, recharge-able batteries are often used and lithium systems ofer the potential for both high energy an~ light weig~t. An important objective in developing a practical rechargeable lithium battery for this application is to provide an inexpensive, high energy 347~

material with excellent c~cle-life and rate capabilities for use as the cathode.
The class of lithium intercalating transition metal oxides are particularly attractive for this purpose because of their tendency to possess high ener~y content. Ho~1ever, the known oxides are either expensive to prepare as is the case with the vanadium oxides or they are electronic insulators thereby preventing their use for high battery curxent applications.
Another difficulty wit'n transition metal oxides, especially V2O5 is susceptibility to over-discharge which results in structural rearrange~ent and severe losses in cell capacity.
The general object of this invention is to provide an improved lithium electrochemical cell. A more particular object of the invention is to provide an inexpensive, high energy material with excellent cycle-life and rate capabilities for use as the cathode of the lithium electrochemical cell.
It has now been found that the aforementioned objects can be attained by providing a new mixed metal oxide of vanadium and molybdenum with the formulation VgMo6O40and solid solutions of VgM& O40 with V2O5 or ~oO3 for use as the cathode active material in a lithium electrochemical cell. ~se of these materials in cathodes for lithium electrochemical cells results in an inexpensive, high energy, high rate ca~hode with good cycle life.
The cathode active materials are prepared by a combination of stoichiometric quantities of V205 and MoO3, high ~ ~8~3~7~

temperature firing in evacuated quartz tubes, followed ~y rapid quenching to assure small particle size. The material~ so obtained are then fabricated into cathodes utilizing an a~ue~us polytetrafluoroethylene tsold under the trade mark Teflon) emulsion. A nickel screen is used as the current collector.
The cathodes are highly ~lexible and not sensitive to exposure to air.
The cathodes ~ade from VgM06040 and solid solutions of V9Mo6040 with V205 or ~loO3 also display minimal losses in capacity upon extended cycling and can be reversibly cycled to lower potentials than the parent oxide V205. Thus, these materials have a greater resistance to over-discharge than V205. An additional advantage of these new cathodes is that they can reversibly handle higher current densities on extended cycling than the parent oxide V205. ~inally, several advantages are observed in the cost and preparation of these ~aterials as cathodes. With regard to ' preparation of the oxides, reagent grade materials are used in the synthesis, and the overall stoichiometry need not be very strictly controlled since solid solutions of VgM~ 040 with V205 or MoO3 display acceptable behavior. I~ith regard to cathode fabrication, a procedure utilizing aqueous Teflon emulsions in a normal air atmosphere ~ay be used yielding highly flexible cathodes. This results in significant advantages over materials such as V205 which is water soluble and TiS2 which is both air and water sensitive, thus excluding the use of aqueous Teflon suspension in cathode fabrication. In addition, cathodes prepared by this procedure are flexible enough to be rolled and can therefore be utilized in a spirally wound configuration.

~.~88~7~

A cathode mix of 70 weight percent active materi~l such as VgMO604o or solid solutions of VgMO604o with V205 or Mo03, 29 weight percent conductive diluent such as Shawinigan Acetylene Black, and 10 weight percent binder such as T~flon is prepared using an aqueous Teflon emulsion. The weight percent of conductive diluent may range from 0 to 30 percent and the weight of binder may range from 1 to 30 percent.
Other conductive diluents such as high surface area carbons, graphites or other conductive materials may be used. In addition, other binders such as polyolefins or elastomers may be substitued for Teflon. The weight percent of active materials may range ~rom 44 to 99 percent. When any component of the cathode mix is changed, the concentrations of the remaining components are adjusted accordingly. The cathode mix is rolled onto an Exmet*
Nickel screen, sintered under vacuum at 280C.
Experimental laboratory test cells include a wick cell configuration utilizing flag electrodes in a pressure reaction vessel. A lithium anode on each side of the cathode is separated by a porous fiber separator (wic~). The electrodes are sealed in polypropylene separator material. Laboratory test cells are equiped witn a lithium reference electrode which is unnecessary in practical configuration.
Cathodes prepared as described in the preferred embodiment are used in cathode limited cells with 2.~M LiAsF6 in methyl formate as the electrolyte. Other stable electrolyte systems may be substituted for LiAsF6 in the aprotic solvent methyl formate. These cells exhibit high experimental energy * denotes trade mark ~.~88472 densities tbased on active material), ranging from 810 r,~Jh/kg - (first cycle) to 250 Wh/kg on the twentieth cycle. Cells -utilizing V9Mo6O40 based cat'nodes exhibit highest energ~ densities and excellent capacity retention at 1.0 mA/cm2. Approxi~ately 2 percent capacity loss is observed after 25 cycles at higher current densities of 2.0 and 5.0 m~/cm~. Cells utilizing cathodes prepared from solid solutions of V6M~ 040 and V2O5 exhi'oit higher capacities on initial cycles (up to fifteen cycles) but show poorer capacity retention on cycling when compared with cathodes prepared fro~ V9~o6O40. Cells utilizing cathodes prepared from solid solutions of VgMO6O40 with MoO3 display similar capacities to cells utilizing cathodes prepared from VgMo6O40 in initial cycles but poorer capacity retention on the ninth and subsequent cycles.
The electroc'nemical cells of this invention can be used as either a rechargeable system or a pril~ary system.
We wish it to be understood that we do not desire to be limited to the exact details of construction shown and described for obvious modifications will occur to a person skilled in the art.

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cathode for use in a lithium electrochemical cell, said cathode comprising a mix of about 40 to 99 weight percent of a mixed metal oxide prepared from V2O5 and MoO3, wherein the mixed metal oxide prepared from V2O5 and MoO3 is selected from the group consisting of V9Mo6O40, a solid solution of V9Mo6O40 with V2O5, and a solid solution of V9Mo6O40 with MoO3, about 0 to 30 weight percent of a conductive diluent and about 1 to 30 weight percent of an aqueous based binder, wherein said mix is rolled onto a nickel screen and sintered under vacuum at about 280°C.
2. A cathode according to claim 1 wherein mixed metal oxide prepared from V2O5 and MoO3 is V9Mo6O40.
3. A cathode according to claim 1 wherein the mixed metal oxide prepared from V2O5 and MoO3 is a solid solution of V9Mo6O40 with V2O5.
4. A cathode according to claim 1 where the mixed metal oxide prepared from V2O5 and MoO3 is a solid solution of V9Mo6O40 with MoO3.
5. A cathode for use in a lithium electrochemical cell, said cathode comprising a mix of about 70 weight percent V9Mo6O40, about 20 weight percent Shawinigan Acetylene Black, and about 10 weight percent aqueous Teflon emulsion, wherein said mix is rolled onto a nickel screen and sintered under vacuum at about 280°C.
6. A lithium electrochemical cell comprising lithium ~ the anode, a cathode mix of about 40 to 99 weight percent of a mixed metal oxide prepared from V2O5 and MoO3, wherein the mixed metal oxide prepared from V2O5 and MoO3 is selected from the group consisting of V9Mo6O40, a solid solution of V9Mo6O40 with V2O5 and a solid solution of V9Mo6O40 with MoO3, about 0 to 30 weight percent of conductive diluent and about 1 to 30 weight precent of an aqueous based binder wherein said mix is rolled onto a nickel screen and sintered under vacuum at about 280°C as the cathode, and an inorganic lithium salt dissolved in an aprotic solvent as the electrolyte.
7. A lithium electrochemical cell according to claim 6 wherein the mixed metal oxide prepared from V2O5 and MoO3 is V9Mo6O40.
8. A lithium electrochemical cell according to claim 6 wherein the mixed metal oxide prepared from V2O5 and MoO3 is a solid solution of V9Mo6O40 with V2O5.
9. A lithium electrochemical cell according to claim 6 wherein the mixed metal oxide Prepared from V2O5 and MoO3 is a solid solution of V9Mo6O40 with MoO3.
10. A lithium electrochemical cell comprising lithium as the anode, a cathode mix of about 70 weight percent V9Mo6O40, about 20 weight percent Shawinigan acetylene Black, and about 10 weight percent aqueous Teflon emulsion wherein said mix is rolled onto a nickel screen sintered under vacuum at about 280°C as the cathode, and a solution of 2 molar LiAsF in methyl formate as the electrolyte.
CA000565443A 1987-06-08 1988-04-28 Cathode material for use in lithium electrochemical cell and lithium electrochemical cell including said cathode material Expired - Lifetime CA1288472C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US059,346 1987-06-08
US07/059,346 US4751157A (en) 1987-06-08 1987-06-08 Cathode material for use in lithium electrochemical cell and lithium electrochemical cell including said cathode material

Publications (1)

Publication Number Publication Date
CA1288472C true CA1288472C (en) 1991-09-03

Family

ID=22022381

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000565443A Expired - Lifetime CA1288472C (en) 1987-06-08 1988-04-28 Cathode material for use in lithium electrochemical cell and lithium electrochemical cell including said cathode material

Country Status (2)

Country Link
US (1) US4751157A (en)
CA (1) CA1288472C (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2797390B2 (en) * 1989-04-03 1998-09-17 ソニー株式会社 Non-aqueous electrolyte secondary battery
US4925752A (en) * 1989-03-03 1990-05-15 Fauteux Denis G Solid state electrochemical cell having porous cathode current collector
FR2644935B1 (en) * 1989-03-21 1996-05-15 Centre Nat Rech Scient NOVEL LIXMZV2´ZO5´T ELECTRODE MATERIAL, MANUFACTURING METHOD THEREOF AND USE IN AN ELECTROCHEMICAL GENERATOR
CA2016517C (en) * 1989-05-11 1999-01-12 Dale R. Shackle Solid state electrochemical cell having microroughened current collector
EP0503901B1 (en) * 1991-03-15 1996-12-04 Honda Giken Kogyo Kabushiki Kaisha Cathode materials for lithium battery and methods for producing the same
US5238761A (en) * 1991-07-29 1993-08-24 The United States Of America As Represented By The Secretary Of The Air Force Cathode material for electrochemical cells
AU665575B2 (en) * 1991-09-30 1996-01-11 Wilson Greatbatch Ltd. Autoclavable electrochemical cell
US5278000A (en) * 1992-09-02 1994-01-11 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Overcharge and overdischarge protection of ambient temperature secondary lithium cells
CA2110097C (en) * 1992-11-30 2002-07-09 Soichiro Kawakami Secondary battery
US5955218A (en) * 1996-12-18 1999-09-21 Medtronic, Inc. Heat-treated silver vanadium oxide for use in batteries for implantable medical devices
US5895733A (en) * 1997-02-03 1999-04-20 Medtronic, Inc. Synthesis method for silver vanadium oxide
US6051339A (en) * 1998-05-26 2000-04-18 Rentech, Inc. Lithiated polyvanadate cathodes and batteries containing such cathodes
US5980855A (en) * 1998-05-26 1999-11-09 Rentech, Inc. Method for preparing lithiated metal oxides
US20100185264A1 (en) * 2002-01-24 2010-07-22 Greatbatch Ltd. Method For Coating A Cathode Active Material With A Metal Oxide For Incorporation Into A Lithium Electrochemical Cell
US7211349B2 (en) * 2002-08-06 2007-05-01 Wilson Greatbatch Technologies, Inc. Silver vanadium oxide provided with a metal oxide coating

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2524774C3 (en) * 1975-06-04 1979-01-04 Volkswagenwerk Ag, 3180 Wolfsburg Negative cobalt electrode for alkaline batteries and process for their manufacture
US4233375A (en) * 1979-08-02 1980-11-11 Exxon Research & Engineering Co. High energy density plural chalcogenide cathode-containing cell
US4310609A (en) * 1979-12-17 1982-01-12 Wilson Greatbatch Ltd. Metal oxide composite cathode material for high energy density batteries
US4675260A (en) * 1984-11-12 1987-06-23 Nippon Telegraph And Telephone Corporation Lithium battery including vanadium pentoxide base amorphous cathode active material

Also Published As

Publication number Publication date
US4751157A (en) 1988-06-14

Similar Documents

Publication Publication Date Title
US4310609A (en) Metal oxide composite cathode material for high energy density batteries
CA1288472C (en) Cathode material for use in lithium electrochemical cell and lithium electrochemical cell including said cathode material
Plichta et al. A rechargeable Li/LixCoO2 cell
US4421834A (en) Liquid cathode cells with a glass fiber separator
CN102792509A (en) Lithium-ion secondary battery
US4786499A (en) Lithium electrochemical cell including aprotic solvent-dialkyl carbonate solvent mixture
US4751158A (en) Amorphous cathode material for use in lithium electrochemical cell and lithium electrochemical cell including the amorphous cathode material
US4167608A (en) Additive for lithium anode, thionyl chloride active cathode electrochemical cell
JP2013254647A (en) Lithium ion-lithium air composite secondary battery, charging/discharging method using the same, and cathode material for lithium ion-lithium air composite secondary battery
CA2863827A1 (en) Energy storage systems having an electrode comprising lixsy
US5213914A (en) Non-aqueous, rechargeable electrochemical cell
AU593980B2 (en) Electrolyte for lithium-sulfur dioxide electrochemical cell
US4390604A (en) Complex metal sulfide cathodes for nonaqueous cells
US4818647A (en) Method of making a cathode for use in a rechargeable lithium battery, cathode so made, and rechargeable lithium battery including the cathode
CA1258107A (en) Secondary lithium cell
USH1076H (en) Lithium ion rechargeable intercallation cell
JPH0745304A (en) Organic electrolyte secondary battery
US6395425B1 (en) Non-aqueous electrolyte secondary battery with a lithium copper titanium oxide electrode
Manickam et al. Lithium intercalation cells LiMn2O4/LiTi2O4 without metallic lithium
JP2965674B2 (en) Lithium secondary battery
US3985577A (en) Lithium/fluorographite primary cell with improved electrolyte
JP3348175B2 (en) Organic electrolyte secondary battery
CA1235735A (en) Rechargeable lithium cell
JPH05325961A (en) Lithium battery
JP3555321B2 (en) Anode material and lithium secondary battery

Legal Events

Date Code Title Description
MKLA Lapsed
MKLA Lapsed

Effective date: 19940305