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WO1999000329A1 - Procede de fabrication d'oxydes mixtes lithium-manganese et leur utilisation - Google Patents

Procede de fabrication d'oxydes mixtes lithium-manganese et leur utilisation Download PDF

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Publication number
WO1999000329A1
WO1999000329A1 PCT/EP1998/003723 EP9803723W WO9900329A1 WO 1999000329 A1 WO1999000329 A1 WO 1999000329A1 EP 9803723 W EP9803723 W EP 9803723W WO 9900329 A1 WO9900329 A1 WO 9900329A1
Authority
WO
WIPO (PCT)
Prior art keywords
production
lithium manganese
elements
manganese oxide
manganese dioxide
Prior art date
Application number
PCT/EP1998/003723
Other languages
German (de)
English (en)
Inventor
Udo Heider
Volker Hilarius
Dietmar Raulin
Original Assignee
Merck Patent Gmbh
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 Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to CA002295175A priority Critical patent/CA2295175A1/fr
Priority to KR19997012336A priority patent/KR20010014235A/ko
Priority to EP98941284A priority patent/EP0991591A1/fr
Priority to JP50525899A priority patent/JP2002506560A/ja
Publication of WO1999000329A1 publication Critical patent/WO1999000329A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
    • 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
    • H01M4/485—Selection 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1235—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)2-, e.g. Li2Mn2O4 or Li2(MxMn2-x)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/52—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (Mn2O4)2-, e.g. Li2(NixMn2-x)O4 or Li2(MyNixMn2-x-y)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/54—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (Mn2O4)-, e.g. Li(NixMn2-x)O4 or Li(MyNixMn2-x-y)O4
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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 present invention relates to a process for producing mixed oxides with easily variable electrochemical properties and spinel-like structures of the formula (I)
  • Me a metal cation from the II., III, IV., V. and VI. Main group or from the I., II., IV., V, VII., Or VIII.
  • Subgroup of the Periodic Table of the Elements in particular a cation from the group of the elements AI, Co, Cr, Fe, Ge, Mg, Nb, Ni Sn
  • Typical components of a lithium secondary cell are a cathode consisting of lithiated metal oxide, an anode, preferably made of carbon, an aprotic electrolyte and an electrolyte-permeable separator material.
  • the separator material located between the electrodes has the task of electronically isolating the two electrodes.
  • a lithium manganese spinel which has a very high electrochemical activity, is often used as the cathode material.
  • manganese dioxide electrodes are usually made of carbon, soot or graphite particles
  • the object of the invention was therefore to provide a simple, fast and energy-saving method for producing suitable lithium-manganese mixed oxides with spinel-like structure with improved properties for cathodes in rechargeable electrochemical cells, which offers the possibility of
  • the object is achieved by a process for producing lithium manganese oxide with easily variable electrochemical properties, in particular with a large surface area and spinel-like structure of the general formula I.
  • Subgroup of the Periodic Table of the Elements in particular a cation from the group of the elements AI, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, W, Zn and
  • the pulverulent material obtained by the nitrate pyrolysis process is subjected to additional tempering steps at temperatures of 500-750 ° C.
  • This tempering can be carried out in an oxygen-containing gas atmosphere, preferably with an oxygen concentration of up to 100%.
  • the invention also relates to the use of the lithium manganese oxide produced by this process for the production of manganese dioxide electrodes for galvanic elements, for electrochemical cells.
  • a powder material which has a homogeneous and stoichiometric composition, so that possible dopants are homogeneously contained in the material, the material has a spinel structure immediately after production and a uniform, very small particle size , advantageously less than 10 ⁇ m.
  • nitrate pyrolysis is suitable in particular a method which nitrate pyrolysis may be characterized in principle as well.
  • This method can with the aid of aqueous solutions of metal nitrate salts, or of a suspension of a component in an aqueous nitrate salt solution of the other components
  • aqueous solutions or suspensions of the nitrate salts or the components can advantageously be used in stoichiometric amounts by spraying the solution or suspension prepared directly in air or in another defined gas atmosphere at temperatures of 400-700 ° C, Especially at 475 - 650 ° C, the desired spinel-like product can be produced phase-pure directly without further after-treatment.
  • Salt solutions which react in an exothermic reaction to the desired mixed oxides are preferably used to carry out the process.
  • This has the advantage that, in order to start the reaction, the reaction space must be brought to a certain temperature at the beginning, but in the best case the reaction is self-supporting and the temperature can be maintained. If necessary, the reaction can also be started by ignition.
  • nitrates salts of the metals which are desired in the product can be used as starting materials for the formation of the lithium manganese oxides of the formula (I).
  • Suitable salts are also acetates, citrates, hydroxides or other organic metal salts soluble in water or water-alcohol mixtures.
  • hydroxides in combination with nitrate salts for the reaction.
  • nitrate salts for the reaction.
  • Subgroup of the Periodic Table of the Elements in particular from the group of the elements AI, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, W, Zn can be used in the process according to the invention.
  • This further salt is also preferably a water-soluble nitrate.
  • the abovementioned salts are brought into solution in the stoichiometric ratio of the desired powder compositions.
  • Solutions in which the salts are present in a total concentration of 5-50%, in particular 30-50%, have particularly good properties.
  • Both salt water solutions are suitable as salt solutions as well as those which contain an organic solvent as the solvent in addition to water.
  • Water-miscible solvents are particularly suitable as organic solvents.
  • Alcohols such as ethanol, methanol or propanol can be used for this purpose.
  • other solvents can also be used, which can also act as complexing agents at the same time, such as. B. diethylene glycol.
  • alcohols are preferably used because of their good water solubility. It is particularly preferred to work with ethanol.
  • the organic solvents contribute in particular to maintaining the temperature during the spray pyrolysis reaction.
  • their concentration and reaction temperature must be selected so that the carbon-containing compounds undergo a complete exothermic reaction, but no carbon residues remain in the mixed oxide formed, since otherwise the formation of a spinel structure is disturbed.
  • solutions can be used in which an organic solvent alone is used, that is to say the concentration of the organic solvent in relation to the total amount of solvent increases to 100%.
  • the salt solutions prepared are sprayed into the NPA reactor (NPA nitrate pyrolysis system) brought to operating temperature.
  • NPA reactor NPA nitrate pyrolysis system
  • This reactor is a specially developed reactor from the applicant. Spraying takes place through a two-component nozzle using a pump. The reaction solution sprayed into the reactor in this way is thermally pyrolyzed and is obtained as a finely divided, free-flowing powder.
  • Another advantage of the method according to the invention is the possibility of being able to produce doped mixed oxides of the above general formula in a simple manner. Even when using the smallest amounts of doping precursor material, a homogeneous distribution in the precursor material for electrodes is guaranteed.
  • the method according to the invention can be carried out simply and quickly, even on a larger scale.
  • This manufacturing process is also characterized by a low energy input due to the self-supporting reaction.
  • the powder produced is directly in the desired phase, the spinel, if the reaction exit temperature of the nitrate pyrolysis plant is selected. It is a finely divided powder with a particle size of less than 10 ⁇ m with a high bulk density.
  • This aftertreatment of the powders in particular affects the crystallinity, the lattice constants, the grain sizes, the specific surface and the capacity.
  • the defined temperature, the heating and cooling rate as well as the annealing time play a decisive role here.
  • the gas atmosphere of the furnaces used and the bed height of the crucibles are important influencing factors.
  • the powdery product obtained is mixed intensively with the other constituents and optionally suspended.
  • Such necessary components such.
  • organic or inorganic binders and conductivity additives such.
  • PVDF and others a are added.
  • binders known to those skilled in the art for this purpose are added.
  • PTFE is particularly suitable.
  • Suitable conductivity additives are carbon black, graphite, steel wool and other conductive fibers. Particularly good results were achieved by adding carbon black and graphite in an amount of 5-50, in particular about 15% by weight, based on the total amount.
  • the powder mixed with all additives is made into electrodes in a manner known per se. This can be done by pressing with very high pressure between wire meshes, consisting of an inert material, such as. B. aluminum. If appropriate, this can be followed by treatment at elevated temperature, the product obtained drying.
  • Electrodes produced in this way can be used in a known manner for the production of secondary galvanic cells in which a carbon electrode usually serves as a counter electrode in the presence of an aprotic electrolyte.
  • Various additives such as gelling agents, silica gel or others, can be used to increase the viscosity of the electrolyte, which is aqueous per se.
  • a suitable polymer fabric or fleece can be attached as a separating material between the electrodes and, if necessary, a spacer should be inserted. Materials consisting of PVA, polypropylene or other inert polymers can serve as the polymer fleece.
  • Spacers as they are known from commercially available batteries, can have a corrugated shape and, for example, consist of PVC.
  • electrodes were produced from the lithium-manganese dioxide mixtures according to the invention by homogenizing the components in a mixer, one in each case Conductivity additive and a binder was added. The mixture thus obtained was pressed into cathodes for button cell batteries and dried.
  • a Schlick two-fluid nozzle, model 970/4, with a bore of 0.8 mm was used.
  • the reactor was cooled during the reaction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé de fabrication d'oxydes mixtes à propriétés électrochimiques faiblement variables et de structures de type spinelle de formule (I): LixMeyMn2-yO4, dans laquelle Me désigne un cation métallique choisi dans le groupe principal II, III, IV, V et VI ou dans le sous-groupe I, II, IV, V, VII ou VIII de la Classification Périodique, en particulier un cation appartenant au groupe des éléments Al, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, W, Zn, et 0≤x≤2 et 0≤y∫2, ainsi que leur utilisation pour la fabrication d'électrodes en dioxyde de manganèse pour des éléments électrolytiques, des piles électrochimiques, des batteries secondaires, en particulier pour des piles prismatiques ou des piles rondes.
PCT/EP1998/003723 1997-06-28 1998-06-18 Procede de fabrication d'oxydes mixtes lithium-manganese et leur utilisation WO1999000329A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002295175A CA2295175A1 (fr) 1997-06-28 1998-06-18 Procede de fabrication d'oxydes mixtes lithium-manganese et leur utilisation
KR19997012336A KR20010014235A (ko) 1997-06-28 1998-06-18 리튬-망간 혼합 산화물의 제조방법 및 그의 용도
EP98941284A EP0991591A1 (fr) 1997-06-28 1998-06-18 Procede de fabrication d'oxydes mixtes lithium-manganese et leur utilisation
JP50525899A JP2002506560A (ja) 1997-06-28 1998-06-18 リチウムマンガン混合酸化物の製造方法およびそれらの使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19727611.3 1997-06-28
DE19727611A DE19727611A1 (de) 1997-06-28 1997-06-28 Verfahren zur Herstellung vom Lithiummanganmischoxiden und deren Verwendung

Publications (1)

Publication Number Publication Date
WO1999000329A1 true WO1999000329A1 (fr) 1999-01-07

Family

ID=7833989

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/003723 WO1999000329A1 (fr) 1997-06-28 1998-06-18 Procede de fabrication d'oxydes mixtes lithium-manganese et leur utilisation

Country Status (8)

Country Link
EP (1) EP0991591A1 (fr)
JP (1) JP2002506560A (fr)
KR (1) KR20010014235A (fr)
CN (1) CN1261330A (fr)
CA (1) CA2295175A1 (fr)
DE (1) DE19727611A1 (fr)
WO (1) WO1999000329A1 (fr)
ZA (1) ZA985626B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000049668A3 (fr) * 1999-02-17 2000-12-07 Valence Technology Inc Materiau actif a base d'oxyde de manganese-lithium ameliore
US6248477B1 (en) 1999-09-29 2001-06-19 Kerr-Mcgee Chemical Llc Cathode intercalation compositions, production methods and rechargeable lithium batteries containing the same
US6465130B1 (en) * 1999-05-21 2002-10-15 Mitsui Mining & Smelting Company, Ltd. Lithium manganese complex oxide anode material for lithium secondary batteries and a lithium secondary battery using the same
US6667131B1 (en) 1998-05-08 2003-12-23 Danionics A/S Electrochemical cell
EP1661013A4 (fr) * 2003-08-08 2006-11-08 Teamon Systems Inc Systeme de communication permettant un equilibrage de charge de serveurs base sur des mesures de sante ponderees ainsi que procedes associes

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6428766B1 (en) * 1998-10-27 2002-08-06 Toda Kogyo Corporation Manganese oxide, lithium manganese complex oxide and cobalt-coated lithium manganese complex oxide, and preparation processes thereof
DE19935091A1 (de) * 1999-07-27 2001-02-08 Emtec Magnetics Gmbh Lithiummanganoxid enthaltende Lithiuminterkalationsverbindungen
WO2001028010A1 (fr) * 1999-10-08 2001-04-19 Yoo Yeong Chang Materiau cathodique actif destine a des piles electrochimiques au lithium
KR100366226B1 (ko) * 2000-02-02 2002-12-31 한국과학기술원 리튬이차전지용 정극재료의 제조방법
WO2004109825A2 (fr) * 2003-06-05 2004-12-16 Showa Denko K.K. Matiere carbonee pour une electrode d'accumulateur, procede de production et utilisation de cette derniere
US7364793B2 (en) * 2004-09-24 2008-04-29 Lg Chem, Ltd. Powdered lithium transition metal oxide having doped interface layer and outer layer and method for preparation of the same
JP2006114408A (ja) * 2004-10-15 2006-04-27 Izumi Taniguchi リチウムマンガン複合酸化物粒子及びそれを用いた二次電池用正極、並びにリチウム二次電池
CN100391855C (zh) * 2005-07-08 2008-06-04 中南大学 一种含锰氧化物的制备方法
US8187705B2 (en) * 2010-07-15 2012-05-29 Silberline Manufacturing Company, Inc. Manganese vanadium tantalum oxide and pigments having a black metallic effect coated with the same
KR101272042B1 (ko) * 2010-11-08 2013-06-07 주식회사 포스코이에스엠 리튬 망간 복합 산화물 및 이의 제조 방법
JP5924237B2 (ja) * 2012-11-08 2016-05-25 ソニー株式会社 リチウムイオン二次電池用活物質、リチウムイオン二次電池用電極、リチウムイオン二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2221213A (en) * 1988-07-12 1990-01-31 Csir Synthesizing lithium manganese oxide
EP0563988A1 (fr) * 1992-04-02 1993-10-06 Fuji Photo Film Co., Ltd. Batterie secondaire non-aqueuse
EP0814524A1 (fr) * 1996-06-17 1997-12-29 Murata Manufacturing Co., Ltd. Oxyde complexe de type lithium-manganèse pour matériau actif cathodique d'une pile secondaire au lithium
EP0820113A1 (fr) * 1996-07-16 1998-01-21 Murata Manufacturing Co., Ltd. Oxyde mixte de manganèse et de lithium de type spinel en tant que matériau actif cathodique pour piles secondaires au lithium à électrolyte non-aqueux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2221213A (en) * 1988-07-12 1990-01-31 Csir Synthesizing lithium manganese oxide
EP0563988A1 (fr) * 1992-04-02 1993-10-06 Fuji Photo Film Co., Ltd. Batterie secondaire non-aqueuse
EP0814524A1 (fr) * 1996-06-17 1997-12-29 Murata Manufacturing Co., Ltd. Oxyde complexe de type lithium-manganèse pour matériau actif cathodique d'une pile secondaire au lithium
EP0820113A1 (fr) * 1996-07-16 1998-01-21 Murata Manufacturing Co., Ltd. Oxyde mixte de manganèse et de lithium de type spinel en tant que matériau actif cathodique pour piles secondaires au lithium à électrolyte non-aqueux

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6667131B1 (en) 1998-05-08 2003-12-23 Danionics A/S Electrochemical cell
WO2000049668A3 (fr) * 1999-02-17 2000-12-07 Valence Technology Inc Materiau actif a base d'oxyde de manganese-lithium ameliore
US6322744B1 (en) 1999-02-17 2001-11-27 Valence Technology, Inc. Lithium manganese oxide-based active material
US6596435B2 (en) 1999-02-17 2003-07-22 Valence Technology, Inc. Lithium manganese oxide-based active material
US6465130B1 (en) * 1999-05-21 2002-10-15 Mitsui Mining & Smelting Company, Ltd. Lithium manganese complex oxide anode material for lithium secondary batteries and a lithium secondary battery using the same
US6248477B1 (en) 1999-09-29 2001-06-19 Kerr-Mcgee Chemical Llc Cathode intercalation compositions, production methods and rechargeable lithium batteries containing the same
EP1661013A4 (fr) * 2003-08-08 2006-11-08 Teamon Systems Inc Systeme de communication permettant un equilibrage de charge de serveurs base sur des mesures de sante ponderees ainsi que procedes associes

Also Published As

Publication number Publication date
DE19727611A1 (de) 1999-02-04
ZA985626B (en) 1999-05-03
KR20010014235A (ko) 2001-02-26
CN1261330A (zh) 2000-07-26
CA2295175A1 (fr) 1999-01-07
JP2002506560A (ja) 2002-02-26
EP0991591A1 (fr) 2000-04-12

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