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WO1996034420A1 - Procede de production d'un spinelle en oxyde de manganese de lithium servant de materiau de cathode pour piles secondaires au lithium - Google Patents

Procede de production d'un spinelle en oxyde de manganese de lithium servant de materiau de cathode pour piles secondaires au lithium Download PDF

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Publication number
WO1996034420A1
WO1996034420A1 PCT/EP1996/001591 EP9601591W WO9634420A1 WO 1996034420 A1 WO1996034420 A1 WO 1996034420A1 EP 9601591 W EP9601591 W EP 9601591W WO 9634420 A1 WO9634420 A1 WO 9634420A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
manganese oxide
spinel
manganese
spinels
Prior art date
Application number
PCT/EP1996/001591
Other languages
German (de)
English (en)
Inventor
Hans-Walter Praas
Sibylle Kemmler-Sack
Peter Endres
Original Assignee
Varta Batterie Aktiengesellschaft
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 Varta Batterie Aktiengesellschaft filed Critical Varta Batterie Aktiengesellschaft
Publication of WO1996034420A1 publication Critical patent/WO1996034420A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • 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
    • 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
    • C01P2002/70—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
    • C01P2006/40—Electric properties
    • 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 invention relates to a process for the production of a Uthium manganese oxide spinel for use as an active material of the positive electrode in lithium secondary batteries.
  • lithium manganese oxide spinels are a promising cathode material for electrochemical secondary elements with negative lithium electrodes.
  • the latter can consist of pure lithium metal or a lithium alloy, but particularly advantageously also of one host structure suitable for storage and removal of lithium, for example be made of a highly porous carbon material.
  • LiMn 2 O 4 spinel If lithium is electrochemically removed from a LiMn 2 O 4 spinel until theoretically only MnO 2 is still present, this corresponds to a charge of the spinel cathode. Conversely, a discharge occurs through the storage of additional lithium.
  • the LiMn 2 O 4 spinel thus forms in one
  • a lithium salt, lithium oxide or lithium hydroxide is mixed with a manganese salt, a manganese oxide, manganese hydroxide or, if appropriate, also with a Uthiummanganoxid and the mixture in a non-reducing atmosphere up to 168 h at temperatures between 350 * C and 900 * C annealed.
  • the invention has for its object to provide a method for producing lithium manganese oxide compounds with spinel structure that can be used as electrode material in lithium secondary batteries, the products of which are characterized by good initial capacities, good cycle stability and by insensitivity to high-temperature storage.
  • the method itself should consist of steps that are as simple as possible to carry out.
  • a lithium compound and a manganese salt are first introduced into a liquid medium and either dissolved or dispersed therein.
  • the highly disperse and therefore particularly evenly distributed components are then reacted with an aliphatic dibasic or polybasic carboxylic acid with a maximum of one hydroxyl group or a salt thereof.
  • the reaction product is then freed from the dispersing agent, which is volatile, by evaporation, at the same time removing volatile by-products of the reaction, for example CO 2 released from MnCO 3 or acetic acid released from manganese acetate.
  • H2O is generally suitable as the dispersant.
  • water-like organic solvents of polar character for example ethanol, and non-polar non-aqueous solvents can also be used.
  • the aliphatic carboxylic acid is selected from the group of citric acid, oxalic acid and apple acid. These acids are capable of forming stable complex salts of the chelate complex type with polyvalent metal cations (M ⁇ ).
  • M ⁇ polyvalent metal cations
  • the separation of the dispersant from the reaction product is usually performed by a drying process at temperatures of over 100 * C.
  • spray drying has proven.
  • the next process step consists in the thermal decomposition of the previously finely ground dry residue in air at temperatures between 300 ° C. and 600 ° C., preferably around 500 ° C. After cooling, the decomposition product is again finely ground and finally annealed or annealed under the temperature conditions just mentioned.
  • the production process according to the invention can be subject to certain modifications. Further below, 3 different synthetic routes are described as exemplary embodiments, in which citric acid is always used as the preferred precipitation reagent. Among other things, the examples also provide more detailed information about the duration of the individual treatment steps.
  • the lithium manganese oxide spinels produced according to the invention have a bulk density which is almost twice as high as that of known lithium manganese oxide spinels. This results in a doubling of the achievable volumetric energy density, expressed in watts per liter.
  • the final product obtained after the thermal decomposition is examined by means of an X-ray powder diffractometer for its single-phase and lattice constant.
  • the mean oxidation level of the manganese is determined by potentiometric titration (Fe (II) / Ce (IV)) and the Li and Mn content of the sample is determined by ICP analysis.
  • the hard, pale yellow mass obtained in this way is ball mill in an agate to a fine powder ground, this in a Korundwanne 4h at 500 * C decomposes in air, taken at this temperature from the oven, cooled in air to room temperature, in a Finely rubbed agate bowl, annealed for another 4 hours at 500 * C and finally cooled in air after another removal at the preparation temperature from the oven.
  • lithium manganese oxide compounds of the general composition Li 1 + x Mn 2 _ x O 4 ⁇ ⁇ f can be represented with 0 ⁇ x ⁇ 0.33 and 0 ⁇ ⁇ ⁇ 0.5 according to the process steps given above, which turn out to be uniform spinels by X-ray.
  • a special property of the spinels produced by the new preparation method is that their lattice constants are significantly smaller than in spinels of the same composition, which were produced in a conventional manner by the ceramic process.
  • the products obtained by the new process are thus clearly defined in their initial state, in which they are used as cathode material and which depends on the "start stoichiometry" x, by the lattice constant, the degree of manganese oxidation and the Mn / O ratio.
  • the lattice constant is reduced even more due to contraction of the oxygen lattice, the charging process consisting of an outsourcing (undoping) of lithium.
  • the charging process consisting of an outsourcing (undoping) of lithium.
  • unloading lithium is re-stored, which can lead to the original othium content.
  • the low synthesis temperature is explained above all in the combustion of the organometallic salt mixture during the decomposition, since this is an exothermic process and requires less external heat. Nevertheless, the production process according to the invention delivers the spinels desired in each case and stoichiometrically pre-calculated from the ratio of the material weights. In the ceramic process, however, lithium-rich spinels are obtained with low-temperature preparation and manganese oxides as foreign phase. The shrunk lattice of spinels produced according to the invention is also responsible for good capacities and cycle stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La réaction d'un sel de manganèse et d'un composé lithium en phase finement dispersée, ou en solution claire avec de l'acide citrique, permet d'obtenir un mélange de sels métallo-organiques. Après séparation de l'agent de dispersion (H2O, éthanol, solvant homopolaire), ledit mélange est décomposé thermiquement par évaporation, de préférence par séchage par pulvérisation, pour donner lieu à un composé oxyde de manganèse de lithium à structure de spinelle. Le produit final obtenu après broyage et trempe ultérieure est à phase pure en dépit d'une température de synthèse relativement basse (∩ 500 °C) et diffère des spinelles de même composition obtenus par procédés céramiques, par une constante réticulaire nettement moindre. La structure réticulaire plus resserrée confère un bon comportement capacitif et une bonne stabilité de cycle.
PCT/EP1996/001591 1995-04-28 1996-04-16 Procede de production d'un spinelle en oxyde de manganese de lithium servant de materiau de cathode pour piles secondaires au lithium WO1996034420A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19515629.3 1995-04-28
DE19515629A DE19515629A1 (de) 1995-04-28 1995-04-28 Verfahren zur Herstellung eines Lithiummanganoxid-Spinells als Kathodenmaterial für Lithium-Sekundärbatterien

Publications (1)

Publication Number Publication Date
WO1996034420A1 true WO1996034420A1 (fr) 1996-10-31

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/001591 WO1996034420A1 (fr) 1995-04-28 1996-04-16 Procede de production d'un spinelle en oxyde de manganese de lithium servant de materiau de cathode pour piles secondaires au lithium

Country Status (2)

Country Link
DE (1) DE19515629A1 (fr)
WO (1) WO1996034420A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903796A4 (fr) * 1996-12-25 2002-11-27 Mitsubishi Electric Corp Materiau anodique actif, son procede de fabrication et pile secondaire aux ions lithium mettant en application ce materiau

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19935091A1 (de) 1999-07-27 2001-02-08 Emtec Magnetics Gmbh Lithiummanganoxid enthaltende Lithiuminterkalationsverbindungen
DE19935090A1 (de) * 1999-07-27 2001-02-08 Emtec Magnetics Gmbh Lithiumoxid enthaltende Lithiuminterkalationsverbindungen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018425A1 (fr) * 1991-04-23 1992-10-29 Bell Communications Research, Inc. PROCEDE DE PREPARATION DE COMPOSES INTERCALAIRES DE LiMn2O4 ET DE LiCoO2 DESTINES A DES PILES SECONDAIRES AU LITHIUM
EP0532084A1 (fr) * 1991-09-09 1993-03-17 SOLVAY (Société Anonyme) Procédé pour la fabrication d'une poudre d'oxydes métalliques mixtes et utilisation de la poudre pour la fabrication de condensateurs et de résistances électriques
WO1994025398A1 (fr) * 1993-04-23 1994-11-10 Centre National De La Recherche Scientifique Procede de preparation d'oxydes mixtes de lithium et de metaux de transition, les oxydes obtenus et leur utilisaton comme materiau d'electrode
JPH07142065A (ja) * 1993-09-22 1995-06-02 Nippondenso Co Ltd リチウム二次電池用活物質の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018425A1 (fr) * 1991-04-23 1992-10-29 Bell Communications Research, Inc. PROCEDE DE PREPARATION DE COMPOSES INTERCALAIRES DE LiMn2O4 ET DE LiCoO2 DESTINES A DES PILES SECONDAIRES AU LITHIUM
EP0532084A1 (fr) * 1991-09-09 1993-03-17 SOLVAY (Société Anonyme) Procédé pour la fabrication d'une poudre d'oxydes métalliques mixtes et utilisation de la poudre pour la fabrication de condensateurs et de résistances électriques
WO1994025398A1 (fr) * 1993-04-23 1994-11-10 Centre National De La Recherche Scientifique Procede de preparation d'oxydes mixtes de lithium et de metaux de transition, les oxydes obtenus et leur utilisaton comme materiau d'electrode
JPH07142065A (ja) * 1993-09-22 1995-06-02 Nippondenso Co Ltd リチウム二次電池用活物質の製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 123, no. 12, 18 September 1995, Columbus, Ohio, US; abstract no. 149032, HAYASHI YASUSHI: "Manufacture of cathodes for secondary lithium batteries" XP002010183 *
MASAKI YOSHIO ET AL: "SYNTHESIS OF LICOO2 FROM COBALT-ORGANIC ACID COMPLEXES AND ITS ELECTRODE BEHAVIOUR IN A LITHIUM SECONDARY BATTERY", JOURNAL OF POWER SOURCES, vol. 40, no. 3, 15 December 1992 (1992-12-15), pages 347 - 353, XP000345088 *
TOMOKI TSUMURA ET AL: "Synthesis of LiMn2O4 Spinel via Tartrates", JOURNAL OF MATERIALS CHEMISTRY, vol. 3, no. 9, 1993, CAMBRIDGE GB, pages 995 - 996, XP002010727 *
YOSHIO M ET AL: "MANGENESE OXIDES AS 3V AND 4V CATHODES MATERIALS FOR RECHARGABLE LITHIUM CELLS", EXTENDED ABSTRACTS, vol. 93/2, 1 January 1993 (1993-01-01), pages 734/735, XP000422399 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903796A4 (fr) * 1996-12-25 2002-11-27 Mitsubishi Electric Corp Materiau anodique actif, son procede de fabrication et pile secondaire aux ions lithium mettant en application ce materiau

Also Published As

Publication number Publication date
DE19515629A1 (de) 1996-10-31

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