Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G45/00—Compounds of manganese
• • 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—Manganates manganites or permanganates
  • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
  • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, 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
  • C01P2002/50—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
  • C01P2002/70—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
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • 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
• • 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
  • C01P2006/80—Compositional purity
• • 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
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49108—Electric battery cell making

Definitions

• the present invention relates to a process for producing a lithium manganese oxide by reacting at least one lithium and at least one manganese compound under hydrothermal conditions, i.e. from heated aqueous solutions at subatmospheric pressures, such a lithium manganese oxide per se and its use as a cathode material for electrochemical cells.
• No. 4,980,251 describes a process for producing a lithium manganese oxide of the formula Li 1 . x Mn 2 O, with 0 ⁇ x ⁇ 1 by means of a solid-state reaction in which, by mixing the corresponding oxides and / or carbonates together and heating the resulting mixtures in an oxidizing atmosphere to a temperature in the range from 200 to 600 ° C., the corresponding lithium Manganese oxide is obtained.
• spinels with exceptionally high BET surface areas of, for example, more than 30 m 2 / g with poor crystallinity are obtained. According to the publication, such spinels are particularly well suited for use in electrochemical cells.
• DE-A-43 27 760 relates to a method for producing a positive
• Electrode for lithium secondary batteries the active material of one
• Lithium-manganese oxide with spinel structure which is obtained by mixing manganese dioxide with lithium formate and / or lithium acetate and then heating the mixture at a temperature of 550 to 800 ° C and subsequent grinding is obtained.
• DE-A 195 19 044 describes spinels containing lithium and manganese (HI / TV) with a specific surface area of 0.1 to 4 m 2 / g and their use as cathode material for electrochemical cells.
• the reaction of the starting compounds at elevated temperature is specified as a process for the preparation of the spinels claimed there.
• the object of the present invention is to provide a method which, on the one hand, makes it possible to use lithium-manganese oxides, in particular i.a. to produce phase-pure lithium manganese oxides with a spinel structure, and furthermore can be carried out on a large industrial scale without any problems and by avoiding unusable or even harmful by-products and leads to lithium manganese oxides with very good electrochemical properties.
• This object is achieved by a process for producing a lithium manganese oxide of the formula Li 1; 5 . x Mn 2 O 4 , where the value for x corresponds to the relation 0 ⁇ x ⁇ 1, 5, which comprises the following level:
• Reaction of at least one lithium and at least one manganese compound characterized in that the reaction is carried out in an aqueous medium at a temperature in the range from 80 to 500 ° C and a pressure of 1 ⁇ 10 5 Pa to 5 • 10 7 Pa.
• a temperature in the range from 80 to 500 ° C and a pressure of 1 ⁇ 10 5 Pa to 5 • 10 7 Pa it is possible within the scope of the method according to the invention to obtain not only lithium-manganese oxides with spinel structure of the approximate composition LiMn 2 O 4 but also oxides with a very low proportion of lithium, including ⁇ -MnO 2 .
• an oxide with a spinel structure is preferably obtained.
• Li 2 O, LiOH, LiCl, LiNO 3 , Li 2 CO 3 , Li carboxylates, such as Li formate or lithium acetate, or a mixture of two, are preferably used or more of them.
• MnO 2 , MnO, MnOOH, Mn 2 O 3 , Mn 3 O 4 , MnCO 3 , Mn (NO 3 ) 2 , Mn carboxylates, such as, for example, Mn formate or Mn acetate or a mixture of two or more, are preferred thereof used as a manganese compound, in particular oxidic manganese raw materials and mixed manganese oxides, such as MnO, MnOOH, Mn 2 O 3 , Mn 3 O 4 , and MnCO 3 , and mixtures of two or more thereof being used.
• the lithium-manganese oxides produced according to the invention can additionally contain a further metal M or a mixture of two or more further metals, preferably a metal from the group Ha, lilac, IVa, Ilb, Illb, IVb, VIb, Vllb or VIII des Periodic table or a mixture of two or more thereof, and in particular iron, cobalt, nickel, titanium, boron, aluminum or a mixture of two or more thereof, wherein oxides of the general formula
• a salt of a metal or a mixture of two or more thereof, as defined above, is preferably made of an Fe, Co, Ni or a mixture of in the reaction according to the invention two or more of them, each used in the desired amount.
• the present invention also relates to a method for producing a lithium manganese oxide of Formula Li 1. 5 x M z Mn 2 . z O 4 , where the value for x corresponds to the relation 0 ⁇ x ⁇ 1.5, M is a metal from the group Ha, lilac, IVa, Ilb, Illb, IVb, VIb, Vllb, or VIII of the periodic table or a mixture of two or more thereof and the value for z corresponds to the relation 0.01 ⁇ z ⁇ 1, preferably the relation 0.1 ⁇ z ⁇ 0.4, which comprises the following step: reaction of at least one lithium, at least one manganese and at least one compound of a metal as defined above, characterized in that the reaction is carried out in an aqueous medium at a temperature in the range from 80 to 500 ° C and a pressure of 1 • 10 5 Pa to 5 • 10 7 Pa.
• the lithium and manganese compound are preferably used in an amount such that the molar ratio of manganese: lithium is 2: approximately 1, but also molar ratios Mn: Li of 2: approximately 1.5 to approximately 2.5, preferably second : about 1.3 to about 0.6.
• the peculiarity of the process according to the invention can be seen in the fact that the lithium and manganese compounds are reacted under hydrothermal conditions. This means that the implementation in one aqueous medium.
• the reaction is carried out at a temperature in the range of about 80 to about 500 ° C, preferably about 100 to about 350 ° C and especially about 150 to about 250 ° C.
• the reaction is carried out at a pressure of about 1 • 10 5 Pa to about 5 • 10 7 Pa, preferably about 1 • 10 6 Pa to about 5 • 10 6 Pa and in particular at about 1.5 • 10 6 Pa to about 2, 5 • 10 6 Pa.
• the actual implementation can be followed by a washing process for removing dissolved impurities that are present in the metal salts used, e.g. Sulfates, Na and K salts, and other components that are not part of the spinel according to the invention, connect.
• a washing process for removing dissolved impurities that are present in the metal salts used, e.g. Sulfates, Na and K salts, and other components that are not part of the spinel according to the invention, connect.
• the product obtained in the reaction can additionally be dried, with temperatures here preferably in a range from approximately 60 to approximately 200 ° C., more preferably approximately 100 to approximately 150 ° C. and in particular approximately 120 to approximately 135 ° C. , be applied.
• the product obtained afterwards can be additionally annealed, here preferably at a temperature in the range from approximately 200 to approximately 900 ° C., more preferably approximately 300 to approximately 850 ° C. and in particular at about 800 ° C.
• the duration of the annealing is preferably at least about one hour, more preferably more than about 15 hours, and in particular approximately 24 hours, the maximum duration of the annealing being approximately 30 hours, particularly for economic reasons.
• An annealing stage is particularly useful if the manganese valence level e.g. is above about 3.5.
• the valence level of the manganese is optimized in the direction of 3.5.
• the valence level indicates the mean value of the oxidation level of the manganese contained in the oxide.
• a reduction of the Li content with increased use of Li or a general reduction of this content is possible after the actual implementation by means of an acid leaching process, which can preferably be done before the optional drying or tempering. It should be noted that the aqueous phase can be separated off before drying, but in general, e.g. spray drying can be dispensed with.
• the crystallinity and the specific surface area of the lithium manganese oxide obtained according to the process according to the invention can be influenced by a specific temperature, pressure and reaction time control during the reaction and / or the subsequent tempering.
• the particle size of the lithium-manganese oxide obtained according to the invention can be influenced by taking the grain fineness of the manganese raw materials used into account by preceding wet or dry grinding processes. It is also possible to grind the wet or dried lithium manganese oxide to refine the grain.
• the spinel obtained according to the invention preferably has an average particle size, measured by means of a Cilas granulometer, in the range from approximately 0.5 to approximately 100 ⁇ m, more preferably from approximately 1 to approximately 50 ⁇ m.
• the BET surface area of the lithium manganese oxide produced according to the invention is preferably below approximately 10 m 2 / g, more preferably below approximately 8 m 2 / g and in particular approximately 5 m 2 / g, the lower limit being approximately 0. 1 m 2 / g.
• MnO- + MnOOH + LiOH LiMn 2 O 4 + H 2 O 2MnO 2 + Mn 2 O 3 + 2LiOH 2LiMn 2 O 4 + H 2 O 10MnO 2 + 2Mn 3 O 4 + 8LiOH 8LiMn 2 O 4 + H 2 O 3MnO 2 + MnCO 3 + 2LiOH 2LiMn 2 O 4 + H 2 O + CO 2
• the present invention also relates to a lithium manganese oxide of the formula L ⁇ 5 _ x Mn 2 O 4 or a lithium manganese oxide of the formula L ⁇ 5 _ x M z Mn 7 _ z O 4 , obtainable by reaction at least one lithium and at least one manganese or at least one lithium, at least one manganese and at least one compound of a metal M, characterized in that the reaction in an aqueous medium at a temperature in the range from 80 to 500 ° C and a Pressure of 1 • 10 5 Pa to 5 • 10 7 Pa is carried out.
• the lithium-manganese oxide described above is preferably one with a spinel structure, in particular a phase-pure Li-Mn oxide with a spinel structure.
• the lithium manganese oxide according to the invention or produced according to the invention, preferably with a spinel structure, is a so-called intercalation compound.
• Such compounds can store active Li + ions in a host lattice, the lithium being stored in interstitial sites of the host material. Accordingly, such intercalation compounds can be used in particular for electrochemical cells.
• the storage and removal can be carried out electrochemically using a lithium ion-conducting electrolyte with high reversibility, preferably LiClO 4 , LiBF 4 , LiPF 6 , LiSO 3 CH 3 , LiAsF 6 .
• Electrochemical cells of this type are known as lithium-ion cells.
• a carbon-containing substance such as graphite or coke, is particularly suitable as the host material for the anode.
• Such a cell could correspond to a short designation Li x C 6 / Li y. ⁇ Mn 2 O 4 .
• the present invention also relates to the use of the lithium manganese oxide according to the invention or produced according to the invention, preferably with a spinel structure, as cathode material or as part thereof for an electrochemical cell.
• the lithium-manganese oxide represents the cathode, optionally in conjunction with a binder such as PTFE and acetylene black, while the anode acts as the host material preferably a carbonaceous substance as defined above or metallic lithium.
• the anode when using the lithium manganese oxide described here as the cathode.
• the compounds that can be used only have to be intercallable for lithium ions and have a higher electrochemical activity than the cathode.
• the preparation of the lithium manganese oxide according to the invention or produced according to the invention, preferably with a spinel structure, as the battery cathode material takes place in a manner known per se.
• this cathode material can be used in a manner known per se against an anode which absorbs lithium cations.
• the electrodes of such cells when fully assembled and closed, are usually uncharged, i.e. all available lithium is stored in the positive electrode, while the host structure of the negative electrode is in a non-lithium-loaded state.
• the lithium is removed from the positive host lattice (cathode) and embedded in the negative host lattice (anode), preferably a carbon matrix.
• a part of the lithium ions which is irreversibly attached to the carbon matrix and which is removed from the further intercalation mechanism can be compensated for by an over-stoichiometric amount of lithium in the lithium-manganese oxide, which preferably has a spinel structure.
• the basic structure of such electrochemical cells is known and is described, inter alia, by JM Tarascon in J. Electrochem. Soc. 140, p. 3071 ff.
• the lithium manganese oxides according to the invention or produced according to the invention preferably with a spinel structure, have good capacitive properties and cycle stability, as is demonstrated by the examples.
• the present invention also relates to an electrochemical cell which has at least one cathode which contains the lithium manganese oxide according to the invention or produced according to the invention, preferably with a spinel structure.
• the solid was then separated from the aqueous phase by filtration, dried and heated at 800 ° C. for 24 hours.
• experiment f a commercially available manganese dioxide raw material was used which, after wet grinding, had an average particle size of 1 ⁇ m.
• the reaction temperature in the autoclave was kept at 195 ° C. for 24 hours in all three experiments, an internal pressure of 16 ⁇ 10 5 Pa (16 bar) being established.

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• 1997
  • 1997-12-22 JP JP52959398A patent/JP2001508391A/ja active Pending
  • 1997-12-22 KR KR1019997005811A patent/KR20000062340A/ko not_active Application Discontinuation
  • 1997-12-22 AU AU57628/98A patent/AU5762898A/en not_active Abandoned
  • 1997-12-22 US US09/331,919 patent/US6706443B1/en not_active Expired - Fee Related
  • 1997-12-22 CA CA002276301A patent/CA2276301A1/en not_active Abandoned
  • 1997-12-22 WO PCT/EP1997/007228 patent/WO1998029342A1/de not_active Application Discontinuation
  • 1997-12-22 EP EP97953902A patent/EP0950023A1/de not_active Withdrawn
  • 1997-12-29 TW TW086119919A patent/TW446685B/zh active

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