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
  • H01M4/13—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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/40—Nickelates
  • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
  • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
  • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/06—Treatment with inorganic compounds
  • C09C3/063—Coating
• • 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
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D15/00—Lithium compounds
  • C01D15/02—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G51/00—Compounds of cobalt
  • C01G51/40—Cobaltates
  • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
  • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
  • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
• • 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
• • 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
• • 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
• • 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 coated lithium mixed oxide particles for improving the high-temperature properties of electrochemical cells.
• the principle of operation of the lithium-ion battery is based on the fact that both the cathode and the anode materials can reversibly intercalate lithium ions. I.e. during charging, the lithium ions migrate out of the cathode, diffuse through the electrolyte and are intercalated in the anode. The same process takes place in the opposite direction when unloading. Because of this mode of operation, these batteries are also called “rocking chairs” or lithium-ion batteries.
• the resulting voltage of such a cell is determined by the lithium intercalation potentials of the electrodes.
• cathode materials that intercalate lithium ions at very high potentials and anode materials that intercalate lithium ions at very low potentials (vs. Li / Li + ).
• Cathode materials that meet these requirements are LiCo0 2 and LiNi0 2 , which have a layer structure, and LiMn 2 0 4 , which has a cubic spatial network structure. These compounds deintercalate lithium ions at potentials around 4V (vs Li / Li + ).
• certain carbon compounds such as. B. Graphite the requirement of low potential and high capacity.
• LiCo0 2 , LiNi0 2 and LiMn 2 0 4 are discussed and used for 4V cathodes.
• Mixtures are used as the electrolyte which, in addition to a conductive salt, also contain aprotic solvents.
• the most commonly used solvents are ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC).
• EC ethylene carbonate
• PC propylene carbonate
• DMC dimethyl carbonate
• DEC diethyl carbonate
• EMC ethyl methyl carbonate
• LiPF 6 is used almost without exception.
• Graphite is usually used as the anode.
• Cathode materials especially the lithium manganese spinel
• lithium manganese spinel is for the cathode
• a disadvantage of the spinel is its lower capacity and its insufficient high-temperature storage capacity and the associated poor cycle stability at high temperatures. The reason for this is considered to be the solubility of the divalent manganese in the electrolyte (Solid State Ionics 69 (1994) 59; J. Power Sources 66 (1997) 129; J. Electrochem. Soc. 144 (1997) 2178).
• the manganese is present in two oxidation states, namely trivalent and tetravalent.
• the LiPF 6 -containing electrolyte always contains water impurities. This water reacts with the conductive salt LiPF 6 to form LiF and acidic components, eg HF.
• One way to increase the stability of the spinel at high temperatures is to dope it.
• part of the manganese ions can be replaced by other, for example trivalent, metal cations.
• Antonini et al. report that spinels doped with gallium and chromium (e.g.
• Li 1.02 Gao . o 25 C-ro . o 25 Mn 1.95 ⁇ 4 ) at 55 ° C show satisfactory storage and cycle stability (J. Electrochem. Soc, 145 (1998) 2726).
• a layer for example a lithium borate glass (Solid State Ionics 104 (1997) 13).
• a spinel is placed in a methanolic solution of H 3 B0 3 , LiBO 2 * 8H 2 0 and LiOH * H 2 0 given and stirred at 50-80 ° C until the solvent has completely evaporated.
• the powder is then heated to 600-800 ° C to ensure the conversion into the borate. This improves the shelf life at high temperatures. However, no improved cycle stability was found.
• WO 98/02930 undoped spinels are treated with alkali metal hydroxide solutions.
• the treated spinel is then heated in a CO 2 atmosphere in order to convert the adhering hydroxides into the corresponding carbonates.
• the spinels modified in this way show improved high-temperature shelf life as well as improved cycle stability at high temperatures.
• the cathode and / or anode is coated in such a way that the active material is pasted onto the current conductor together with binder and a conductive material. Then a paste consisting of the
• Coating material, binder and / or solvent applied to the electrode Inorganic and / or organic materials which can be conductive are named as coating materials, e.g. B. Al 2 0 3 , nickel, graphite, LiF, PVDF etc. Lithium-ion batteries that contain electrodes coated in this way show high voltages and capacities as well as improved safety characteristics (EP 836238).
• the electrode paste (cathode material: lithium manganese spinel) is first produced and applied to the current conductor. Then the protective layer, consisting of a metal oxide and binder, is pasted onto the electrode.
• Metal oxides used are, for example, aluminum oxide, titanium oxide and zirconium oxide.
• JP 08236114 likewise first produces the electrode, preferably LiNi 0 5 C0 0.5 O 2 as the active material, and then one Oxide layer applied by sputtering, vacuum evaporation or CVD.
• JP 09147916 a protective layer consisting of solid oxide particles, for example MgO, CaO, SrO, Zr0 2 , Al 2 0 3 Si0 2 , and a polymer is applied to the side of the current collector that contains the electrode.
• a protective layer consisting of solid oxide particles, for example MgO, CaO, SrO, Zr0 2 , Al 2 0 3 Si0 2 , and a polymer is applied to the side of the current collector that contains the electrode.
• JP 09165984 Another way is described in JP 09165984.
• the lithium manganese spinel which is coated with boron oxide, serves as the cathode material. This coating is created during the spinel synthesis.
• a lithium, manganese and boron compound are calcined in an oxidizing atmosphere.
• the boron oxide-coated spinels obtained in this way show no manganese dissolution at high voltages.
• JP 08250120 is used for coating with sulfides, selenides and tellurides
• the object of the present invention is to provide electrode materials which do not have the disadvantages of the prior art and which have improved storage stability and cycle stability at high temperatures, in particular at temperatures above room temperature.
• the object according to the invention is achieved by lithium mixed oxide particles which are coated with one or more metal oxides.
• the invention also relates to a method for coating the lithium mixed oxide particles and the use in electrochemical cells, batteries and secondary lithium batteries.
• the present invention relates to undoped and doped mixed oxides as cathode materials selected from the group Li (MnMe z ) 2 0 4 , Li (CoMe z ) 0 2 , Li (Ni 1 - x - y Co x Me y ) 0 2 , where Me is at least is a metal cation from the groups Ila, lila, IVa, Ilb, Illb, IVb, VIb, Vllb, VIII of the periodic table.
• Particularly suitable metal cations are copper, silver, nickel, magnesium, zinc, aluminum, iron, cobalt, chromium, titanium and zircon, and also lithium for the spinel compounds.
• the present invention also relates to other lithium intercalation and insertion compounds which are suitable for 4V cathodes with improved high-temperature properties, in particular at temperatures above room temperature, their production and use, in particular as cathode material in electrochemical cells.
• the lithium mixed oxide particles are coated with metal oxides in order to obtain improved storage stability and cyclability at high temperatures (above room temperature).
• metal oxides in particular oxides or mixed oxides of Zr, Al, Zn, Y, Ce, Sn, Ca, Si, Sr, Mg and Ti and mixtures thereof, for example ZnO, CaO, SrO, Si0 2 , CaTi0 3 , are suitable as coating materials.
• Particle has some advantages over the coating of the electrode strips. If the electrode material is damaged, a large part of the active material can attack the coated tapes, while these undesired reactions remain highly localized when the individual particles are coated.
• the coating process achieves layer thicknesses between 0.03 ⁇ m and 5 ⁇ m. Preferred layer thicknesses are between 0.05 ⁇ m and 3 ⁇ m.
• the lithium mixed oxide particles can be coated one or more times.
• the coated lithium mixed oxide particles can be processed with the usual carriers and auxiliaries to 4V cathodes for lithium-ion batteries.
• the coating is carried out at the supplier so that the battery manufacturer does not have to make the process changes necessary for the coating.
• the undesirable reactions of the electrode material with the electrolyte are strongly inhibited, and thus an improvement in the shelf life and cycle stability at higher temperatures is achieved.
• the cathode material according to the invention can be used in secondary lithium-ion batteries with common electrolytes.
• electrolytes with conductive salts selected from the group LiPF 6 , LiBF 4 , LiCI0 4 , LiAsF 6 , LiCF 3 S0 3 , LiN (CF 3 S0 2 ) 2 or LiC (CF 3 S0 2 ) 3 and mixtures thereof are suitable.
• the electrolytes can too contain organic isocyanates (DE 199 44 603) to reduce the water content.
• the electrolytes can also contain organic alkali salts (DE 199 10 968) as an additive.
• Alkali borates of the general formula are suitable
• R 1 and R 2 are the same or different
• each individually or jointly having the meaning of an aromatic or aliphatic carbon, dicarbon or sulfonic acid radical, or in each case individually or jointly meaning an aromatic ring from the group consisting of phenyl, naphthyl and anthracenyl or phenanthrenyl, which can be unsubstituted or substituted one to four times by A or shark, or in each case individually or jointly the meaning of a heterocyclic aromatic ring from the group pyridyl, pyrazyl or bipyridyl, which is unsubstituted or mono- to triple by A or shark may be substituted, or in each case individually or jointly, have the meaning of an aromatic hydroxy acid from the group of aromatic hydroxy-carboxylic acids or aromatic hydroxy-sulfonic acids, which may be unsubstituted or substituted one to four times by A or shark, and
• A is alkyl with 1 to 6 carbon atoms, which can be halogenated one to three times.
• Alkaline alcoholates of the general formula are also suitable Li + OR " , in which R has the meaning of an aromatic or aliphatic carbon, dicarbon or sulfonic acid residue, or
• aromatic hydroxy acid from the group of aromatic hydroxy-carboxylic acids or aromatic hydroxy-sulfonic acids, which can be unsubstituted or substituted one to four times by A or shark,
• a alkyl with 1 to 6 carbon atoms which can be halogenated one to three times.
• R 1 and R 2 are the same or different, optionally connected directly to one another by a single or double formation, each individually or jointly the meaning of an aromatic Rings from the group phenyl, naphthyl, anthracenyl or
• Phenanthrenyl which is unsubstituted or one to six times by alkyl
• Alkyl (Ci to C 6 ), alkoxy groups (d to C 6 ) or halogen (F, Cl, Br) can be substituted,
• R 3 -R 6 can each have the following meaning individually or in pairs, optionally directly linked to one another by a single or double bond:
• alkyl (d to C 6 ), alkyloxy (d to C 6 ) or halogen (F, Cl, Br)
• Phenyl, naphthyl, anthracenyl or phenanthrenyl which can be unsubstituted or monosubstituted to sixfold substituted by alkyl (d to C 6 ), alkoxy groups (d to C 6 ) or halogen (F, Cl, Br),
• Pyridyl, pyrazyl or pyrimidyl which can be unsubstituted or mono- to tetrasubstituted by alkyl (d to C 6 ), alkoxy groups (d to C 6 ) or halogen (F, Cl, Br),
• the end product is isolated can be contained in the electrolyte.
• electrolytes can be compounds of the following formula (DE 199 41 566)
• A N, P, P (O), O, S, S (O), S0 2 , As, As (O), Sb, Sb (O)
• A can be enclosed in different positions in R 1 , R 2 and / or R 3 ,
• Kt can be enclosed in a cyclic or heterocyclic ring
• the groups bound to Kt can be the same or different
• D + selected from the group of alkali metals in a polar organic solvent with a salt of the general formula
• Kt, A, R 1 , R 2 , R 3 , k, I, x and y have the meaning given above and
• R 1 to R 5 are the same or different, optionally connected directly to one another by a single or double formation, each individually or jointly the meaning
• alkyl or alkoxy radical (d to C 8 ) which can be partially or completely substituted by F, Cl, Br,
• an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, optionally bonded via oxygen, which may be unsubstituted or monosubstituted to sixfold substituted by alkyl (d to C 8 ) or F, Cl, Br an aromatic heterocyclic ring, optionally bonded via oxygen, from the group pyridyl, pyrazyl or pyrimidyl, which may be unsubstituted or substituted one to four times by alkyl (d to C 8 ) or F, Cl, Br and
• R 6 to R 8 are the same or different, optionally connected directly to one another by a single or double bond, each individually or jointly the meaning
• a hydrogen or the meaning as R 1 to R 5 prepared by reacting a corresponding boron or phosphorus-Lewis acid solvency adduct with a lithium or tetraalkylammonium imide, methanide or triflate can be used.
• borate salts (DE 199 59 722) of the general formula
• M is a metal ion or tetraalkylammonium ion
• R 1 to R 4 may be the same or different, optionally by means of a single or double bond directly bonded alkoxy or carboxy radicals (CC 8 ).
• These borate salts are prepared by reacting lithium tetraalcoholate borate or a 1: 1 mixture of lithium alcoholate with a boric acid ester in an aprotic solvent with a suitable hydroxyl or carboxyl compound in a ratio of 2: 1 or 4: 1.
• cathode materials in particular materials with a layer structure (for example Li (CoMe z ) 0 2 or Li (Ni 1. X - y Co x Me y ) 0 2 ) and spinels (for example Li (MnMe z ) 2 0 4 ) suspended in polar organic solvents such as alcohols, aldehydes, halides or ketones, spinels also in water and placed in a reaction vessel.
• polar organic solvents such as alcohols, aldehydes, halides or ketones
• spinels also in water and placed in a reaction vessel.
• the materials can also be suspended in non-polar organic solvents, such as cycloalkanes or aromatics.
• the reaction vessel can be heated and is equipped with a stirrer. The reaction solution is heated to temperatures between 10 and 100 ° C, depending on the boiling point of the solvent.
• Soluble metal salts selected from the group of zirconium, aluminum, zinc, yttrium, cerium, tin, calcium, silicon, strontium, titanium and magnesium salts and their mixtures, which are in organic solvents, are used as the coating solution , or water are soluble. Acids, bases or water are suitable as the hydrolysis solution, depending on the solvent used for the coating solution.
• the coating solution and the hydrolysis solution are slowly metered in.
• the dosing quantities and speeds depend on the desired layer thicknesses and the metal salts used.
• the hydrolysis solution is added in excess.
• the solution is filtered off and the powder obtained is dried.
• the dried powder In order to ensure complete conversion into the metal oxide, the dried powder must still be calcined.
• the powder is heated to 400 ° C. to 1000 ° C., preferably 700 to 850 ° C., and kept at this temperature for 10 minutes to 5 hours, preferably 20 to 60 minutes.
• the particles can be coated one or more times. If desired, the first coating can be carried out with a metal oxide and the next coatings with the oxides of other metals.
• Tetrapropyl orthozirconate (26.58 g), which is dissolved in ethanol (521.8 ml), serves as the coating solution.
• Water (14.66 g) is used as the hydrolysis solution. Both solutions are slowly added. The addition of zirconium propylate is complete after approx. 6.5 hours. To ensure that the hydrolysis reaction also takes place quantitatively, water (36.4 g) is added for the further hydrolysis for a further 16.2 hours.
• the ethanolic solution is filtered off and the powder obtained is dried at about 100.degree. To ensure complete conversion into the Zr0 2 , the dried powder must still be calcined. After drying, the powder is therefore heated to 800 ° C. and kept at this temperature for 30 minutes.
• Electrolyte mixed (LP600 Selectipur ® from Merck, EC: DEC: PC 2: 1: 3 1M LiPF 6 ).
• the aluminum bottles are then sealed gas-tight. These preparations are all carried out in an argon-flushed glove box.
• the bottles prepared in this way are then removed from the glove box and stored in a drying cabinet at 80 ° C. for 6 or 13 days.
• the aluminum bottles cooled to room temperature are reinserted into the glove box and opened there.
• the electrolyte is filtered off and the amount of manganese dissolved in the electrolyte is determined quantitatively by means of ICP-OES.
• Table 1 compares the analytical results of the uncoated and coated lithium manganese spinels.
• the cathode powder is mixed well with 15% conductive carbon black and 5% PVDF (binder material).
• the paste thus produced is applied to an aluminum mesh, which serves as a current conductor, and dried overnight at 175 ° C. under an argon atmosphere and under reduced pressure.
• the dried electrode is introduced into the glove box flushed with argon and the measuring cell is installed.
• Lithium metal serves as the counter and reference electrode.
• LP 50 Selectipur ® from Merck is used as the electrolyte (1 M LiPF 6 in EC: EMC 50: 50% by weight).
• the measuring cell with the electrodes and the electrolyte is placed in a steel container, which is sealed gas-tight.
• the cell produced in this way is removed from the glove box and placed in a climatic cabinet which is set to 60 ° C. After connecting the measuring cell to one

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• 1999
  • 1999-05-15 DE DE19922522A patent/DE19922522A1/de not_active Withdrawn
• 2000
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