WO2012000123A1 - Lithium metal aryloxide clusters as starting products for oxide materials - Google Patents

Lithium metal aryloxide clusters as starting products for oxide materials Download PDF

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WO2012000123A1
WO2012000123A1 PCT/CH2011/000149 CH2011000149W WO2012000123A1 WO 2012000123 A1 WO2012000123 A1 WO 2012000123A1 CH 2011000149 W CH2011000149 W CH 2011000149W WO 2012000123 A1 WO2012000123 A1 WO 2012000123A1
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compound
coli
lithium
thf
solvent
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PCT/CH2011/000149
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French (fr)
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Katharina M. Fromm
Aurélien CROCHET
Jean-Pierre Brog
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University Of Fribourg
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • 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 method for producing lithium metal oxide materials in particular for the use in electrodes and batteries as well as to a method for producing a precursor for the production of lithium metal oxide materials. Further, the invention relates to the use of this precursor for producing lithium metal oxide materials.
  • batteries include primary batteries, i.e. batteries designed for use through a single charging cycle, and secondary batteries designed to be rechargeable. Some batteries designed essentially as primary batteries may be rechargeable to some extent. Batteries based on lithium have been the subject of considerable development effort and are being sold commercially. Lithium-based batteries generally use electrodes for these batteries which can include lithium metal or alloy (lithium batteries), or compositions that intercalate lithium (lithium ion batteries).
  • compositions that intercalate lithium for use in the positive electrodes, generally are chalcogenides such as metal oxides that incorporate the lithium ions into their lattice.
  • the oxides Li 0 2 where M represents cobalt or nickel, are used as cathode materials of lithium batteries.
  • the cathode half reaction is: LiCo0 2 ⁇ Li ⁇ CoOz + x Lr + x e "
  • lithium metal oxides such as lithium cobalt oxides, lithium nickel oxides and derivatives thereof have been noted as promising materials for use in positive electrodes for lithium-based batteries.
  • lithium titanium oxides have been considered as promising materials for use in negative electrodes for lithium-based secondary batteries.
  • These lithium metal oxides are useful for the production of lithium-based secondary batteries.
  • oxide materials can be achieved by organo-metallic synthesis using alkali aryloxide reagents. The use of alkali aryloxide reagents in organo-metallic synthesis often depends on their solubility, a property derived from their structure.
  • alkali aryloxides also resides in the discovery of high-temperature superconducting compounds which has generated a great interest in the formation of oxide materials and other ceramics.
  • oxide materials many alkoxides of yttrium and copper are common precursors for oxide materials.
  • heterobimetallic alkoxides has provided a facile route for obtaining soluble, volatile, and generally monomeric species. These heterobimetallic complexes can thus serve as valuable precursors for making metal oxides.
  • solv can either be THF (tetrahydrofuran) or pyridine, "Me” stands for a metal and “Ar” stands for an aryl group. With this method it is possible to synthesize some precursor for lithium cobalt oxide.
  • lithium cobalt oxide is synthesized as powder from a heating of a stoechiometric mixture of Li + and M 2+ salts (ex. LiOH and Co(OH) 2 or Li 2 C0 3 and CoC0 3 or C0 3 O 4 ) at 600 °C under 0 2 for 12 h, followed by two subsequent heat-treatments at 400°C and 900 °C under 0 2 .
  • Li + and M 2+ salts ex. LiOH and Co(OH) 2 or Li 2 C0 3 and CoC0 3 or C0 3 O 4
  • this oxide is synthesized as powder from stoichiometric mixtures of Li 2 C0 3 and Co 3 0 4 at 600 °C under O z for 12 h, followed by two subsequent thermal treatments at 900 °C under 0 2 for 24 h and 12 H.
  • the first heat-treatment gives the compound LT-LiCo0 2 (where LT denotes low temperature) and the second HT-LiCo0 2 (where HT denotes high temperature) which is more stable to charging and discharging.
  • LT denotes low temperature
  • HT HT denotes high temperature
  • Prior art I The synthesis of the two starting products is rather complicated and requires expensive starting materials and inert gas conditions during synthesis, which complicates the synthesis of these precursors.
  • Prior art II The synthesis is complicated, takes only place at high temperatures and therefore requires much energy. Further, the starting materials are expensive.
  • Another object of the present invention is to present a method for producing a precursor compound for the production of lithium metal oxide materials.
  • a compound of the formula [(M') a (Li) b (OR) c (L) d ] n is used for the production of lithium metal oxide materials, where M 1 is a metal, a and b are integers equal or bigger than one, OR is an alkyl, aryl, alkoxy and/or aryloxide group, c is an integer such that the compound has an overall charge of zero, L is a neutral ligand who coordinate the lithium ion or ions, d is an integer such that lithium ion or ions are well coordinated and n is the degree of polymerization of the compound.
  • the compound is heated to get a powder, in particular a powder comprising nanoparticles of the oxide material.
  • a powder in particular a powder comprising nanoparticles of the oxide material.
  • metal refers to a metal of any one group of the periodic table in the form of its cation (i.e. positive ion).
  • alkyl, aryl, alkoxide and/or aryloxide group refers to an aliphatic or aromatic group, optionally with an alcoholate function, the aromatic group may be substituted (mono- or poly-) or unsubstituted, fused or unfused. Suitable substituents include halo-, alkoxy, nitro-, an alkyl group, or cyclic groups. The aliphatic group may also be substituted in any other way.
  • the term "and/or" between the last two compounds of a list of compounds separated by comma denotes an arbitrarily subset of the list of compounds. In particular, the list can be read as if each comma is replaced by the term "and/or”.
  • solvent refers to a molecule that is able to coordinate the lithium ions in compound of the formula [(M 1 ) a (Li) b (OR) c (L) d ] n .
  • the degree of polymerization n is defined by the parameters of synthesis, i.e. by the temperature and by the selection of the subcompounds, i.e. metal M 1 , alkoxide and/or aryloxide group OR and ligand L. Therefore, it can vary in broad range. However, if e.g. THF is used as a ligand, n is one, i.e. the formula is not polymeric, but a discrete structure.
  • M is one ore more of cobalt, nickel, titanium, manganese; and/or OR is one of phenolate (OPh), 2-methylphenolate (oMP), 2,6-dimethylphenolate (oDMP), 2- isopropylphenolate (oPP) and 2,6-diisopropylphenolate (oDIP); and/or L is one of tetrahydrofuran (THF), dioxane, pyridine, dimethoxyethane (glyme), tetramethylethylenediamme (TMEDA) and tert-butoxide (O'Bu).
  • THF tetrahydrofuran
  • dioxane dioxane
  • pyridine dimethoxyethane
  • TEDA tetramethylethylenediamme
  • O'Bu tert-butoxide
  • the alkoxides or aryloxides are bound to the metal M 1 .
  • the invention is not restricted to the above mentioned metals.
  • suitable metals which can be used for a compound of the formula [(M 1 ) a (Li) b (OR) c (L) d J n .
  • other OR's and ligands L can be suitable to built the compound of the formula [(M 1 ) a (Li) b (OR) c (L) d ] n , as the skilled person interpolate the above mentioned list.
  • the said compound is selected from the following:
  • the invention is not restricted to the above mentioned list.
  • the list shows compounds, which have been determined experimentally as to be particularly appropriate for the production of lithium metal oxide.
  • cobalt was experimentally shown as a metal with outstanding properties for this synthesis.
  • the ligands THF, TMEDA, glyme, dioxane and pyridine are commercial available in large quantity and therefore cheap.
  • OPh, oMP, oDMP, oPP, oDIP and O'Bu are also commercial available or easy and cheap to synthetisize and comprise optimal chemical properties for bounding cobalt.
  • alkoxides or aryloxides with the ligands depends on the steric structure of both.
  • OPh can be almost generally combined with ligands to achieve an optimal compound for the synthesis of lithium metal oxide, except with pyridine, which combination is less optimal.
  • oMP, oDMP, oPP and oDIP have been shown as being optimal coordinated by THF or pyridine.
  • the compound is heated to a temperature between 300 and 700°C, preferably between 400 and 600°C, more preferably between 450 and 550°C.
  • the heating temperature is significant lower and therefore the inventive method can be established in a energy and cost saving manner.
  • the temperature can also be different, e.g. higher or lower than mentioned above.
  • the optimal temperature is dependent of the compound which is heated.
  • Advantageously heating is established in air. This allows for a simple and cheap synthesis of the compound of the formula [(M 1 ) a (Li) b (OR) c (L) d ] n . In particular, costly inert gas conditions can be avoided.
  • the air is enriched by oxygen.
  • the synthesis can be more efficient.
  • the oxygen enrichment can also be omitted.
  • the compound is heated for 6 to 18h, preferably for 9 to 15h, more preferably for 1 1 to 13h.
  • the heating time period can further depend on the batch size and can therefore also differ from afore mentioned time periods. These time periods are typically for a laboratory scale. The skilled person would be able to adapt the time period according to the batch size, if required.
  • the powder is washed.
  • the concentration of lithium metal oxide material in the powder can be increased; in particular it can be purified.
  • the raw powder can be dissolved in a solvent, which does only solve one of the compound or the impurities. After the suspension is filtered and either the bulk is dried or the solvent is evaporated to get the purified powder.
  • the skilled person knows also other methods for separating mixtures of substances.
  • the washing is performed with water.
  • water is a cheap solvent which further is nonhazardous, i.e. incombustible etc. and nontoxic, i.e. ecological in use.
  • other washing solvent can be used, advantageously a polar solvent like a short chained alcohol, carbonic acid and similar solvents. Alcohol would have the advantage that drying needs less energy, however they are typically combustible and more expensive than water.
  • the washing is performed at least twice. Experiments have shown that washing twice results in an acceptable purity of the lithium metal oxide material. Depending on the required purity of the lithium metal oxide material, also further washings can take place. Further also different solvents can be used for the at least two washing procedures.
  • the lithium metal oxide material bulk is dried. Drying can be established by heating, where the heating temperature depends on the solvent in the bulk, in particular on the boiling point of the solvent. Clearly, also other method for drying can be used, i.e. vacuum evaporation etc. Further procedures can also be useful to purify the lithium metal oxide material. After purification, also other processing can take place, like milling etc.
  • the byproduct in particular lithium carbonate
  • the byproduct is recuperated after the washing.
  • lithium carbonate is produced during the synthesis of the lithium metal oxide as a byproduct.
  • lithium carbonate is washed by a solvent and recuperated.
  • the washed and recuperated lithium carbonate can be parallel formatted as antidepressiva or used in other applications.
  • a method for producing a compound of the formula [(M 1 ) a (Li) b (OR) c (L) d ] n where M 1 is a metal, a and b are integers equal or bigger than one, OR is an alkyl, aryl, alkoxy and/or aryloxide group, c is an integer such that the compound has an overall charge of zero, L is an a neutral ligand who coordinate the lithium ion or ions, d is an integer such that lithium ion or ions are well coordinated and n is the degree of polymerization of the compound, is established by adding MX y to (Li) b (OR) c , where X is a halogen.
  • a simple inexpensive method for producing the precursour can be established.
  • M MX y is added to (Li) b (OR) c ,and disolved in a first solvent to get a mixture thereof.
  • the mixture is heated to get a solution thereof.
  • other methods to achieve a solution e.g. stirring, shaking or vibrating.
  • the solution is achieved by both, stirring and heating.
  • the solution is filtered and evaporated.
  • the filtration and the evaporation takes place after the mixture has been heated.
  • M is cobalt.
  • other metals can be used, as mentioned before.
  • OR is aryloxide, preferably phenoxide.
  • other substaces can be used for OR, in particular the afore mentioned substances.
  • the mixture is stirred and heated preferably between 10 and 60 minutes, more preferably for about 30 minutes.
  • time periods have been determined in a laboratory scale. The time period can depend on the batch size and may vary also in dependence of the used substances (e.g. solvent etc.).
  • the first solvent is THF or dioxane.
  • suitable solvents which can be used instead of THF and dioxane.
  • the invention is not restricted to these solvents.
  • the first solvent is replaced by a second solvent
  • the first solvent is THF and the second solvent is one of dioxane or TMEDA.
  • the replacement can be established by e.g. evaporating the first solvent and dissolving the remaining solid in the second solvent.
  • the compound of formula [(M 1 ) a (Li) b (OR)c(L) d ]n is used as starting product for elaboration of lithium metal oxide, wherein M 1 is a metal; a and b are integers equal or bigger than one; OR is alkyl, aryl, alkoxy and/or aryloxide group; c is an integer such that the compound has an overall charge of zero; L is an a neutral ligand who coordinate the lithium ion or ions; d is an integer such that lithium ion or ions are well coordinated; n is the degree of polymerization of the compound.
  • said lithium metal oxide is used for elaboration of lithium metal oxide nanoparticles.
  • the nanoparticles have a diameter range between 1 and 2500 nm (nanometers), preferably between 1 and 1000 nm, more preferably between 1 and 250 nm.
  • the preferred diameter of the nanoparticles depends on the use of them.
  • lithium metal oxide is used for electrodes and/or batteries.
  • other suitable applications are conceivable.
  • Other advantageous embodiments and combinations of features come out from the detailed description below and the totality of the claims.
  • the syntheses of LiM0 2 starts by the preparation of aryloxide cluster of transition and alkali metal ions. This cluster is burned at 400°C in an air flow to give HT- LiM0 2 , where HT stands for "high tempereature".
  • OR is defined as above and X represents halogen ions.
  • solvent refers to a molecule that is able to coordinate the lithium ions in the compound.
  • the by-product Li 2 C0 3 can be easily washed out with water and recycled, while the HT- phase of LiM0 2 (lithium metal oxide) is recovered as pure product.
  • Example 1 One equivalent of CoCI 2 is dissolved in 4 equivalents of lithium phenoxide in solution of THF. The mixture is stirred and heated to reflux for 30 min, then the solution is filtered and evaporated to dryness. The bulk material is compound of formula [CoLi 2 (OPh) 4 (THF) 4 ] .
  • CoCI 2 is dissolved in 4 equivalent of lithium phenoxide in solution of dioxane. The mixture is stirred and heated to reflux for 30 min, then the solution is filtered and evaporated to dryness. The bulk material is compound of formula [CoLi 2 (OPh) 4 (dioxane) 3 ] n .
  • CoCI 2 is dissolved in 4 equivalents of lithium phenoxide in solution of THF. The mixture is stirred and heated to reflux for 30 min. The solvent is evaporated to dryness. The solid was dissolved in dioxane, heated to reflux, filtered and evaporated to dryness. The bulk material is compound of formula [CoLi 2 (OPh) 4 (dioxane) 3 ] n .
  • the chemical structure is the same as displayed in example 2 above.
  • CoCI 2 is dissolved in 4 equivalents of lithium phenoxide in solution of THF. The mixture is stirred and heated to reflux for 30 min. The solution is evaporated to dryness. The solid was dissolved in TMEDA, heated to reflux, filtered and evaporated to dryness. The bulk material is compound of general formula [CoLi 2 (OPh) 4 (T EDA) z ].
  • M MX y (solvent 1 ) z is added to "2y" equivalent of e.g. lithium aryloxide, LiOAr, dissolved in solvent 1 or in another solvent.
  • the mixture is stirred and heated to reflux for 30 min, after which the solution is filtered to eliminate the produced LiX, and evaporated to dryness.
  • the bulk material is compound of general formula [(M') a (Li) b (OR) c (L) d ] n .
  • MX y (solvent 1 ) z is added to "2y" equivalent of e.g. lithium aryloxide, LiOAr, dissolved in solvent 1 or in another solvent.
  • the mixture is stirred and heated to reflux for 30 min, after which the solution is filtered to eliminate the produced LiX. After that, the solution is crystallized.
  • the crystallized material is the corresponding compound of general formula [(M 1 ) a (Li) b (OR) c (L) d ] n .
  • Drying can generally be established by combusting in an oven under atmospheric air. However, also spin-coating can be used for drying the compound instead of an oven. Also further methods for drying, known by the skilled person, could be feasible.
  • the production of the compound of general formula [(M 1 )-(Li) b (OR) c (L) d ] n is not limited to the above described Examples. The skilled person is able to vary the synthesis according to the mentioned variations in the summary of the invention.
  • Example 2 [CoLi 2 (OPh) 4 (THF) 4 ] is heated to 450°C at air during 12 h to give grey powder. This powder is washed twice with water and the resulting black powder is HT-LiCo0 2 . Structural anaylsis of LiCo0 2 can be performed using XPD (x-ray photoelectron diffraction).
  • the temperature is not limited to 450°C. Also other temperatures can give the desired product. However, experiments have shown, that around 450°C the reaction rate as well as the time duration of the reaction is in an acceptable range.

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Abstract

A alternative method for producing lithium metal oxide materials in particular for the use in electrodes and batteries is presented, where a compound of the formula [(M1)a(Li)b(OR)c(L)d]n is used, where M1 is a metal, OR is an alkyl, aryl, alkoxy and/or aryloxide group, c is an integer such that the compound has an overall charge of zero, L is an a neutral ligand who coordinate the lithium ions, d is an integer such that lithium ions are well coordinated and n is the degree of polymerization of the compound. The compound is heated to get a powder thereof, in particular a powder comprising nanoparticles of the lithium metal oxide material. Further, a method for producing the compound of formula [(M1)a(Li)b(OR)c(L)d]n is presented, where MXy is added to (Li)b(OR)c, where X is a halogen.

Description

LITHIUM METAL ARYLOXIDE CLUSTERS AS
STARTING PRODUCTS FOR OXIDE MATERIALS
Technical Field
The invention relates to a method for producing lithium metal oxide materials in particular for the use in electrodes and batteries as well as to a method for producing a precursor for the production of lithium metal oxide materials. Further, the invention relates to the use of this precursor for producing lithium metal oxide materials. Background Art
The microminiaturization of electronic components has created widespread growth in the use of portable electronic devices such as cellular phones, pagers, video cameras, facsimile machines, portable stereophonic equipment, personal organizers and personal computers. The growing use of portable electronic equipment has created an ever increasing demand for improved power sources for these devices. Relevant batteries include primary batteries, i.e. batteries designed for use through a single charging cycle, and secondary batteries designed to be rechargeable. Some batteries designed essentially as primary batteries may be rechargeable to some extent. Batteries based on lithium have been the subject of considerable development effort and are being sold commercially. Lithium-based batteries generally use electrodes for these batteries which can include lithium metal or alloy (lithium batteries), or compositions that intercalate lithium (lithium ion batteries). Preferred electroactive materials for incorporation into the positive electrodes are compositions that intercalate lithium. The compositions that intercalate lithium, for use in the positive electrodes, generally are chalcogenides such as metal oxides that incorporate the lithium ions into their lattice.
Among others, the oxides Li 02, where M represents cobalt or nickel, are used as cathode materials of lithium batteries. For lithium batteries using LiCo02, the cathode half reaction is: LiCo02 <→ Li^CoOz + x Lr + x e"
A variety of lithium metal oxides, such as lithium cobalt oxides, lithium nickel oxides and derivatives thereof have been noted as promising materials for use in positive electrodes for lithium-based batteries. Similarly, lithium titanium oxides have been considered as promising materials for use in negative electrodes for lithium-based secondary batteries. These lithium metal oxides are useful for the production of lithium-based secondary batteries. Because of the interest in lithium metal oxides, several approaches have been developed for producing lithium metal oxide powders. Such oxide materials can be achieved by organo-metallic synthesis using alkali aryloxide reagents. The use of alkali aryloxide reagents in organo-metallic synthesis often depends on their solubility, a property derived from their structure. The regain of interest of alkali aryloxides also resides in the discovery of high-temperature superconducting compounds which has generated a great interest in the formation of oxide materials and other ceramics. Thus, many alkoxides of yttrium and copper are common precursors for oxide materials. Moreover, the synthesis of heterobimetallic alkoxides has provided a facile route for obtaining soluble, volatile, and generally monomeric species. These heterobimetallic complexes can thus serve as valuable precursors for making metal oxides.
Prior art I
In 2004, Buzzeo et al. published some homoleptic cobalt phenolate compounds of the type K2[Co(OAr)4] (OAr = OC6F5 " or 3,5-OC6H3(CF3)2 ), in which the effect of fluorination of phenoxide on (K18C6)2[Co(OAr)4] was investigated (M. C. Buzzeo et. al., inorg. chem.. 2004, 43, 7709 - 7725). In 2003, Boyle et. al published some lithium cobalt double aryloxide compounds, and nanoparticles of LiCo02 were generated by injection of a solution of this compound into boiling methyl-imidazole (Melm/H20 95:5) (T. J. Boyle et. al., Chem. Mater. 2003, 15, 3903 - 3912). These complexes of lithium cobalt aryloxides are synthesized by reaction between LiN(SiMe3)2 and Co(N(SiMe3)2)2 in THF and an aryl alcohol is added after, 2-methylphenol (oMP), 2-isopropylphenol (oPP), 2,6-dimethylphenol (oDMP), 2,6- diispropylphenol (oDIP).
2Li[N(SiMe3 ) 2 ] + Co[N(SiMe3 ) 2 ]2 + 6HOAr so,v > Co[(/ - OAr) 2 Li(solv) 2 ]2
In the above mentioned equation, "solv" can either be THF (tetrahydrofuran) or pyridine, "Me" stands for a metal and "Ar" stands for an aryl group. With this method it is possible to synthesize some precursor for lithium cobalt oxide.
Prior art II
Classically, lithium cobalt oxide is synthesized as powder from a heating of a stoechiometric mixture of Li+ and M2+ salts (ex. LiOH and Co(OH)2 or Li2C03 and CoC03 or C03O4) at 600 °C under 02 for 12 h, followed by two subsequent heat-treatments at 400°C and 900 °C under 02.
According to S.-H. Yang, L. Croguennec, C. Delmas, E. C. Nelson and M. A. O'Keefe, Nat. Mater., 2003, 2, 464 - 467, this oxide is synthesized as powder from stoichiometric mixtures of Li2C03 and Co304 at 600 °C under Oz for 12 h, followed by two subsequent thermal treatments at 900 °C under 02 for 24 h and 12 H.
The first heat-treatment gives the compound LT-LiCo02 (where LT denotes low temperature) and the second HT-LiCo02 (where HT denotes high temperature) which is more stable to charging and discharging. The synthesis is thus time consuming, expensive and costly in energy.
The known synthesis of lithium metal oxide materials have the following disadvantages:
Prior art I: The synthesis of the two starting products is rather complicated and requires expensive starting materials and inert gas conditions during synthesis, which complicates the synthesis of these precursors. Prior art II: The synthesis is complicated, takes only place at high temperatures and therefore requires much energy. Further, the starting materials are expensive.
Summary of the invention
It is the object of the invention to create an alternative, in particular cost saving method to form lithium metal oxide materials. Another object of the present invention is to present a method for producing a precursor compound for the production of lithium metal oxide materials.
The solution of the invention is specified by the features of claim 1. According to the invention a compound of the formula [(M')a(Li)b(OR)c(L)d]n is used for the production of lithium metal oxide materials, where M1 is a metal, a and b are integers equal or bigger than one, OR is an alkyl, aryl, alkoxy and/or aryloxide group, c is an integer such that the compound has an overall charge of zero, L is a neutral ligand who coordinate the lithium ion or ions, d is an integer such that lithium ion or ions are well coordinated and n is the degree of polymerization of the compound. The compound is heated to get a powder, in particular a powder comprising nanoparticles of the oxide material. As used herein, the term "metal" refers to a metal of any one group of the periodic table in the form of its cation (i.e. positive ion).
As used herein the term "alkyl, aryl, alkoxide and/or aryloxide group" refers to an aliphatic or aromatic group, optionally with an alcoholate function, the aromatic group may be substituted (mono- or poly-) or unsubstituted, fused or unfused. Suitable substituents include halo-, alkoxy, nitro-, an alkyl group, or cyclic groups. The aliphatic group may also be substituted in any other way.
As used herein, the term "and/or" between the last two compounds of a list of compounds separated by comma denotes an arbitrarily subset of the list of compounds. In particular, the list can be read as if each comma is replaced by the term "and/or". As used herein the term "solvent" refers to a molecule that is able to coordinate the lithium ions in compound of the formula [(M1)a(Li)b(OR)c(L)d]n.
The degree of polymerization n is defined by the parameters of synthesis, i.e. by the temperature and by the selection of the subcompounds, i.e. metal M1, alkoxide and/or aryloxide group OR and ligand L. Therefore, it can vary in broad range. However, if e.g. THF is used as a ligand, n is one, i.e. the formula is not polymeric, but a discrete structure.
The use of a compound of the formula [(Iv ^LiyORJciL - allows for a simple, inexpensive and time-saving synthesis of lithium metal oxide materials at relatively low temperatures. The lithium metal oxide materials is easy to separate from byproducts. The byproducts may find further use. Finally, the starting materials for the compound of the formula l(M1)a(Li)b(OR)c(L)d]n are cheap and easy to synthetisize.
Preferably, M is one ore more of cobalt, nickel, titanium, manganese; and/or OR is one of phenolate (OPh), 2-methylphenolate (oMP), 2,6-dimethylphenolate (oDMP), 2- isopropylphenolate (oPP) and 2,6-diisopropylphenolate (oDIP); and/or L is one of tetrahydrofuran (THF), dioxane, pyridine, dimethoxyethane (glyme), tetramethylethylenediamme (TMEDA) and tert-butoxide (O'Bu). Preferably the alkoxides or aryloxides are bound to the metal M1. These substances are commercial available. Therefore strategies of synthesis of these substances are omitted. However, the synthesis of this compound is further discussed in detail below as an other aspect of the invention.
The invention is not restricted to the above mentioned metals. The skilled person knows other suitable metals which can be used for a compound of the formula [(M1)a(Li)b(OR)c(L)dJn. Also other OR's and ligands L can be suitable to built the compound of the formula [(M1)a(Li)b(OR)c(L)d]n, as the skilled person interpolate the above mentioned list. Advantageously the said compound is selected from the following:
[CoLi2(OPh)4(THF)4]
[CoLi2(OPh)4(TMEDA)2]
[CoLi2(OPh)4(glyme)2] n
[CoLi2(OPh)4(dioxane)3]n
[CoLi2(oMP)4(THF)4]
[CoLi2(oMP)4(pyridine)4] n
[CoLi2(oDMP)4(THF)4]
[CoLi2(oDMP)4(pyridine)4] n
[CoLi2(oPP)4(THF)4]
[CoLi2(oPP)4(pyridine)4] n
[CoLi2(oDIP)4(THF)2]
[CoLi2(oDIP)4(pyridine)2] n
[Co2Li2(OPh)4(OtBu)2(THF)4]
[Co.LyO'Bu^THF),]
The invention is not restricted to the above mentioned list. However, the list shows compounds, which have been determined experimentally as to be particularly appropriate for the production of lithium metal oxide. Out of the list of cobalt, nickel, titanium and manganese; cobalt was experimentally shown as a metal with outstanding properties for this synthesis. Further, the ligands THF, TMEDA, glyme, dioxane and pyridine are commercial available in large quantity and therefore cheap. Finally, OPh, oMP, oDMP, oPP, oDIP and O'Bu are also commercial available or easy and cheap to synthetisize and comprise optimal chemical properties for bounding cobalt. The combination of alkoxides or aryloxides with the ligands depends on the steric structure of both. OPh can be almost generally combined with ligands to achieve an optimal compound for the synthesis of lithium metal oxide, except with pyridine, which combination is less optimal. oMP, oDMP, oPP and oDIP have been shown as being optimal coordinated by THF or pyridine.
A skilled person who takes into account the list above will be able to amend it by other suitable formulas. Also other parts can be found to produce said compound which can be used for the synthesis of lithium metal oxide materials. E.g. as a neutral donor ligand L also a crown ether or other ligands known by the skilled person can be used. There are also a further suitable alkyl, aryl, alkoxy and/or aryloxides (OR) or metals ( 1) which can be used in a compound of the formula [(M1)a(Li)b(OR)c(L)d]n.
In a preferred embodiment, the compound is heated to a temperature between 300 and 700°C, preferably between 400 and 600°C, more preferably between 450 and 550°C. By comparing with the prior art, the heating temperature is significant lower and therefore the inventive method can be established in a energy and cost saving manner.
The temperature can also be different, e.g. higher or lower than mentioned above. The optimal temperature is dependent of the compound which is heated. Advantageously heating is established in air. This allows for a simple and cheap synthesis of the compound of the formula [(M1)a(Li)b(OR)c(L)d]n. In particular, costly inert gas conditions can be avoided.
However, also other gases can be suitable to establish the heating.
According to a preferred embodiment, the air is enriched by oxygen. Therewith, the synthesis can be more efficient.
Alternatively, the oxygen enrichment can also be omitted. Preferably the compound is heated for 6 to 18h, preferably for 9 to 15h, more preferably for 1 1 to 13h. The heating time period can further depend on the batch size and can therefore also differ from afore mentioned time periods. These time periods are typically for a laboratory scale. The skilled person would be able to adapt the time period according to the batch size, if required.
Advantageously, the powder is washed. By washing the powder, the concentration of lithium metal oxide material in the powder can be increased; in particular it can be purified. There are several methods for separating a mixture of substances. The raw powder can be dissolved in a solvent, which does only solve one of the compound or the impurities. After the suspension is filtered and either the bulk is dried or the solvent is evaporated to get the purified powder. However, the skilled person knows also other methods for separating mixtures of substances.
In a preferred embodiment, the washing is performed with water. This has the advantage, that water is a cheap solvent which further is nonhazardous, i.e. incombustible etc. and nontoxic, i.e. ecologic in use. However, also other washing solvent can be used, advantageously a polar solvent like a short chained alcohol, carbonic acid and similar solvents. Alcohol would have the advantage that drying needs less energy, however they are typically combustible and more expensive than water.
Preferably the washing is performed at least twice. Experiments have shown that washing twice results in an acceptable purity of the lithium metal oxide material. Depending on the required purity of the lithium metal oxide material, also further washings can take place. Further also different solvents can be used for the at least two washing procedures.
However, depending on the amount of water used for the washing, also a single washing procedure could be enough; but in this case, the yield would be probably smaller. Advantageously, after the washing the lithium metal oxide material bulk is dried. Drying can be established by heating, where the heating temperature depends on the solvent in the bulk, in particular on the boiling point of the solvent. Clearly, also other method for drying can be used, i.e. vacuum evaporation etc. Further procedures can also be useful to purify the lithium metal oxide material. After purification, also other processing can take place, like milling etc.
Advantageously, the byproduct, in particular lithium carbonate, is recuperated after the washing. Typically, lithium carbonate is produced during the synthesis of the lithium metal oxide as a byproduct. After the synthesis, lithium carbonate is washed by a solvent and recuperated. Furthermore, the washed and recuperated lithium carbonate can be parallel formatted as antidepressiva or used in other applications. Therewith, an economic and ecologic production of lithium metal oxide material can be established and an amount of waste can be minimized. Preferably a method for producing a compound of the formula [(M1)a(Li) b(OR)c(L)d]n, where M1 is a metal, a and b are integers equal or bigger than one, OR is an alkyl, aryl, alkoxy and/or aryloxide group, c is an integer such that the compound has an overall charge of zero, L is an a neutral ligand who coordinate the lithium ion or ions, d is an integer such that lithium ion or ions are well coordinated and n is the degree of polymerization of the compound, is established by adding MXy to (Li) b(OR)c, where X is a halogen. Therewith, a simple inexpensive method for producing the precursour can be established.
In a preferred embodiment, M MXy is added to (Li) b(OR)c,and disolved in a first solvent to get a mixture thereof.
Preferably the mixture is heated to get a solution thereof. However, also other methods to achieve a solution could be used, e.g. stirring, shaking or vibrating. Preferably, the solution is achieved by both, stirring and heating.
Advantageously, one equivalent of MXy is added to an equivalent according to 2x of (Li) b(OR)c. If e.g. x=2, then one equivalent of X2 is added to four equivalent of (Li)b(OR)c. Therewith, the synthesis can be optimized. However, also an overage of either MXy or (Li) b(OR)c can be usefull to increase the yield. The overage could be recuperated after synthesis and recycled.
In a preferred embodiment, the solution is filtered and evaporated. Advantageously, the filtration and the evaporation takes place after the mixture has been heated. Preferably M is cobalt. However, also other metals can be used, as mentioned before.
Advantageously, OR is aryloxide, preferably phenoxide. Also other substaces can be used for OR, in particular the afore mentioned substances.
In a preferred embodiment, the mixture is stirred and heated preferably between 10 and 60 minutes, more preferably for about 30 minutes. These time periods have been determined in a laboratory scale. The time period can depend on the batch size and may vary also in dependence of the used substances (e.g. solvent etc.).
Preferably the first solvent is THF or dioxane. The skilled person knows other suitable solvents, which can be used instead of THF and dioxane. There are plenty of solvents which have similar properties. The invention is not restricted to these solvents.
Advantageously, before filtering, the first solvent is replaced by a second solvent, in particular, the first solvent is THF and the second solvent is one of dioxane or TMEDA. The replacement can be established by e.g. evaporating the first solvent and dissolving the remaining solid in the second solvent. These solvents have been evaluated as being applicable for this procedure. However, also other solvents in even other combinations (first and second solvent) could be possible.
Preferably the compound of formula [(M1)a(Li) b(OR)c(L)d]n is used as starting product for elaboration of lithium metal oxide, wherein M1 is a metal; a and b are integers equal or bigger than one; OR is alkyl, aryl, alkoxy and/or aryloxide group; c is an integer such that the compound has an overall charge of zero; L is an a neutral ligand who coordinate the lithium ion or ions; d is an integer such that lithium ion or ions are well coordinated; n is the degree of polymerization of the compound.
Advantageously, said lithium metal oxide is used for elaboration of lithium metal oxide nanoparticles. The nanoparticles have a diameter range between 1 and 2500 nm (nanometers), preferably between 1 and 1000 nm, more preferably between 1 and 250 nm. The preferred diameter of the nanoparticles depends on the use of them.
Preferably said lithium metal oxide is used for electrodes and/or batteries. However, also other suitable applications are conceivable. Other advantageous embodiments and combinations of features come out from the detailed description below and the totality of the claims.
Preferred embodiments
As an example, the syntheses of LiM02 starts by the preparation of aryloxide cluster of transition and alkali metal ions. This cluster is burned at 400°C in an air flow to give HT- LiM02, where HT stands for "high tempereature"..
4LiOR + MX2 S0lV6nt > Li2M(OR)4 (solvent)x + 2LiCI
OR is defined as above and X represents halogen ions. As used, herein the term "solvent" refers to a molecule that is able to coordinate the lithium ions in the compound. The by-product Li2C03 can be easily washed out with water and recycled, while the HT- phase of LiM02 (lithium metal oxide) is recovered as pure product.
Synthesis of compound of f(M1) Li) JOR LLU
First method: General: One equivalent of MXy is added to "2y" equivalent of lithium aryloxide, LiOAr, dissolved in solvent. The mixture is stirred and heated to reflux for 30 min, after which the solution is filtered to eliminate the produced LiX, and evaporated to dryness. The bulk material is compound of formula [(M1)a(Li)b(OR)c(L)d]n.
Example 1: One equivalent of CoCI2 is dissolved in 4 equivalents of lithium phenoxide in solution of THF. The mixture is stirred and heated to reflux for 30 min, then the solution is filtered and evaporated to dryness. The bulk material is compound of formula [CoLi2(OPh)4(THF)4] .
Below, a chemical structure of [CoLi2(OPh)4(THF)4] is shown: with
Figure imgf000013_0001
Example 2:
One equivalent of CoCI2 is dissolved in 4 equivalent of lithium phenoxide in solution of dioxane. The mixture is stirred and heated to reflux for 30 min, then the solution is filtered and evaporated to dryness. The bulk material is compound of formula [CoLi2(OPh)4(dioxane)3]n.
Below, a chemical structure of [CoLi2(OPh)4(dioxane)3]n is shown:
Figure imgf000013_0002
with The formula in the brackets points out a monomer unit of the compound with the chemical formula [CoLi2(OPh)4(dioxane)3].
Second method:
General: One equivalent of MXy is dissolved in "2y" equivalent of lithium aryloxide, LiOAr in solution of THF. The mixture is stirred and heated to reflux for 30 min, then the THF is replaced by another solvent after evaporation to dryness. The new solvent is added, the mixture is heated to reflux and filtrated to eliminate LiX, and finally evaporated to dryness. The bulk material is a compound of general formula [( ')a(Li)b(UOAr)c(L)d]n. Example 3:
One equivalent of CoCI2 is dissolved in 4 equivalents of lithium phenoxide in solution of THF. The mixture is stirred and heated to reflux for 30 min. The solvent is evaporated to dryness. The solid was dissolved in dioxane, heated to reflux, filtered and evaporated to dryness. The bulk material is compound of formula [CoLi2(OPh)4(dioxane)3]n. The chemical structure is the same as displayed in example 2 above.
Example 4:
One equivalent of CoCI2 is dissolved in 4 equivalents of lithium phenoxide in solution of THF. The mixture is stirred and heated to reflux for 30 min. The solution is evaporated to dryness. The solid was dissolved in TMEDA, heated to reflux, filtered and evaporated to dryness. The bulk material is compound of general formula [CoLi2(OPh)4(T EDA)z].
Below, a chemical structure of [CoLi2(OPh)4(TMEDA)2] is shown:
Figure imgf000014_0001
Third method:
General:
One equivalent of M MXy(solvent1)z is added to "2y" equivalent of e.g. lithium aryloxide, LiOAr, dissolved in solvent1 or in another solvent. The mixture is stirred and heated to reflux for 30 min, after which the solution is filtered to eliminate the produced LiX, and evaporated to dryness. The bulk material is compound of general formula [(M')a(Li)b(OR)c(L)d]n.
Example 5:
One equivalent of MCIy(solvent)z is dissolved in "2y" equivalent of lithium aryloxide, LiOAr in solution of THF. The mixture is stirred and heated to reflux for 30 min, then the THF is replaced by another solvent after evaporation to dryness. The new solvent is added, the mixture is heated to reflux and filtrated to eliminate LiCI, and finally evaporated to dryness. The bulk material is the corresponding compound of general formula [(M1)a(Li)b(OR)c(L)d]n.
Fourth method: General:
One equivalent of MXy(solvent1)z is added to "2y" equivalent of e.g. lithium aryloxide, LiOAr, dissolved in solvent1 or in another solvent. The mixture is stirred and heated to reflux for 30 min, after which the solution is filtered to eliminate the produced LiX. After that, the solution is crystallized. The crystallized material is the corresponding compound of general formula [(M1)a(Li)b(OR)c(L)d]n.
Example 6:
One equivalent of MCIy(solvent)z is dissolved in M2y" equivalent of lithium aryloxide, LiOAr in solution of THF. The mixture is stirred and heated to reflux for 30 min, then the THF is replaced by another solvent after crystallization. The new solvent is added, the mixture is heated to reflux and filtrated to eliminate LiCI, and finally evaporated to dryness. The bulk material is the corresponding compound of general formula [(M1)a(Li)b(OR)c(L)d]n. Example 7:
One equivalent of MCIy(solvent)z is dissolved in "2y" equivalent of lithium aryloxide, LiOAr in solution of THF. The mixture is stirred and heated to reflux for 30 min, then the THF is replaced by another solvent after crystallization. The new solvent is added, the mixture is heated to reflux and filtrated to eliminate LiCI, and crystallized. The bulk material is the corresponding compound of general formula [(M1)a(Li)b(OR)c(L)d]n.
Drying can generally be established by combusting in an oven under atmospheric air. However, also spin-coating can be used for drying the compound instead of an oven. Also further methods for drying, known by the skilled person, could be feasible. The production of the compound of general formula [(M1)-(Li)b(OR)c(L)d]n is not limited to the above described Examples. The skilled person is able to vary the synthesis according to the mentioned variations in the summary of the invention.
Lithium metal oxide synthesis using a compound of formula [(M )3(Li) QR) L)d1„
General: A compound of general formula [(M1)a(Li)b(OR)c(L)d]n is heated to around 450°C in air during 12h to form a grey powder of the lithium metal oxide and lithium carbonate. The powder is washed twice with water and the resulting black powder is lithium metal oxide. Lithium carbonate, which remains solved in the water, can be recuperated from the aqueous phase. Example 1:
[CoLi2(OPh)4(dioxane)3]n is heated to 450°C in air during 12 h to give a grey powder. This powder is washed twice with water and the resulting black powder is HT-LiCoOz, where HT stands for "high tempereature".
Example 2: [CoLi2(OPh)4(THF)4] is heated to 450°C at air during 12 h to give grey powder. This powder is washed twice with water and the resulting black powder is HT-LiCo02. Structural anaylsis of LiCo02 can be performed using XPD (x-ray photoelectron diffraction).
Generally, the temperature is not limited to 450°C. Also other temperatures can give the desired product. However, experiments have shown, that around 450°C the reaction rate as well as the time duration of the reaction is in an acceptable range.

Claims

Method for producing lithium metal oxide materials in particular for the use in electrodes and batteries, characterized by using a compound of the formula [(M1)a(Li)b(OR)c(L)d]n, where M1 is a metal, a and b are integers equal or bigger than one, OR is an alkyl, aryl, alkoxy and/or aryloxide group, c is an integer such that the compound has an overall charge of zero, L is an a neutral ligand that coordinates the lithium ion or ions, d is an integer such that lithium ion or ions are well coordinated and n is the degree of polymerization of the compound, wherein the compound is heated to get a powder, in particular a powder comprising nanoparticles of the lithium metal oxide material.
Method according to claim ^ characterized in that
a) M is one ore more of cobalt, nickel, titanium, manganese; and/or
b) OR is one of phenolate (OPh), 2-methylphenolate (oMP), 2,6-dimethylphenolate (oDMP), 2-isopropylphenolate (oPP),2,6-diisopropylphenolate (oDIP) and tert- butoxide (O'Bu); and/or
c) L is one of tetrahydrofuran (THF), dioxane, pyridine and tetramethylethylenediamine (TMEDA).
Method according to claim 1 or 2, characterized in that said compound is selected from the following:
[CoLi2(OPh)4(THF)4]
[CoLi2(OPh)4(TMEDA)2]
[CoLi2(OPh)4(glyme)2]
[CoLi2(OPh)4(dioxane)3]n
[CoLi2(oMP)4(THF)4]
[CoLi2(oMP)4(pyridine)4] [CoLi2(oDMP)4(THF)4]
[CoLi2(oDMP)4(pyridine)4]
[CoLi2(oPP)4(THF)4]
[CoLi2(oPP)4(pyridine)4]
[CoLi2(oDIP)4(THF)2]
[CoLi2(oDIP)4(pyridine)2]
[0ο2ίί2(ΟΡΓΐ)4(Ο'Βυ)2(ΤΗΡ)4]
[0ο2ϋ2(ΟιΒυ)6(ΤΗΙ=)2]
4. Method according to one of claims 1 to 3, characterized in that the compound is heated to a temperature between 300 and 700°C, preferably between 400 and 600°C, more preferably between 450 and 550°C.
5. Method according to one of claims 1 to 4, characterized in that heating is established in air.
6. Method according to claim 5, characterized in that the air is enriched by oxygen. 7. Method according to one of claims 1 to 6, characterized in that, the compound is heated for 6 to 18h, preferably for 9 to 15h, more preferably for 1 1 to 13h.
8. Method according to one of claims 1 to 7, characterized in that, the powder is washed.
9. Method according to claim 8, characterized in that the washing is performed with water.
10. Method according to claim 8 or 9, characterized in that, the washing is performed at least twice.
1 1. Method according to one of claims 8 to 10, characterized in that, a byproduct, in particular lithium carbonate, is recuperated after the washing.
12. Method for producing a compound of the formula [(M1)a(Li) b(OR)c(L)d]n, where M1 is a metal; a and b are integers equal or bigger than one; OR is an alkyl, aryl, alkoxy and/or aryloxide group; c is an integer such that the compound has an overall charge of zero; L is an a neutral ligand who coordinate the lithium ion or ions; d is an integer such that lithium ions are well coordinated; and n is the degree of polymerization of the compound, wherein MXy is added to (Li) b(OR)c, where X is a halogen.
13. Method according to 12, characterized in that MXy is added to (Li) b(OR)c,and disolved in a first solvent to get a mixture thereof.
14. Method according to claim 13, characterized in that the mixture is heated to get a solution thereof.
15. Method according to one of claims 12 to 14, characterized in that one equivalent of MXy is added to an equivalent according to 2y of (Li)b(OR)c. 16. Method according to claim 14, characterized in that the solution is filtered and evaporated.
17. Method according to one of claims 12 to 16, characterized in that M is cobalt and X is one of chlorine and bromine.
18. Method according to one of claims 12 to 17, characterized in that OR is aryloxide, preferably phenoxide.
19. Method according to one of claims 12 to 18, characterized in that the mixture is stirred and heated preferably between 10 and 60 minutes, more preferably for about 30 minutes.
20. Method according to 13, characterized in that the first solvent is THF or dioxane. 21. Method according to 13 or 20, characterized in that before filtering the first solvent is replaced by a second solvent, in particular, the first solvent is THF and the second solvent is one of dioxane and TMEDA.
22. Use of a compound of formula [(M')a(Li) b(OR)c(L)d]n as starting product for elaboration of lithium metal oxide, wherein M1 is a metal; a and b are integers equal or bigger than one; OR is an alkyl, aryl, alkoxy and/or aryloxide group; c is an integer such that the compound has an overall charge of zero; L is an a neutral ligand who coordinate the lithium ion or ions; d is an integer such that lithium ion or ions are well coordinated; and n is the degree of polymerization of the compound.
23. Use according to claim 22 wherein said lithium metal oxide is used for elaboration of lithium metal oxide nanoparticles.
24. Use according to claim 22 or 23 wherein said lithium metal oxide is used for electrodes and/or batteries.
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