CN100572287C - 制备γ-LiV2O5的方法 - Google Patents
制备γ-LiV2O5的方法 Download PDFInfo
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- CN100572287C CN100572287C CNB2005800361507A CN200580036150A CN100572287C CN 100572287 C CN100572287 C CN 100572287C CN B2005800361507 A CNB2005800361507 A CN B2005800361507A CN 200580036150 A CN200580036150 A CN 200580036150A CN 100572287 C CN100572287 C CN 100572287C
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- lithium
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910006305 γ-LiV2O5 Inorganic materials 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000007669 thermal treatment Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012429 reaction media Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- MVXFVWAONSSTPH-UHFFFAOYSA-N [Li].C(C(=O)C)(=O)O Chemical compound [Li].C(C(=O)C)(=O)O MVXFVWAONSSTPH-UHFFFAOYSA-N 0.000 claims description 2
- OEFANHJWTFZDRE-UHFFFAOYSA-N [Li].C(C)C(=O)C(=O)C Chemical compound [Li].C(C)C(=O)C(=O)C OEFANHJWTFZDRE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000011872 intimate mixture Substances 0.000 claims description 2
- 150000002641 lithium Chemical group 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- ZPPPLBXXTCVBNC-ZVGUSBNCSA-M lithium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Li+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O ZPPPLBXXTCVBNC-ZVGUSBNCSA-M 0.000 claims description 2
- GKQWYZBANWAFMQ-UHFFFAOYSA-M lithium;2-hydroxypropanoate Chemical compound [Li+].CC(O)C([O-])=O GKQWYZBANWAFMQ-UHFFFAOYSA-M 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 3
- 229910006594 α-V2O5 Inorganic materials 0.000 abstract 1
- 229910006598 α−V2O5 Inorganic materials 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- -1 polyoxyethylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 150000001722 carbon compounds Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910008365 Li-Sn Inorganic materials 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910006759 Li—Sn Inorganic materials 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229910002975 Cd Pb Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910007894 Li-Al-Mn Inorganic materials 0.000 description 1
- 229910008367 Li-Pb Inorganic materials 0.000 description 1
- 229910010547 Li4XO4—Li2BXO4 Inorganic materials 0.000 description 1
- 229910010549 Li4XO4—Li3YO4 Inorganic materials 0.000 description 1
- 229910011508 LiF—Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910008475 Li—Al—Mn Inorganic materials 0.000 description 1
- 229910006738 Li—Pb Inorganic materials 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
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- 239000002070 nanowire Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
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- H—ELECTRICITY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/405—Alloys based on lithium
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- 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
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Abstract
本发明涉及一种制备任选含碳的γ-LiV2O5材料的方法。该方法是制备由碳和Li与V的前体形成的组合物，并将所述组合物进行热处理。通过使碳、α-V2O5和Li前体接触，它们的量使得[V2O5]/[Li]浓度的比为介于0.95和1.05之间，碳相对于化学计量比过量至少25%。热处理在两个阶段实施：在氮气或氩气气氛下或在真空下，第一阶段在90-150℃之间的温度下1-12小时，第二阶段在420-500℃之间的温度下的时间为10分钟至1小时。应用：正极活性材料。
Description
本发明涉及一种制备γ-LiV2O5的方法。
包括由电解质分开的正极和负极的电池是公知的，所述电解质包含溶于溶剂中的锂盐。这些电池的运转是通过在电极之间的电解质中可逆循环锂离子来进行的。正极通常由复合材料构成，该复合材料包括活性材料、粘结剂、提供电子传导的材料以及任选的提供离子传导的化合物。提供电子传导的化合物可以是碳黑，其在高电位时不催化电解质的氧化。
公知在经由电极通过在阳极和阴极之间的锂离子交换来运转的电池中使用γ-LixV2O5化合物作为正极活性材料。J.Barker等人描述了制备γ-LiV2O5的方法[Journal of the Electrochemical Society，150，(6)A684-A688(2003)]。所述方法为：制备Li2CO3、V2O5和碳的混合物，压缩该混合物，以便由其形成球粒，然后将球粒在600℃的炉中于氩气气氛下进行热处理60分钟。规定了在525℃下需要10小时的时间，以便得到纯γ-LiV2O5。另外，US-6 716 372描述了一种方法，其包括：混合Li2CO3、V2O5和碳，压缩混合物以便由其形成球粒，使混合物以2℃/min的速率达到介于400-650℃的温度，在此温度保持一定时间，然后以2℃/min的速率冷却。维持高温度的时间在600或650℃为1小时左右，在500℃为8小时左右。
本发明的目的是提供简单且便宜的制备由纯γ-LiV2O5或γ-LiV2O5作为与碳的紧密混合物组成的材料的方法。
根据本发明的方法是制备由碳和Li与V的前体形成的组合物，并将所述组合物进行热处理。其特征在于：
-组合物通过使碳、α-V2O5和Li前体接触来制备，它们的量使得[V2O5]/[Li]浓度的比为介于0.95和1.05之间，碳相对于化学计量比过量至少25％。
-热处理在两个阶段实施：在氮气或氩气气氛下或在真空下，第一阶段在90-150℃之间的温度下1-12小时，第二阶段在420-500℃之间的温度下的时间为10分钟至1小时。
第一阶段在强力搅拌下实施。在优选的实施方案中，其在玻珠研磨机内实施。
热处理的第一阶段可以在空气中实施。此阶段的时间取决于温度。通过将待处理的组合物形成薄层的形式，该时间可以减低到约1小时。
如果热处理的第二阶段的时间小于10分钟，或者如果热处理的第二阶段的温度小于420℃，则所得到的材料不是纯γ-LiV2O5；它包括Li1+αV3O8和/或β-LixV2O5(0＜x＜0.7)。持续时间大于1小时导致微晶的尺寸增加，从而导致较差的电池性能。
热处理的第一阶段可以在烘箱内进行，然后将组合物引入用于热处理第二阶段的炉中。如果该炉包括至少两个处理区，一个在第一阶段的温度，另一个在第二阶段的温度，则热处理的第一阶段也可在用于第二阶段的炉内进行。
在第一实施方案中，Li前体是LiOH·H2O或Li2CO3。将钒前体α-V2O5、锂前体和碳引入一定量的水中，以便得到粘稠悬浮液，并保持强力搅拌1-2小时的时间。前体的浓度可以变化，对于α-V2O5可以介于0.5mol/l和5mol/l之间，对于锂前体Li2CO3可以介于0.25mol/l和2.5mol/l之间，对于锂前体LiOH·H2O可以介于0.5mol/l和5mol/l之间。
如果在无水情况下混合相同的前体，碳与Li和V的前体所形成的组合物在第二热处理后产生γ-LiV2O5和β-LixV2O5(0＜x＜0.7)的混合物。
在第二实施方案中，将包括10-50体积％的过氧化氢的水溶液加入反应介质中，并且保持强力搅拌5分钟。可以使用的限制浓度对于α-V2O5为0.05mol/l至2mol/l，对于Li前体为0.025mol/l至2mol/l。
在第二实施方案中：
锂前体可以选自Li2CO3、LiOH·H2O、LiCl、LiNO3或羧酸的锂盐，例如选自乙酰丙酮锂、乙酸锂、硬脂酸锂、甲酸锂、草酸锂、柠檬酸锂、乳酸锂、酒石酸锂或丙酮酸锂；
制备α-V2O5和碳的水悬浮液，并向其中加入过氧化物水溶液，在添加过氧化物溶液之前或者在添加过氧化物溶液之后，也就是在胶体形成期间，可将锂前体引入α-V2O5和碳的水悬浮液内，混合物在强力搅拌下保持5分钟。
Li前体和α-V2O5在反应介质中的各自量优选为0.1/z mol.l-1＜[Li]＜1 l/zmol.l-1；0.1mol.l-1＜[V2O5]＜1mol.l-1，z是前体的每个化学式单元中的锂原子数。
过高的反应物浓度可以带来发泡，而过低的浓度产生沉淀。
当反应介质中碳的过量不大于25％时，通过本发明方法得到的材料是由小的γ-LiV2O5针状物的附聚体组成的材料。
当反应介质中碳的过量大于25％时，所得到的材料由围绕着球形碳颗粒的非连续层的小的γ-LiV2O5针状物的附聚体组成。这样的材料在下文由含碳γ-LiV2O5表示。
可使用通过本发明的方法得到的材料制备用于锂电池或锂离子电池的复合材料正极。
在特别的实施方案中，本发明的正极由包括以下成分的复合材料构成：
·通过本发明方法得到的含碳化合物或不含碳化合物，
·赋予机械强度的粘结剂，
·任选的提供电子传导的化合物，
·任选的提供离子传导的化合物。
含碳或不含碳γ-LiV2O5的含量优选为90-100重量％。粘结剂的含量优选小于10重量％。提供电子传导的化合物的含量优选小于或等于5重量％，提供离子传导的材料的含量优选小于或等于5重量％。对于由不含碳γ-LiV2O5构成的电极，优选构成正极的复合材料包括提供电子传导的化合物和粘结剂。
粘结剂可以由非溶剂化聚合物、溶剂化聚合物、或溶剂化聚合物与非溶剂化聚合物的混合物构成。其可另外包括一种或多重液体极性疏质子化合物。非溶剂化聚合物可以选自偏氟乙烯均聚物和共聚物，乙烯、丙烯和二烯的共聚物、四氟乙烯均聚物和共聚物，N-乙烯基吡咯烷酮均聚物和共聚物，丙烯腈均聚物和共聚物、甲基丙烯腈均聚物和共聚物。聚偏氟乙烯是特别优选的。非溶剂化聚合物可以带有离子官能团。这样的聚合物的实例可以提及聚全氟醚磺酸盐(其中一些以商标
来出售)和聚苯乙烯磺酸盐。
溶剂化聚合物可以例如选自：基于聚环氧乙烷的线性、梳状或嵌段结构的聚醚，其可以或不可以形成网络；包括环氧乙烷或环氧丙烷或烯丙基缩水甘油醚单元的共聚物；聚膦腈；由异氰酸酯交联的基于聚乙二醇的交联网络；环氧乙烷和表氯醇的共聚物；以及通过缩聚得到的网络，该网络带有可能与可交联基团结合的基团。
极性疏质子化合物可以选自线性或环状碳酸酯、线性或环醚、线性或环酯、线性或环砜、硫酰胺和腈。
提供离子传导的化合物有利的是选自LiClO4、LiPF6、LiAsF6、LiBF4、LiRFSO3、LiCH3SO3、二全氟烷基磺酰亚胺锂或二全氟磺酰甲基化锂或三全氟磺酰甲基化锂的锂盐。
提供电子传导的化合物可以例如选自碳黑、石墨、碳纤维、碳纳米线或碳纳米管。
根据本发明的复合材料正极可以通过以下过程来制备：使含碳或不含碳γ-LiV2O5与粘结剂在合适溶剂中混合，并且任选混合锂盐；将所得混合物展开在作为集电体的金属盘(例如铝盘)上；然后在氮气氛于加热条件下蒸发溶剂。溶剂根据所用粘结剂来选择。另外，正极可以通过挤出其组分的混合物来制备。
如此构成的电极可用于包括由包含溶于溶剂中的锂盐的电解质分开的正极和负极的电池中。这样的电池的运转是通过在电极之间电解质的锂离子的可逆循环来提供。本发明的主题之一是一种电池，其中电解质包括溶于溶剂中的锂盐，其特征在于它包括含有根据本发明方法制备的作为活性材料的含碳和不含碳γ-LiV2O5的正极。
在本发明的电池中，电解质包括至少一种溶于溶剂中的锂盐。作为盐的实例，可以提到LiClO4、LiAsF6、LiPF6、LiBF4、LiRFSO3、LiCH3SO3、LiN(RFSO2)2、LiC(RFSO2)3和LiCF(RFSO2)2，RF代表具有1-8个碳原子的全氟烷基或者氟原子。
电解质的溶剂可以由一种或多种选自以下的极性疏质子化合物构成：线性或环状碳酸酯、线性或环醚、线性或环酯、线性或环砜、硫酰胺和腈。溶剂优选由选自以下的至少两种碳酸酯组成：碳酸亚乙酯、碳酸亚丙酯、碳酸二甲酯、碳酸二乙酯以及碳酸乙基甲基酯。具有极性疏质子溶剂电解质的电池通常在-20℃至60℃的温度范围下运转。
电解质的溶剂另外可以是溶剂化聚合物。作为溶剂化聚合物的实例，可以提及的是基于聚环氧乙烷的线性、梳状或嵌段结构的聚醚，其可以或不可以形成网络；包括环氧乙烷或环氧丙烷或烯丙基缩水甘油醚单元的共聚物；聚膦腈；由异氰酸酯交联的基于聚乙二醇的交联网络；FR-2 770 034公开的环氧乙烷和表氯醇的共聚物；以及通过缩聚得到的网络，该网络带有能与可交联基团结合的基团。还可提及其中一些嵌段带有具有氧化还原性能的官能团的嵌段共聚物。具有聚合物溶剂电解质的电池通常在60-120℃的温度范围内运转。
此外，电解质的溶剂可以是选自上述液体极性疏质子化合物的液体极性疏质子化合物与溶解化聚合物的混合物。取决于希望是具有低含量极性疏质子化合物的塑化电解质或具有高含量极性疏质子化合物的胶凝电解质，其可以包括2-98体积％的液体溶剂。当电解质的聚合物溶剂带有离子官能团时，锂盐是任选的。
电解质的溶剂也可以是上述极性疏质子化合物或上述溶剂化聚合物与包括含有至少一个杂原子的非溶剂化聚合物的混合物，所述杂原子选自硫、氧、氮和氟。这样的非溶剂化聚合物可以选自丙烯腈均聚物和共聚物、偏氟乙烯均聚物和共聚物、以及N-乙烯基吡咯烷酮均聚物和共聚物。另外，非溶剂化聚合物可以是带有离子取代基的聚合物，尤其是全氟醚磺酸盐(例如上述
)或者聚苯乙烯磺酸盐。
在另一个实施方案中，本发明的电池的电解质可以是无机传导固体，选自通常由Lisicon表示的化合物，即Li4XO4-Li3YO4(X＝Si或Ge或Ti；Y＝P或As或V)、Li4XO4-Li2AO4(X＝Si或Ge或Ti；A＝Mo或S)、Li4XO4-LiZO2(X＝Si或Ge或Ti；Z＝Al或Ga或Cr)、Li4XO4-Li2BXO4(X＝Si或Ge或Ti；B＝Ca或Zn)、LiO2-GeO2-P2O5、LiO2-SiO2-P2O5、LiO2-B2O3-Li2SO4、LiF-Li2S-P2S5、Li2O-GeO2-V2O5或LiO2-P2O5-PON固溶体。包括这样的电解质的锂电池在非常宽的温度范围(20-100℃的级别)内运转。
当然，本发明的电池的电解质可另外包括常规用于此类型材料中的添加剂，尤其是增塑剂、填料、其他盐、以及类似物。
电池的负极可以由锂金属或锂合金构成，所述锂合金可选自以下合金：β-LiAl、γ-LiAl、Li-Pb(例如Li7Pb2)、Li-Cd-Pb、Li-Sn、Li-Sn-Cd、在各种基体(尤其是含氧基体或金属基体(例如Cu、Ni、Fe或Fe-C))中的Li-Sn、或Li-Al-Mn。然后电池是锂电池。当通过本发明的方法得到的化合物γ-LiV2O5用于制备正极时，电池处于放电状态。
另外，电池的负极可以由包括粘结剂和能够在低氧化还原电位可逆地插入锂离子的材料(下文表示为插入材料)的复合材料组成，所述复合材料可以在初始阶段锂化。插入材料可以选自天然或合成含碳材料。这些含碳材料可例如为石油焦、石墨、石墨晶须、碳纤维、内消旋碳微球、沥青焦或针状焦。插入材料还可以选自氧化物如LixMoO2、LixWO2、LixFe2O3、Li4Ti5O12或LixTiO2，或者选自硫化物如Li9Mo6S6和LiTiS2，或者选自氧硫化物。也可以利用能够在低电位可逆地储存锂的化合物如无定形钒酸盐(例如LixNiVO4)，氮化物(例如Li2.6-xCo0.4N、Li2+xFeN2或Li7+xMnN4)、磷化物(例如Li9-xVP4)、砷化物(例如Li9-xVAs4)以及可逆降解的氧化物(例如CoO、CuO或Cu2O)。粘结剂是在负极运转范围内电化学稳定的有机粘结剂。举例而言，可以提及聚偏氟乙烯均聚物或乙烯/丙烯/二烯共聚物。特别优选聚偏氟乙烯。复合材料电极可以通过以下过程制备：将含碳化合物引入粘结剂在极性疏质子溶剂中的溶液中，通过将所得混合物展开到用作集电体的铜盘上，然后通过于惰性气氛中在加热条件下蒸发溶剂。当负极由插入材料构成时，电池被成为“锂离子电池”。当使用根据本发明方法得到的γ-LiV2O5化合物来制备这样电池的正极时，电池处于充电状态。
包括固体电解质的根据本发明的电池可以以连续多层的形式提供，所述层分别由本发明的正极的材料和其集电体、固体电解质、以及负极和任选的其集电体构成。
包括液体电解质的根据本发明的电池也可以以连续多层的形式提供，所述层分别由本发明的正极和其集电体的材料、由液体电解质浸渍的隔离物、以及构成负极和任选的其集电体的材料构成。
本发明通过以下给出的实施例来更详细地阐述，然而并不局限于此。
实施例1
将24.0810g(0.88M)的α-V2O5、4.7916g(0.44M)的Li2CO3和3.5g的碳加入到150ml水中。由碳和Li与V的前体形成的组合物在玻珠研磨机中搅拌2小时后形成。随后，所述组合物在空气中于90℃下干燥2小时，然后在氩气气氛中于420℃下处理15分钟。所得产物下文由GliV2O5-420表示，其包括8％的残余碳。
实施例2
采用实施例1的制备方法，但是处理是在470℃而非420℃下进行15分钟。所得到的化合物由GliV2O5-470a表示，其包括8％的残余碳。
实施例3
将24.0810g(0.29M)的α-V2O5、4.7916g(0.146M)的Li2CO3和1.49g的碳加入50ml水中。由碳和和Li与V的前体形成的组合物在玻珠研磨机中搅拌2小时后形成。随后，所述组合物在空气中于90℃下干燥2小时，然后在氩气中于470℃下处理15分钟。所得产物下文由GliV2O5-470b表示，其包括1％的残余碳。
实施例4
采用实施例3的制备方法，但是处理是在350℃而非470℃下进行30分钟。所得化合物由GliV2O5-LIV-350表示。
实施例5
将1g的V2O5、0.2306g的LiOH·H2O和0.1453g的碳加入到15ml的30％过氧化氢水溶液中。由碳和Li与V的前体形成的组合物在几分钟内形成。
所述组合物在空气中于90℃下干燥整夜，然后在氩气中于420℃下热处理15分钟。所得化合物由GliV2O5ph-420表示。
实施例6(比较)
使用实施例2的制备方法，但是实施研磨而不添加水，并且在470℃处理进行45分钟，而非15分钟。所得化合物由GliV2O5-BSEC-470表示，其包括β-LixV2O5作为杂质。
实施例7
X-射线衍射分析
图1中给出了化合物GliV2O5-420、GliV2O5-470a和GliV2O5-BSEC-470的X-射线衍射图谱，以及对应于在玻珠研磨机中搅拌2小时且在空气中于90℃下干燥2小时后形成的、未经第二阶段热处理的由碳和和Li与V的前体形成的组合物的X-射线衍射图谱。这些图谱显示，化合物含碳γ-LiV2O5可由在420℃退火15分钟得到。此外，其说明在研磨期间使用水使得可改进由碳和和Li与V的前体形成的组合物的活性，因为干燥混合物在470℃即使在45分钟后也显示杂质β-LixV2O5型(
)。再者，根据比较例6制备的由碳和和Li与V的前体形成的组合物的X-射线衍射图谱显示，除了碳(11％)，其还包括薄片状的式Li1+aV3O8·1H2O的水合物。
实施例8
性能测量
根据实施例3制备的化合物GliV2O5-470b、以及根据实施例4制备的化合物GliV2O5-LIV-350的电化学性能在以下类型的Swagelok实验室电池中测试：Li/液体电解质(EC+DMC+LiPF6)/GliV2O5-470b，在环境温度下操作。对于正极，向本发明的化合物中加入5重量％的化合物。
化合物GliV2O5-470b所得结果在图2中给出。循环条件对应于每化学式基团每小时在还原时0.5Li，在氧化时0.2Li。电位窗为3V至4V对于循环0-8，然后12到40(I区和III区)。电位窗为3V到3.75V对于循环9到11(II区)
化合物GliV2O5-LIV-350所得结果在图3中给出。循环在3.7V和2V之间进行，对于第一个12循环，循环速率对应于每化学式基团每小时0.4Li，然后为每化学式基团每小时0.4Li
图2和3表示对于每种材料的容量变化。因此在图2中确定，在每小时每化学式单元0.5Li的循环速率下，根据本发明制备的化合物含碳γ-LiV2O5(1％的残余碳)显示了类似于现有技术(US-6 716 372)的容量和循环性能。
因此，使用根据本发明方法制备的氧化物γ-Li2V2O5可实质上在制造用于锂电池的正极材料过程中节省能量。
Claims (18)
1.一种制备由γ-LiV2O5构成或γ-LiV2O5作为与碳的紧密混合物构成的材料的方法，其是制备由碳和Li与V的前体形成的组合物，并将所述组合物进行热处理，其特征在于：
-所述组合物通过使碳、α-V2O5和Li前体接触来制备，它们的量使得[V2O5]/[Li]浓度的摩尔比为介于0.95和1.05之间，碳相对于化学计量比过量至少25％。
-热处理在两个阶段实施：在氮气或氩气气氛下或在真空下，第一阶段在90-150℃之间的温度下1-12小时，第二阶段在420-500℃之间的温度下的时间为10分钟至1小时。
2.权利要求1的方法，其特征在于所述第一阶段在强力搅拌下进行。
3.权利要求1的方法，其特征在于所述Li前体是LiOH·H2O或Li2CO3，将钒前体α-V2O5、锂前体和碳引入一定量的水中，以便得到粘稠悬浮液，并保持强力搅拌1-2小时的时间。
4.权利要求3的方法，其特征在于前体的浓度是变化的，对于α-V2O5介于0.5mol/l和5mol/l之间，对于锂前体Li2CO3介于0.25mol/l和2.5mol/l之间，对于锂前体LiOH·H2O介于0.5mol/l和5mol/l之间。
5.权利要求1的方法，其特征在于将包括10-50体积％的过氧化氢的水溶液加入反应介质中，保持强力搅拌5分钟，并且可以使用的限制浓度对于α-V2O5为0.05mol/l至2mol/l，对于Li前体为0.025mol/l至2mol/l。
6.权利要求5的方法，其特征在于所述锂前体选自Li2CO3、LiOH·H2O、LiCl、LiNO3或羧酸的锂盐。
7.权利要求6的方法，其特征在于所述锂盐选自乙酰丙酮锂、乙酸锂、硬脂酸锂、甲酸锂、草酸锂、柠檬酸锂、乳酸锂、酒石酸锂或丙酮酸锂。
8.权利要求5的方法，其特征在于：制备α-V2O5和碳的水悬浮液，并向其中加入过氧化氢水溶液，在添加过氧化氢溶液之前或者在添加过氧化氢溶液之后，也就是在胶体形成期间，将锂前体引入α-V2O5和碳的水悬浮液内，并将混合物在强力搅拌下保持5分钟。
9.权利要求5的方法，其特征在于：Li前体和α-V2O5在反应介质中的各自量为0.1/z mol.l-1＜[Li]＜1 1/z mol.l-1；0.1mol.l-1＜[V2O5]＜1mol.l-1，z是前体的每个化学式单元中的锂原子数。
10.根据权利要求1-9之一的方法得到的材料。
11.一种用于锂电池的复合材料正极，其特征在于其由包括权利要求10的材料的复合材料构成。
12.权利要求11的复合材料正极，其特征在于所述复合材料还包括
●赋予机械强度的粘结剂，
●提供电子传导的化合物，
●任选的提供离子传导的化合物。
13.权利要求12的复合材料正极，其特征在于：
-权利要求12的材料的含量为90-10重量％；
-粘结剂的含量小于10重量％；
-提供电子传导的化合物的含量小于或等于5重量％；
-提供离子传导的材料的含量小于5重量％。
14.权利要求12的电极，其特征在所述粘结剂由溶剂化聚合物构成。
15.权利要求12的电极，其特征在于所述粘结剂是溶剂化聚合物与非溶剂化聚合物的混合物。
16.权利要求12-15之一的电极，其特征在于所述粘结剂另外包括极性疏质子化合物。
17.权利要求12的电极，其特征在于提供离子传导的化合物是选自LiClO4、LiPF6、LiAsF6、LiBF4、LiRFSO3、LiCH3SO3、二全氟烷基磺酰亚胺锂或二全氟磺酰甲基化锂或三全氟磺酰甲基化锂的锂盐，其中RF代表具有1-8个碳原子的全氟烷基或氟原子。
18.由被电解质分开的正极和负极构成的电池，所述电解质由溶于溶剂中的锂盐构成，其特征在于所述正极是权利要求11-17之一的电极。
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| FR2877146B1 (fr) | 2004-10-22 | 2007-01-19 | Batscap Sa | Materiau nanostructure, procede pour sa preparation. |
| JP2008123822A (ja) * | 2006-11-10 | 2008-05-29 | Fuji Heavy Ind Ltd | 電極材料の製造方法、電極材料及び非水系リチウム二次電池 |
| JP2008123826A (ja) * | 2006-11-10 | 2008-05-29 | Fuji Heavy Ind Ltd | 蓄電デバイス |
| FR2912263B1 (fr) * | 2007-02-06 | 2009-05-15 | Batscap Sa | "module de batterie, pack de modules, chargeur pour le module" |
| FR2912264B1 (fr) * | 2007-02-06 | 2009-04-10 | Batscap Sa | Module de batterie de puissance, batterie, procede de charge du module, vehicule ayant la batterie |
| FR2912265B1 (fr) * | 2007-02-06 | 2009-04-24 | Batscap Sa | Batterie a modules de cellules en serie, et vehicule equipe de celle-ci |
| US20080305256A1 (en) * | 2007-06-08 | 2008-12-11 | Conocophillips Company | Method for producing lithium vanadium polyanion powders for batteries |
| CN102557131A (zh) * | 2010-12-07 | 2012-07-11 | 吉林师范大学 | 一种NaV2O5的制备方法 |
| CN114314663B (zh) * | 2021-11-19 | 2023-11-10 | 攀钢集团研究院有限公司 | 一种五氧化二钒正极材料的制备方法 |
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| EP1831109B1 (fr) | 2013-12-04 |
| US20110033752A1 (en) | 2011-02-10 |
| CA2584227A1 (fr) | 2006-05-04 |
| US20080076025A1 (en) | 2008-03-27 |
| EP1831109A1 (fr) | 2007-09-12 |
| FR2876998A1 (fr) | 2006-04-28 |
| JP2008516884A (ja) | 2008-05-22 |
| JP5112071B2 (ja) | 2013-01-09 |
| CA2584227C (fr) | 2013-02-05 |
| KR101275776B1 (ko) | 2013-06-19 |
| US7842273B2 (en) | 2010-11-30 |
| CN101065326A (zh) | 2007-10-31 |
| WO2006045921A1 (fr) | 2006-05-04 |
| KR20070085425A (ko) | 2007-08-27 |
| FR2876998B1 (fr) | 2007-01-19 |
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