CN109473636A - A kind of solid state lithium battery surface modified anode material and preparation method thereof - Google Patents
A kind of solid state lithium battery surface modified anode material and preparation method thereof Download PDFInfo
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- CN109473636A CN109473636A CN201810412171.3A CN201810412171A CN109473636A CN 109473636 A CN109473636 A CN 109473636A CN 201810412171 A CN201810412171 A CN 201810412171A CN 109473636 A CN109473636 A CN 109473636A
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- Prior art keywords
- solid state
- lithium battery
- state lithium
- surface modified
- source
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- 239000007787 solid Substances 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- 239000010405 anode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 claims abstract description 29
- 229910006183 NixCOyMn1-x-y-zMz Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000007873 sieving Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 229920000867 polyelectrolyte Polymers 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002345 surface coating layer Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 230000004087 circulation Effects 0.000 description 8
- 238000005253 cladding Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229910011956 Li4Ti5 Inorganic materials 0.000 description 4
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910011933 Li4Ti4.8Mo0.2O12 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QQGWBRJQPRTJDA-UHFFFAOYSA-N [Li].CC(O)=O Chemical compound [Li].CC(O)=O QQGWBRJQPRTJDA-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910003327 LiNbO3 Inorganic materials 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/58—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
- H01M4/582—Halogenides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of solid state lithium battery surface modified anode materials and preparation method thereof, and the modified anode material is by positive electrode active material matrix LiaNixCoyMn1‑x‑y‑zMzO2And surface coating layer Li4‑αM'αTi5‑β‑γM"βM"'γO12‑δGδComposition.For the clad it is possible to prevente effectively from positive electrode active material matrix is provided simultaneously with good lithium ion, electronic conduction ability to the catalyzed corrosion of solid polyelectrolyte, raising positive electrode interface stability reduces interface impedance.Solid state lithium battery using positive electrode of the present invention preparation has outstanding electrical property.
Description
Technical field
The present invention relates to a kind of solid state lithium battery surface modified anode materials and preparation method thereof, belong to lithium battery neck
Domain.
Background technique
Solid state lithium battery substitutes conventional liquid electrolyte using solid electrolyte, and greatly simplified battery structure has Gao An
Entirely, the characteristics of high-energy density, it has also become the important directions of advanced lithium battery development.
Polymer matrix solid electrolyte high-temperature working performance is preferable, and easily film forming, easy processing, can prepare hull cell and big
Capacity batteries, thus polymer-based solid state lithium battery takes the lead in realizing and commercially produce on a small scale.Bollor é company uses phosphorus at present
Sour iron lithium (LiFePO4) anode preparation polymer-based solid state lithium battery served France shared automobile and small-sized electric bar
Scholar.
Compared to LiFePO4, anode is using high capacity, high voltage ternary nickle cobalt lithium manganate (LiNixCoyMn1-x-yO2, referred to as
NCM it) can further improve solid state battery energy density.However, polymer solid electrolysis is easily catalytically decomposed in nickel, cobalt in such material
Matter leads to cell performance decay.How to improve tertiary cathode material and solid polyelectrolyte compatibility becomes the high ratio of exploitation
One of the critical issue of energy polymer-based solid state lithium battery.
The avoidable anode of clad is done using lithium ion conductor directly to contact with solid electrolyte, is to solve positive electrode to exist
The effective means of solid state battery system compatibility.Wherein, the selection of covering material, the control of coating thickness, covering rate tune
Section determines that performance of the modified anode material in solid state battery system plays.Patent CN106099050A is by lithium ion conductor
LiNbO3Corrosion of the sulfide solid electrolyte to positive electrode has effectively been blocked as clad, improves positive electrode compatibility
And promote battery performance.
However, for NCM in the study on the modification of polymer-based solid state battery system (under the conditions of especially high working voltage)
Also in the initial stage.Li4Ti5O12With good lithium ion conduction ability, have with solid polyelectrolyte good simultaneous
Capacitive (bibliography: power technology, 2013,37 (1): 74-77), but electronic conductance is relatively low.Modified Li4Ti5O12It has both
Excellent ion, electronic conduction ability can be used as positive electrode clad, improve NCM in the electrical property of polymer-based solid state battery.
Summary of the invention
In view of the above-mentioned problems, an object of the present invention is to provide a kind of solid state lithium battery surface modified anode material.
By designing positive electrode active material matrix LiaNixCoyMn1-x-y-zMzO2, surface-active clad Li4-αM'αTi5-β-γM"βM"'γ
O12-δGδThe Nomenclature Composition and Structure of Complexes, regulate and control coating thickness, be prepared for modified anode of the surface with macroion, electronic conduction ability
Material.The positive electrode realizes that the ion between active matter matrix and solid polyelectrolyte passes using surface-active clad
It is defeated, it is possible to prevente effectively from catalyzed corrosion of the active matter matrix to solid polyelectrolyte, improves compatibility.It is provided by the invention
Modified anode material shows excellent electrical property in polymer-based solid state lithium battery, and material preparation method is simple, at low cost
It is honest and clean.
Solid state lithium battery provided by the invention surface modified anode material, including positive electrode active material matrix and matrix surface
Active clad, average grain diameter D50It is 2~30 μm；
The positive electrode active material matrix is nickle cobalt lithium manganate, chemical formula LiaNixCoyMn1-x-y-zMzO2, wherein 0.95≤a≤
In 1.05,0≤z≤0.05, x+y+z=1, M Ga, Sc, In, Y, Ce, Co, La, Cr, Mo, Mn, Fe, Hf, Zr, W, Nb, Sm, Al
At least one element；
The chemical formula of the activity clad is Li4-αM'αTi5-β-γM"βM"'γO12-δGδ, wherein 0≤α≤0.4,0≤β≤
0.4,0≤γ≤0.4,0≤δ≤0.5, and α, β, δ are not zero simultaneously；M' is at least one of Cu, Mg, Zn, Ca element；
M " is at least one of W, Mo, Nb, V element；M " ' is at least one of Ce, Zr, Ge, Al element；G is in F, Cl, Br, I
At least one element.
The active coating thickness of solid state lithium battery surface modified anode material is 2~100nm, covering rate 70
~100%。
M in above-mentioned positive electrode active material matrix is preferably at least one of La, Mo, Zr, W, Nb, Al element.
M' in above-mentioned activity clad is preferably at least one of Mg, Zn, Ca element.
M'' in above-mentioned activity clad is preferably at least one of W, Mo, V element.
It is described the present invention also provides a kind of polymer-based solid state lithium battery, including anode, cathode and polymer dielectric
Anode include above-mentioned solid state lithium battery surface modified anode material.
Another object of the present invention is to provide a kind of solid state lithium battery preparation method of surface modified anode material, packets
Include following steps:
(1) dopant solution, aqueous slkali and the complexing of the mixing salt solution, the source containing M of transition metal Ni, Co, Mn are prepared respectively
Agent solution；
(2) continuous in manner of cocurrent flow to add by the mixing salt solution of step (1), dopant solution, aqueous slkali and enveloping agent solution
Enter in reactor and reacted, product is obtained into presoma after being filtered, washed, drying, sieve；
(3) by lithium source and presoma, mixing treatment is carried out according to molar ratio Li/(Ni+Co+Mn+M)=0.95 ~ 1.05,600
~1100 DEG C of calcinings 4 ~ for 24 hours, finally sintered product is crushed excessively, being sieved obtains positive electrode active material matrix；
(4) according to coating Li4-αM'αTi5-β-γM"βM"'γO12-δGδStoichiometric ratio, by titanium source, lithium source, the source M', M " source,
M " ' source, the source anion G are dissolved in solvent, and additive are added, and form mixed liquor A after being sufficiently stirred；
(5) positive electrode active material matrix is added to the mixed liquor A of step (4), continuous heating stirs 1 ~ 5h at 50 ~ 100 DEG C, then
It is dry, obtain dry powder；
(6) it will be calcined after dry powder sieving processing, be cooled to room temperature after reaction, crush, be sieved, obtain solid-state lithium
Battery surface modified anode material；
In above-mentioned preparation method, the source M be Ga, Sc, In, Y, Ce, Co, La, Cr, Mo, Mn, Fe, Hf, Zr, W, Nb, Sm,
The metal salt of at least one of Al element；
In above-mentioned preparation method, the source M' is the metal salt of at least one of Cu, Mg, Zn, Ca element；The source M " be W, Mo,
The metal salt of at least one of Nb, V element；M " ' source is the metal salt of at least one of Ce, Zr, Ge, Al element；The source G is solvable
At least one of the metal halide of Li, M', M " or M " ' element of property.
In above-mentioned preparation method, the enveloping agent solution is citric acid, salicylic acid, ammonium hydroxide, sulfosalicylic acid, ethylenediamine
One or more of tetraacethyl；In above-mentioned preparation method, the aqueous slkali is sodium hydroxide, potassium hydroxide, lithium hydroxide
One or more of solution；In above-mentioned preparation method, the lithium source is LiOH, Li2CO3、LiNO3、CH3Appointing in COOLi
It anticipates one kind.
In above-mentioned preparation method, calcination temperature described in step (3) is preferably 600~1000 DEG C, and calcination time is preferred
For 5~15h.
In above-mentioned preparation method, titanium source described in step (4) is titanyl sulfate, in butyl titanate, isopropyl titanate
Any one.
In above-mentioned preparation method, additive described in step (4) be citric acid, ethylene glycol, triethanolamine, glycine,
At least one of ammonium hydroxide.
In above-mentioned preparation method, calcination temperature described in step (6) is 400~900 DEG C, and calcination time is 2~10h.
Beneficial effects of the present invention are as follows:
(1) active clad Li4-αM'αTi5-β-γM"βM"'γO12-δGδIt is good with solid polyelectrolyte compatibility, it is coated on
Positive-active matrix surface, it is possible to prevente effectively from improving the circulation of solid state battery to the catalyzed corrosion of solid polyelectrolyte
Stability.
(2) above-mentioned active clad has good lithium ion conduction ability, for positive active matrix and polymer solid
Electrolyte provides unobstructed ion transmission channel, and interface resistance can be effectively reduced, and the performance of battery is promoted to play.
(3) M' introduced in above-mentioned active matter clad can realize Li doping；The M ", M " ' of introducing can be achieved Ti
Doping introduces the alternative Lattice Oxygen of anion element, makes part Ti4+It is changed into Ti3+, to generate charge compensation, significantly improve
The electronic conduction ability of clad；When clad 100% covers positive electrode substrate, guarantee between positive electrode active material matrix and electrode
Electric charge transfer, significantly alleviation electrode polarization.
(4) clad structure can be stablized by rationally introducing M " ' element in active clad, regulated and controled coating thickness, promoted
Lithium ion diffusion.
Detailed description of the invention
Fig. 1 is the transmission electron microscopy figure of surface modified anode material prepared by embodiment 1.
Fig. 2 is surface modified anode material and positive electrode active material the matrix 0.1C in solid state lithium battery prepared by embodiment 1
Under loop test figure.
Fig. 3 is surface modified anode material prepared by embodiment 1 and surface modified anode material prepared by comparative example solid
The electrochemical AC impedance figure measured in state lithium battery.
Specific embodiment
Drawings and the specific embodiments are described further the present invention with reference to embodiments, these embodiments are only used for
The bright present invention is not limiting the scope of the invention.
The microscopic appearance of material is measured by transmission electron microscope in following embodiment.
The electrochemical AC impedance of material is measured by electrochemical workstation in following embodiment.
Solid state lithium battery packaging technology in following example 1 ~ 6 are as follows:
(1) preparation of anode pole piece: PEO, PS, LiTFSI are dissolved in acetonitrile according to weight ratio 2:1 and form homogeneous solution, then will
Modified anode material, acetylene black are added above-mentioned solution according to 5 times of lithium salts weight, 2 times respectively and are prepared into slurry.It then will be described
Slurry is coated on carbon-coated aluminum foils, and in 60 DEG C of vacuum drying 10h, obtains anode pole piece.
(2) preparation of solid electrolyte: by PEO, LiTFSI, solid electrolyte Li7La3Zr2O12Nano particle is according to weight
Ratio than 6:3:1 is dissolved in acetonitrile, forms slurry after evenly mixing.The slurry is applied to polytetrafluoroethylene film, it is dry at 60 DEG C
After dry 12h, throws off polytetrafluoroethylene film and obtain solid electrolyte.
(3) preparation of solid state lithium battery: above-mentioned anode pole piece, solid electrolyte, metal lithium sheet are superimposed, roll-in
After obtain solid state lithium battery.
Above-mentioned cell assembling processes are completed in the glove box full of argon gas, and battery testing is complete under 60 DEG C of constant temperatures
At.
Comparative example
(1) according to Ni, Co, Mn, La elemental mole ratios be 6:2:1.8:0.2 ratio, prepare 2mol/L nickel sulfate, cobaltous sulfate,
Manganese sulfate and lanthanum nitrate mixing salt solution.Prepare 7mol/L sodium hydroxide aqueous slkali；Prepare 6mol/L ammonium hydroxide enveloping agent solution.
(2) mixing salt solution, aqueous slkali, ammonium hydroxide enveloping agent solution are continuously added to carry out in blender in manner of cocurrent flow
Reaction, speed of agitator are 120 revs/min.Controlling mixing salt solution feed liquor flow simultaneously is 40L/h, controls aqueous slkali feed liquor stream
Amount is 15~25L/h, and enveloping agent solution feed liquor flow is 5~8L/h, and control pH is 11.5~11.7, the control of whole system temperature
At 55 DEG C.When reaction is completed, holding temperature, speed of agitator are constant, continue to stir 20min, the nickel cobalt manganese hydrogen-oxygen that then will be obtained
Compound slurry is separated by solid-liquid separation, is washed, and sieves after 100 DEG C of drying 10h of filter cake, product is washed, filtered and is dried, is obtained
To the presoma of La element doping.
(3) above-mentioned presoma and lithium carbonate are uniformly mixed with the ratio of Li/ (Ni+Co+Mn+La)=1.02,880
DEG C sintering 10h, product is crushed excessively, sieving processing, obtain positive electrode active material matrix, average grain diameter D50It is 10 μm.
(4) according to coating Li4Ti5O12Middle each element metering ratio weighs raw acetic acid lithium, butyl titanate.By above-mentioned original
Material is dissolved in ethanol solution, and stirring at normal temperature after 0.01mol/L citric acid is added, and forms pH then to ammonium hydroxide is added in above-mentioned solution
=10 mixed solution.
(5) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 1h at 60 DEG C, transfers them to vacuum
It is completely dried at 100 DEG C of drying box, obtains dry powder.
(6) above-mentioned dry powder sieving is handled, subsequent 600 DEG C of sintering 5h, after being cooled to room temperature, crushes, sieving, obtains
Li4Ti5O12The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 10nm, and covering rate is
100%。
The positive modified material of this comparative example preparation is assembled into solid state lithium battery, battery after 0.1C circulation 100 times
Energy density is 275 Wh/kg.
Embodiment 1
(1) preparation method with comparative example of positive electrode active material matrix are consistent.
(2) according to coating Li3.9Mg0.1Ti4.9Zr0.1O12Middle each element measures ratio, weigh raw acetic acid lithium, magnesium carbonate,
Butyl titanate, zirconium nitrate solution.Above-mentioned raw materials are dissolved in ethanol solution, and stirring at normal temperature after 0.01mol/L citric acid is added,
Then to the mixed solution that ammonium hydroxide formation pH=10 are added in above-mentioned solution.
(3) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 1h at 60 DEG C, transfers them to vacuum
It is completely dried at 100 DEG C of drying box, obtains dry powder.
(4) above-mentioned dry powder sieving is handled, subsequent 600 DEG C of sintering 5h, after being cooled to room temperature, crushes, sieving, obtains
Li3.9Mg0.1Ti4.9Zr0.1O12The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 10nm,
Covering rate is 100%.
Fig. 1 transmission electron microscope is this it appears that Li3.9Mg0.1Ti4.9Zr0.1O12Coating thickness is only 10nm, and
It is evenly coated at positive electrode active material matrix surface.
Fig. 2 is the cycle performance curve of surface modified anode material and active matter matrix, it can be seen that by uniformly cladding
Modified positive electrode cycle performance is substantially better than matrix, and battery energy density still reaches 300Wh/kg after 100 weeks circulations；It says
Bright clad effectively prevents active matter matrix to the catalyzed corrosion of solid polyelectrolyte, to significantly increase solid state battery
Electrical property.In addition, the made positive electrode of the present embodiment cycle performance in solid state battery is substantially better than comparative example, illustrate to wrap
Be conducive to cathode material structure after coating introducing Mg, Zr element to stablize.
Fig. 3 is electrochemical AC impedance figure, can be seen that 1 impedance of embodiment is significantly less than comparative example in figure, illustrates to coat
The electronic conduction ability of positive electrode is promoted after layer introducing Mg, Zr element.
Embodiment 2
(1) preparation method of positive electrode active material matrix is consistent with comparative example.
(2) according to coating Li4Ti4.8Mo0.2O12Middle each element metering ratio weighs raw material lithium nitrate, titanyl sulfate, molybdic acid
Ammonium.Above-mentioned raw materials are dissolved in ethyl alcohol and water mixed solution (ethyl alcohol: water=1:3), stirring at normal temperature, then to being added in above-mentioned solution
The mixed solution of triethanolamine formation pH=9.2.
(3) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 1h at 70 DEG C, transfers them to vacuum
It is completely dried at 120 DEG C of drying box.
(4) above-mentioned desciccate sieving is handled, subsequent 700 DEG C of sintering 6h, after being cooled to room temperature, crushes, sieving, obtains
To Li4Ti4.8Mo0.2O12The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 15nm, are coated
Rate is 70%.
Anode modified material manufactured in the present embodiment is assembled into solid state lithium battery, battery after 0.1C circulation 100 times
Energy density is that 283 Wh/kg are higher than corresponding 260 Wh/kg of battery energy density of active matter matrix.
Embodiment 3
(1) preparation method with comparative example of positive electrode active material matrix are consistent.
(2) according to coating Li4Ti5O11.8Br0.2Middle each element metering ratio weighs raw material lithium bromide, titanyl sulfate.It will be upper
It states raw material and is dissolved in ethyl alcohol and water mixed solution (ethyl alcohol: water=1:3), stirring at normal temperature is formed then to ammonium hydroxide is added in above-mentioned solution
The mixed solution of pH=9.8.
(3) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 50min at 80 DEG C, is transferred them to
It is completely dried at 120 DEG C of vacuum oven.
(4) above-mentioned desciccate sieving is handled, subsequent 750 DEG C of sintering 5h, after being cooled to room temperature, crushes, sieving, obtains
To Li4Ti5O11.8Br0.2The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 20nm, are coated
Rate is 70%.
Anode modified material manufactured in the present embodiment is assembled into solid state lithium battery, battery after 0.1C circulation 100 times
Energy density is that 280 Wh/kg are higher than the corresponding battery energy density 260Wh/kg of active matter matrix.
Embodiment 4
(1) 1.5mol/L nickel sulfate, cobaltous sulfate, sulfuric acid are prepared according to the ratio that Ni, Co, Mn elemental mole ratios are 8.3:1:0.7
Manganese mixing salt solution.Prepare 6.5mol/L sodium hydroxide aqueous slkali；Prepare 6.5mol/L ammonium hydroxide enveloping agent solution.
(2) mixing salt solution, aqueous slkali, ammonium hydroxide enveloping agent solution are continuously added to carry out in blender in manner of cocurrent flow
Reaction, speed of agitator are 110 revs/min.Controlling mixing salt solution feed liquor flow simultaneously is 40L/h, controls aqueous slkali feed liquor stream
Amount is 16~24L/h, and enveloping agent solution feed liquor flow is 4~8L/h, and control pH is 11.2~11.5, the control of whole system temperature
At 60 DEG C.When reaction is completed, holding temperature, speed of agitator are constant, continue to stir 30min, the precursor pulp that then will be obtained
It is separated by solid-liquid separation, washed, sieved after 100 DEG C of drying 5h of filter cake, product is washed, filtered and is dried.
(3) above-mentioned presoma and lithium hydroxide are uniformly mixed with the ratio of 1:1.03, under oxygen atmosphere, 750 DEG C of burnings
12h is tied, product is crushed, sieving processing excessively, obtains positive electrode active material matrix.
(4) according to coating Li4Ti4.9Ce0.1O11.8F0.2Middle each element metering, which is compared, weighs raw material lithium nitrate, titanyl sulfate,
Cerous acetate, lithium fluoride.Above-mentioned raw materials are dissolved in stirring at normal temperature after aqueous solution, form pH then to ethylene glycol is added in above-mentioned solution
=9.7 mixed solution.
(5) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 1.5h at 60 DEG C, is transferred them to true
It is completely dried at 100 DEG C of empty drying box.
(6) above-mentioned desciccate sieving is handled, subsequent 600 DEG C of sintering 8h, after being cooled to room temperature, crushes, sieving, obtains
To Li4Ti4.9Ce0.1O11.8F0.2The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 20nm,
Covering rate is 75%.
Anode modified material manufactured in the present embodiment is assembled into solid state lithium battery, battery after 0.1C circulation 100 times
Energy density is that 290 Wh/kg are higher than the corresponding battery energy density 270Wh/kg of active matter matrix.
Embodiment 5
(1) 2mol/L nickel sulfate, cobaltous sulfate, sulphur are prepared according to the ratio that Ni, Co, Mn, Zr elemental mole ratios are 6:2:1.9:0.1
Sour manganese and zirconium nitrate mixing salt solution.Prepare 7mol/L sodium hydroxide aqueous slkali；Prepare 6mol/L ammonium hydroxide enveloping agent solution.
(2) mixing salt solution, aqueous slkali, ammonium hydroxide enveloping agent solution are continuously added to carry out in blender in manner of cocurrent flow
Reaction, speed of agitator are 110 revs/min.Controlling mixing salt solution feed liquor flow simultaneously is 40L/h, controls aqueous slkali feed liquor stream
Amount is 14~24L/h, and enveloping agent solution feed liquor flow is 5~9L/h, and control pH is 11.5~11.7, the control of whole system temperature
At 60 DEG C.When reaction is completed, holding temperature, speed of agitator are constant, continue to stir 20min, the nickel cobalt manganese hydrogen-oxygen that then will be obtained
Compound slurry is separated by solid-liquid separation, is washed, and sieves after 100 DEG C of drying 10h of filter cake, product is washed, filtered and is dried, is obtained
To presoma.
(3) above-mentioned presoma and lithium carbonate are uniformly mixed with the ratio of Li/ (Ni+Co+Mn+Zr)=1.03, at 870 DEG C
It is sintered 10h, product is crushed, sieving processing excessively, obtains positive electrode active material matrix, average grain diameter D50It is 12 μm.
(4) according to coating Li4Ti4.8V0.1Al0.1O12Middle each element metering ratio weighs oxide spinel lithium, aluminum nitrate, vanadic acid
Ammonium, butyl titanate.Above-mentioned raw materials are dissolved in stirring at normal temperature after ethanol solution, are formed then to citric acid is added in above-mentioned solution
The mixed solution of pH=9.6.
(5) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 1h at 60 DEG C, transfers them to vacuum
It is completely dried at 100 DEG C of drying box.
(6) above-mentioned desciccate sieving is handled, subsequent 650 DEG C of sintering 5h, after being cooled to room temperature, crushes, sieving, obtains
To Li4Ti4.8V0.1Al0.1O12The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 22nm,
Covering rate is 85%.
Anode modified material manufactured in the present embodiment is assembled into solid state lithium battery, battery after 0.1C circulation 100 times
Energy density is 278 Wh/kg.
Embodiment 6
(1) preparation method with embodiment 5 of positive electrode active material matrix is consistent.
(2) according to coating Li4Ti5O11.8F0.2Middle each element metering is than weighing raw material fluorinated lithium, isopropyl titanate, carbonic acid
Lithium.Above-mentioned raw materials are dissolved in stirring at normal temperature after ethanol solution, then to the mixing for ammonium hydroxide is added in above-mentioned solution forming pH=10.1
Solution.
(5) positive electrode active material matrix is added in above-mentioned mixed solution, after stirring 1h at 60 DEG C, transfers them to vacuum
It is completely dried at 100 DEG C of drying box.
(6) above-mentioned desciccate sieving is handled, subsequent 600 DEG C of sintering 6h, after being cooled to room temperature, crushes, sieving, obtains
To Li4Ti5O11.8F0.2The solid state lithium battery of cladding surface modified anode material, the material coating thickness are 15nm, are coated
Rate is 90%.
Anode modified material manufactured in the present embodiment is assembled into solid state lithium battery, battery after 0.1C circulation 100 times
Energy density is 282 Wh/kg.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (12)
1. a kind of solid state lithium battery surface modified anode material, which is characterized in that including positive electrode active material matrix and matrix table
The active clad in face, average grain diameter D50It is 2~30 μm；
The positive electrode active material matrix is nickle cobalt lithium manganate, chemical formula LiaNixCoyMn1-x-y-zMzO2, wherein 0.95≤a≤
In 1.05,0≤z≤0.05, x+y+z=1, M Ga, Sc, In, Y, Ce, Co, La, Cr, Mo, Mn, Fe, Hf, Zr, W, Nb, Sm, Al
At least one element；
The chemical formula of the activity clad is Li4-αM'αTi5-β-γM"βM"'γO12-δGδ, wherein 0≤α≤0.4,0≤β≤0.4,
0≤γ≤0.4,0≤δ≤0.5, and α, β, δ are not zero simultaneously；M' is at least one of Cu, Mg, Zn, Ca element；M " is
W, at least one of Mo, Nb, V element；M " ' is at least one of Ce, Zr, Ge, Al element；G be F, Cl, Br, I in extremely
A kind of few element.
2. solid state lithium battery according to claim 1 surface modified anode material, which is characterized in that the activity packet
Coating thickness is 2~100nm, and covering rate is 70 ~ 100%.
3. solid state lithium battery according to claim 1 surface modified anode material, which is characterized in that the anode is living
M in property object matrix is preferably at least one of La, Mo, Zr, W, Nb, Al element.
4. solid state lithium battery according to claim 1 surface modified anode material, which is characterized in that the activity packet
M' in coating is preferably at least one of Mg, Zn, Ca element.
5. solid state lithium battery according to claim 1 surface modified anode material, which is characterized in that the activity packet
M'' in coating is preferably at least one of W, Mo, V element.
6. a kind of solid state lithium battery, including anode, cathode and polymer dielectric, which is characterized in that the anode includes power
Benefit requires the solid state lithium battery of 1-5 any one surface modified anode material.
7. a kind of solid state lithium battery preparation method of surface modified anode material, which comprises the following steps:
(1) dopant solution, aqueous slkali and the complexing of the mixing salt solution, the source containing M of transition metal Ni, Co, Mn are prepared respectively
Agent solution；
(2) continuous in manner of cocurrent flow to add by the mixing salt solution of step (1), dopant solution, aqueous slkali and enveloping agent solution
Enter in reactor and reacted, product is obtained into presoma after being filtered, washed, drying, sieve；
(3) by lithium source and presoma, mixing treatment is carried out according to molar ratio=0.95 Li/(Ni+Co+Mn+M) ~ 1.05,
600~1100 DEG C of calcinings 4 ~ for 24 hours, finally sintered product is crushed excessively, being sieved obtains positive electrode active material matrix；
(4) according to coating Li4-αM'αTi5-β-γM"βM"'γO12-δGδStoichiometric ratio, by titanium source, lithium source, the source M', M " source,
M " ' source, the source anion G are dissolved in solvent, and additive are added, and form mixed liquor A after being sufficiently stirred；
(5) positive electrode active material matrix is added to the mixed liquor A of step (4), continuous heating stirs 1 ~ 5h at 50 ~ 100 DEG C, then
It is dry, obtain dry powder；
(6) it will be calcined after dry powder sieving processing, be cooled to room temperature after reaction, crush, be sieved, obtain solid-state lithium
Battery surface modified anode material；
The source M is at least one of Ga, Sc, In, Y, Ce, Co, La, Cr, Mo, Mn, Fe, Hf, Zr, W, Nb, Sm, Al element
Metal salt；
The source M' be Cu, Mg, Zn, Ca, at least one of element metal salt；The source M " is at least one of W, Mo, Nb, V
The metal salt of element；M " ' source is the metal salt of at least one of Ce, Zr, Ge, Al element；The source G be soluble Li, M', M " or
At least one of the metal halide of M " ' element.
8. the solid state lithium battery according to claim 7 preparation method of surface modified anode material, which is characterized in that institute
The enveloping agent solution stated is one or more of citric acid, salicylic acid, ammonium hydroxide, sulfosalicylic acid, ethylenediamine tetra-acetic acid；It is described
Aqueous slkali be one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide solution；The lithium source be LiOH,
Li2CO3、LiNO3、CH3Any one in COOLi.
9. the solid state lithium battery according to claim 7 preparation method of surface modified anode material, which is characterized in that step
Suddenly calcination temperature described in (3) is preferably 600~1000 DEG C, and calcination time is preferably 5~15h.
10. the solid state lithium battery according to claim 7 preparation method of surface modified anode material, which is characterized in that
Titanium source described in step (4) is titanyl sulfate, butyl titanate, any one in isopropyl titanate.
11. the solid state lithium battery according to claim 7 preparation method of surface modified anode material, which is characterized in that
Additive described in step (4) is at least one of citric acid, ethylene glycol, triethanolamine, glycine, ammonium hydroxide.
12. the solid state lithium battery according to claim 7 preparation method of surface modified anode material, which is characterized in that
Calcination temperature described in step (6) is 400~900 DEG C, and calcination time is 2~10h.
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| CN114447296A (en) * | 2021-12-30 | 2022-05-06 | 北京当升材料科技股份有限公司 | Cathode material, preparation method and application thereof, and lithium ion battery |
| CN114784235A (en) * | 2022-03-29 | 2022-07-22 | 万向一二三股份公司 | High-voltage composite positive plate, preparation method thereof and all-solid-state lithium battery |
| CN115036509A (en) * | 2022-07-11 | 2022-09-09 | 天津市捷威动力工业有限公司 | Positive electrode material for solid-state battery and preparation method and application thereof |
| CN115084472A (en) * | 2022-06-30 | 2022-09-20 | 北京当升材料科技股份有限公司 | Surface-coated positive electrode material, preparation method thereof and lithium ion battery |
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| CN114447296A (en) * | 2021-12-30 | 2022-05-06 | 北京当升材料科技股份有限公司 | Cathode material, preparation method and application thereof, and lithium ion battery |
| CN114447296B (en) * | 2021-12-30 | 2024-05-03 | 江苏当升材料科技有限公司 | Positive electrode material, preparation method and application thereof, and lithium ion battery |
| CN114784235A (en) * | 2022-03-29 | 2022-07-22 | 万向一二三股份公司 | High-voltage composite positive plate, preparation method thereof and all-solid-state lithium battery |
| CN114784235B (en) * | 2022-03-29 | 2024-02-02 | 万向一二三股份公司 | High-voltage composite positive plate, preparation method thereof and all-solid-state lithium battery |
| CN115084472A (en) * | 2022-06-30 | 2022-09-20 | 北京当升材料科技股份有限公司 | Surface-coated positive electrode material, preparation method thereof and lithium ion battery |
| WO2023236906A1 (en) * | 2022-06-30 | 2023-12-14 | 北京当升材料科技股份有限公司 | Surface-coated positive electrode material and preparation method therefor, and lithium ion battery |
| US11984586B1 (en) | 2022-06-30 | 2024-05-14 | Beijing Easpring Material Technology Co., Ltd. | Surface-coated positive electrode material and preparation method therefor, and lithium ion battery |
| CN115036509A (en) * | 2022-07-11 | 2022-09-09 | 天津市捷威动力工业有限公司 | Positive electrode material for solid-state battery and preparation method and application thereof |
| CN115036509B (en) * | 2022-07-11 | 2023-07-07 | 天津市捷威动力工业有限公司 | Positive electrode material for solid-state battery and preparation method and application thereof |
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