CN106602024B - Surface in-situ modification type lithium-rich material and preparation method thereof - Google Patents
Surface in-situ modification type lithium-rich material and preparation method thereof Download PDFInfo
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- CN106602024B CN106602024B CN201611237904.1A CN201611237904A CN106602024B CN 106602024 B CN106602024 B CN 106602024B CN 201611237904 A CN201611237904 A CN 201611237904A CN 106602024 B CN106602024 B CN 106602024B
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- lithium
- rich material
- phosphate
- situ
- equal
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- 239000000463 material Substances 0.000 title claims abstract description 218
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 164
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 73
- 238000012986 modification Methods 0.000 title claims abstract description 43
- 230000004048 modification Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 85
- 239000011247 coating layer Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract description 30
- 150000002641 lithium Chemical class 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 3
- 150000003891 oxalate salts Chemical class 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 33
- 239000012266 salt solution Substances 0.000 claims description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 235000021317 phosphate Nutrition 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 24
- 239000010452 phosphate Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- 239000011572 manganese Substances 0.000 description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002002 slurry Substances 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 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
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
Classifications
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- 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
- H01M4/485—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
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Abstract
The invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, the lithium-rich material precursor is a mixture of at least one of oxides, hydroxides, carbonates and oxalates of MnMA and a lithium source, M is a metal element, and A is at least one of S, P, B and F. The preparation method is also disclosed, and the in-situ modified lithium-rich material is formed by coating a metal phosphate compound on the lithium-rich material precursor particles and then sintering at high temperature. The in-situ modification structure has the advantages that the surface stability and the conductivity of the lithium-rich material are greatly improved, so that the charge-discharge specific capacity, the efficiency, the multiplying power and the cycle performance of the material are obviously improved; the preparation method has the advantages of simple preparation process, low cost and good result reproducibility, and is suitable for large-scale popularization.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a surface in-situ modification type lithium-rich material and a preparation method thereof.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life, environmental protection, low cost and the like, is rapidly developed in more than 20 years, and is applied to the fields of communication, traffic, military, medical treatment, entertainment and the like. With the rapid development of electric vehicles and the like in recent years, high-specific-energy and high-power lithium ion batteries become essential for the development of future lithium ion batteriesBut in a different direction. Current commercial positive electrode materials, such as LiCoO2、LiFePO4、LiMn2O4Ternary materials, etc., all having a low specific capacity: (<200 mAh/g). Since the positive electrode material is a main factor limiting the specific energy of the battery, in order to develop a high specific energy battery, a positive electrode material with a higher specific capacity is urgently needed to be found.
In recent years, lithium-rich materials have attracted much attention because of their high specific capacity, good safety, low cost, and the like. The specific capacity of the material is generally over 250mAh/g, and even reaches 300mAh/g in some reports (NanoLett.,2008,8(3): 957-. Although the lithium-rich material has high capacity, the lithium-rich material has poor cycle performance and serious voltage attenuation problems, thereby restricting the commercial application of the lithium-rich material. It is therefore desirable to modify lithium-rich materials to improve their specific capacity and voltage holding ratio during cycling.
The main methods for improving the electrochemical performance of lithium-rich materials are coating and doping (adv. mater.2012,24, 1192-. The most common coating method is to use Al (OH)3、Al2O3、TiO2The inert materials are used for carrying out surface coating (Electrochimica Acta 50(2005) 4784-. Patent publication No. CN 103035906A adopts wet coating method to coat Li [ Li ](1-2x)/3MxMn(2-x)/3]O2Coated with 3-10 wt% LiMnPO4Is beneficial to the improvement of the rate capability of the material, and LiMnPO4PO of (1)4 3-Can effectively inhibit the dissolution of electrode materials in electrolyte, prevent hydrofluoric acid in the electrolyte from corroding the surface of the active material, and improve the thermodynamic stability of the material. The patent with publication number CN101859887 discloses a technical scheme that a phosphate is coated on a positive electrode material, so that the positive electrode material can play a role in protecting the material and improving capacity and rate performance. Disclosed is aThe patent No. CN 103904311a discloses a technical solution of coating a layer of lithium iron phosphate on the surface of a lithium-rich material finished product, where the lithium source used by the lithium iron phosphate is from lithium in the lithium-rich material, and the result shows that "surplus" lithium in the lithium-rich material is reduced, which is beneficial to the stability of the material structure, but this post-coating on the lithium-rich material finished product by a liquid phase method requires that the lithium-rich material finished product is first immersed in a solution, and then undergoes a series of treatment processes such as precipitation, filtration, washing, drying, and heat treatment, which is complicated. In addition, the coating layer is not uniform, and the binding degree between the coating layer and the lithium-rich material is not compact enough. Therefore, the precipitation of oxygen and the migration of transition metals cannot be fundamentally reduced or suppressed, and thus the problems of poor cycle performance, voltage decay, and the like of the material cannot be effectively solved.
The research for improving the structural stability and the electrochemical performance of the lithium-rich material realizes the beneficial effects of improving the capacity and the rate performance to a certain extent, but the research is considered in the comprehensive market, the lithium-rich material is improved, the preparation method is simple, the selected material is low in cost, and the method can be popularized in a market way.
Disclosure of Invention
In order to solve the technical problems, the invention provides a surface in-situ modification type lithium-rich material and a preparation method thereof, and aims to improve the surface stability and the conductivity of the lithium-rich material and obviously improve the charge-discharge specific capacity, the efficiency, the multiplying power and the cycle performance of the material.
In order to achieve the purpose, the technical scheme disclosed by the invention is as follows: the raw materials of the surface in-situ modification type lithium-rich material developed by the invention comprise a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, the lithium-rich material precursor is a mixture of at least one of oxides, hydroxides, carbonates and oxalates of MnMA and a lithium source, M is a metal element, and A is at least one of S, P, B and F. The lithium-rich material precursor is coated with metal phosphate, the coating layer is uniform and high in binding degree, and the coating layer and the raw material of the lithium-rich material can generate interfacial reaction to form a lithium-containing intermediate layer (inter layer) with high conductivity, so that the ionic conductivity and the electrochemical performance of the material are improved.
Further, the metal phosphate is at least one of corresponding phosphates of Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni and Mo. The selected metal phosphate can coat the lithium-rich material precursor to obtain the lithium-rich material with high charge-discharge specific capacity, efficiency, multiplying power and cycle performance.
Furthermore, the metal M in the lithium-rich material precursor is at least one of Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn.
Further, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium acetate and lithium nitrate, wherein the molar ratio of Li to MnMA is 1-2.5: 1.
further, the molar weight percentage of the coating layer in the raw material is 0.01% -12%, and the molar weight percentage of the lithium-rich material precursor is 88% -99.99%. The selected coating molar weight percentage gives consideration to the thickness of a material coating layer and the performance of the material, and the material with high charge-discharge specific capacity, efficiency, multiplying power and cycle performance can be obtained through the verification of the lithium-rich material obtained in the subsequent steps, and meanwhile, the used raw material has the lowest quantity and low cost.
Furthermore, the chemical formula of the in-situ modification type lithium-rich material obtained by the invention is (1-a) Li1+ xMnyMzAwOr-aLibMecPO4Wherein a is more than or equal to 0.0001 and less than or equal to 0.12, b is more than or equal to 0 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 1.5, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, w is more than or equal to 0 and less than or equal to 0.
The invention also discloses a method for preparing the lithium-rich material, which comprises the steps of coating a metal phosphate compound on the lithium-rich material precursor particles, and then sintering at high temperature to form the in-situ modified lithium-rich material. The coating layer of the in-situ coated lithium-rich material obtained by the coating method is uniform, and the coating layer and the lithium-rich material have good binding degree and stability, so that negative reaction generated by contact of the lithium-rich material and electrolyte is effectively prevented; and simultaneously, the redundant lithium source in the lithium-rich precursor and the coating material are subjected to in-situ chemical reaction to form a lithium-containing high-conductivity layer. Thereby obviously improving the discharge capacity, the first charge-discharge efficiency and the rate capability of the lithium-rich material, and effectively improving the problems of the cycle performance, the voltage attenuation and the like of the material.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; wherein the molar weight of the soluble phosphate is 1-3 times of that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001-0.12: 0.9999-0.88.
(2) Continuously stirring the mixed solution obtained in the step (1), and then drying;
(3) and (3) performing heat preservation on the material dried in the step (2) twice, and obtaining the surface in-situ modification type lithium-rich material after heat preservation.
Furthermore, in the step (1), the concentration of the soluble metal salt solution in the step (1) is 0.001-10mol/L, the concentration of the soluble phosphate salt solution is 0.001-10mol/L, the selected mass concentration is convenient to dissolve, and the lithium-rich material obtained through the subsequent steps is verified to obtain a material with high charge-discharge specific capacity, efficiency, multiplying power and cycle performance, so that the beneficial effects are obtained, and meanwhile, the used raw material is the lowest in quantity and low in cost.
Further, the soluble phosphate in step (1) includes at least one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate.
Further, the soluble metal salt in the step (1) is at least one of soluble salts of Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni and Mo.
Further, in the step (2), the mixed solution obtained in the step (1) is continuously stirred for 10min-12h, and then is dried. Drying here includes any form of drying known in the art, for example heat drying, forced air drying, vacuum drying, spray drying, microwave drying and centrifugal drying are possible.
In the step (1), the concentration of the soluble metal salt solution is 0.001-10mol/L, and the concentration of the soluble phosphate salt solution is 0.001-10 mol/L.
Further, in the step (2), the mixed solution obtained in the step (1) is continuously stirred for 10min-12h, and then is dried.
Further, the two heat preservation operations in the step (3) refer to the operations of sequentially preserving heat at 400-.
The selection of temperature and other parameter conditions in the steps of the method is favorable for the uniformity of the coating layer; on the other hand, the coating layer and the lithium-rich material are sintered at the same time, so that the bonding degree of the coating layer and the lithium-rich material is increased, and the stability of the coating layer is improved; and the coating layer and the raw material of the lithium-rich material can also generate interface reaction in the sintering process to form a lithium-containing intermediate layer (interlayer) with higher conductivity, thereby improving the ionic conductivity and the electrochemical performance of the material.
The positive progress effects of the invention are as follows: the in-situ modification structure greatly improves the surface stability and the conductivity of the lithium-rich material, so that the charge-discharge specific capacity, the efficiency, the multiplying power and the cycle performance of the material are obviously improved; the preparation method has the advantages of simple preparation process, low cost and good result reproducibility, and is suitable for large-scale popularization.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the synthesized comparative example 1, example 1 and example 2 cathode materials according to the present invention.
Fig. 2 is a graph comparing the first charge and discharge curves of the positive electrode materials of comparative example 1, example 1 and example 2 synthesized according to the present invention, in which curve 1 is comparative example 1, curve 2 is example 1, and curve 3 is example 2.
Fig. 3 is a graph comparing discharge curves at different current densities for the synthesized positive electrode materials of comparative example 1, example 1 and example 2 according to the present invention.
Fig. 4 is a graph comparing the cycle performance curves of comparative example 1, example 1 and example 2 cathode materials synthesized according to the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific examples.
The first embodiment is as follows: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically ferric phosphate, the ferric phosphate is prepared from diammonium hydrogen phosphate and ferric nitrate nonahydrate, and the lithium-rich material precursor is Ni0.13Co0.13Mn0.54O2And lithium hydroxide, wherein the molar ratio of the coating layer to the raw material is 0.01%, and the molar ratio of the lithium-rich material precursor is 99.99%, wherein Li and Ni0.13Co0.13Mn0.54The molar ratio of (A) to (B) is 1.5:1, and the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.9999Li1.5Mn0.54Ni0.13Co0.13O2-0.0001FePO4。
The lithium-rich material precursor can be prepared by adopting the prior art, and the in-situ modified lithium-rich material coated with the metal phosphate in the embodiment can also be prepared by adopting a method for preparing the lithium-rich material by adopting the prior art.
Example two: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically manganese phosphate, the manganese phosphate is prepared from ammonium dihydrogen phosphate and manganese acetate, and the lithium-rich material precursor is AlCr0.5The mol weight of the coating layer accounts for 12 percent of the raw material, 88 percent of the lithium-rich material precursor and AlCr0.5The molar ratio of Mn to Li is 1:2.5, and the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.88Li2MnAlCr0.5O3-0.12LiMnPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
The specific parameters such as the temperature and the like are adopted according to the achievement of the final product.
Example three: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically nickel phosphate, the nickel phosphate is prepared from ammonium dihydrogen phosphate and nickel nitrate hexahydrate, and the lithium-rich material precursor is Mg0.13Mo0.13Mn0.54S0.2Mixtures of carbonates with lithium acetate, Li and Mg0.13Mo0.13Mn0.54S0.2The molar ratio is 1:1, the molar weight of the coating layer accounts for 0.01 percent of the raw material, the lithium-rich material precursor accounts for 99.99 percent, and the obtained surface in-situ modification type lithium-rich material has the chemical formula of 0.9999LiMn0.54Mg0.13Mo0.1 3S0.2O1.8-0.0001LiNiPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 0.001mol/L, and the concentration of the selected soluble phosphate salt solution is 0.001 mol/L; wherein the molar weight of the soluble phosphate is 1 time of that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001: 0.9999.
(2) continuously stirring the mixed solution obtained in the step (1) for 10min, and then carrying out spray drying on the mixed solution;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 600 ℃ for 2 hours and preserving heat at 1000 ℃ for 3 hours.
Example four: the invention develops a surface in-situ modificationThe lithium-rich material comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically cobalt phosphate, the cobalt phosphate is prepared from sodium phosphate and cobalt nitrate hexahydrate, and the lithium-rich material precursor is Ti0.13Zr0.13Mn0.54P0.1The mixture of oxalate and lithium nitrate, the mol of the coating layer accounts for 0.01 percent of the raw material, and the balance is a lithium-rich material precursor, wherein Li and Ti0.13Zr0.13Mn0.54P0.1The molar ratio is 1.2: 1, the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.9999Li1.2Mn0.54Ti0.13Zr0.13P0.1O2-0.0001LiCoPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 10mol/L, and the concentration of the selected soluble phosphate salt solution is 10 mol/L; the molar weight of the soluble phosphate is 3 times that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001: 0.9999.
(2) continuously stirring the mixed solution obtained in the step (1) for 12 hours, filtering and washing the mixed solution, and drying;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 400 ℃ for 8 hours and preserving heat at 700 ℃ for 36 hours.
Example five: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically aluminum phosphate, the aluminum phosphate is prepared from potassium phosphate and aluminum nitrate, and the lithium-rich material precursor is Fe0.1Ru0.1Mn0.54B0.1O2And lithium hydroxide, wherein the coating layer accounts for 12 mol percent of the raw materials, and the balance is a lithium-rich material precursor, wherein Li and Fe0.1Ru0.1Mn0.54B0.1In a molar ratio of 1.5:1, the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.88Li1.23Mn0.5Fe0.1Ru0.14B0.1O2-0.12AlPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 1mol/L, and the concentration of the selected soluble phosphate salt solution is 1 mol/L; wherein the molar weight of the soluble phosphate is 2 times of that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.12: 0.88.
(2) continuously stirring the mixed solution obtained in the step (1) for 1h, filtering and washing the mixed solution, and drying;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 450 ℃ for 5 hours and preserving heat at 800 ℃ for 25 hours.
Example six: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically zirconium phosphate, the zirconium phosphate is prepared from ammonium dihydrogen phosphate and zirconium isopropoxide, and the lithium-rich material precursor is Cu0.1Sn0.1Mn0.54F0.1O2With lithium hydroxide, in which Li is present in combination with Cu0.1Sn0.1Mn0.54F0.1In a molar ratio of 1.5:1, the molar weight of the coating layer accounts for 0.01 percent of the raw material, the rest is a lithium-rich material precursor, and the obtained surface in-situ modification type lithium-rich materialChemical formula of 0.9999Li1.23Mn0.54Cu0.1Sn0.1F0. 1O2-0.0001LiZr0.5PO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 2mol/L, and the concentration of the selected soluble phosphate salt solution is 2 mol/L; wherein the molar weight of the soluble phosphate is 1 time of that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001: 0.9999.
(2) continuously stirring the mixed solution obtained in the step (1) for 1h, and then carrying out spray drying on the mixed solution;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 500 ℃ for 2 hours and preserving heat at 850 ℃ for 20 hours.
Example seven: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically titanium phosphate, the titanium phosphate is prepared from phosphoric acid and tetrabutyl titanate, and the lithium-rich material precursor is Ni0.10Co0.10Mn0.57O2With lithium hydroxide, in which Li is mixed with Ni0.10Co0.10Mn0.57The molar ratio is 1.3: 1, the molar weight of the coating layer accounts for 12 percent of the raw material, the rest is a lithium-rich material precursor, and the obtained surface in-situ modification type lithium-rich material has a chemical formula of 0.88Li1.23Mn0.57Ni0.10Co0.10O2-0.12Ti0.75PO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 3mol/L, and the concentration of the selected soluble phosphate salt solution is 3 mol/L; wherein the molar weight of the soluble phosphate is 1-3 times of that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.12: 0.88.
(2) continuously stirring the mixed solution obtained in the step (1) for 2 hours, and then carrying out spray drying on the mixed solution;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 500 ℃ for 2 hours and preserving heat at 850 ℃ for 20 hours.
Example eight: the invention discloses a surface in-situ modification type lithium-rich material, which comprises a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically magnesium phosphate, the magnesium phosphate is prepared from diammonium hydrogen phosphate and magnesium sulfate, and the lithium-rich material precursor is Ni0.30Mn0.48Fe0.08O2And lithium hydroxide, the mass of the coating layer accounts for 12% of the mass of the raw materials, and the balance is a lithium-rich material precursor, wherein Li and Ni0.30Mn0.48Fe0.08In a molar ratio of 1.7: 1, the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.88Li1。13Mn0.48Ni0.30Fe0.08O2-0.12LiMgPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 4mol/L, and the concentration of the selected soluble phosphate salt solution is 4 mol/L; wherein the molar weight of the soluble phosphate is 3 times that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.12: 0.88.
(2) continuously stirring the mixed solution obtained in the step (1) for 6 hours, and then carrying out spray drying on the mixed solution;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 600 ℃ for 4 hours and preserving heat at 860 ℃ for 16 hours.
Example nine: the invention discloses a surface in-situ modification type lithium-rich material, which comprises raw materials of a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically zinc phosphate, the zinc phosphate is prepared from potassium phosphate and zinc sulfate, and the lithium-rich material precursor is Ni0.30Mn0.48Fe0.08O2And lithium hydroxide, the molar weight of the coating layer accounts for 0.01 percent of the raw material, and the balance is a lithium-rich material precursor, wherein Li and Ni0.30Mn0.48Fe0.08In a molar ratio of 1.3: 1, the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.9999Li1。13Mn0.48Ni0.30Fe0.08O2-0.0001LiZnPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 5mol/L, and the concentration of the selected soluble phosphate salt solution is 5 mol/L; wherein the molar weight of the soluble phosphate is 3 times that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001: 0.9999.
(2) continuously stirring the mixed solution obtained in the step (1) for 6 hours, filtering and washing the mixed solution, and then drying;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 600 ℃ for 4 hours and preserving heat at 860 ℃ for 16 hours.
Example ten: the invention discloses a surface in-situ modification type lithium-rich material which is developed by the invention, and the raw materials comprise a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate, specifically copper phosphate, the copper phosphate is prepared from ammonium phosphate and copper sulfate, and the lithium-rich material precursor is Ni0.30Mn0.48Fe0.08O2And lithium hydroxide, the molar weight of the coating layer accounts for 0.01 percent of the mass percent of the raw materials, and the balance is a lithium-rich material precursor, wherein Li and Ni0.30Mn0.48Fe0.08In a molar ratio of 1.12: 1 the chemical formula of the obtained surface in-situ modification type lithium-rich material is 0.9999Li1。1Mn0.48Ni0.30Fe0.08O2-0.00001CuPO4。
According to the method for preparing the in-situ modified lithium-rich material, the lithium-rich material precursor particles are coated with the metal phosphate compound, and then the in-situ modified lithium-rich material is formed through high-temperature sintering.
Adding soluble phosphate into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring; the concentration of the soluble metal salt solution is 6mol/L, and the concentration of the selected soluble phosphate salt solution is 6 mol/L; wherein the molar weight of the soluble phosphate is 3 times that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001: 0.9999.
(2) continuously stirring the mixed solution obtained in the step (1) for 6 hours, filtering and washing the mixed solution, and then drying;
(3) and (3) performing heat preservation on the material dried in the step (2) twice to obtain the surface in-situ modification type lithium-rich material, wherein the heat preservation operation twice refers to the operation of sequentially preserving heat at 600 ℃ for 4 hours and preserving heat at 860 ℃ for 16 hours.
The following are the data of the test performed on the surface in-situ modified lithium-rich material obtained by the present invention:
first, comparative examples 1 to 3 were set, and comparative examples 1 to 3 were all lithium-rich materials obtained in the prior art, comparative example 1: step 1, precursor synthesis
Nickel protoxide, cobalt oxide, manganese dioxide and lithium carbonate are weighed according to the mass ratio (Li: Ni: Co: Mn: 1.24:0.13:0.13:0.54), wherein the lithium carbonate is excessive by 3%, and after mixing for 12 hours in a mixer, deionized water is added according to the proportion of 20 wt% of solid content, and then the slurry is poured into a ball mill to be ground until the medium particle size is less than 0.3 micron. Finally spray drying the obtained slurry to obtain Li [ Li ]0.20Ni0.13Co0.13Mn0.54]O2The precursor of (1).
The precursor is kept at 450 ℃ for 5 hours, then is continuously heated to 800 ℃ and is kept at the temperature for 25 hours; finally naturally cooling to room temperature to obtain Li [ Li ]0.20Ni0.13Co0.13Mn0.54]O2A material.
Comparative example 2: step 1, precursor synthesis
Nickel protoxide, cobalt oxide, manganese dioxide and lithium carbonate are weighed according to the mass ratio (Li: Ni: Co: Mn: 1.27:0.10:0.10:0.57), wherein the lithium carbonate is excessive by 3%, and after mixing for 12 hours in a mixer, deionized water is added according to the proportion of 20 wt% of solid content, and then the slurry is poured into a ball mill to be ground until the medium particle size is less than 0.3 micron. Finally, the obtained slurry is stirred on a water bath at 60 ℃ until the slurry is dried, and then the dried slurry is dried in a vacuum constant temperature oven at 100 ℃ for 12 hours to obtain Li [ Li ]0.23Ni0.10Co0.10Mn0.57]O2The precursor of (1).
The precursor is kept at 500 ℃ for 2 hours, then is continuously heated to 850 ℃ and is kept at the temperature for 20 hours; finally naturally cooling to room temperature to obtain Li [ Li ]0.23Ni0.10Co0.10Mn0.57]O2A material.
Comparative example 3: step 1, precursor synthesis
Nickel protoxide, ferric nitrate, manganese dioxide and lithium carbonate are weighed according to the mass ratio (Li: Ni: Fe: Mn: 1.16:0.30:0.08:0.48), wherein the lithium carbonate is excessive by 3%, and after mixing for 12 hours in a mixer, deionized water is added according to the proportion of 20 wt% of solid content, and then the slurry is poured into a ball mill to be ground until the medium particle size is less than 0.3 micron. Finally, the obtained slurry is filtered, fully washed and dried in a blast oven at 100 ℃ for 6 hours to obtain Li [ Li ]0.13Ni0.30Mn0.48Fe0.08]O2The precursor of (1).
The precursor is kept at 600 ℃ for 4 hours, then is continuously heated to 860 ℃ and kept at the temperature for 16 hours; finally naturally cooling to room temperature to obtain Li [ Li ]0.13Ni0.30Mn0.48Fe0.08]O2A material.
In order to test the electrochemical performance of the materials of examples 1 to 10 and comparative examples 1 to 3 of the invention, the prepared materials are used as positive electrode materials, a button cell is assembled, and a charge and discharge experiment is carried out, wherein the specific experimental steps are as follows:
1) mixing the active material, conductive carbon black (super P) and polyvinylidene fluoride (PVDF) according to a ratio of 80:10:10, adding N-methyl-2-pyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on an aluminum foil, drying and cutting the aluminum foil into a circular pole piece with the diameter of 1.4 cm.
2) The pole piece is rolled and dried in a vacuum drying box at 120 ℃ for 12 hours, and then in a glove box filled with argon, a pure lithium piece is taken as a negative electrode material, 1mol/L LiPF6-EC + DEC + DMC (volume ratio of 1:1:1) is taken as electrolyte, and Celgard2300 is taken as a diaphragm, so that the CR2032 type button cell is assembled.
3) The assembled button experiment battery is subjected to charge and discharge tests on a charge and discharge tester, wherein the voltage range of charge and discharge is as follows: 2-4.8V, the current density of 200mA/g is defined as 1C, and the charge-discharge system of the multiplying power performance test is as follows: sequentially charging and discharging at current density of 0.1C, 0.2C, 0.5C, 1C, and 3C for 3 weeks. The charge-discharge system of the cycle performance test is as follows: first, constant current charging and discharging are carried out for 3 weeks in a voltage range of 2-4.8V and a current density of 0.1C, and then constant current charging and discharging are carried out in a voltage range of 2-4.6V and a current density of 1C.
The test results of the 0.1C specific discharge capacity, the 3C specific discharge capacity and the 200-cycle capacity retention rate of the experimental battery prepared according to the method are shown in Table 1.
From the charge and discharge test results, the first discharge capacity, the 3C discharge capacity and the cycle performance of the composite lithium-rich material with the in-situ surface coating in the examples 1 to 10 of the invention are improved to different degrees compared with the lithium-rich material without the surface coating in the comparative example.
TABLE 1 electrochemical Performance test data Table of materials prepared in the inventive example and comparative example
FIG. 1 is an X-ray diffraction pattern of the materials prepared in comparative example 1, example 1 and example 2 (XRD patterns of the materials prepared in other specific examples are similar and omitted), and it can be seen that XRD patterns of the materials before and after coating are α -NaFeO2Layered structure, illustrating that the coating has no significant effect on the basic layered structure of the lithium-rich material, wherein Li-like can be seen in the coated graph3PO4Diffraction peaks of the structure indicating the presence of Li-like in the coated material3PO4Thereby contributing to the improvement of the electrical conductivity of the material.
Fig. 2, 3 and 4 are a first charge-discharge comparison graph, a rate-discharge capacity comparison graph and a cycle performance comparison graph of example 1, example 2 and comparative example 1, respectively. It can be seen from the figure that the initial discharge capacity, rate capability and cycle capacity retention rate of the surface in-situ coated examples 1 and 2 are all significantly improved.
The surface in-situ coated composite lithium-rich material provided by the invention has high specific capacity and good rate capability and cycle performance, and can be used as a power lithium ion battery anode material for pure electric vehicles and plug-in hybrid electric vehicles. And the preparation is simple and easy for industrial production.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The method is characterized by comprising the steps of coating a metal phosphate compound on lithium-rich material precursor particles, and then sintering at high temperature to form the in-situ modified lithium-rich material, wherein the raw material comprises a coating layer and a lithium-rich material precursor, the coating layer is metal phosphate, the lithium-rich material precursor is a mixture of at least one of oxides, hydroxides, carbonates and oxalates of MnMA and a lithium source, M is a metal element, A is at least one of S, P, B and F, and the finally obtained modified lithium-rich material coating material contains Li-like compounds3PO4Structure;
adding soluble phosphate or a phosphoric acid solution into a lithium-rich material precursor, and dropwise adding a soluble metal salt solution while stirring, wherein the molar weight of the soluble phosphate or the phosphoric acid is 1-3 times that of the soluble metal salt, and the molar ratio of the soluble metal salt to the lithium-rich material precursor is 0.0001-0.12: 0.9999-0.88;
(2) continuously stirring the mixed solution obtained in the step (1), and then drying;
(3) performing heat preservation on the material dried in the step (2) twice, and obtaining a surface in-situ modification type lithium-rich material after heat preservation;
the soluble phosphate in the step (1) comprises at least one of ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate;
the soluble metal salt in the step (1) is at least one of soluble salts of Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni and Mo;
the two heat preservation operations in the step (3) refer to the operations of sequentially preserving heat at 400-600 ℃ for 2-8h and preserving heat at 700-1000 ℃ for 3-36 h.
2. The method for preparing the in-situ surface-modified lithium-rich material as claimed in claim 1, wherein the concentration of the soluble metal salt solution in the step (1) is 0.001-10mol/L, and the concentration of the soluble phosphate or phosphoric acid solution is 0.001-10 mol/L.
3. The method for preparing the in-situ surface-modified lithium-rich material as claimed in claim 1, wherein the step (2) is carried out by stirring the mixed solution obtained in the step (1) for 10min-12h and then drying.
4. The surface in-situ modification type lithium-rich material prepared by the method according to any one of claims 1 to 3, wherein the metal phosphate is at least one of corresponding phosphates of Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni and Mo;
the metal M in the lithium-rich material precursor is at least one of Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn;
the chemical formula of the in-situ modified lithium-rich material is (1-a) Li1+xMnyMzAwOr-aLibMecPO4Wherein a is more than or equal to 0.0001 and less than or equal to 0.12, b is more than or equal to 0 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 1.5, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, w is more than or equal to 0 and less than or equal to 0.
5. The surface in-situ modification type lithium-rich material according to claim 4, wherein the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium acetate and lithium nitrate, and the molar ratio of Li to MnMA is 1-2.5: 1.
6. the surface in-situ modification type lithium-rich material as claimed in claim 4, wherein the molar weight percentage of the cladding layer in the raw material is 0.01% -12%, and the molar weight percentage of the lithium-rich material precursor is 88% -99.99%.
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