CN106602024A - In-situ surface-modified lithium-rich material and preparation method thereof - Google Patents
In-situ surface-modified lithium-rich material and preparation method thereof Download PDFInfo
- Publication number
- CN106602024A CN106602024A CN201611237904.1A CN201611237904A CN106602024A CN 106602024 A CN106602024 A CN 106602024A CN 201611237904 A CN201611237904 A CN 201611237904A CN 106602024 A CN106602024 A CN 106602024A
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- China
- Prior art keywords
- lithium material
- modification type
- lithium
- phosphate
- situ modification
- Prior art date
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Links
- 239000000463 material Substances 0.000 title claims abstract description 243
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 150000002641 lithium Chemical class 0.000 title abstract 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 202
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 201
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims description 73
- 230000004048 modification Effects 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 150000003016 phosphoric acids Chemical class 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 239000010452 phosphate Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical group [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 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
- 229910052748 manganese 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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 229910052750 molybdenum 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
- 230000008569 process Effects 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
- 239000005696 Diammonium 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
- 229910052789 astatine Inorganic materials 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate 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
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 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
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 2
- 239000011572 manganese Substances 0.000 description 42
- 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 21
- 230000000052 comparative effect Effects 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000012774 insulation material Substances 0.000 description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005253 cladding Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 2
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 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
- 238000010406 interfacial reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 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
- 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
- 239000010446 mirabilite Substances 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004044 response Effects 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 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
- 238000007605 air drying Methods 0.000 description 1
- 239000005030 aluminium foil Substances 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
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940125717 barbiturate Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 210000004247 hand Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RQIHICWHMWNVSA-UHFFFAOYSA-N propan-1-ol;zirconium Chemical compound [Zr].CCCO RQIHICWHMWNVSA-UHFFFAOYSA-N 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011593 sulfur Substances 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
- 238000011282 treatment Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical class [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 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
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
- H01M4/485—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 an in-situ surface-modified lithium-rich material. Raw materials include a coating layer and a lithium-rich material precursor, wherein the coating layer is metal phosphate; and the lithium-rich material precursor is a mixture of at least one of an MnMA oxide, hydroxide, carbonate and oxalate and a lithium source, wherein M is a metal element and A is at least one of S, P, B and F. The invention further discloses a preparation method. A metal phosphate compound coats lithium-rich material precursor particles and then the in-situ modified lithium-rich material is formed through high-temperature sintering. The in-situ surface-modified lithium-rich material has the advantages that the surface stability and the conductivity of the lithium-rich material are greatly improved by an in-situ modified structure; the charge-discharge specific capacity, the efficiency, the rate and the cycle performance of the material are obviously improved; and the in-situ surface-modified lithium-rich material is simple in preparation process, low in cost, good in result reproducibility and suitable for large-scale popularization.
Description
Technical field
The invention belongs to technical field of lithium ion, specially a kind of surface in situ modification type richness lithium material and its preparation
Method.
Background technology
Lithium ion battery because energy density is high, have extended cycle life, environmental protection, low cost the features such as, in 20 years
In obtained swift and violent development, its application be related to the numerous areas such as communication, traffic, military affairs, medical treatment, amusement.Recently as
The fast development of electric automobile etc., high specific energy, high power lithium ion cell become the inevitable direction of following lithium ion battery development.
Current business-like positive electrode, such as LiCoO2、LiFePO4、LiMn2O4, ternary material etc., specific capacity it is relatively low (<200mAh/
g).And positive electrode is the principal element for limiting battery specific energy, therefore in order to develop high specific energy batteries, it is felt to be desirable to find
Positive electrode with more height ratio capacity.
In recent years, the features such as having specific capacity height, good safety, low cost due to rich lithium material, rich lithium material is caused
The extensive concern of people.Its specific capacity is generally more than 250mAh/g, and 300mAh/g (Nano have been even up in the report having
Lett.,2008,8(3):957-961).Although rich lithium material capacity is high, its cycle performance is poor, and exists serious
Voltage droop problem, so as to constrain its business-like application.Therefore need to be modified rich lithium material, to improve its circulation
During specific capacity and voltage retention.
The main method for improving rich lithium material chemical property at present be coat and adulterate (Adv.Mater.2012,24,
1192–1196；Adv.Funct.Mater.2014,1-7).Modal method for coating is using Al (OH)3、Al2O3、TiO2Deng
Inert material carries out Surface coating (Electrochimica Acta 50 (2005) 4784-4791, Journal to rich lithium material
The 1334-1339 of of Power Sources 159 (2006)), these claddings typically serve to protect rich lithium material surface texture, resistance
Only material and electrolyte contacts and there is the effect of negative response, the first charge-discharge effect of rich lithium material is improve to a certain extent
Rate and cycle performance.The patent of the A of Publication No. CN 103035906 is coated on Li [Li using wet method(1-2x)/3MxMn(2-x)/3]
O2Surface coating 3-10wt% LiMnPO4, be conducive to the raising of material high rate performance, and LiMnPO4In PO4 3-Can have
Effect suppresses electrode material dissolving in the electrolytic solution, prevents corrosion of the Fluohydric acid. to surface of active material in electrolyte, improves material
The thermodynamic stability of material.Technical scheme disclosed in the patent of Publication No. CN101859887 is to wrap using on positive electrode
Phosphate is covered, protection materials, and the effect for improving capacity and high rate performance can be played.Publication No. CN 103904311A
Patent disclosed in technical scheme be, in one layer of LiFePO4 of Surface coating of rich lithium material finished product, wherein used by LiFePO4
Lithium of the lithium source in rich lithium material, as a result shows the lithium for reducing " more than needed " in rich lithium material, is conducive to stablizing for material structure,
But the rear cladding that this employing liquid phase method is carried out on rich lithium material finished product, needs are first immersed in the finished product of rich lithium material molten
Liquid, then again through a series of processing procedures such as precipitation, filtration, washing, drying, heat treatments, method is complex.Also deposit in addition
The problems such as clad is uneven, clad is not fine and close enough with the conjugation of rich lithium material.So can not fundamentally reduce or
Suppress the precipitation of oxygen and the migration of transition metal, thus cannot effectively solving material cycle performance difference and voltage attenuation etc. ask
Topic.
Research done by above-mentioned structural stability and chemical property to improve rich lithium material, although to a certain degree
On, realizing improves the beneficial effect of capacity and high rate performance, but comprehensive market considers, while rich lithium material is improved, system
Preparation Method is simple, and selected the cost of material is low, be only it is a kind of can the method promoted of the marketization, in field of lithium, assistant officer waits to solve
Technical problem certainly be set up it is a kind of it is simple, effectively, be easy to large-scale promotion surface modification cladding is carried out to rich lithium material
Method, the lithium battery product high so as to obtain cycle life height, specific capacity, high rate performance.
The content of the invention
To solve above-mentioned technical problem, the invention provides a kind of surface in situ modification type richness lithium material and its preparation side
Method, realizes the surface stability and electrical conductivity for improving rich lithium material, makes the charging and discharging capacity of material, efficiency, multiplying power and follows
The purpose that ring performance is all improved significantly.
To achieve these goals, technical scheme disclosed by the invention is：A kind of surface in situ that the present invention is developed is repaiied
Decorations type richness lithium material, raw material includes clad, rich lithium material presoma, and the clad is metal phosphate, rich lithium material
Presoma is the mixture of at least one and lithium source in oxide, hydroxide, carbonate, the oxalates of MnMA, and wherein M is
Metallic element, A is at least one in S, P, B and F.Coated in rich lithium material presoma from metal tripolyphosphate salt, clad
Uniformly, conjugation is high, and clad can occur interfacial reaction with the raw material of rich lithium material, formed conductivity it is higher containing in lithium
Interbed (inter layer), so as to improve the ionic conductivity and chemical property of material.
Further, the metal phosphate is that Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni are corresponding with Mo
At least one of phosphate.Selected metal phosphate, can coat to rich lithium material presoma, obtain discharge and recharge
The high rich lithium material of specific capacity, efficiency, multiplying power and cycle performance.
Further, the metal M in the rich lithium material presoma be Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr,
At least one in Ru and Sn.
Further, the lithium source be Lithium hydrate, lithium carbonate, lithium acetate, lithium nitrate at least one, wherein Li with
The mol ratio of MnMA is 1-2.5：1.
Further, in the raw material clad mole percentage ratio be 0.01%-12%, the rich lithium material forerunner
The mole percentage ratio of body is 88%-99.99%.Selected cladding mole percentage ratio has taken into account the thickness of material clad
With the performance of material property, the rich lithium material checking that Jing subsequent steps are obtained, charging and discharging capacity, efficiency, multiplying power can be obtained
The material high with cycle performance, former material doses used at the same time is minimum, with low cost.
Further, the chemical formula of the in-situ modification type richness lithium material that the present invention is obtained is (1-a) Li1+ xMnyMzAwOr-aLibMecPO4, wherein, 0.0001≤a≤0.12,0≤b≤3,0≤c≤1.5,0 ＜ x≤1,0 ＜ y≤1,0≤
Z ＜ 1,0≤w≤0.2,1.8≤r≤3.
The invention also discloses the method for preparing above-mentioned rich lithium material, coats metal phosphorus in rich lithium material precursor particle
Barbiturates compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.The original position obtained by this method for coating
Equably, and clad has good conjugation and stability to the clad of cladded type richness lithium material with rich lithium material, effectively
The negative response for preventing rich lithium material to produce because of contact with electrolyte；Simultaneously using " unnecessary " in rich lithium precursor lithium source with
There is " original position " chemical reaction in clad material, form a kind of high conductivity layer containing lithium.So as to significantly improve rich lithium material
Discharge capacity, first charge-discharge efficiency, high rate performance, and effectively improve cycle performance and voltage attenuation of material etc. and ask
Topic.
Further, the method comprises the steps that soluble phosphoric acid salt is added into rich lithium material presoma by (1)
In, Deca soluble metal salt solution while stirring；The mole of wherein soluble phosphate is the 1-3 of soluble metallic salt
Times, soluble metallic salt is 0.0001-0.12 with rich lithium material presoma mol ratio：0.9999-0.88.
(2) mixed solution for obtaining step (1) continues to stir, and is then dried process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material.
Further, soluble metal salt solution concentration is 0.001-10mol/ in step (1) described in the step (1)
L, the concentration of soluble phosphoric acid salt solution is 0.001-10mol/L, and selected mass concentration is easy to dissolving, Jing subsequent steps
Rich lithium material checking is obtained, the high material of charging and discharging capacity, efficiency, multiplying power and cycle performance can be obtained, obtaining beneficial
It is minimum that effect obtains former material doses used at the same time, with low cost.
Further, soluble phosphate includes phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen two in the step (1)
At least one of ammonium, sodium phosphate, potassium phosphate.
Further, in the step (1) soluble metallic salt be Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co,
At least one in the soluble-salt of Ni and Mo.
Further, the mixed solution for obtaining step (1) in the step (2) continues to stir after 10min-12h, is entering
Row dried.Drying herein includes the drying of any one form of prior art, such as heat drying, forced air drying, vacuum
It is dried, is spray-dried, microwave drying and centrifugal drying is all possible.
Soluble metal salt solution concentration is 0.001-10mol/L in the step (1), soluble phosphoric acid salt solution
Concentration is 0.001-10mol/L.
Further, the mixed solution for obtaining step (1) in the step (2) continues to stir after 10min-12h, is entering
Row dried.
Further, be incubated twice in the step (3) operation refer to successively 400-600 DEG C be incubated 2-8h, in 700-
The operation of 1000 DEG C of insulation 3-36h.
The selection of the Parameter Conditions such as temperature, is conducive to the uniformity of clad in said method step；On the other hand because
Clad sinters to be formed simultaneously with rich lithium material, increased the conjugation of clad and rich lithium material, improves the steady of clad
It is qualitative；And clad can also occur interfacial reaction with the raw material of rich lithium material in sintering process, form conductivity higher
Intermediate layer containing lithium (inter layer), so as to improve the ionic conductivity and chemical property of material.
The present invention positive effect be：The in-situ modification type structure of the present invention greatly improves the table of rich lithium material
Face stability and electrical conductivity, charging and discharging capacity, efficiency, multiplying power and the cycle performance for making material is all significantly improved；This
Invention preparation process is simple, and with low cost, as a result favorable reproducibility, is suitable to large-scale promotion.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis
Spectrum.
Fig. 2 is the first charge-discharge curve comparison of the comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis
Figure, in figure, curve 1 is comparative example 1, curve 2 is embodiment 1, and curve 3 is embodiment 2.
Fig. 3 is comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis under different electric current densities
Discharge curve comparison diagram.
Fig. 4 is the cycle performance curve comparison of the comparative example 1, embodiment 1 and the positive electrode of embodiment 2 of present invention synthesis
Figure.
Specific embodiment
The present invention is described in further detail below by specific embodiment.
Embodiment one：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad be metal phosphate, be specifically iron phosphate, the iron phosphate by diammonium phosphate, nine
Liquid glauber salt acid is iron to be obtained, and the rich lithium material presoma is Ni0.13Co0.13Mn0.54O2With the mixture of Lithium hydrate, clad accounts for
The mol ratio of raw material is 0.01%, and rich lithium material presoma is 99.99%, wherein, Li and Ni0.13Co0.13Mn0.54Mole
Than for 1.5:1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1.5Mn0.54Ni0.13Co0.13O2-
0.0001FePO4。
The rich lithium material presoma can be obtained using prior art, and the side that prior art prepares rich lithium material may also be employed
Method prepares the in-situ modification type richness lithium material coated with metal phosphate of above-described embodiment.
Embodiment two：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically manganese phosphate, and the manganese phosphate is by ammonium dihydrogen phosphate, vinegar
Sour manganese is obtained, and the rich lithium material presoma is AlCr0.5The hydroxide of Mn and the mixture of lithium carbonate, clad mole
It is 12% that amount accounts for raw material percentages, rich lithium material presoma 88%, AlCr0.5The mol ratio of Mn and Li is 1:2.5, obtain
Surface in situ modification type richness lithium material chemical formula is 0.88Li2MnAlCr0.5O3-0.12LiMnPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
The design parameters such as the temperature for being adopted are can realize that obtaining final product is defined.
Embodiment three：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad be metal phosphate, be specifically nickel phosphate, the nickel phosphate by ammonium dihydrogen phosphate, six
Water nickel nitrate is obtained, and the rich lithium material presoma is Mg0.13Mo0.13Mn0.54S0.2Carbonate and lithium acetate mixture, Li
With Mg0.13Mo0.13Mn0.54S0.2Mol ratio is 1:1, it is 0.01% that the mole of clad accounts for the percentage ratio of raw material, rich lithium material
Material precursor is 99.99%, and the surface in situ modification type richness lithium material chemical formula for obtaining is
0.9999LiMn0.54Mg0.13Mo0.13S0.2O1.8-0.0001LiNiPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 0.001mol/L, the soluble phosphoric acid of selection
The concentration of saline solution is 0.001mo l/L；The mole of wherein soluble phosphate is 1 times of soluble metallic salt, solvable
Property slaine and rich lithium material presoma mol ratio be 0.0001：0.9999.
(2) mixed solution for obtaining step (1) continues to stir 10min, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 2h at 600 DEG C successively, the operation of 3h is incubated at 1000 DEG C.
Example IV：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically C.I. Pigment Violet 14, and the C.I. Pigment Violet 14 is by sodium phosphate, six liquid glauber salt
Sour cobalt is obtained, and the rich lithium material presoma is Ti0.13Zr0.13Mn0.54P0.1Oxalates and lithium nitrate mixture, clad
Mole account for raw material 0.01%, remaining as rich lithium material presoma, wherein Li and Ti0.13Zr0.13Mn0.54P0.1Mol ratio is
1.2：1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1.2Mn0.54Ti0.13Zr0.13P0.1O2-
0.0001LiCoPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 10mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 10mol/L；The mole of soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt and richness
Lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution for obtaining step (1) continues to stir 12h, then by mixed solution filtration washing, then is done
Dry process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 8h at 400 DEG C successively, the operation of 36h is incubated at 700 DEG C.
Embodiment five：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically aluminum phosphate, and the aluminum phosphate is by potassium phosphate, aluminum nitrate
It is obtained, the rich lithium material presoma is Fe0.1Ru0.1Mn0.54B0.1O2With the mixture of Lithium hydrate, clad accounts for raw material
Molar percentage is 12%, remaining as rich lithium material presoma, wherein Li and Fe0.1Ru0.1Mn0.54B0.1Mol ratio be 1.5：
1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.88Li1.23Mn0.5Fe0.1Ru0.14B0.1O2-0.12AlPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 1mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 1mol/L；The mole of wherein soluble phosphate is 2 times of soluble metallic salt, soluble metallic salt with
Rich lithium material presoma mol ratio is 0.12：0.88.
(2) mixed solution for obtaining step (1) continues to stir 1h, then by mixed solution filtration washing, then is done
Dry process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 5h at 450 DEG C successively, the operation of 25h is incubated at 800 DEG C.
Embodiment six：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically zirconium phosphate, and the zirconium phosphate is by ammonium dihydrogen phosphate, different
Propanol zirconium is obtained, and the rich lithium material presoma is Cu0.1Sn0.1Mn0.54F0.1O2With the mixture of Lithium hydrate, wherein Li with
Cu0.1Sn0.1Mn0.54F0.1Mol ratio be 1.5：1, it is 0.01% that the mole of clad accounts for the percentage ratio of raw material, remaining as
Rich lithium material presoma, obtain surface in situ modification type richness lithium material chemical formula be
0.9999Li1.23Mn0.54Cu0.1Sn0.1F0.1O2-0.0001LiZr0.5PO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 2mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 2mol/L；The mole of wherein soluble phosphate is 1 times of soluble metallic salt, soluble metallic salt with
Rich lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution for obtaining step (1) continues to stir 1h, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 2h at 500 DEG C successively, the operation of 20h is incubated at 850 DEG C.
Embodiment seven：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically titanium phosphate, and the titanium phosphate is by phosphoric acid, the fourth of metatitanic acid four
Ester is obtained, and the rich lithium material presoma is Ni0.10Co0.10Mn0.57O2With the mixture of Lithium hydrate, wherein Li with
Ni0.10Co0.10Mn0.57Mol ratio is 1.3：1, it is 12% that the mole of clad accounts for the percentage ratio of raw material, remaining as rich lithium material
Material precursor, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.88Li1.23Mn0.57Ni0.10Co0.10O2-
0.12Ti0.75PO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 3mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 3mol/L；The mole of wherein soluble phosphate is 1-3 times of soluble metallic salt, soluble metallic salt
It is 0.12 with rich lithium material presoma mol ratio：0.88.
(2) mixed solution for obtaining step (1) continues to stir 2h, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 2h at 500 DEG C successively, the operation of 20h is incubated at 850 DEG C.
Embodiment eight：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically magnesium phosphate, and the magnesium phosphate is by diammonium phosphate, sulfur
Sour magnesium is obtained, and the rich lithium material presoma is Ni0.30Mn0.48Fe0.08O2With the mixture of Lithium hydrate, the quality of clad
The mass percent for accounting for raw material is 12%, remaining as rich lithium material presoma, wherein Li and Ni0.30Mn0.48Fe0.08Mole
Than for 1.7：1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.88Li1。13Mn0.48Ni0.30Fe0.08O2-
0.12LiMgPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 4mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 4mol/L；The mole of wherein soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt with
Rich lithium material presoma mol ratio is 0.12：0.88.
(2) mixed solution for obtaining step (1) continues to stir 6h, is then spray-dried mixed solution；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 4h at 600 DEG C successively, the operation of 16h is incubated at 860 DEG C.
Embodiment nine：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically zinc phosphate, and the zinc phosphate is by potassium phosphate, zinc sulfate
It is obtained, the rich lithium material presoma is Ni0.30Mn0.48Fe0.08O2With the mixture of Lithium hydrate, the mole of clad accounts for
The percentage ratio of raw material is 0.01%, remaining as rich lithium material presoma, wherein Li and Ni0.30Mn0.48Fe0.08Mol ratio be
1.3：1, the surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1。13Mn0.48Ni0.30Fe0.08O2-
0.0001LiZnPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 5mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 5mol/L；The mole of wherein soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt with
Rich lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution that obtains step (1) continues to stir 6h, then by mixed solution filtration washing after, then carry out
Dried；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 4h at 600 DEG C successively, the operation of 16h is incubated at 860 DEG C.
Embodiment ten：A kind of surface in situ modification type richness lithium material that the present invention is developed, raw material includes clad, richness
Lithium material presoma, the clad is metal phosphate, is specifically cupric phosphate, and the cupric phosphate is by ammonium phosphate, copper sulfate
It is obtained, the rich lithium material presoma is Ni0.30Mn0.48Fe0.08O2With the mixture of Lithium hydrate, the mole of clad accounts for
The matter percentage ratio of raw material is 0.01%, remaining as rich lithium material presoma, wherein Li and Ni0.30Mn0.48Fe0.08Mol ratio
For 1.12：The 1 surface in situ modification type richness lithium material chemical formula for obtaining is 0.9999Li1。1Mn0.48Ni0.30Fe0.08O2-
0.00001CuPO4。
The method for preparing the in-situ modification type richness lithium material coats metal phosphate in rich lithium material precursor particle
Class compound, then Jing high temperature sinterings form in-situ modification type richness lithium material.
Specific preparation method comprises the steps that (1) is added into soluble phosphoric acid salt in rich lithium material presoma,
Deca soluble metal saline solution while stirring；Soluble metal salt solution concentration be 6mol/L, the soluble phosphoric acid salt of selection
The concentration of solution is 6mol/L；The mole of wherein soluble phosphate is 3 times of soluble metallic salt, soluble metallic salt with
Rich lithium material presoma mol ratio is 0.0001：0.9999.
(2) mixed solution that obtains step (1) continues to stir 6h, then by mixed solution filtration washing after, then carry out
Dried；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation
Material, twice insulation operation refers to and be incubated 4h at 600 DEG C successively, the operation of 16h is incubated at 860 DEG C.
The following is the data of the test that the surface in situ modification type richness lithium material obtained to the present invention is carried out：
First, comparative example 1-3 is set, and comparative example 1-3 is the rich lithium material that prior art is obtained, comparative example 1：Step 1,
Precursor synthesis
According to the ratio (Li of the amount of material:Ni:Co:Mn=1.24:0.13:0.13:0.54) nickel protoxide, oxidation are weighed
Cobalt, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 3%, after mixing 12 hours in batch mixer, by solid content 20wt%'s
Ratio adds deionized water, then pours slurry into grinding in ball grinder and is less than 0.3 micron to middle granularity.Finally by the slurry for obtaining
Material is spray-dried, that is, obtain Li [Li0.20Ni0.13Co0.13Mn0.54]O2Presoma.
Step 2, high temperature sintering
Presoma is incubated 5 hours at 450 DEG C, then proceedes to be warmed up to 800 DEG C, is incubated 25 hours；Finally it is naturally cooling to
Room temperature, that is, obtain Li [Li0.20Ni0.13Co0.13Mn0.54]O2Material.
Comparative example 2：Step 1, precursor synthesis
According to the ratio (Li of the amount of material:Ni:Co:Mn=1.27:0.10:0.10:0.57) nickel protoxide, oxidation are weighed
Cobalt, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 3%, after mixing 12 hours in batch mixer, by solid content 20wt%'s
Ratio adds deionized water, then pours slurry into grinding in ball grinder and is less than 0.3 micron to middle granularity.Finally by the slurry for obtaining
Material is stirred to after doing in 60 DEG C of water-baths, is dried 12 hours in 100 DEG C of vacuum constant-temperature container, that is, obtain Li
[Li0.23Ni0.10Co0.10Mn0.57]O2Presoma.
Step 2, high temperature sintering
Presoma is incubated 2 hours at 500 DEG C, then proceedes to be warmed up to 850 DEG C, is incubated 20 hours；Finally it is naturally cooling to
Room temperature, that is, obtain Li [Li0.23Ni0.10Co0.10Mn0.57]O2Material.
Comparative example 3：Step 1, precursor synthesis
According to the ratio (Li of the amount of material:Ni:Fe:Mn=1.16:0.30:0.08:0.48) nickel protoxide, nitric acid are weighed
Ferrum, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 3%, after mixing 12 hours in batch mixer, by solid content 20wt%'s
Ratio adds deionized water, then pours slurry into grinding in ball grinder and is less than 0.3 micron to middle granularity.Finally by the slurry for obtaining
Material is filtered, and fully after washing, is dried 6 hours in 100 DEG C of convection ovens, that is, obtain Li [Li0.13Ni0.30Mn0.48Fe0.08]O2's
Presoma.
Step 2, high temperature sintering
Presoma is incubated 4 hours at 600 DEG C, then proceedes to be warmed up to 860 DEG C, is incubated 16 hours；Finally it is naturally cooling to
Room temperature, that is, obtain Li [Li0.13Ni0.30Mn0.48Fe0.08]O2Material.
In order to test the chemical property of the material of embodiment of the present invention 1-10 and comparative example 1-3, by material obtained above
Expect for positive electrode, to be assembled into button cell, carry out charge-discharge test, specific experiment step is as follows：
1) above-mentioned active material, conductive carbon black (Supper P) and Kynoar (PVDF) are pressed into 80:10:10 ratio
Mixing, adds METHYLPYRROLIDONE (NMP) to make slurry, is evenly applied on aluminium foil, is cut into after drying a diameter of
1.4 centimetres of circular pole piece.
2) will be dried 12 hours in 120 degree of vacuum drying oven after above-mentioned pole piece roll-in, then in the handss full of argon
In casing, with pour lithium slice as negative material, with 1mol/L LiPF6-EC+DEC+DMC, (volume ratio is 1:1:1) it is electrolyte, with
Celgard2300 is barrier film, dresses up CR2032 type button cells.
3) the button experimental cell of assembling is carried out into charge-discharge test, the voltage range of discharge and recharge on charge-discharge test instrument
For：2～4.8V, the electric current density for defining 200mA/g is 1C, and the discharge and recharge system of high rate performance test is：Successively with 0.1C,
The electric current density constant current charge-discharge of 0.2C, 0.5C, 1C, 3C is each 3 weeks.Cycle performance test discharge and recharge system be：First in 2-
4.8V voltage ranges with the electric current density constant current charge-discharge 3 weeks of 0.1C, then in 2-4.6V voltage ranges with the electric current density of 1C
Carry out constant current charge-discharge.
Experimental cell 0.1C first discharge specific capacities, 3C specific discharge capacities and the 200 weeks appearances prepared according to the method described above
The test result of amount conservation rate is listed in table 1.
From the point of view of charge-discharge test result, the compound rich lithium material of the surface in situ of embodiment of the present invention 1-10 cladding with it is right
Do not carry out surface coated rich lithium material in ratio to compare, the discharge capacity first of material, 3C discharge capacities and cycle performance are equal
There is different degrees of raising.
The electrochemical property test tables of data of prepared material in the embodiment of the present invention of table 1 and comparative example
Fig. 1 is X ray diffracting spectrum (other specific embodiments of material prepared by comparative example 1, embodiment 1 and embodiment 2
The XRD spectrum of the material of preparation is similar, omits), the XRD figure of material is all α-NaFeO before and after as can be seen from the figure coating2Layer
Shape structure, illustrates to coat the basic layer structure on rich lithium material without significantly impact, wherein can see in the figure after cladding
To there is class Li3PO4The diffraction maximum of structure, illustrates there is class Li in the material for coating3PO4This structure, so as to be conducive to improve
The electrical conductivity of material.
Fig. 2, Fig. 3 and Fig. 4 are respectively first charge-discharge comparison diagram, the multiplying power discharging of embodiment 1, embodiment 2 and comparative example 1
Capacity comparison figure and cycle performance comparison diagram.As can be seen from the figure the initial discharge of embodiment 1 and 2 is coated through surface in situ
Capacity, high rate performance and circulation volume conservation rate are all significantly improved.
The compound rich lithium material specific capacity height of the surface in situ cladding that the present invention is provided, high rate performance and good cycle,
Can be used as pure electric automobile, the power lithium-ion battery positive electrode of plug-in hybrid-power automobile.And prepare simply, hold
Easy industrialized production.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (13)
1. a kind of surface in situ modification type richness lithium material, it is characterised in that raw material includes clad, rich lithium material presoma,
The clad is metal phosphate, and rich lithium material presoma is in oxide, hydroxide, carbonate, the oxalates of MnMA
At least one mixture with lithium source, wherein M is metallic element, and A is at least one in S, P, B and F.
2. in-situ modification type according to claim 1 richness lithium material, it is characterised in that the metal phosphate be Ti, Mg,
At least one of Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni corresponding with Mo phosphate.
3. in-situ modification type according to claim 1 richness lithium material, it is characterised in that in the rich lithium material presoma
Metal M is at least one in Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn.
4. in-situ modification type according to claim 1 richness lithium material, it is characterised in that the lithium source is Lithium hydrate, carbon
At least one in sour lithium, lithium acetate, lithium nitrate, wherein Li are 1-2.5 with the mol ratio of MnMA：1.
5. in-situ modification type according to claim 1 richness lithium material, it is characterised in that clad mole in the raw material
Amount percentage ratio is 0.01%-12%, and the mole percentage ratio of the rich lithium material presoma is 88%-99.99%.
6. in-situ modification type according to claim 1 richness lithium material, it is characterised in that the in-situ modification type richness lithium material
Chemical formula be (1-a) Li1+xMnyMzAwOr-aLibMecPO4, wherein, 0.0001≤a≤0.12,0≤b≤3,0≤c≤1.5,
0 ＜ x≤1,0 ＜ y≤1,0≤z ＜ 1,0≤w≤0.2,1.8≤r≤3.
7. it is a kind of prepare described in claim 1-6 any one in-situ modification type richness lithium material method, it is characterised in that should
Method is included in rich lithium material precursor particle and coats metal phosphate compounds, and then Jing high temperature sinterings form in-situ modification
Type richness lithium material.
8. it is according to claim 7 prepare in-situ modification type richness lithium material method, it is characterised in that the method include as
Lower step, (1) is added into soluble phosphate in rich lithium material presoma, while stirring Deca soluble metal salt solution,
The mole of wherein soluble phosphate is 1-3 times of soluble metallic salt, and soluble metallic salt rubs with rich lithium material presoma
You are than being 0.0001-0.12：0.9999-0.88.
(2) mixed solution for obtaining step (1) continues to stir, and is then dried process；
(3) the dried material of step (2) is incubated twice, surface in situ modification type richness lithium material is obtained after insulation.
9. it is according to claim 8 prepare in-situ modification type richness lithium material method, it is characterised in that the step (1)
Middle soluble phosphate includes at least one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, sodium phosphate, potassium phosphate.
10. it is according to claim 8 prepare in-situ modification type richness lithium material method, it is characterised in that the step (1)
Middle soluble metallic salt is at least one in the soluble-salt of Ti, Mg, Zr, Zn, Cr, Cu, V, Fe, Mn, Al, Co, Ni and Mo.
11. methods for preparing in-situ modification type richness lithium material according to claim 8, it is characterised in that the step (1)
Middle soluble metal salt solution concentration is 0.001-10mol/L, and the concentration of soluble phosphoric acid salt solution is 0.001-10mol/
L。
12. methods for preparing in-situ modification type richness lithium material according to claim 8, it is characterised in that the step (2)
The middle mixed solution for obtaining step (1) continues to stir after 10min-12h, is being dried process.
13. methods for preparing in-situ modification type richness lithium material according to claim 8, it is characterised in that the step (3)
In twice insulation operation refer to successively 400-600 DEG C be incubated 2-8h, 700-1000 DEG C be incubated 3-36h operation.
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| CN109244366A (en) * | 2018-11-27 | 2019-01-18 | 国联汽车动力电池研究院有限责任公司 | A kind of richness surface recombination modified method of the lithium material and its rich lithium material of preparation |
| CN109888248A (en) * | 2019-03-26 | 2019-06-14 | 湖北锂诺新能源科技有限公司 | Manganese phosphate coats the preparation method of rich oxidate for lithium positive electrode |
| CN109921013A (en) * | 2017-12-13 | 2019-06-21 | 微宏动力***（湖州）有限公司 | A kind of positive electrode material precursor of modification, preparation method, modification positive electrode and lithium battery |
| CN112542576A (en) * | 2019-09-23 | 2021-03-23 | 荆门市格林美新材料有限公司 | Coated LiFePO4Preparation method of Al-doped nickel-cobalt-manganese ternary cathode material of coating |
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| CN109244366A (en) * | 2018-11-27 | 2019-01-18 | 国联汽车动力电池研究院有限责任公司 | A kind of richness surface recombination modified method of the lithium material and its rich lithium material of preparation |
| CN109888248A (en) * | 2019-03-26 | 2019-06-14 | 湖北锂诺新能源科技有限公司 | Manganese phosphate coats the preparation method of rich oxidate for lithium positive electrode |
| CN112542576A (en) * | 2019-09-23 | 2021-03-23 | 荆门市格林美新材料有限公司 | Coated LiFePO4Preparation method of Al-doped nickel-cobalt-manganese ternary cathode material of coating |
| CN114447290A (en) * | 2021-12-21 | 2022-05-06 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN114284472A (en) * | 2021-12-23 | 2022-04-05 | 北京理工大学重庆创新中心 | Single crystal lithium-rich material with superconducting modification layer and preparation method and application thereof |
| CN114284472B (en) * | 2021-12-23 | 2023-11-03 | 北京理工大学重庆创新中心 | Monocrystalline lithium-rich material with superconductive modification layer, and preparation method and application thereof |
| CN115020673A (en) * | 2022-07-01 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | Modified nickel-cobalt-manganese ternary cathode material, preparation method thereof and lithium ion battery |
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