CN118099409A - Monocrystal lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Monocrystal lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN118099409A CN118099409A CN202410075792.2A CN202410075792A CN118099409A CN 118099409 A CN118099409 A CN 118099409A CN 202410075792 A CN202410075792 A CN 202410075792A CN 118099409 A CN118099409 A CN 118099409A
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- Prior art keywords
- lithium
- positive electrode
- electrode material
- equal
- rich manganese
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- 239000011572 manganese Substances 0.000 title claims abstract description 194
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 182
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 156
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 229910016612 MnaNibCoc Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 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
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000002243 precursor Substances 0.000 claims description 51
- 238000005245 sintering Methods 0.000 claims description 48
- 238000005303 weighing Methods 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- 238000003825 pressing Methods 0.000 claims description 23
- 239000010405 anode material Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000012266 salt solution Substances 0.000 claims description 22
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 20
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 13
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- GLVGLXXAZUYQQV-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[La+3] GLVGLXXAZUYQQV-UHFFFAOYSA-N 0.000 claims description 2
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005056 compaction Methods 0.000 abstract description 14
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 description 60
- 239000000243 solution Substances 0.000 description 47
- 230000001276 controlling effect Effects 0.000 description 42
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 40
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 40
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 39
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- LHGJTWLUIMCSNN-UHFFFAOYSA-L disodium;sulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O LHGJTWLUIMCSNN-UHFFFAOYSA-L 0.000 description 16
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910008514 Li1.2Mn0.54Ni0.13Co0.13O2 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QBXVTOWCLDDBIC-UHFFFAOYSA-N [Zr].[Ta] Chemical compound [Zr].[Ta] QBXVTOWCLDDBIC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a monocrystal lithium-rich manganese-based positive electrode material, a preparation method thereof and a lithium ion battery. The chemical formula of the positive electrode material is Li xMnaNibCocMdNeOg, wherein M is one of W, mo, la, zr, nb, ta, V, hf, N is one of F, B, cl, br, S, P, x is more than or equal to 1 and less than or equal to 1.3,0.5, a is more than or equal to 0.8,0.1 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.1,2 and g is more than or equal to 2.2,0.1 and less than or equal to d/e is more than or equal to 5. The compaction density of the positive electrode material can reach 3.6g/cm 3 at the highest, the specific surface area is only 0.25m 2/g at the lowest, the contact surface of the positive electrode material and electrolyte can be greatly reduced, the interface side reaction is further inhibited, and the volume energy density and the cycle life of the lithium-rich manganese-based positive electrode material are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a monocrystal lithium-rich manganese-based positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The high specific energy, low cost and high safety are important technical breakthrough points of long-term continuous healthy development of the lithium ion battery industry, are also powerful guarantees for realizing high-efficiency utilization of resources and strengthening quality of an industrial chain, and are in line with the idea of double-carbon development. The quality and cost ratio of the positive electrode material in the lithium ion battery are up to 40-50%, and the key performances of the battery such as energy density, safety, service life and the like are determined to a great extent. The lithium-rich manganese-based positive electrode material has low raw material cost, high thermal stability and specific capacity exceeding 250mAh/g, is regarded as a preferred material for supporting the technical upgrading of lithium batteries recently, but has the technical problems of poor cycle performance, fast voltage decay, low compaction density and the like, which cannot be broken through for a long time, and prevents the commercialized application and industrialization process of the lithium-rich manganese-based positive electrode material.
The main current lithium-rich manganese-based positive electrode material is a secondary spherical positive electrode particle formed by random orientation agglomeration of nanoscale primary particles, the positive electrode particle is continuously expanded and contracted in the lithium removal and intercalation process, stress is easily concentrated at a crystal boundary and microcracks are generated, the particles are broken and pulverized, and the collapse of the material structure and the collapse of the electrochemical performance are caused; meanwhile, the polycrystalline particles have more electrode-electrolyte interfaces, and the adverse side reactions are more; on the other hand, the surface and the inside of the secondary particles have more pores, which can reduce the compaction density of the material. Research shows that single crystal material has the advantages of less reaction interface, high compaction density, strong structural stability, good safety and the like, and single crystallization has become an important technical direction of positive electrode materials. The main synthesis method of the monocrystal lithium-rich manganese-based positive electrode material is a high-temperature solid-phase method, a precursor and excessive lithium salt are usually adopted, a large amount of fluxing agent (molten salt) is added at the same time, and the heat preservation is carried out at a high temperature for a certain time to promote the continuous growth of crystal particles, but the agglomeration of the product is usually serious, monodisperse monocrystal particles are difficult to form, and meanwhile, the adverse doping of a cosolvent, the subsequent cleaning and the corrosion to equipment are all difficult problems. For example, the Chinese patent with publication number CN116143200A adopts coprecipitation precursors, lithium sources and molten salt mixing, adopts a method of stepwise lithium distribution, calcination and suction filtration washing to obtain the monocrystal lithium-rich manganese-based material with high compaction density, has a better monocrystal structure and excellent performance, but has a relatively complex technological process. The Chinese patent with publication number CN116632218A adopts a high-temperature solid phase method to obtain a monodisperse monocrystal lithium-rich manganese-based positive electrode material, and the monodisperse monocrystal lithium-rich manganese-based positive electrode material is prepared by high-temperature sintering of precursors, lithium salt, fluxing agent, additives and the like, and then washing and secondary sintering are required. Chinese patent publication No. CN116623295A discloses a tantalum-zirconium co-doped cobalt-free monocrystal lithium-rich manganese-based positive electrode material and a preparation method thereof, and the monocrystal lithium-rich manganese-based material is obtained by adopting a ball milling mixing and high-temperature sintering one-step method, and the technological method is simpler, but the monocrystal grain size is relatively smaller and the dispersibility is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a monocrystal lithium-rich manganese-based positive electrode material, a preparation method thereof and a lithium ion battery, and the monocrystal lithium-rich manganese-based positive electrode material with a good crystal structure, monodispersion and uniform size can be obtained.
According to a first aspect of the invention, the invention provides a single crystal lithium-rich manganese-based positive electrode material, which has a chemical formula of Li xMnaNibCocMdNeOg, wherein M is one of W, mo, la, zr, nb, ta, V, hf, N is one of F, B, cl, br, S, P, x is more than or equal to 1 and less than or equal to 1.3,0.5, a is more than or equal to 1 and less than or equal to 0.8,0.1 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.1,2 and g is more than or equal to 0 and less than or equal to 2.2,0.1 and d/e is less than or equal to 5.
The monocrystal lithium-rich manganese-based positive electrode material is prepared from Li element, mn element, ni element, co element, M element, N element and O element, wherein the M element has the function of refining grains, the N element has the function of assisting sintering, and the specific selection of the M element and the N element is carried out, and meanwhile, the dosage proportion of the elements is adjusted to achieve the synergistic effect of the elements, so that the obtained positive electrode material forms a monocrystal morphology, has high compaction density and low specific surface area, further the contact surface of the positive electrode material and electrolyte is reduced, further the interface side reaction is inhibited, and the volume energy density and the cycle life of the lithium-rich manganese-based positive electrode material are improved.
In order to improve the compaction density of the positive electrode material and reduce the specific surface area of the positive electrode material to a greater extent, x is more than or equal to 1 and less than or equal to 1.2,0.5 and less than or equal to 0.6, b is more than or equal to 0.1 and less than or equal to 0.3,0.1 and less than or equal to c and less than or equal to 0.15, d is more than or equal to 0.01 and less than or equal to 0.05,0.01 and e is more than or equal to 0.07.
Further, the positive electrode material satisfies at least one of the following features (1) to (4):
(1) The positive electrode material has a lithium-rich lamellar phase crystal structure;
(2) The morphology of the positive electrode material is single-dispersed monocrystalline particles, and the median particle diameter D 50 is 1-10 mu m;
(3) The specific surface area of the positive electrode material is less than or equal to 1m 2/g;
(4) The compacted density of the positive electrode material was 3.0g/cm 3-3.6g/cm3.
According to a second aspect of the present invention, the present invention also provides a method for preparing the above positive electrode material, including the steps of:
step (1): dissolving soluble manganese salt, soluble nickel salt and soluble cobalt salt in water according to the chemical formula of the anode material to prepare a metal salt solution, controlling the temperature and pH value of a reaction system, adding a precipitator and a complexing agent to perform precipitation reaction, and washing, filtering and drying after the precipitation reaction is finished to obtain a lithium-rich manganese-based precursor;
Step (2): weighing corresponding amounts of the lithium-rich manganese-based precursor, the first additive containing M element, the second additive containing N element and the lithium source according to a chemical formula, uniformly mixing the materials, and pressing the materials to obtain a mixture; if d+e in the chemical formula of the positive electrode material is more than or equal to 0.08, at least two lithium sources are needed to be added, wherein the at least two lithium sources comprise a first lithium source and a second lithium source;
Step (3): and (3) sintering the mixture obtained in the step (2) at a high temperature to obtain the positive electrode material.
In the scheme, the preparation method of the positive electrode material adopts the coprecipitation technology to prepare the lithium-rich manganese-based precursor, and then uniformly mixes the lithium-rich manganese-based precursor, the first additive containing M element, the second additive containing N element and the lithium source, and presses the mixture into particles or sheets with a regular shape and size so as to adapt to the subsequent sintering process, thereby being beneficial to improving the compactness of the sintered positive electrode material, regulating and controlling the microstructure and the grain size of the positive electrode material, and further improving the electrochemical performance of the positive electrode material. Furthermore, if d+e is more than or equal to 0.08, the first lithium source and the second lithium source are required to be added simultaneously, because if the addition amount of M and N elements is too high, the crystal structure of the synthesized target material has a hetero-phase, and a great amount of experiments show that the addition of the second lithium source can effectively eliminate the hetero-phase, so that the lithium-rich manganese-based positive electrode material with a complete crystal structure and good single crystal morphology is formed, the improvement of the compaction density and the reduction of the specific surface area of the positive electrode material are facilitated, and the volume energy density and the cycle life of the lithium-rich manganese-based positive electrode material can be improved. The preparation method does not need to use a large amount of fluxing agent and subsequent washing process used by the traditional process, and the prepared monocrystal material has good dispersibility and uniform particle size distribution, is easy to amplify in batches and can be used for industrial production.
Further, in the step (2), the first lithium source is at least one of lithium carbonate, lithium hydroxide and lithium chloride;
And/or, the second lithium source is lithium nitrate;
And/or, the molar ratio of the addition amount of the lithium source to the lithium-rich manganese-based precursor is 1:1-1.3:1 based on Li;
And/or, if d+e is not less than 0.08, the molar ratio of the first lithium source to the second lithium source is 0.05 to 0.5 in terms of Li;
And/or, if d+e < 0.08, the second lithium source need not be added in step (2).
Further, in the step (2), the pressure used for pressing is not less than 0.05mPa.
Further, in the step (2), the first additive containing the M element is one of tungsten oxide, molybdenum oxide, lanthanum oxide, zirconium oxide, niobium oxide, tantalum oxide, vanadium oxide, hafnium oxide, lithium tungstate, lithium molybdate, lithium lanthanum oxide, lithium zirconate, lithium niobate, lithium tantalate and lithium vanadate;
and/or the second additive containing N element is one of lithium fluoride, ammonium fluoride, boric acid, ammonium chloride, boron oxide, ammonium bromide, ammonium sulfate and ammonium phosphate.
Further, in the step (3), the atmosphere of high-temperature sintering is oxygen-containing atmosphere, the sintering system is that the temperature is firstly increased to 400-700 ℃ at the rate of 0.1-10 ℃/min, the heat is preserved for 2-10 h, then the temperature is increased to 800-1100 ℃ at the rate of 0.1-10 ℃/min, the heat is preserved for 5-20 h, and the anode material is obtained after natural cooling, crushing and sieving.
Further, in the step (1), the soluble manganese salt comprises one or more of sulfate, nitrate, acetate and chloride of manganese element;
and/or the soluble nickel salt comprises one or more of sulfate, nitrate, acetate and chloride of nickel element;
and/or the soluble cobalt salt comprises one or more of sulfate, nitrate, acetate and chloride of cobalt element;
and/or the precipitant is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
and/or the complexing agent is at least one of ammonia water, citric acid and oxalic acid;
and/or the temperature of the precipitation reaction is 40-70 ℃;
And/or when the precipitant is sodium carbonate or potassium carbonate, the pH value of the precipitation reaction is 6-9, and when the precipitant is sodium hydroxide or potassium hydroxide, the pH value of the precipitation reaction is 9-12.
According to a third aspect of the present invention, the present invention also provides a lithium ion battery, including a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode includes the positive electrode material described above or the positive electrode material prepared by the preparation method described above.
The invention has the beneficial effects that:
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention obtains the monocrystal lithium-rich manganese-based positive electrode material, the compaction density can reach 3.6g/cm 3 at the highest, the specific surface area is only 0.25m 2/g at the lowest, the contact surface between the positive electrode material and electrolyte can be greatly reduced, the interface side reaction is further inhibited, and the volume energy density and the cycle life of the lithium-rich manganese-based positive electrode material are improved.
(2) The invention develops a simple preparation method of the monocrystal lithium-rich manganese-based positive electrode material, a large amount of fluxing agent and subsequent washing process used by the traditional process are not needed, and the synthesized monocrystal material has good dispersibility and uniform particle size distribution, is easy to amplify in batches, and can be used for industrial production.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction chart of the positive electrode materials of example 1 and example 2 of the present invention;
FIG. 2 is an SEM image of the positive electrode material of example 1 of the present invention;
FIG. 3 is an SEM image of the positive electrode material of example 2 of the present invention;
FIG. 4 is an SEM image of the positive electrode material of example 3 of the present invention;
FIG. 5 is an X-ray diffraction chart of the positive electrode materials of example 3 and comparative example 4 of the present invention;
FIG. 6 is an X-ray diffraction chart of the positive electrode material of comparative example 1 of the present invention;
FIG. 7 is an SEM image of the positive electrode material of comparative example 1 of the present invention;
FIG. 8 is an X-ray diffraction chart of the positive electrode material of comparative example 2 of the present invention;
fig. 9 is an SEM image of the positive electrode material of comparative example 2 of the present invention;
FIG. 10 is an SEM image of the positive electrode material of comparative example 3 of the present invention;
Fig. 11 is an SEM image of the positive electrode material of comparative example 4 of the present invention;
fig. 12 is an SEM image of the positive electrode material of comparative example 5 of the present invention;
Fig. 13 is a graph showing the first charge and discharge of the batteries prepared from the positive electrode materials of example 1, example 2 and comparative example 1 according to the present invention;
fig. 14 is a graph showing cycle performance of batteries prepared from the positive electrode materials of example 1, example 2 and comparative example 1 according to the present invention;
fig. 15 is a graph of the first charge and discharge of the batteries prepared with the positive electrode materials of example 3 and comparative example 4 of the present invention;
fig. 16 is a graph showing cycle performance of batteries prepared from the positive electrode materials of example 3 and comparative example 4 according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The examples and comparative examples are not to be construed as specifying the particular technology or conditions, as described in the literature in this field, or as per the product specifications. The equipment and other manufacturers are not noted, and the conventional products can be purchased through regular channel providers. The chemical raw materials used in the invention can be conveniently purchased in the domestic chemical product market.
Example 1
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 3F0.02O2.085.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13C00.13W0.03F0.02O2.085, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the sintering atmosphere to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 2
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 3B0.03O2.14.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and boric acid according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03B0.03O2.14, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 3
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 3B0.05O2.17.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (accounting for 90% of the addition amount of lithium in terms of Li), lithium nitrate (accounting for 10% of the addition amount of lithium in terms of Li), tungsten oxide (accounting for W) and boric acid according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03B0.05O2.17, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material.
Example 4
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13La0.03B0.03O2.095.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium hydroxide (calculated by Li), lanthanum oxide (calculated by La) and boric acid according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13La0.03B0.03O2.095, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the materials to 500 ℃ at a heating rate of 3 ℃/min in the presence of air, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 5
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13La0.03Cl0.01O2.045.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium hydroxide (calculated by Li), lanthanum oxide (calculated by La) and ammonium chloride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13La0.03Cl0.01O2.045, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 6
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13Mo0.02F0.02O2.055.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), molybdenum oxide (calculated by Mo) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13Mo0.02F0.02O2.055, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the sintering atmosphere to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 7
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13Nb0.02F0.02O2.045.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), niobium oxide (calculated by Nb) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13Nb0.02F0.02O2.045, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the materials to 500 ℃ at a heating rate of 3 ℃/min in the presence of air, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 8
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 1F0.07O2.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li and accounting for 85 percent of the addition amount of lithium), lithium nitrate (calculated by Li and accounting for 15 percent of the addition amount of lithium), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.01F0.07O2, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets into an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the single-crystal lithium-rich manganese-based positive electrode material.
Example 9
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 5F0.01O2.15.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.05F0.01O2.15, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the sintering atmosphere to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 10
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 3F0.02O2.085.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium carbonate in water to prepare a 2mol/L precipitator solution B, slowly dripping the solution A and the solution B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 8.5, controlling the temperature of the system to be 50 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13CO3.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03F0.02O2.085, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the sintering atmosphere to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 11
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 3F0.02O2.085.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03F0.02O2.085, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the sintering atmosphere to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 800 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 12
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13W0.0 3F0.02O2.085.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03F0.02O2.085, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, heating the sintering atmosphere to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 1100 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 13
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13Zr0.02Br0.02O2.035.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), zirconium oxide (calculated by Zr) and ammonium bromide according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13Zr0.02Br0.02O2.035, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, directly placing the materials into an atmosphere furnace for sintering, heating the materials to 500 ℃ at a heating rate of 3 ℃/min in the presence of air, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 14
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13Ta0.02Cl0.02O2.045.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tantalum oxide (calculated by Ta) and ammonium chloride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13Ta0.02Cl0.02O2.045, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, directly placing the materials into an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Example 15
The embodiment provides a monocrystal lithium-rich manganese-based positive electrode material, and the chemical formula of the monocrystal lithium-rich manganese-based positive electrode material is Li 1.2Mn0.54Ni0.13Co0.13Hf0.03Cl0.02O2.055.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), hafnium oxide (calculated by Hf) and ammonium chloride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03F0.02O2.04, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, directly placing the materials into an atmosphere furnace for sintering, heating the materials to 500 ℃ at a heating rate of 3 ℃/min in the presence of air, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Comparative example 1
The comparative example provides a lithium-rich manganese-based positive electrode material having a chemical formula of Li 1.2Mn0.54Ni0.13Co0.13O2.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor and lithium carbonate (calculated by Li) according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13O2, putting the materials into a high-speed mixer, uniformly mixing and pressing into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the conventional lithium-rich manganese-based anode material.
Comparative example 2
The comparative example provides a single crystal lithium-rich manganese-based positive electrode material having a chemical formula of Li 1.2Mn0.54Ni0.13Co0.13W0.0 3O2.095.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li) and tungsten oxide (calculated by W) according to a chemical formula Li 1.2Mn0.5aNi0.13Co0.13W0.03O2.095, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 10 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Comparative example 3
The comparative example provides a single crystal lithium-rich manganese-based positive electrode material having a chemical formula of Li 1.2Mn0.54Ni0.13Co0.13F0.0 2O1.995.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13F0.02O1.995, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 10 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Comparative example 4
The comparative example provides a single crystal lithium-rich manganese-based positive electrode material having a chemical formula of Li 1.2Mn0.54Ni0.13Co0.13W0.0 3B0.05O2.17.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the cobalt sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and boric acid according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03B0.05O2.17, putting the materials into a high-speed mixer, uniformly mixing and pressing the materials into tablets, placing the tablets in an atmosphere furnace for sintering, wherein the sintering atmosphere is air, heating to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the monocrystal lithium-rich manganese-based anode material.
Comparative example 5
The comparative example provides a lithium-rich manganese-based positive electrode material having a chemical formula of Li 1.2Mn0.54Ni0.13Co0.13W0.03F0.0 2O2.085.
The preparation method of the positive electrode material comprises the following steps:
Weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and a sodium sulfate heptahydrate according to the molar ratio of 0.54:0.13:0.13, and dissolving the manganese sulfate monohydrate, the nickel sulfate hexahydrate and the sodium sulfate heptahydrate in deionized water to prepare a metal salt solution A with the concentration of 2 mol/L; dissolving sodium hydroxide in water to prepare 2mol/L precipitant solution B, slowly dripping the solutions A and B into deionized water under the stirring condition of 500rpm/min, controlling the pH value of a reaction system to be 11.5, controlling the temperature of the system to be 55 ℃, washing, suction-filtering and drying the obtained precipitate after the reaction is carried out for 20 hours, thus obtaining the lithium-rich manganese-based precursor Mn 0.54Ni0.13Co0.13(OH)2.
Weighing corresponding amounts of a lithium-rich manganese-based precursor, lithium carbonate (calculated by Li), tungsten oxide (calculated by W) and ammonium fluoride according to a chemical formula Li 1.2Mn0.54Ni0.13Co0.13W0.03F0.02O2.085, putting the materials into a high-speed mixer, uniformly mixing, directly placing the materials into an atmosphere furnace for sintering, heating the materials to 500 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 950 ℃ at the same rate, keeping the temperature for 15 hours, and cooling to room temperature to obtain the lithium-rich manganese-based anode material.
Experimental example
1. X-ray diffraction test and SEM test were performed on the positive electrode materials of examples 1 to 3 and comparative examples 1 to 5.
As can be seen from fig. 1, the main diffraction peaks of the positive electrode materials in the embodiments 1 and 2 of the present invention are consistent with the α3nafeo 2 with the space group of R3-m, and weak superlattice diffraction peaks appear in the range of 10-30 °, which indicates that the positive electrode materials have typical lithium-rich manganese-based layered structure and do not contain other impurity phases.
As can be seen from the SEM images of fig. 2, 3 and 4, the morphology of the positive electrode material of the present invention is single-dispersed single-crystal particles, and the median particle diameter D 50 is 1-10 μm.
As can be seen from fig. 5, the positive electrode material of example 3 of the present invention has a lithium-rich layered phase crystal structure, contains no other impurity phases, and the positive electrode material of comparative example 4 contains an impurity phase.
As can be seen from fig. 6, the crystal structure of the cathode material of comparative example 1 is similar to that of example 1, and is also a pure lithium-rich manganese-based layered structure, and as can be seen from fig. 7, the morphology of the cathode material of comparative example 1 is that of polycrystalline particles having a secondary sphere structure, the primary particles are in the form of flakes, and the thickness of the flakes is 200-300nm.
As can be seen from fig. 8, the crystal structure of the positive electrode material of comparative example 2 is similar to that of example 1, and is also a pure lithium-rich manganese-based layered structure, and as can be seen from fig. 9, the morphology of the positive electrode material of comparative example 2 is polycrystalline particles having a secondary sphere structure, the primary particles are flaky and granular, and the thickness of the flaky layer is 100-200nm.
As can be seen from fig. 10, the morphology of the positive electrode material of comparative example 3 is divided into two types, one being polycrystalline particles having a secondary sphere structure, the primary particles of which are polyhedral; the other is large particles with a particle size exceeding 2 μm. As can be seen from fig. 11, the morphology of the positive electrode material of comparative example 4 is monodisperse single crystal particles, and the median particle diameter D 50 is 1.5 to 2 μm. As can be seen from FIG. 12, the positive electrode material of comparative example 5 was heterogeneous in morphology, mostly in polycrystalline particles having a secondary sphere structure, and the primary particles were nearly spherical with a diameter of 100 to 200nm, and the small portions were single crystal particles with a diameter of 2 μm or more.
2. The cathode materials of examples 1 to 15 and comparative example 5 were subjected to the following electrochemical performance tests:
Mixing a positive electrode material, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil sheet to obtain a positive electrode sheet; and then, taking a lithium sheet as a negative electrode sheet, taking 1mol/L of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1:1) as electrolyte, and assembling in a glove box to obtain the lithium ion battery.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, and the first charge and discharge performance of the battery is tested under the condition that the current density is 0.1C (1 C=200 mAg -1) and the charge and discharge voltage ranges from 4.8V to 2.0V. The cycle performance was tested at a regime of 2.0-4.8V, 1C/1C.
The test results obtained are shown in table 1 below.
Table 1 electrochemical properties of the cathode materials of examples 1 to 15 and comparative example 5
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As can be seen from the experimental results in Table 1, the compaction density of the single crystal lithium-rich manganese-based positive electrode material is more than 3.0g/cm 3, the highest compaction density can be 3.6g/cm 3, the specific surface area is less than 0.8m 2/g, and the lowest compaction density is only 0.25m 2/g, so that the contact surface between the positive electrode material and electrolyte can be greatly reduced, further the interface side reaction is inhibited, and the volume energy density and the cycle life of the lithium-rich manganese-based positive electrode material are improved. The battery prepared by the positive electrode material has the first charge specific capacity of more than 310mAh/g, the first discharge specific capacity of more than 240mAh/g, the first coulomb efficiency of more than 76% and the capacity retention rate of more than 89% in 500 weeks.
From the experimental results of example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 in table 1, and the results of fig. 13 and 14, it can be seen that the addition of M element and N element in a single crystal lithium-rich manganese-based positive electrode material of the present invention has an important effect on the compacted density and specific surface area of the positive electrode material of the present invention, and removal of one or both of M element and N element reduces the compacted density, increases the specific surface area, and further affects the volumetric energy density and cycle life of the lithium-rich manganese-based positive electrode material.
As can be seen from the experimental results of example 3 and comparative example 4 in Table 1 and with reference to FIGS. 15 and 16, if d+e is greater than or equal to 0.08 in the preparation process, the first lithium source and the second lithium source are required to be added simultaneously, so that the reduction of the compaction density and the improvement of the specific surface area of the positive electrode material are facilitated, and the volumetric energy density and the cycle life of the lithium-rich manganese-based positive electrode material can be further improved. As can be seen from the experimental result of comparative example 5, the mixture of the invention is pressed before high-temperature sintering, which is beneficial to the contact of the raw materials to be more compact, the solid phase reaction and the crystal growth in the sintering process to be more beneficial to the uniformity of the obtained material, the formation of single crystals with good dispersibility and uniform granularity to be more beneficial to the reduction of the compaction density of the positive electrode material and the improvement of the specific surface area.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The single crystal lithium-rich manganese-based positive electrode material is characterized in that the chemical formula of the positive electrode material is Li xMnaNibCocMdNeOg, wherein M is one of W, mo, la, zr, nb, ta, V, hf, N is one of F, B, cl, br, S, P, 1<x is less than or equal to 1.3,0.5< a is less than or equal to 0.8,0.1 and less than or equal to b is less than or equal to 0.5,0< c is less than or equal to 0.5,0< d is less than or equal to 0.1,0< e is less than or equal to 0.1,2 and g is less than or equal to 2.2,0.1 and less than or equal to d/e is less than or equal to 5.
2. The positive electrode material according to claim 1, wherein 1<x.ltoreq.1.2, 0.5< a.ltoreq.0.6, 0.1.ltoreq.b.ltoreq.0.15, 0.1< c.ltoreq.0.15, 0.01.ltoreq.d.ltoreq. 0.05,0.01.ltoreq.e.ltoreq.0.07.
3. The positive electrode material according to claim 1 or 2, characterized in that the positive electrode material satisfies at least one of the following features (1) to (4):
(1) The positive electrode material has a lithium-rich lamellar phase crystal structure;
(2) The morphology of the positive electrode material is single-dispersed monocrystalline particles, and the median particle diameter D 50 is 1-10 mu m;
(3) The specific surface area of the positive electrode material is less than or equal to 1m 2/g;
(4) The compacted density of the positive electrode material was 3.0g/cm 3-3.6g/cm3.
4. A method for producing the positive electrode material according to any one of claims 1 to 3, comprising the steps of:
Step (1): dissolving soluble manganese salt, soluble nickel salt and soluble cobalt salt in water according to the chemical formula of the anode material to prepare a metal salt solution, controlling the temperature and pH value of a reaction system, adding a precipitator and a complexing agent to perform precipitation reaction, and washing, filtering and drying after the precipitation reaction is finished to obtain a lithium-rich manganese-based precursor;
Step (2): weighing corresponding amounts of the lithium-rich manganese-based precursor, the first additive containing M element, the second additive containing N element and the lithium source according to a chemical formula, uniformly mixing the materials, and pressing the materials to obtain a mixture; if d+e in the chemical formula of the positive electrode material is more than or equal to 0.08, at least two lithium sources are needed to be added, wherein the at least two lithium sources comprise a first lithium source and a second lithium source;
Step (3): and (3) sintering the mixture obtained in the step (2) at a high temperature to obtain the positive electrode material.
5. The method according to claim 4, wherein in the step (2), the first lithium source is at least one of lithium carbonate, lithium hydroxide, and lithium chloride;
And/or, the second lithium source is lithium nitrate;
And/or, the molar ratio of the addition amount of the lithium source to the lithium-rich manganese-based precursor is 1:1-1.3:1 based on Li;
And/or, if d+e is not less than 0.08, the molar ratio of the first lithium source to the second lithium source is 0.05 to 0.5 in terms of Li;
And/or if d+e <0.08, the second lithium source need not be added in step (2).
6. The process according to claim 4, wherein in step (2), the pressure used for the pressing is not less than 0.05mPa.
7. The method according to claim 4, wherein in the step (2), the first additive containing M element is one of tungsten oxide, molybdenum oxide, lanthanum oxide, zirconium oxide, niobium oxide, tantalum oxide, vanadium oxide, hafnium oxide, lithium tungstate, lithium molybdate, lithium lanthanum oxide, lithium zirconate, lithium niobate, lithium tantalate, and lithium vanadate;
and/or the second additive containing N element is one of lithium fluoride, ammonium fluoride, boric acid, ammonium chloride, boron oxide, ammonium bromide, ammonium sulfate and ammonium phosphate.
8. The method according to claim 4, wherein in the step (3), the atmosphere for high-temperature sintering is an oxygen-containing atmosphere, the sintering schedule is that the temperature is raised to 400-700 ℃ at a rate of 0.1-10 ℃/min, the temperature is kept for 2-10 h, the temperature is raised to 800-1100 ℃ at a rate of 0.1-10 ℃/min, the temperature is kept for 5-20 h, and the anode material is obtained after natural cooling, crushing and sieving.
9. The method according to claim 4, wherein in the step (1), the soluble manganese salt comprises one or more of sulfate, nitrate, acetate and chloride of manganese element;
and/or the soluble nickel salt comprises one or more of sulfate, nitrate, acetate and chloride of nickel element;
and/or the soluble cobalt salt comprises one or more of sulfate, nitrate, acetate and chloride of cobalt element;
and/or the precipitant is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
and/or the complexing agent is at least one of ammonia water, citric acid and oxalic acid;
and/or the temperature of the precipitation reaction is 40-70 ℃;
And/or when the precipitant is sodium carbonate or potassium carbonate, the pH value of the precipitation reaction is 6-9, and when the precipitant is sodium hydroxide or potassium hydroxide, the pH value of the precipitation reaction is 9-12.
10. A lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the positive electrode material according to any one of claims 1 to 3 or the positive electrode material prepared by the preparation method according to any one of claims 4 to 9.
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