CN115465900A - Spinel phase lithium nickel manganese oxide positive electrode material, preparation method thereof and battery - Google Patents
Spinel phase lithium nickel manganese oxide positive electrode material, preparation method thereof and battery Download PDFInfo
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- CN115465900A CN115465900A CN202211177022.6A CN202211177022A CN115465900A CN 115465900 A CN115465900 A CN 115465900A CN 202211177022 A CN202211177022 A CN 202211177022A CN 115465900 A CN115465900 A CN 115465900A
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- Prior art keywords
- nickel
- manganese
- spinel
- lithium
- manganese oxide
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 21
- 239000011029 spinel Substances 0.000 title claims abstract description 21
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 19
- 150000003624 transition metals Chemical class 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000004090 dissolution Methods 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 description 37
- 239000012071 phase Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 10
- 239000001099 ammonium carbonate Substances 0.000 description 10
- 239000010405 anode material Substances 0.000 description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- ZWEKKXQMUMQWRN-UHFFFAOYSA-J manganese(2+);nickel(2+);dicarbonate Chemical compound [Mn+2].[Ni+2].[O-]C([O-])=O.[O-]C([O-])=O ZWEKKXQMUMQWRN-UHFFFAOYSA-J 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- MZGCONFLQMEINW-UHFFFAOYSA-N CNC.OS(=O)(=O)C=C Chemical compound CNC.OS(=O)(=O)C=C MZGCONFLQMEINW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- KIPMDPDAFINLIV-UHFFFAOYSA-N 2-nitroethanol Chemical compound OCC[N+]([O-])=O KIPMDPDAFINLIV-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- -1 transition metal cations Chemical class 0.000 description 3
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 2
- YISPKQZWSIMXMX-UHFFFAOYSA-N 3-nitropropan-1-ol Chemical compound OCCC[N+]([O-])=O YISPKQZWSIMXMX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229950006187 hexamethonium bromide Drugs 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940045996 isethionic acid Drugs 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 2
- XWIJIXWOZCRYEL-UHFFFAOYSA-M potassium;methanesulfonate Chemical compound [K+].CS([O-])(=O)=O XWIJIXWOZCRYEL-UHFFFAOYSA-M 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- SPALIFXDWQTXKS-UHFFFAOYSA-M tetrapentylazanium;bromide Chemical compound [Br-].CCCCC[N+](CCCCC)(CCCCC)CCCCC SPALIFXDWQTXKS-UHFFFAOYSA-M 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- DHAWHVVWUNNONG-UHFFFAOYSA-M tributyl(methyl)azanium;bromide Chemical compound [Br-].CCCC[N+](C)(CCCC)CCCC DHAWHVVWUNNONG-UHFFFAOYSA-M 0.000 description 2
- FAPSXSAPXXJTOU-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dibromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C FAPSXSAPXXJTOU-UHFFFAOYSA-L 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a spinel phase lithium nickel manganese oxide positive electrode material, a preparation method thereof and a battery; the preparation method comprises the steps of mixing a nickel-manganese compound precursor with a lithium source and an additive, calcining at high temperature, annealing and crushing to prepare a spinel-phase lithium nickel manganese oxide cathode material; wherein the additive has electron rich groups. The spinel-phase lithium nickel manganese oxide positive electrode material prepared by the preparation method disclosed by the invention is stable in structure, and can effectively inhibit side reaction between the surface of the spinel-phase lithium nickel manganese oxide positive electrode material and an electrolyte and dissolution of transition metal, so that the cycle performance of a battery can be improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a spinel phase lithium nickel manganese oxide positive electrode material, a preparation method thereof and a battery.
Background
Spinel phase lithium nickel manganese oxide (LiNi) 0.5 Mn 1.5 O 4 ) As a high voltage positive electrode material, it is widely regarded as a high energy, stable in structure, and safe.
However, the preparation method provided by the related art produces LiNi 0.5 Mn 1.5 O 4 There are some problems in application, lithium nickel manganese oxide (LiNi) of spinel phase at high voltage 0.5 Mn 1.5 O 4 ) The positive electrode material is easy to generate side reaction with the electrolyte, which causes the problems of electrolyte decomposition, structural damage, transition metal dissolution and the like, reduces the cycle performance of the battery and shortens the service life of the battery.
In lithium ion batteries, lithium ion diffusion typically occurs at the electrode/electrolyte interface. For LiNi 0.5 Mn 1.5 O 4 For materials, different crystal plane orientations determine the difference of crystal forms and have important influence on electrochemical properties, which is mainly similar to Li + In LiNi 0.5 Mn 1.5 O 4 The anisotropic kinetics of medium diffusion are related. The related art indicates that LiNi 0.5 Mn 1.5 O 4 Regular octahedral monocrystal is formed along the (111) crystal face to generate a stable CEI layer, so that the decomposition of electrolyte under high voltage is reduced, and the cycle performance and the rate capability of the material are improved. It is also known that the growth along the (100) crystal planes forms truncated octahedra with higher Li at high voltage + Diffusion coefficient, and stable contact interface with electrolyte. Related technologies indicate that Mn ions in the spinel material are the cause of side reactions between the (110) crystal plane and the electrolyte, and are not favorable for cycling stability at high voltage. Therefore, among the three crystal planes (111), (100), (110), (111) and (100) are advantageous for improved cycle performance and rate performance, while (1)10 ) crystal planes are not good for cycling stability. Thus, liNi was improved by 0.5 Mn 1.5 O 4 The stability of the surface of the anode material plays an important role in improving the electrochemical performance of the lithium ion battery.
Disclosure of Invention
The spinel-phase lithium nickel manganese oxide positive electrode material prepared by the preparation method disclosed by the invention is stable in structure, and can effectively inhibit side reaction between the surface of the spinel-phase lithium nickel manganese oxide positive electrode material and electrolyte and dissolution of transition metal, so that the cycle performance of the battery can be improved.
The invention is realized by the following steps:
in a first aspect, the invention provides a preparation method of a spinel-phase lithium nickel manganese oxide positive electrode material, which comprises the following steps:
mixing a nickel-manganese compound precursor with a lithium source and an additive, calcining at high temperature, annealing and crushing to obtain a spinel-phase lithium nickel manganese oxide positive electrode material; wherein the additive has electron rich groups.
In an alternative embodiment, the additive includes at least one of an organic containing sulfonic acid groups, nitro groups, and halogen groups.
In an optional embodiment, the mass of the effective group in the additive is 0.2-1% of the mass of the nickel-manganese compound precursor. The effective group includes at least one of a sulfonic acid group, a nitro group and a halogen group.
Preferably, the preparation method of the nickel manganese compound precursor comprises the following steps:
preparing a transition metal mixed solution by using a manganese source and a nickel source;
and adding excessive precipitator into the transition metal mixed solution to prepare the nickel-manganese compound precursor.
Further preferably, the reaction at a set temperature is carried out after excessive precipitant is added, and the reaction is carried out after cooling, suction filtration, washing and drying.
In an alternative embodiment, the molar ratio of lithium ions in the lithium source, manganese ions in the manganese source, and nickel ions in the nickel source is (0.5-0.6): 1 (1.3-1.8).
In an alternative embodiment, the molar ratio of the anionic groups forming the transition metal precipitate to the total amount of transition metal ions in the nickel-manganese compound suspension is (5-8): 1.
In an alternative embodiment, the source of manganese comprises at least one of manganese hydroxide, manganese sulfate, manganese carbonate, manganese acetate;
the nickel source comprises at least one of nickel hydroxide, nickel sulfate, nickel carbonate and nickel acetate;
the lithium source includes at least one of lithium hydroxide, lithium sulfate, lithium carbonate, and lithium acetate.
In an alternative embodiment, the additive is at least one of sodium dodecyl sulfonate, potassium methylsulfonate, isethionic acid, dimethylamine vinylsulfonate, cetyltrimethylammonium bromide, tetramethylammonium bromide, tetrapropylammonium bromide, hexamethonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tributylmethylammonium bromide, 2-nitropropane, nitrocyclohexane, 3-nitropropanol, 2-nitroethanol.
In an alternative embodiment, the precipitant comprises at least one of a carbonate, ammonia, and a metal hydroxide.
In an alternative embodiment, the precipitant is at least one of ammonium bicarbonate, sodium bicarbonate, ammonium carbonate, sodium carbonate, aqueous ammonia, and sodium hydroxide.
In a second aspect, the present invention provides a spinel phase lithium nickel manganese oxide positive electrode material obtained by the method for preparing a spinel phase lithium nickel manganese oxide positive electrode material according to any one of the foregoing embodiments.
In a third aspect, the present invention provides a battery comprising the spinel phase lithium nickel manganese oxide positive electrode material of the foregoing embodiment.
Compared with the prior art, the invention has the following beneficial effects:
for LiNi 0.5 Mn 1.5 O 4 In terms of materials, different crystal plane orientations not only determine the difference of crystal forms, but also have important influence on electrochemical properties, and among three crystal planes (111), (100) and (110), the crystal planes (111) and (100) are beneficial to improvementCycling performance and rate performance, while the (110) crystal face is not good for cycling stability. The additive used in the preparation method of the spinel-phase lithium nickel manganese oxide cathode material provided by the embodiment of the invention has an electron-rich group, can form a stable ionic bond with transition metal cations, promotes the ordered arrangement of the cations, reduces the surface energy of crystals, and promotes the growth of the material along crystal faces (111) and (100) with lower surface energy, so that the dissolution of the transition metal in the charging and discharging process is reduced, and the cycle stability is improved.
The spinel-phase lithium nickel manganese oxide positive electrode material provided by the embodiment of the invention is prepared by the preparation method, has a stable structure, and can effectively inhibit side reaction between the surface of the spinel-phase lithium nickel manganese oxide positive electrode material and electrolyte and dissolution of transition metal, so that the cycle performance of a battery can be improved.
The battery provided by the embodiment of the invention comprises the spinel-phase lithium nickel manganese oxide cathode material, so that the cycle performance of the battery is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM photograph of the material of example 1;
FIG. 2 is the XRD pattern of the material of example 1;
FIG. 3 is an SEM photograph of the material of example 2;
FIG. 4 is the XRD pattern of the material of example 2;
FIG. 5 is an SEM photograph of the material in example 3;
figure 6 is the XRD pattern of the material in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
LiNi 0.5 Mn 1.5 O 4 The main modification methods include ion doping, surface coating, morphology and crystal face regulation; liNi 0.5 Mn 1.5 O 4 The main synthesis methods of the material include a sol-gel method, a hydrothermal method, a solid phase method, a coprecipitation method and the like. The related art provides a spinel type lithium ion battery anode active material and a preparation method thereof; according to the preparation method, hexamethylenetetramine is selected as a precipitator, a mixed solution of diethylene glycol and deionized water is used as a solvent, then manganese acetate and nickel acetate are added into the mixed solvent for dissolution, then a solvothermal reaction is carried out, finally lithium acetate is uniformly distributed on carbonate precipitates through absolute ethyl alcohol, and sintering is carried out after the absolute ethyl alcohol is evaporated to obtain the spinel type lithium ion battery anode active material, wherein the main exposed crystal face of the spinel type lithium ion battery anode active material is a (111) crystal face. The oxidation degree of the precursor is controlled within a specific range in the growth process of the precursor, so that the growth priority of the crystal face of the precursor is changed, the proportion of the (100) crystal face to the (101) crystal face of a precursor finished product is improved, and meanwhile, the precursor with the required morphology is obtained by adjusting the supply amount and pH of metal salt in the reaction process, so that the precursor of the hollow cathode material with the controllable crystal face is obtained; the inventor researches and discovers that the method provided by the related technology needs to be optimized on the growth of precursors of a lithium source and a manganese source, is limited in regulation and control process and cannot be applied to a synthesis method of various cathode materials.
The invention provides a preparation method of a spinel-phase lithium nickel manganese oxide positive electrode material, which does not need to optimize the growth of precursors of a lithium source and a manganese source, but adds an additive in the calcination process of the precursors and the lithium source to regulate and control the crystal face, greatly simplifies the regulation and control method of the crystal face of the spinel positive electrode material, can be suitable for the synthesis methods of most positive electrode materials, including a sol-gel method, a hydrothermal method, a solid phase method, a microwave synthesis method, a coprecipitation method and the like, has a simple preparation process, and can be produced in a large scale.
The preparation method of the spinel-phase lithium nickel manganese oxide cathode material comprises the following steps:
mixing a nickel-manganese compound precursor with a lithium source and an additive, calcining at high temperature, annealing and crushing to obtain a spinel-phase lithium nickel manganese oxide positive electrode material; wherein the additive has electron rich groups.
Further, the preparation method of the nickel manganese compound precursor comprises the following steps:
preparing a transition metal mixed solution by using a manganese source and a nickel source;
adding excessive precipitator into the transition metal mixed solution to prepare nickel-manganese compound suspension;
and (3) reacting the nickel-manganese compound suspension at a set temperature, cooling, performing suction filtration, and washing to obtain the nickel-manganese compound precursor.
In some embodiments, the nickel-manganese compound precursor is a nickel-manganese compound suspension, and the nickel-manganese compound suspension as a nickel-manganese compound precursor is mixed with a lithium source and an additive, and then dried at a set temperature, and then subjected to high-temperature calcination, annealing and crushing to obtain the spinel-phase lithium nickel manganese oxide positive electrode material.
The additive used in the preparation method has an electron-rich group, can form a stable ionic bond with transition metal cations, promotes the ordered arrangement of the cations, reduces the surface energy of crystals, is an octahedral particle with better crystallinity, reduces the growth of the octahedral particle along a (110) crystal plane, and promotes the growth of materials along (111) and (100) crystal planes with lower surface energy, so that the dissolution of the transition metal in the charging and discharging processes is reduced, and the circulation stability is improved.
The set temperature can be selected according to requirements, such as: 80 ℃ to 180 ℃ and the like, and is not particularly limited herein.
The method for preparing the nickel-manganese compound precursor is not limited to the method described in the present disclosure, and when preparing the spinel-phase lithium nickel manganese oxide positive electrode material, the nickel-manganese compound precursor may be a commercially available product or prepared by other related methods, and is not particularly limited herein.
When the precipitant is added to the transition metal mixed solution, the transition metal mixed solution may be added to a high-temperature high-pressure reaction kettle, and an excessive precipitant solution may be slowly added while stirring to obtain a nickel-manganese compound suspension.
In some embodiments, the additive comprises at least one of an organic containing sulfonic acid groups, nitro groups, and halogen groups.
The carbon chains in the additive are decomposed into carbon dioxide and water vapor in high-temperature calcination, and the conductivity and the electrochemical performance of the material are not influenced.
Further, the mass of the effective groups in the additive is 0.2-1% of the mass of the nickel-manganese compound precursor, such as: 0.2%, 0.5%, 1%, etc., and is not particularly limited herein. The mass ratio of effective groups in the additive is optimized, so that the structural stability of the prepared anode material can be further ensured, the side reaction generated by the anode material and the electrolyte is reduced, and the cycle performance is improved. The effective group includes at least one of a sulfonic acid group, a nitro group and a halogen group.
Optionally, the additive is at least one of sodium dodecyl sulfonate, potassium methyl sulfonate, isethionic acid, dimethylamine vinylsulfonate, cetyltrimethylammonium bromide, tetramethylammonium bromide, tetrapropylammonium bromide, hexamethonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tributylmethylammonium bromide, 2-nitropropane, nitrocyclohexane, 3-nitropropanol, 2-nitroethanol.
In some embodiments, the molar ratio of lithium ions in the lithium source, manganese ions in the manganese source, and nickel ions in the nickel source is (0.5-0.6) to 1 (1.3-1.8), such as: 0.5. Optimizing the molar ratio of lithium, manganese and lithium is beneficial to preparing the cathode material with more excellent cycle performance and rate performance.
Further, the lithium source comprises at least one of lithium hydroxide, lithium sulfate, lithium carbonate and lithium acetate; the manganese source comprises at least one of manganese hydroxide, manganese sulfate, manganese carbonate and manganese acetate; the nickel source includes at least one of nickel hydroxide, nickel sulfate, nickel carbonate, and nickel acetate.
In some embodiments, the precipitating agent comprises at least one of a carbonate, ammonia, metal hydroxide.
Optionally, the precipitant is at least one of ammonium bicarbonate, sodium bicarbonate, ammonium carbonate, sodium carbonate, ammonia water, and sodium hydroxide.
Furthermore, the molar ratio of the anionic groups forming the transition metal precipitate to the total amount of transition metal ions in the nickel-manganese compound suspension is (5-8): 1, for example: 5.
The spinel-phase lithium nickel manganese oxide cathode material prepared by the preparation method can be used for preparing batteries and can improve the cycle performance of the batteries.
The present invention will be described in further detail with reference to examples.
Example 1
(1) Weighing 1kg of manganese sulfate, weighing nickel sulfate according to a stoichiometric ratio of nickel sulfate to manganese sulfate of 1. Weighing ammonium bicarbonate as a precipitator according to the stoichiometric ratio of the total amount of the transition metal ions to the carbonate ions 1. Slowly adding the ammonium bicarbonate solution into the transition metal ion mixed solution while stirring, and continuously stirring for half an hour after the solution is mixed to obtain a suspension. And pouring the suspension into a high-temperature high-pressure reaction kettle, preserving heat for 8 hours at the temperature of 180 ℃, cooling to room temperature after finishing, performing suction filtration, washing, and drying for 12 hours at the temperature of 80 ℃ to obtain nickel-manganese carbonate precursor powder.
(2) Weighing lithium carbonate and vinyl sulfonic acid dimethylamine, wherein the stoichiometric ratio of Li to Mn is 0.55. Lithium carbonate, dimethylamine vinylsulfonate and the precursor obtained in step (1)And mixing the bulk powder uniformly. The mixture is placed in a muffle furnace for sintering at 900 ℃ for 8h, annealing at 500 ℃ for 4h, and cooling to room temperature. Ball-milling and crushing the blocky high-temperature sintered product to obtain LiNi 0.5 Mn 1.5 O 4 And positive electrode material powder.
EXAMPLE 1 preparation of LiNi by high temperature solid phase Process 0.5 Mn 1.5 O 4 The positive electrode material, fig. 1 is an SEM image, the particles of which are regular octahedral single crystals, and fig. 2 is an XRD image of the resulting product, showing no impurity phase.
Example 2
(1) Weighing 1kg of manganese sulfate, weighing nickel sulfate according to a stoichiometric ratio of nickel sulfate to manganese sulfate of 1. Weighing ammonium bicarbonate as a precipitator according to the stoichiometric ratio of the total amount of the transition metal ions to the carbonate ions 1. Slowly adding the ammonium bicarbonate solution into the transition metal ion mixed solution while stirring, and continuously stirring for 30min after the solution is mixed to obtain the nickel-manganese carbonate suspension.
(2) Weighing lithium carbonate with the stoichiometric ratio of Li to Mn of 0.55.
(3) Weighing tetramethylammonium bromide, wherein the mass ratio of bromine is 0.5 percent of the nickel-manganese carbonate suspension, and adding 0.5L of deionized water for dissolving to obtain a tetramethylammonium bromide solution.
(4) Slowly adding the nickel-manganese carbonate suspension into the lithium salt solution and the tetramethylammonium bromide solution while stirring, continuously stirring for 30min after adding the solution, centrifuging, washing with water for three times, filtering, and drying at 80 ℃ for 12h. The powder is placed in a muffle furnace for sintering at 900 ℃ for 8h, annealing at 500 ℃ for 4h, and cooling to room temperature. And ball-milling and crushing the blocky high-temperature sintering product to obtain the anode material powder.
Example 2 preparation of LiNi by coprecipitation method 0.5 Mn 1.5 O 4 The positive electrode material, fig. 3 is an SEM image of the resulting product, the particles of which are regular octahedral single crystals, and fig. 4 is an XRD image of the resulting product, showing no impurity phase.
Example 3
(1) Weighing 1kg of manganese sulfate, weighing nickel sulfate according to a stoichiometric ratio of nickel sulfate to manganese sulfate of 1. Weighing ammonium bicarbonate as a precipitator according to the stoichiometric ratio of the total amount of the transition metal ions to the carbonate ions 1. Slowly adding the ammonium bicarbonate solution into the metal mixed solution while stirring, and continuously stirring for 30min after the solution is mixed to obtain the nickel-manganese carbonate suspension.
(2) Weighing lithium carbonate with the stoichiometric ratio of Li to Mn of 0.55.
(3) Weighing 2-nitroethanol, wherein the mass ratio of the nitro group is 0.5 percent of the nickel-manganese carbonate suspension, and adding 0.5L of deionized water for dissolving to obtain a nitro solution.
(4) Slowly adding the lithium salt solution and the nitro solution into the nickel-manganese carbonate suspension while stirring, continuously stirring for 30min after adding the solution, centrifuging, washing with water for three times, filtering, and drying at 80 ℃ for 12h. The powder was heated at 900 ℃ for 15min with microwaves of 2.45GHz frequency and cooled to room temperature. And ball-milling and crushing the blocky high-temperature sintering product to obtain the anode material powder.
Example 3 preparation of LiNi by microwave Synthesis 0.5 Mn 1.5 O 4 The cathode material, fig. 5 is an SEM image of the resulting product, and the particles of the material are regular octahedral single crystals. Fig. 6 is an XRD pattern of the resulting product showing no impurity phases.
Comparative example 1:
comparative example 1 differs from example 1 only in that the LiNi 0.5 Mn 1.5 O 4 In the preparation of the cathode material, the dimethylamine vinylsulfonate is not added as an additive, but the sodium sulfate with the same S content is added.
Comparative example 2:
comparative example 2 differs from example 2 only in that the LiNi 0.5 Mn 1.5 O 4 In the preparation of the anode material, tetramethyl ammonium bromide is not added as an additive, but addedAmmonium bromide with the same Br content.
Comparative example 3:
comparative example 3 differs from example 3 only in that the LiNi 0.5 Mn 1.5 O 4 In the preparation of the anode material, 2-nitroethanol is not added as an additive, but sodium nitrate with the same N content is added.
LiNi prepared in examples 1 to 3 and comparative examples 1 to 3 0.5 Mn 1.5 O 4 The XRD spectrums of the cathode material are shown in Table 1, wherein I (111), I (400) and I (440) are respectively corresponding to crystal plane orientations of (111), (100) and (110). As can be seen from Table 1, the method for regulating and controlling the crystal face is suitable for a high-temperature solid phase method, a coprecipitation method and a microwave synthesis method.
To further verify the influence of crystal plane orientation on Mn dissolution and cycling performance, liNi obtained in examples and comparative examples was used 0.5 Mn 1.5 O 4 The button full cell is prepared from the anode material and a commercial graphite cathode, and the button full cell is cycled for 50 circles at 45 ℃ under the voltage of 3.0-4.9V and 0.2C. And (4) disassembling the battery after circulation, and testing the EDS by using the obtained negative plate. Table 1 also lists the cycling performance and Mn content of the negative electrode deposit. The results show that the cathode material with lower I (440) has better cycle performance and lower Mn elution amount, so that the growth of the (110) crystal face is reduced through crystal face regulation, and LiNi is facilitated 0.5 Mn 1.5 O 4 And (3) the cycling stability of the anode material.
TABLE 1
In conclusion, the spinel-phase lithium nickel manganese oxide cathode material provided by the invention has the advantages that the additive with rich electron groups is added, so that a stable ionic bond can be formed with transition metal cations in the cathode material, the ordered arrangement of the cations is promoted, the surface energy of crystals is reduced, the growth of crystal faces is regulated, the growth of (110) crystal faces is reduced, the side reaction and Mn dissolution of the cathode and an electrolyte are reduced, and the circulation stability is improved.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a spinel-phase lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps:
mixing a nickel-manganese compound precursor with a lithium source and an additive, calcining at high temperature, annealing and crushing to obtain a spinel-phase lithium nickel manganese oxide positive electrode material; wherein the additive has electron rich groups.
2. The method for preparing a spinel phase lithium nickel manganese oxide positive electrode material according to claim 1, wherein the additive comprises at least one of organic substances containing sulfonic acid groups, nitro groups and halogen groups.
3. The method for preparing the spinel phase lithium nickel manganese oxide cathode material according to claim 2, wherein the mass of the effective group in the additive is 0.2-1% of the mass of the nickel manganese compound precursor.
4. The method for preparing the spinel-phase lithium nickel manganese oxide cathode material of claim 1, wherein the nickel manganese compound precursor is a nickel manganese compound suspension, and the method comprises the following steps:
preparing a transition metal mixed solution by using a manganese source and a nickel source;
and adding excessive precipitator into the transition metal mixed solution to prepare the nickel-manganese compound suspension.
5. The method for preparing the spinel-phase lithium nickel manganese oxide cathode material according to claim 1, wherein the method for preparing the nickel manganese compound precursor comprises the following steps:
preparing a transition metal mixed solution by using a manganese source and a nickel source;
adding excessive precipitator into the transition metal mixed solution to prepare nickel-manganese compound suspension;
and (3) reacting the nickel-manganese compound suspension at a set temperature, cooling, performing suction filtration, washing and drying to obtain the nickel-manganese compound precursor.
6. The method for preparing the spinel-phase lithium nickel manganese oxide cathode material according to claim 4 or 5, wherein the molar ratio of lithium ions in the lithium source, manganese ions in the manganese source and nickel ions in the nickel source is (0.5-0.6): 1 (1.3-1.8).
7. The method for preparing the spinel phase lithium nickel manganese oxide cathode material according to claim 4 or 5, wherein the molar ratio of the anion groups forming the transition metal precipitate in the nickel manganese compound suspension to the total amount of transition metal ions is (5-8): 1.
8. The method for preparing the spinel phase lithium nickel manganese oxide positive electrode material according to claim 4 or 5, wherein the manganese source comprises at least one of manganese hydroxide, manganese sulfate, manganese carbonate and manganese acetate;
the nickel source comprises at least one of nickel hydroxide, nickel sulfate, nickel carbonate and nickel acetate;
the lithium source comprises at least one of lithium hydroxide, lithium sulfate, lithium carbonate and lithium acetate;
the precipitant includes at least one of carbonate, ammonia water, and metal hydroxide.
9. A spinel phase lithium nickel manganese oxide positive electrode material is characterized by being prepared by the preparation method of the spinel phase lithium nickel manganese oxide positive electrode material in any one of claims 1 to 8.
10. A battery comprising the spinel phase lithium nickel manganese oxide positive electrode material according to claim 9.
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| CN104538623B (en) * | 2015-01-20 | 2016-10-05 | 河北工业大学 | The preparation method of one kind spherical nickel-lithium manganate anode material |
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