CN109437339A - Nickelic quaternary positive electrode material precursor and nickelic quaternary positive electrode, preparation method and purposes - Google Patents
Nickelic quaternary positive electrode material precursor and nickelic quaternary positive electrode, preparation method and purposes Download PDFInfo
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- CN109437339A CN109437339A CN201811464604.6A CN201811464604A CN109437339A CN 109437339 A CN109437339 A CN 109437339A CN 201811464604 A CN201811464604 A CN 201811464604A CN 109437339 A CN109437339 A CN 109437339A
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- positive electrode
- nickelic
- quaternary positive
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- sintering
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- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 87
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 150000002696 manganese Chemical class 0.000 claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 150000002500 ions Chemical class 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 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
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 229910019421 CoxAly Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004146 energy storage Methods 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 10
- 150000001868 cobalt Chemical class 0.000 abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 52
- 238000010792 warming Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000010405 anode material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 5
- 239000001433 sodium tartrate Substances 0.000 description 5
- 229960002167 sodium tartrate Drugs 0.000 description 5
- 235000011004 sodium tartrates Nutrition 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910017166 Ni0.815CO0.15Al0.035 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供一种高镍四元正极材料前驱体及高镍四元正极材料、制备方法和用途，高镍四元正极材料的化学式如式Lia(Ni1‑x‑y‑ zCoxAlyMnz)O2；x、y、z、a为摩尔分数，0.03＜x≤0.15，0.01＜y＜0.05，0.01＜z＜0.05，0.6＜1‑x‑y＜0.9，1≤a≤1.1。本发明将可溶性镍盐、可溶性钴盐、可溶性铝盐和可溶性锰盐配成溶液，镍盐、钴盐、铝盐和锰盐能够均匀的分布在溶液中，采用均匀分布镍盐、钴盐、铝盐和锰盐的溶液制备高镍四元正极材料前驱体。然后采用该高镍四元正极材料前驱体与锂盐混合经过四次烧结得到高镍四元正极材料。本发明的高镍四元正极材料结构稳定，安全性能高，且循环寿命长、热稳定性好。The present invention provides a high-nickel quaternary positive electrode material precursor, a high-nickel quaternary positive electrode material, a preparation method and application, and the chemical formula of the high-nickel quaternary positive electrode material is as follows: Li a (Ni 1-x-y- z Co x Al y Mn z )O 2 ; x, y, z, and a are mole fractions, 0.03＜x≤0.15, 0.01＜y＜0.05, 0.01＜z＜0.05, 0.6＜1‑x‑y＜0.9, 1≤a≤ 1.1. In the invention, soluble nickel salts, soluble cobalt salts, soluble aluminum salts and soluble manganese salts are formulated into a solution, and the nickel salts, cobalt salts, aluminum salts and manganese salts can be evenly distributed in the solution, and uniformly distributed nickel salts, cobalt salts, The solution of aluminum salt and manganese salt is used to prepare high nickel quaternary cathode material precursor. Then, the high-nickel quaternary positive electrode material precursor is mixed with lithium salt to obtain a high-nickel quaternary positive electrode material after four times of sintering. The high-nickel quaternary positive electrode material of the invention has stable structure, high safety performance, long cycle life and good thermal stability.
Description
Technical field
The present invention relates to electrode material fields, and in particular to a kind of nickelic quaternary positive electrode material precursor, nickelic quaternary are just
Pole material, Preparation method and use.
Background technique
Lithium ion battery is as a kind of novel green energy resource, with specific energy is high, self discharge is small, open-circuit voltage is high, nothing
Memory effect, have extended cycle life, non-environmental-pollution the advantages that, therefore be widely used as mobile phone, laptop, digital camera etc.
The power supply of electronic product, meanwhile, lithium ion battery is also electric car power supply, and is the accumulation power supply of solar energy renewable energy.
Ion battery positive electrode known to us mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, ternary material and LiFePO4
Deng, but due to cobalt resource scarcity, and be more toxic, cause cobalt acid lithium production cost high, and producing to environment can not
The influence of reverse；Lithium nickelate rich material resources all have advantage in terms of the performance of gram volume and specific energy, but it is recycled
Performance is poor, limits the application of its industrialization；LiMn2O4 is with resourceful, at low cost, pollution-free, safety is good, multiplying power
The advantages that performance is good, but its cycle performance and electrochemical stability are poor, and greatly limit its industrialization；LiFePO 4 material
Safety and cycle life have the advantages that significant, but material itself compacted density is too low, causes battery specific energy not high,
So limiting the space that vehicle is promoted in terms of course continuation mileage；The cost of ternary material is low, is equivalent to the 1/4 of cobalt acid lithium and more
Environmentally protective, other different materials that compare improve the energy density of battery, but its safety at present is not high enough.
Summary of the invention
We are bright to be designed to provide a kind of excellent nickelic quaternary positive electrode of security performance；And provide the anode material
The purposes of the preparation method of material and the positive electrode, to promote lithium ion battery further genralrlization application.
In order to solve the above-mentioned technical problem, the technical scheme is that a kind of nickelic quaternary positive electrode, described nickelic
Shown in the chemical formula of quaternary positive electrode such as formula (I):
Ni1-x-y-zCoxAlyMnz(OH)2 (I)
X, y, z is molar fraction, 0.03 0.05,0.01 < z < of < x≤0.15,0.01 < y <, 0.05,0.6 < 1-x-y
< 0.9.
In order to solve the above-mentioned technical problem, the invention also discloses the preparations of above-mentioned nickelic quaternary positive electrode material precursor
Method, comprising the following steps:
Step (a), the molar ratio Ni:Co:Al:Mn=(0.6~0.9): (0.03~0.15) according to each element:
(0.01~0.05): (0.01~0.05) calculates and weighs soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese
Salt；They are added in deionized water the solution A for carrying out being hybridly prepared into 0.5-3.5mol/L together；
The solution B for being configured to 0.05-0.2mol/L is added in deionized water in complexing agent by step (b)；
The solution C for being formulated as 0.5-2mol/L is added in deionized water in precipitating reagent by step (c)；
Step (d) will be stirred mixing in solution A, solution B and solution C addition reactor, and adjust the pH of mixed liquor
Sediment is filtered, wash, is dried after then carrying out coprecipitation reaction for 7.0-8.5, obtains dry nickelic quaternary
Positive electrode material precursor.
Further, step (b) complexing agent is at least one of ammonia, ammonium carbonate or ammonium hydrogen carbonate；The complexing
Agent may be one or both of sodium tartrate, sodium citrate, sodium pyrophosphate, sodium tripolyphosphate.
Further, step (c) precipitating reagent is at least one of potassium hydroxide, sodium hydroxide or lithium hydroxide.
The precipitating reagent may be at least one of sodium carbonate, manganese carbonate, sodium hydroxide.
In order to solve the above-mentioned technical problem, the invention also discloses a kind of nickelic quaternary positive electrode, the nickelic quaternarys
Shown in the chemical formula of positive electrode such as formula (I):
Lia(Ni1-x-y-zCoxAlyMnz)O2(I)；X, y, z, a are molar fraction, 0.03 < x≤0.15,0.01 < y <
0.05,0.01 < z <, 0.05,0.6 < 1-x-y < 0.9,1≤a≤1.1.
In order to solve the above-mentioned technical problem, the invention also discloses the preparation method of above-mentioned nickelic quaternary positive electrode,
The following steps are included:
Step (1) prepares nickelic quaternary positive electrode material precursor；
Step (2), first sintering: the quaternary positive electrode material precursor that the step (1) is obtained is sintered；
Step (3) is sintered for the second time: lithium source is added in the step (2) sintering gains, water-soluble sintering aid, is mixed
Grinding is closed to be sintered after grinding uniformly, after the completion of sintering, then carry out cooling annealing；
Step (4), third time are sintered: the step (3) sintering gains being sintered, are obtaining the nickelic quaternary of target just
Pole material, the nickel element nickelic quaternary positive electrode of equally distributed layer structure in the grain.
Further, the 4th burning is carried out the method also includes cleaning the product of the step (4), after cleaning
Knot.
Further, the cleaning way is to be rinsed with carbon dioxide gas stream.
Further, the cleaning way is to be cleaned with carbonated water.
Further, the sintering time of the 4th sintering is 0.5-12 hours, and sintering temperature is 100-1000 DEG C.
Further, the preparation method of the nickelic quaternary positive electrode material precursor, comprising the following steps:
Step (a), the molar ratio Ni:Co:Al:Mn=(0.6~0.9): (0.03~0.15) according to each element:
(0.01~0.05): (0.01~0.05) calculates and weighs soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese
Salt；They are added in deionized water the solution A for carrying out being hybridly prepared into 0.5-3.5mol/L together；
Complexing agent is configured to the solution B of 0.05-0.2mol/L by being added in deionized water by step (b)；
The solution C for being formulated as 0.5-2mol/L is added in deionized water in precipitating reagent by step (c)；
Step (d) will be stirred mixing in solution A, solution B and solution C addition reactor, and adjust the pH of mixed liquor
Sediment is filtered, wash, is dried after then carrying out coprecipitation reaction for 7.0-8.5, obtains dry nickelic quaternary
Positive electrode material precursor.
Further, in the step (2), sintering time 6-20 hours, 200-1000 DEG C of sintering temperature.
Further, in the step (3), the lithium source is a hydronium(ion) lithia, lithium hydroxide, lithium acetate, oxalic acid
One of lithium, lithium carbonate, lithium nitrate, lithium chloride and lithium fluoride.
Further, the water-soluble sintering aid is water soluble sulfate, soluble chloride salt dissolving.
Further, in the step (3), sintering time 8-24 hours, 500-1000 DEG C of sintering temperature.
Further, in the step (3), it is 0.01-2.5 DEG C/min that the cooling annealing, which is rate of temperature fall,.
Further, in the step (3), rate of temperature fall is 0.02-1 DEG C/min.
Further, in the step (3), the additional amount of lithium source is in Li in lithium source and quaternary positive electrode material precursor
(Ni+Co+Al+Mn) molar ratio is 1~1.1:1.
Further, sintering carries out in air or oxygen atmosphere in the step (3).
Further, the step (4) sintering time 1-12 hours, 500-1000 DEG C of sintering temperature.
In order to solve the above-mentioned technical problem, the invention also discloses a kind of lithium ion batteries, including anode, cathode, electrolysis
Liquid and diaphragm, which is characterized in that the anode includes above-mentioned nickelic quaternary positive electrode or the side by preceding claim
The nickelic quaternary positive electrode that method is prepared.
In order to solve the above-mentioned technical problem, the invention also discloses a kind of above-mentioned nickelic quaternary positive electrode or by upper
The nickelic quaternary positive electrode that the method stated is prepared prepare lithium ion battery, electronic product energy storage, industrial electric power storage energy storage,
Application in electric car and electric bicycle power supply.
The present invention is by soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt wiring solution-forming, nickel salt, cobalt
Salt, aluminium salt and manganese salt can be evenly distributed in solution, using be uniformly distributed nickel salt, cobalt salt, aluminium salt and manganese salt solution system
Standby nickelic quaternary positive electrode material precursor.Since the sedimentation equilibrium constant Ksp of Ni, Co, Al, Mn are different, will affect Ni, Co, Al,
Mn forms the sequence of precipitating in the solution, and the present invention is by the way that reaction temperature, PH, solution concentration, mixing speed is optimized, right
Technique carries out creative improvement, realizes the consistent of Ni, Co, Al, Mn precipitation sequence, homogeneous precipitation is formed, using party's legal system
Standby obtained nickelic quaternary positive electrode material precursor, nickel salt, cobalt salt, aluminium salt and manganese salt are evenly distributed in particle, using this
Nickelic quaternary positive electrode material precursor is mixed with lithium salts, obtains nickelic quaternary positive electrode by being sintered three times, crystal structure is more
Uniform, skeleton structure is stronger, is conducive to the performance of material property, effectively improve nickelic quaternary positive electrode capacity and times
Rate performance.In addition, water-soluble sintering aid helps to reduce sintering temperature, avoid high temperature sintering to the particle shape of high-nickel material
And the influence of performance；Meanwhile annealing process eliminates material during the sintering process because of the oxygen defect that local burning is formed, so that
The material arrived has higher crystallinity, and material structure stability is more preferable.Therefore, nickelic quaternary cathode material structure of the invention
Stablize, security performance is excellent, and have extended cycle life, thermal stability it is good.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical scheme and beneficial effects, with reference to embodiments into one
Walk the present invention is described in detail.However, it should be understood that the embodiment of the present invention is not just for the sake of explaining the present invention
The limitation present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.
Below with reference to embodiment respectively to nickelic quaternary positive electrode material precursor of the invention and preparation method thereof, nickelic four
First positive electrode and preparation method thereof is described in detail.
Firstly, illustrating nickelic quaternary positive electrode material precursor and preparation method thereof of the invention with embodiment.
Embodiment 1
A kind of nickelic quaternary positive electrode material precursor, chemical formula Ni0.815Co0.15Al0.0175Mn0.0175(OH)2, preparation
Method are as follows:
Step (a) is calculated according to the molar ratio Ni:Co:Al:Mn=0.815:0.15:0.0175:0.0175 of each element
And weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added together in deionized water into
Row is hybridly prepared into the solution A of 0.5mol/L；
The solution B for being configured to 0.05mol/L is added in deionized water in sodium tartrate by step (b)；
The solution C for being formulated as 1mol/L is added in deionized water in sodium hydroxide by step (c)；
Solution A, solution B and solution C are added in reactor at 40 DEG C for step (d), control system reaction temperature, control
Mixing speed is 800 revs/min, and the pH for adjusting mixed solution is 7.5, and after carrying out coprecipitation reaction 3h, sediment is carried out
It is filtered, washed, dries, wherein drying temperature is 100 DEG C, the time is for 24 hours, to obtain the dry nickelic quaternary with layer structure
Positive electrode material precursor.
Embodiment 2
A kind of nickelic quaternary positive electrode material precursor, chemical formula Ni0.815Co0.15Al0.014Mn0.021(OH)2, preparation side
Method are as follows:
Step (a) calculates simultaneously according to the molar ratio Ni:Co:Al:Mn=0.815:0.15:0.014:0.021 of each element
Weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added in deionized water together and is carried out
It is hybridly prepared into the solution A of 1mol/L；
The solution B for being configured to 0.2mol/L is added in deionized water in ammonium hydroxide by step (b)；
The solution C for being formulated as 2mol/L is added in deionized water in sodium hydroxide by step (c)；
Solution A, solution B and solution C are added in reactor at 40 DEG C for step (d), control system reaction temperature, control
Mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, and after carrying out coprecipitation reaction 3h, sediment is carried out
It is filtered, washed, dries, wherein drying temperature is 100 DEG C, the time is for 24 hours, to obtain the dry nickelic quaternary with layer structure
Positive electrode material precursor.
Embodiment 3
A kind of nickelic quaternary positive electrode material precursor, chemical formula Ni0.815Co0.15Al0.021Mn0.014(OH)2, preparation side
Method are as follows:
Step (a) calculates simultaneously according to the molar ratio Ni:Co:Al:Mn=0.815:0.15:0.021:0.014 of each element
Weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added in deionized water together and is carried out
It is hybridly prepared into the solution A of 2mol/L；
The solution B for being configured to 0.05mol/L is added in deionized water in sodium tartrate by step (b)；
The solution C for being formulated as 1mol/L is added in deionized water in potassium hydroxide by step (c)；
Solution A, solution B and solution C are added in reactor at 40 DEG C for step (d), control system reaction temperature, control
Mixing speed is 800 revs/min, and the pH for adjusting mixed solution is 7.5, and after carrying out coprecipitation reaction 3h, sediment is carried out
It is filtered, washed, dries, wherein drying temperature is 100 DEG C, the time is for 24 hours, to obtain dry nickelic quaternary positive electrode forerunner
Body.
Embodiment 4
A kind of nickelic quaternary positive electrode material precursor, chemical formula Ni0.815Co0.15Al0.009Mn0.026(OH)2, preparation side
Method are as follows:
Step (a) calculates simultaneously according to the molar ratio Ni:Co:Al:Mn=0.815:0.15:0.009:0.026 of each element
Weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added in deionized water together and is carried out
It is hybridly prepared into the solution A of 3.5mol/L；
The solution B for being configured to 3.5mol/L is added in deionized water in sodium tartrate by step (b)；
The solution C for being formulated as 0.5mol/L is added in deionized water in sodium hydroxide by step (c)；
Solution A, solution B and solution C are added in reactor at 40 DEG C for step (d), control system reaction temperature, control
Mixing speed is 800 revs/min, and the pH for adjusting mixed solution is 7.5, and after carrying out coprecipitation reaction 3h, sediment is carried out
It is filtered, washed, dries, wherein drying temperature is 100 DEG C, the time is for 24 hours, to obtain dry nickelic quaternary positive electrode forerunner
Body.
Embodiment 5
A kind of nickelic quaternary positive electrode material precursor, chemical formula Ni0.815Co0.15Al0.026Mn0.009(OH)2, preparation side
Method are as follows:
Step (a) calculates simultaneously according to the molar ratio Ni:Co:Al:Mn=0.815:0.15:0.026:0.009 of each element
Weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added in deionized water together and is carried out
It is hybridly prepared into the solution A of 3mol/L；
The solution B for being configured to 0.05mol/L is added in deionized water in sodium tartrate by step (b)；
The solution C for being formulated as 1mol/L is added in deionized water in sodium hydroxide by step (c)；
Solution A, solution B and solution C are added in reactor at 40 DEG C for step (d), control system reaction temperature, control
Mixing speed is 800 revs/min, and the pH for adjusting mixed solution is 7.5, and after carrying out coprecipitation reaction 3h, sediment is carried out
It is filtered, washed, dries, wherein drying temperature is 100 DEG C, the time is for 24 hours, to obtain dry nickelic quaternary positive electrode forerunner
Body.
Embodiment 6
A kind of nickelic quaternary positive electrode material precursor, chemical formula Ni0.815Co0.15Al0.02Mn0.015(OH)2, preparation side
Method are as follows:
Step (a) calculates simultaneously according to the molar ratio Ni:Co:Al:Mn=0.815:0.15:0.02:0.015 of each element
Weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added in deionized water together and is carried out
It is hybridly prepared into the solution A of 1.5mol/L；
The solution B for being configured to 0.05mol/L is added in deionized water in ammonium hydroxide by step (b)；
The solution C for being formulated as 1mol/L is added in deionized water in potassium hydroxide by step (c)；
Solution A, solution B and solution C are added in reactor at 40 DEG C for step (d), control system reaction temperature, control
Mixing speed is 800 revs/min, and the pH for adjusting mixed solution is 7.5, and after carrying out coprecipitation reaction 3h, sediment is carried out
It is filtered, washed, dries, wherein drying temperature is 100 DEG C, the time is for 24 hours, to obtain dry nickelic quaternary positive electrode forerunner
Body.
Secondly, nickelic quaternary positive electrode and preparation method thereof of the invention is described in detail with embodiment.
Embodiment 7
A kind of nickelic quaternary positive electrode Li1.035(Ni0.815Co0.15Mn0.0175Al0.0175)O2, preparation method are as follows:
Step (1), first sintering: the nickelic quaternary positive electrode material precursor that embodiment 1 is prepared is sintered, heating
It is reacted 10 hours to 500 DEG C；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid sodium sulphate mixed grinding, the dosage of a hydronium(ion) lithia is a hydrated hydroxide
Changing (Ni+Co+Al+Mn) molar ratio in the Li and ternary anode material precursor in lithium is 1.035:1, water-soluble sintering aid sulphur
The additional amount of sour sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 715 DEG C and is sintered 16.5 hours,
Then cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 650 DEG C of sintering 3.5 hours, drop
To room temperature to get arriving target product, the nickel element nickelic quaternary positive electrode of equally distributed layer structure in the grain.
Embodiment 8
A kind of nickelic quaternary positive electrode Li1.035(Ni0.815Co0.15Al0.014Mn0.021)O2, preparation method are as follows:
Step (1), first sintering: the nickelic quaternary positive electrode material precursor that embodiment 2 is prepared is sintered, heating
It is reacted 6.5 hours to 600 DEG C；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid NaCl mixed grinding, the dosage of a hydronium(ion) lithia is hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid sulfuric acid
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 775 DEG C of sintering 8 hours, then
Cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 615 DEG C of sintering 5 hours, is down to
Room temperature is to get arriving target product, the nickel element nickelic quaternary positive electrode of equally distributed layer structure in the grain.
Embodiment 9
A kind of nickelic quaternary positive electrode Li1.035(Ni0.815Co0.15Al0.021Mn0.014)O2, preparation method are as follows:
Step (1), first sintering: the nickelic quaternary positive electrode material precursor that embodiment 3 is prepared is sintered, heating
It is reacted 10 hours to 500 DEG C；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) gains and water-soluble sintering aid Na are sintered2SO4Mixed grinding, the dosage of a hydronium(ion) lithia are hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid sulfuric acid
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 715 DEG C of sintering 16.5 hours, so
Carry out cooling annealing again afterwards；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 650 DEG C of sintering 3.5 hours, drop
To room temperature；
Step (4), the 4th sintering: the step (3) sintering gains are rinsed with carbonated water, the substance liter after cleaning
Temperature to 350 DEG C be sintered 5 hours, be down to room temperature, obtain target product, equally distributed layer structure is nickelic in the grain for nickel element
Quaternary positive electrode.
Embodiment 10
A kind of nickelic quaternary positive electrode Li1.035(Ni0.815Co0.15Al0.009Mn0.026)O2, preparation method are as follows:
Step (1), first sintering: the nickelic quaternary positive electrode material precursor that embodiment 4 is prepared is sintered, heating
It is reacted 6.5 hours to 600 DEG C；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid NaCl mixed grinding, the dosage of a hydronium(ion) lithia is hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid sulfuric acid
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 775 DEG C of sintering 8 hours, then
Cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 615 DEG C of sintering 5 hours, is down to
Room temperature；
Step (4), the 4th sintering: the step (3) sintering gains are rinsed with carbon dioxide gas stream, after cleaning
Substance is warming up to 250 DEG C and is sintered 3 hours, is down to room temperature, obtains target product, nickel element equally distributed stratiform knot in the grain
The nickelic quaternary positive electrode of structure.
Embodiment 11
A kind of nickelic quaternary positive electrode Li1.035(Ni0.815Co0.15Al0.026Mn0.009)O2, preparation method are as follows:
Step (1), first sintering: the nickelic quaternary positive electrode material precursor that embodiment 5 is prepared is sintered, heating
It is reacted 10 hours to 500 DEG C；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid sodium sulphate mixed grinding, the dosage of a hydronium(ion) lithia is a hydrated hydroxide
Changing (Ni+Co+Al+Mn) molar ratio in the Li and ternary anode material precursor in lithium is 1.035:1, water-soluble sintering aid sulphur
The additional amount of sour sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 715 DEG C and is sintered 16.5 hours,
Then cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 650 DEG C of sintering 3.5 hours, drop
To room temperature to get arriving target product, the nickel element nickelic quaternary positive electrode of equally distributed layer structure in the grain.
Step (4), the 4th sintering: the step (3) sintering gains are rinsed with carbonated water, the substance liter after cleaning
Temperature to 350 DEG C be sintered 5 hours, be down to room temperature, obtain target product, equally distributed layer structure is nickelic in the grain for nickel element
Quaternary positive electrode.
Embodiment 12
A kind of nickelic quaternary positive electrode Li1.035(Ni0.815Co0.15Al0.02Mn0.015)O2, preparation method are as follows:
Step (1), first sintering: the nickelic quaternary positive electrode material precursor that embodiment 6 is prepared is sintered, heating
It is reacted 6.5 hours to 600 DEG C；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid NaCl mixed grinding, the dosage of a hydronium(ion) lithia is hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid sulfuric acid
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 775 DEG C of sintering 8 hours, then
Cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 615 DEG C of sintering 5 hours, is down to
Room temperature；
Step (4), the 4th sintering: the step (3) sintering gains are rinsed with carbon dioxide gas stream, after cleaning
Substance is warming up to 250 DEG C and is sintered 3 hours, is down to room temperature, obtains target product, nickel element equally distributed stratiform knot in the grain
The nickelic quaternary positive electrode of structure
Comparative example 1
A kind of tertiary cathode material, chemical formula are Li1.035Ni0.815Co0.15Al0.035O2, preparation method are as follows:
Step (1), first sintering: by ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；Ternary anode material precursor Ni1-x-yCoxAly(OH)2+yIt can be obtained with commercial sources；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, the dosage of a hydronium(ion) lithia are that Li rubs with (Ni+Co+Al) in ternary anode material precursor
Your ratio is 1.035, after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 715 DEG C and reacts 16.5 hours；
Step (3), third time are sintered: the step (2) sintering gains being warming up to 650 DEG C and are sintered 3.5 hours, are down to
Room temperature to get arrive contrast material Li1.035Ni0.815Co0.15Mn0.035O2。
Comparative example 2
A kind of tertiary cathode material, chemical formula are Li1.035Ni0.815Co0.15Al0.035O2, preparation method are as follows:
Step (1), first sintering: by ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
600 DEG C are reacted 6.5 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, the dosage of a hydronium(ion) lithia are that Li rubs with (Ni+Co+Al) in ternary anode material precursor
Your ratio is 1.035, after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775 DEG C and reacts 8 hours；
Step (3), third time are sintered: the step (2) sintering gains being warming up to 615 DEG C and are sintered 5 hours, room is down to
Temperature to get arrive contrast material Li1.035Ni0.815Co0.15Mn0.035O2。
Table 1: embodiment 7~12,1~2 reaction condition of comparative example and product.
The assembling of CR2032 model button cell:
The tertiary cathode material of the nickelic quaternary positive electrode, the preparation of comparative example 1~2 that are prepared with embodiment 7~12 is positive
The active matter of pole, cathode use metal lithium sheet, and diaphragm uses 2500 diaphragm of Celgard, and electrolyte is that Buddhist match new material in Suzhou has
Limit company fosai LB-002 electrolyte assembles CR2032 model button cell, assembling sequence by art methods are as follows: anode
Lid lay flat, place spring leaf, place stainless steel substrates, place positive plate, infuse electrolyte, place diaphragm, place lithium piece, cover it is negative
Polar cap, sealing, is completed.Battery is assembled in the dry glove box full of argon gas.After being completed, battery is carried out
Performance test, test result are shown in Table 2.
1, cycle performance
Test equipment title: new prestige battery testing system, model: BTS-5V10mA
Test equipment producer: new Weir Electronics Co., Ltd., Shenzhen；
Test method: at 25 DEG C, with 1C constant-current charge to 4.3V, 4.3V constant pressure to 0.05C, then 1C is discharged to 3V,
100 above-mentioned charge and discharge cycles are repeated, electric discharge when measuring the discharge capacity and the 100th circulation when recycling for the first time is held
Amount, the capacity retention ratio after calculating circulation 100 times, formula are as follows: capacity retention ratio=(putting when the 100th circulation after circulation
Capacitance)/(discharge capacity when recycling for the first time) * 100%.
2, high-temperature storage performance: at 25 DEG C, with 0.5C (=1225mA) constant-current charge to 4.3V, 4.3V constant pressure is extremely
0.05C (=123mA), then 0.5C (=1225mA) is discharged to 3V, records its first time discharge capacity；Then, at 25 DEG C,
With 0.5C (=1225mA) constant-current charge to 4.3V, 4.3V constant pressure to 0.05C (=123mA), the cell thickness before measurement storage；
Then, by the above-mentioned battery completely filled, after being stored 100 days in 60 DEG C of baking ovens, while hot test storage after cell thickness, by with
The comparison of cell thickness before storing, finds out the expansion rate of battery after storage；And will by storage battery core by 0.5C (=
1225mA) constant-current charge is to 4.3V, and 4.3V constant pressure to 0.05C (=123mA), then 0.5C (=1225mA) is discharged to 3V, into
Row five times circulations, record its last discharge capacity, the capacity retention ratio compared with first time discharge capacity, after being stored；
Wherein, after storage battery expansion rate=(thickness of battery before thickness-storage of battery after storage)/(store before battery thickness
Degree) × 100%；Capacity retention ratio=(discharge capacity after storage in 100 days)/(electric discharge appearance when recycling for the first time after storage
Amount) × 100%；
3, security performance is tested: at 25 DEG C, with 0.5C (=1225mA) constant-current charge to 4.3V, 4.3V constant pressure is extremely
0.05C (=123mA)；Battery is dismantled in the glove box of argon gas protection, is cleaned in DMC solution after taking out positive plate；To
After DMC volatilizees completely, lower electrode material is scraped from positive plate surface, the electrode material for weighing 10mg is put into special aluminium crucible,
And it is sealed after the electrolyte of 0.1uL is added；DSC test scanning temperature range be 50~500 DEG C, heating rate be 10 DEG C/
min。
4, surface residual alkali weight testing method: acid-base titration.
(1) it prepares the positive electrode stillness of night: W is weighed with the precision of 0.0001g1The positive material of (30.0000 ± 0.0040g)
Material weighs W with the precision of 0.01g2(100 ± 0.1g) deionized water mixes positive electrode with deionized water, and argon gas displacement is mixed
The air in liquid is closed, is stirred, filtering obtains filtrate, pipettes 50mL filtrate, is put into 100mL beaker, prepares titration；
(2) LiOH content is measured: using phenolphthalein as indicator, with the titration of 0.05mol/L hydrochloric acid standard solution, when titration end-point
Consumed hydrochloric acid standard liquid volume V1；
(3) Li is measured2CO3Content: CO in the clear liquid after argon gas displacement step (2) titration2, then with methyl red indicator,
With the titration of 0.05mol/L hydrochloric acid standard solution, when titration end-point consumed hydrochloric acid standard liquid volume V2；
LiOH content (wt%) calculation formula: ω1=(2V1-V2)*0.05*2.395*W2/W1/50；
Li2CO3Content (wt%) calculation formula: ω2=(V2-V1)*0.05*7.389*W2/W1/50；
2.395: the quality with the comparable LiOH indicated with g of hydrochloric acid standard liquid (1.000mol/L)；
7.389: with the comparable Li indicated with g of hydrochloric acid standard liquid (2.000mol/L)2CO3Quality；
Positive electrode surface residual alkali amount=ω1+ω2。
The performance test results of table 2, embodiment 7~12 and comparative example 1~2.
As can be seen from Table 2:
(1) nickelic quaternary positive electrode of the invention, the charge-discharge performance at 3.0V~4.3V have obtained significantly
Raising: the cycle performance of embodiment 7~12 and comparative example 1~2 it can be found that by 100 times circulation after, the present invention nickelic four
The capacity retention ratio of first positive electrode is higher than tertiary cathode material；This explanation is compared with tertiary cathode material, the present invention nickelic four
First positive electrode has more stable cycle performance.
(2) nickelic quaternary positive electrode of the invention, the high-temperature storage performance at 4.3V are significantly improved: being implemented
Example 7~12 and the comparison of 1~2 test data of comparative example are as can be seen that lithium ion prepared by nickelic quaternary positive electrode of the invention
Cell thickness expansion rate tertiary cathode material of the battery after charging to 4.3V after storage in 60 DEG C/100 days；This illustrates this hair
Bright nickelic quaternary positive electrode has preferable cycle performance, and the high-temperature storage performance at high voltage 4.3V has obtained significantly
Improve, the reason is that nickelic quaternary positive electrode chemical stability with higher and electrochemical stability.
(3) the nickelic quaternary positive electrode of the present invention, the security performance at 4.3V are significantly improved: comparative example
7~12 and comparative example 1~2 as can be seen that the lithium ion battery of the present invention nickelic quaternary positive electrode preparation is charging to 4.3V
The thermal discharge of DSC is lower than tertiary cathode material afterwards, and the temperature at most strongly exothermic peak is also above tertiary cathode material；This explanation nickelic four
First positive electrode has stable crystal structure, and thermal stability is good, and security performance is excellent, to improve the security performance of battery.
(4) then the nickelic quaternary positive electrode that embodiment 9~12 is cleaned using carbon dioxide gas stream or carbonated water is sintered
Target product is obtained, compared with the unwashed nickelic quaternary positive electrode of embodiment 7~8, using carbon dioxide gas stream or carbonic acid
The nickelic quaternary positive electrode surface residual alkali amount of water cleaning is effectively reduced, and helps to reduce in positive electrode configuration process, high
Attack of the alkaline matter on nickel quaternary positive electrode surface to binder in positive glue avoids binder from forming double bond, improves
Painting effect helps to improve battery core performance.
Those skilled in the art can carry out various modification and variations without departing from spirit and model of the invention to invention
It encloses.In this way, if these modifications and changes of the present invention is within the scope of the claims of the present invention and its equivalent technology, then
The invention is also intended to include including these modification and variations.
Claims (22)
1. a kind of nickelic quaternary positive electrode material precursor, which is characterized in that the chemistry of the nickelic quaternary positive electrode material precursor
Formula is Ni1-x-y-zCoxAlyMnz(OH)2, x, y, z is molar fraction, 0.03 0.05,0.01 < z < of < x≤0.15,0.01 < y <
0.05,0.6 < 1-x-y < 0.9.
2. a kind of preparation method of nickelic quaternary positive electrode material precursor, which comprises the following steps:
Step (a), the molar ratio Ni:Co:Al:Mn=(0.6~0.9): (0.03~0.15) according to each element: (0.01~
0.05): (0.01~0.05) calculates and weighs soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；By it
Together be added deionized water in carry out the solution A for being hybridly prepared into 0.5-3.5mol/L；
The solution B for being configured to 0.05-0.2mol/L is added in deionized water in complexing agent by step (b)；
The solution C for being formulated as 0.5-2mol/L is added in deionized water in precipitating reagent by step (c)；
Step (d) will be stirred mixing in solution A, solution B and solution C addition reactor, and the pH for adjusting mixed liquor is
Sediment is filtered, washs, dries after then carrying out coprecipitation reaction by 7.0-8.5, is obtaining dry nickelic quaternary just
Pole material precursor.
3. preparation method according to claim 2, it is characterised in that: step (b) complexing agent is ammonia, ammonium carbonate or carbon
At least one of sour hydrogen ammonium.
4. preparation method according to claim 2, it is characterised in that: step (c) precipitating reagent is potassium hydroxide, hydrogen-oxygen
Change at least one of sodium or lithium hydroxide.
5. a kind of nickelic quaternary positive electrode, which is characterized in that chemical formula such as formula (I) institute of the nickelic quaternary positive electrode
Show:
Lia(Ni1-x-y-zCoxAlyMnz)O2(I)；
X, y, z, a are molar fraction, 0.03 0.05,0.01 < z < of < x≤0.15,0.01 < y <, 0.05,0.6 < 1-x-y <
0.9,1≤a≤1.1.
6. a kind of preparation method of nickelic quaternary positive electrode described in claim 1, which comprises the following steps:
Step (1) prepares nickelic quaternary positive electrode material precursor；
Step (2), first sintering: the quaternary positive electrode material precursor that the step (1) is obtained is sintered；
Step (3) is sintered for second: the step (2) sintering gains addition lithium source, water-soluble sintering aid, mixing are ground
Mill is sintered after grinding uniformly, after the completion of sintering, then carries out cooling annealing；
Step (4), third time are sintered: the step (3) sintering gains being sintered, are obtaining the nickelic quaternary of target product just
Pole material.
7. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that the method also includes will
The product of the step (4) is cleaned, and the 4th sintering is carried out after cleaning.
8. the preparation method of nickelic quaternary positive electrode as claimed in claim 7, which is characterized in that the cleaning way is to use
Carbon dioxide gas stream is rinsed.
9. the preparation method of nickelic quaternary positive electrode as claimed in claim 7, which is characterized in that the cleaning way is to use
Carbonated water cleaning.
10. the preparation method of nickelic quaternary positive electrode as claimed in claim 7, which is characterized in that the 4th sintering
Sintering time be 0.5-12 hours, sintering temperature is 100-1000 DEG C.
11. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that the nickelic quaternary
The preparation method of positive electrode material precursor, comprising the following steps:
Step (a), the molar ratio Ni:Co:Al:Mn=(0.6~0.9): (0.03~0.15) according to each element: (0.01~
0.05): (0.01~0.05) calculates and weighs soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；By it
Together be added deionized water in carry out the solution A for being hybridly prepared into 0.5-3.5mol/L；
Complexing agent is configured to the solution B of 0.05-0.2mol/L by being added in deionized water by step (b)；
The solution C for being formulated as 0.5-2mol/L is added in deionized water in precipitating reagent by step (c)；
Step (d) will be stirred mixing in solution A, solution B and solution C addition reactor, and the pH for adjusting mixed liquor is
Sediment is filtered, washs, dries after then carrying out coprecipitation reaction by 7.0-8.5, obtains dry described nickelic
Quaternary positive electrode material precursor.
12. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that in the step (2),
Sintering time 6-20 hours, 200-1000 DEG C of sintering temperature.
13. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that in the step (3),
The lithium source is a hydronium(ion) lithia, lithium hydroxide, lithium acetate, lithium oxalate, lithium carbonate, lithium nitrate, lithium chloride and lithium fluoride
One of.
14. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that the water-soluble sintering
Auxiliary agent is water soluble sulfate, soluble chloride salt dissolving.
15. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that in the step (3),
Sintering time 8-24 hours, 500-1000 DEG C of sintering temperature.
16. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that in the step (3),
It is 0.01-2.5 DEG C/min that the cooling annealing, which is rate of temperature fall,.
17. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that in the step (3),
Rate of temperature fall is 0.02-1 DEG C/min.
18. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that in the step (3),
The additional amount of lithium source is that Li and (Ni+Co+Al+Mn) molar ratio in quaternary positive electrode material precursor are 1~1.1:1 in lithium source.
19. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that burnt in the step (3)
Knot carries out in air or oxygen atmosphere.
20. the preparation method of nickelic quaternary positive electrode as claimed in claim 6, which is characterized in that step (4) sintering
Time 1-12 hour, 500-1000 DEG C of sintering temperature.
21. a kind of lithium ion battery, including anode, cathode, electrolyte and diaphragm, which is characterized in that the anode includes right
It is required that nickelic quaternary positive electrode or the height being prepared by method described in claim 6 to 20 any one described in 5
Nickel quaternary positive electrode.
22. nickelic quaternary positive electrode described in a kind of claim 5 passes through side described in claim 6 to 20 any one
The nickelic quaternary positive electrode that method is prepared is preparing lithium ion battery, electronic product energy storage, industrial electric power storage energy storage, electronic vapour
Application in vehicle and electric bicycle power supply.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473657A (en) * | 2018-12-03 | 2019-03-15 | 林奈（中国）新能源有限公司 | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use |
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| CN113998742A (en) * | 2021-09-27 | 2022-02-01 | 中天新兴材料有限公司 | Recycling method of nickel-cobalt-manganese ternary lithium battery |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529459A (en) * | 2016-03-02 | 2016-04-27 | 合肥国轩高科动力能源有限公司 | High-nickel quaternary positive electrode material of lithium ion battery and preparation method thereof |
| CN106058172A (en) * | 2016-06-13 | 2016-10-26 | 合肥国轩高科动力能源有限公司 | Quaternary nickel-cobalt-magnesium-titanium positive electrode material of lithium ion battery and preparation method thereof |
| CN108288711A (en) * | 2018-02-12 | 2018-07-17 | 成都理工大学 | A kind of quaternary lithium-ion battery positive electrode material and preparation method |
| CN108428871A (en) * | 2018-03-21 | 2018-08-21 | 苏州林奈新能源有限公司 | A kind of nickel cobalt aluminium ternary method for preparing anode material of lithium-ion battery |
| CN108502937A (en) * | 2018-04-17 | 2018-09-07 | 哈尔滨工业大学 | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application |
-
2018
- 2018-12-03 CN CN201811464604.6A patent/CN109437339A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529459A (en) * | 2016-03-02 | 2016-04-27 | 合肥国轩高科动力能源有限公司 | High-nickel quaternary positive electrode material of lithium ion battery and preparation method thereof |
| CN106058172A (en) * | 2016-06-13 | 2016-10-26 | 合肥国轩高科动力能源有限公司 | Quaternary nickel-cobalt-magnesium-titanium positive electrode material of lithium ion battery and preparation method thereof |
| CN108288711A (en) * | 2018-02-12 | 2018-07-17 | 成都理工大学 | A kind of quaternary lithium-ion battery positive electrode material and preparation method |
| CN108428871A (en) * | 2018-03-21 | 2018-08-21 | 苏州林奈新能源有限公司 | A kind of nickel cobalt aluminium ternary method for preparing anode material of lithium-ion battery |
| CN108502937A (en) * | 2018-04-17 | 2018-09-07 | 哈尔滨工业大学 | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 万惠霖等: "《固体表面物理化学若干研究前沿》", 31 March 2006, 厦门大学出版社 * |
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