CN107845784A - A kind of nickel-cobalt-manganternary ternary anode material preparation method - Google Patents
A kind of nickel-cobalt-manganternary ternary anode material preparation method Download PDFInfo
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- CN107845784A CN107845784A CN201710835416.9A CN201710835416A CN107845784A CN 107845784 A CN107845784 A CN 107845784A CN 201710835416 A CN201710835416 A CN 201710835416A CN 107845784 A CN107845784 A CN 107845784A
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- 239000010405 anode material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000013049 sediment Substances 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000012266 salt solution Substances 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 29
- 150000002696 manganese Chemical class 0.000 claims abstract description 22
- 150000002815 nickel Chemical class 0.000 claims abstract description 22
- 150000001868 cobalt Chemical class 0.000 claims abstract description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- -1 neopelex Chemical compound 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- OZWCNMUNEZKIPW-UHFFFAOYSA-N benzenesulfinic acid zinc Chemical compound [Zn].OS(=O)c1ccccc1.OS(=O)c1ccccc1 OZWCNMUNEZKIPW-UHFFFAOYSA-N 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- SRJQTHAZUNRMPR-UYQKXTDMSA-N spinosyn A Chemical compound O([C@H]1CCC[C@@H](OC(=O)C[C@H]2[C@@H]3C=C[C@@H]4C[C@H](C[C@H]4[C@@H]3C=C2C(=O)[C@@H]1C)O[C@H]1[C@@H]([C@H](OC)[C@@H](OC)[C@H](C)O1)OC)CC)[C@H]1CC[C@H](N(C)C)[C@@H](C)O1 SRJQTHAZUNRMPR-UYQKXTDMSA-N 0.000 claims description 3
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229940048842 sodium xylenesulfonate Drugs 0.000 claims description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 abstract 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 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 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical group [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of nickel-cobalt-manganternary ternary anode material preparation method, comprises the following steps：1) cobalt salt solution, manganese salt solution and nickel salt solution are configured, reaction generation sediment A in 60 90 DEG C of water bath with thermostatic control is put into after mixing；2) filter out sediment A and be added to after washing, drying in a certain amount of water, by adhesive, dispersant and AlCl3Add in the sediment A aqueous solution, be then placed in reaction generation sediment B in 60 90 DEG C of water bath with thermostatic control；3) filter out sediment B and after washing, drying, sediment B and sulfonate are added in N methylpyrrolidone solutions, aging in 60 70 DEG C of water bath with thermostatic control is then placed in and generates sediment C for a period of time；4) centrifuge out sediment C and be heat-treated at a temperature of 600 800 DEG C, to obtain nickel-cobalt-manganternary ternary anode material presoma；5) by lithium salts and nickel-cobalt-manganternary ternary anode material presoma according to 1：It is calcined after the molar ratio of (1 1.5) is well mixed at a temperature of 800 900 DEG C.
Description
【Technical field】
The invention belongs to cell positive material technical field, more particularly to a kind of nickel-cobalt-manganternary ternary anode material preparation side
Method.
【Background technology】
Lithium ion battery is because it has the advantages such as higher than energy, voltage is high, operating temperature range is wide, service life is long,
It is widely used in the fields such as electric car.It is nickel cobalt using ripe extensive positive electrode in the lithium ion battery of commercialization at present
Manganese systems ternary material, the positive electrode have the advantages that cost is relatively low, has a safety feature.But nickel-cobalt-manganternary ternary anode material master
Gram volume is improved by the increase of nickel content, increase nickel content can cause electrolyte under stability of material change low and high temperature to exist
Positive electrode surface occurs side reaction and produces a large amount of gases, so as to bring serious potential safety hazard.Therefore, it is necessary in fact to nickel cobalt
Manganese tertiary cathode material optimizes improvement, to improve the stability of material while material gram volume is improved.
【The content of the invention】
Present invention proposition is a kind of can be modified nickel-cobalt-manganternary ternary anode material to improve the nickel-cobalt-manganese ternary of its stability just
Pole material preparation method.
The present invention provides a kind of nickel-cobalt-manganternary ternary anode material preparation method, comprises the following steps：
1) be respectively configured certain density cobalt salt solution, manganese salt solution and nickel salt solution and by above-mentioned three kinds of solution mix and
Cobalt, manganese, the molar ratio of three kinds of elements of nickel are 1 in mixed solution：(1-3)：(2-5), and mixed solution is put into
Reaction generation sediment A in 60-90 DEG C of water bath with thermostatic control；
2) filter out the sediment A and be added to after washing, drying in a certain amount of water, by adhesive, dispersant
And AlCl3Add in the aqueous solution of the sediment A and make the binding agent, dispersant and AlCl3Molar concentration be respectively 2-
4mol/L, 2-4mol/L and 3-5mol/L, it is then placed in reaction generation sediment B in 60-90 DEG C of water bath with thermostatic control；
3) filter out the sediment B and after washing, drying, 0.5-0.8g sulfonate is corresponded to according to every gram of sediment B
Ratio the sediment B and the sulfonate are added in 1-METHYLPYRROLIDONE solution, be then placed in 60-70 DEG C of constant temperature
Aging generates sediment C for a period of time in water-bath；
4) centrifuge out the sediment C and be heat-treated at a temperature of 600-800 DEG C, to obtain nickel cobalt manganese three
First positive electrode material precursor；
5) by lithium salts and the nickel-cobalt-manganternary ternary anode material presoma according to 1：The molar ratio of (1-1.5) is well mixed
It is calcined afterwards at a temperature of 800-900 DEG C, to obtain nickel-cobalt-manganternary ternary anode material.
In a preferred embodiment, in step 1), cobalt salt, manganese salt and nickel salt is respectively adopted it is dissolved into water configuration and rub
Your concentration is the 2-5mol/L cobalt salt solution, the manganese salt solution and the nickel salt solution；The cobalt salt is solubility
Cobalt salt, preferably cobaltous sulfate, cobalt nitrate or cobalt chloride；The manganese salt is soluble manganese salt, preferably manganese sulfate, manganese nitrate or
Person's manganese chloride；The nickel salt is soluble nickel salt, preferably nickel sulfate, nickel nitrate or nickel chloride.
In a preferred embodiment, in step 1), put after the cobalt salt solution, manganese salt solution and nickel salt solution mixing
Enter in water bath with thermostatic control, controlled pH value in 12-13 by the way that ammoniacal liquor or sodium hydroxide solution is added dropwise.
In a preferred embodiment, in step 1) to step 2), the cobalt salt solution, manganese salt solution and nickel salt solution
It is put into after mixing in water bath with thermostatic control, stirs 6-8h, is stood 2-4h and filter out the sediment A afterwards.
In a preferred embodiment, in step 2), the proportional arrangement institute of 100mL water is corresponded to according to every gram of sediment A
State the sediment A aqueous solution；Described adhesive be preferably triethoxysilane, polyvinyl alcohol, sodium carboxymethylcellulose, starch or
Person's dextrin；The dispersant is preferably salicylide or acetone.
In a preferred embodiment, in step 2) to step 3), described adhesive, the dispersant and AlCl3Add
It is put into after entering to the aqueous solution of the sediment A in water bath with thermostatic control, stirs 6-8h, is stood 2-4h and filter out the sediment afterwards
B。
In a preferred embodiment, in step 3) to step 4), the sediment B and the sulfonate are added to
1-METHYLPYRROLIDONE solution is simultaneously put into water bath with thermostatic control, stirs 5-6h, the precipitation is centrifuged out after aging 12-24h
Thing C.
In a preferred embodiment, the sulfonate is dodecyl sodium sulfate, neopelex, diformazan
Benzene sulfonic acid sodium salt, Amcide Ammate, sodium alkyl benzene sulfonate, benzene sulfonic acid, 4- cumene sodium sulfonates, benzene sulfinic acid sodium salt and benzenesulfinic acid zinc
In one or more.
In a preferred embodiment, in step 4), the sediment C is heat-treated at a temperature of 600-800 DEG C
Time be 3-12h.
In a preferred embodiment, in step 5), the lithium salts and the nickel-cobalt-manganternary ternary anode material presoma
Roasting is carried out after mixing to be in nitrogen protection atmosphere, and the roasting time at a temperature of 800-900 DEG C is 6-12h；Institute
It is preferably lithium carbonate, lithium hydroxide or lithium chloride to state lithium salts.
In nickel-cobalt-manganternary ternary anode material preparation method provided by the invention, using nickle cobalt lithium manganate as matrix, surface
The aluminium element of specified quantitative is adulterated, and carries out sulfonic group cladding, by prepared by the raising of the synergy of aluminium ion and sulfonic acid group
The lithium ion diffusivity of nickel-cobalt-manganternary ternary anode material, cation mixing phenomenon is reduced, it is steady so as to improve the electrochemistry of material
It is qualitative.In addition, the preparation method technique is simple, is easy to industrialized production, the electricity of the nickel-cobalt-manganternary ternary anode material assembling of preparation
Pond has good cycle performance.
【Brief description of the drawings】
Fig. 1 is the nickel cobalt manganese three that nickel-cobalt-manganternary ternary anode material preparation method provided by the invention obtains according to embodiment 1
The SEM figures of first positive electrode.
Fig. 2 is the battery and existing routine that the nickel-cobalt-manganternary ternary anode material obtained according to embodiment 1 shown in Fig. 1 assembles
The cycle performance correlation curve of the battery of nickel-cobalt-manganternary ternary anode material assembling.
【Embodiment】
The present invention provides a kind of nickel-cobalt-manganternary ternary anode material preparation method, comprises the following steps：
1) be respectively configured certain density cobalt salt solution, manganese salt solution and nickel salt solution and by above-mentioned three kinds of solution mix and
Cobalt, manganese, the molar ratio of three kinds of elements of nickel are 1 in mixed solution：(1-3)：(2-5), and mixed solution is put into
Reaction generation sediment A in 60-90 DEG C of water bath with thermostatic control；
2) filter out the sediment A and washing, dry after add in a certain amount of water, by adhesive, dispersant and
AlCl3Add in the aqueous solution of the sediment A and make the binding agent, dispersant and AlCl3Molar concentration be respectively 2-
4mol/L, 2-4mol/L and 3-5mol/L, it is then placed in reaction generation sediment B in 60-90 DEG C of water bath with thermostatic control；
3) filter out the sediment B and after washing, drying, 0.5-0.8g sulfonate is corresponded to according to every gram of sediment B
Ratio the sediment B and the sulfonate are added in 1-METHYLPYRROLIDONE solution, be then placed in 60-70 DEG C of constant temperature
Aging obtains sediment C for a period of time in water-bath；
4) centrifuge out the sediment C and be heat-treated at a temperature of 600-800 DEG C, to obtain nickel cobalt manganese three
First positive electrode material precursor；
5) by lithium salts and the nickel-cobalt-manganternary ternary anode material presoma according to 1：The molar ratio of (1-1.5) is well mixed
It is calcined afterwards at a temperature of 800-900 DEG C, to obtain nickel-cobalt-manganternary ternary anode material.
Specifically, in step 1), it is 2- that cobalt salt, manganese salt and nickel salt, which is respectively adopted, and is dissolved into configuration molar concentration in water
The 5mol/L cobalt salt solution, the manganese salt solution and the nickel salt solution.Further, in step 1), the cobalt salt is molten
It is put into after liquid, manganese salt solution and nickel salt solution mixing in water bath with thermostatic control, by the way that ammoniacal liquor or sodium hydroxide solution is added dropwise by pH value
Control is in 12-13.
In step 1) to step 2), it is put into after the cobalt salt solution, manganese salt solution and nickel salt solution mixing in water bath with thermostatic control,
6-8h is stirred, 2-4h is stood and filters out the sediment A afterwards.
In step 2), the aqueous solution of sediment A described in the proportional arrangement of 100mL water is corresponded to according to every gram of sediment A.
In step 2) to step 3), described adhesive, the dispersant and AlCl3Add the aqueous solution of the sediment A
After be put into water bath with thermostatic control, stir 6-8h, stand 2-4h after filter out the sediment B.
In step 3) to step 4), the sediment B is added into 1-METHYLPYRROLIDONE solution with the sulfonate and put
Enter in water bath with thermostatic control, stir 5-6h, the sediment C is centrifuged out after aging 12-24h.Wherein, the N- crassitudes
Ketone solution is according to 1 by 1-METHYLPYRROLIDONE and water：1 volume ratio mixes.
In step 4), the time that the sediment C is heat-treated at a temperature of 600-800 DEG C is 3-12h.
In step 5), the lithium salts carries out roasting after being mixed with the nickel-cobalt-manganternary ternary anode material presoma be to be in nitrogen
In gas shielded atmosphere, and the roasting time at a temperature of 800-900 DEG C is 6-12h.
Specifically, the cobalt salt is soluble cobalt, preferably cobaltous sulfate, cobalt nitrate or cobalt chloride.The manganese salt is
Soluble manganese salt, preferably manganese sulfate, manganese nitrate or manganese chloride.The nickel salt is soluble nickel salt, preferably nickel sulfate, nitre
Sour nickel or nickel chloride.
Described adhesive is preferably triethoxysilane, polyvinyl alcohol, sodium carboxymethylcellulose, starch or dextrin.Institute
It is preferably salicylide or acetone to state dispersant.
The sulfonate is preferably dodecyl sodium sulfate, neopelex, sodium xylene sulfonate, sulfamic acid
One or more in ammonium, sodium alkyl benzene sulfonate, benzene sulfonic acid, 4- cumene sodium sulfonates, benzene sulfinic acid sodium salt and benzenesulfinic acid zinc.
The lithium salts is preferably lithium carbonate, lithium hydroxide or lithium chloride.
Embodiment 1
In present embodiment, cobalt chloride, manganese chloride and nickel chloride is respectively adopted it is dissolved into ultra-pure water and configure molar concentration
It is 2mol/L cobalt chloride solution, manganese chloride solution and nickel chloride solution, above-mentioned three kinds of solution is mixed and made mixed
Cobalt, manganese, the molar ratio of three kinds of elements of nickel are 1 in solution：1：2, then mixed solution is put into 60 DEG C of water bath with thermostatic control
In, 2h is stood after stirring reaction 1h, during this period, the pH value of mixed solution is controlled in 12-13 by the way that ammoniacal liquor is added dropwise, connect
Get off and filter out the sediment A for reacting generation.
Dried after the sediment A is washed into three times with deionized water, the ratio of 100mL water is corresponded to according to every gram of sediment A
Example adds the sediment A in ultra-pure water, then by triethoxysilane, salicylide and AlCl3It is added to the sediment A
The aqueous solution in, and make triethoxysilane, salicylide and AlCl3Molar concentration respectively in 2mol/L, 2mol/L and 3mol/
L.Sediment A, triethoxysilane, salicylide and AlCl will be contained3Mixed liquor be put into 60 DEG C of water bath with thermostatic control, stirring is anti-
2h is stood after answering 6h, next filters out the sediment B for reacting generation.
Dried after the sediment B is washed into three times with deionized water, 0.5g dodecyls are corresponded to according to every gram of sediment B
The ratio of sodium sulfonate adds the sediment B and dodecyl sodium sulfate in 1-METHYLPYRROLIDONE solution, wherein, the N-
Methylpyrrolidone solution is according to 1 by 1-METHYLPYRROLIDONE and ultra-pure water：1 volume ratio mixes.Then will contain
The mixed liquor of the sediment B, dodecyl sodium sulfate and 1-METHYLPYRROLIDONE is put into 60 DEG C of water bath with thermostatic control, stirs 5h
Aging 12h afterwards, next the sediment C of generation is centrifuged out.
The sediment C is placed in 600 DEG C of Muffle furnace and is heat-treated 3h acquisition nickel-cobalt-manganternary ternary anode material forerunners
Body.Finally by lithium carbonate and the nickel-cobalt-manganternary ternary anode material presoma according to 1：1 molar ratio is well mixed to be placed on
800 DEG C of Muffle kiln roasting 6h, obtain nickel-cobalt-manganternary ternary anode material.
Embodiment 2
In present embodiment, cobalt chloride, manganese chloride and nickel chloride is respectively adopted it is dissolved into ultra-pure water and configure molar concentration
It is 5mol/L cobalt chloride solution, manganese chloride solution and nickel chloride solution, above-mentioned three kinds of solution is mixed and made mixed
Cobalt, manganese, the molar ratio of three kinds of elements of nickel are 1 in solution：3：5, then mixed solution is put into 90 DEG C of water bath with thermostatic control
In, 4h is stood after stirring reaction 2h, during this period, is controlled the pH value of mixed solution in 12- by the way that sodium hydroxide is added dropwise
13, next the sediment A for reacting generation is filtered out.
Dried after the sediment A is washed into three times with deionized water, the ratio of 100mL water is corresponded to according to every gram of sediment A
Example adds the sediment A in ultra-pure water, then by triethoxysilane, salicylide and AlCl3It is added to the sediment A
The aqueous solution in, and make triethoxysilane, salicylide and AlCl3Molar concentration respectively in 4mol/L, 4mol/L and 5mol/
L.Sediment A, triethoxysilane, salicylide and AlCl will be contained3Mixed liquor be put into 90 DEG C of water bath with thermostatic control, stirring is anti-
3h is stood after answering 8h, next filters out the sediment B for reacting generation.
Dried after the sediment B is washed into three times with deionized water, 0.8g dodecyls are corresponded to according to every gram of sediment B
The ratio of sodium sulfonate adds the sediment B and dodecyl sodium sulfate in 1-METHYLPYRROLIDONE solution, wherein, the N-
Methylpyrrolidone solution is according to 1 by 1-METHYLPYRROLIDONE and ultra-pure water：1 volume ratio mixes.Then will contain
The mixed liquor of the sediment B, dodecyl sodium sulfate and 1-METHYLPYRROLIDONE is put into 70 DEG C of water bath with thermostatic control, stirs 6h
Aging 18h afterwards, next the sediment C of generation is centrifuged out.
The sediment C is placed in 800 DEG C of Muffle furnace and is heat-treated 3h acquisition nickel-cobalt-manganternary ternary anode material forerunners
Body.Finally by lithium carbonate and the nickel-cobalt-manganternary ternary anode material presoma according to 1：1.5 molar ratio is well mixed to be placed
In 900 DEG C of Muffle kiln roasting 6h, nickel-cobalt-manganternary ternary anode material is obtained.
The nickel-cobalt-manganternary ternary anode material obtained using SEM to embodiment 1 is observed, it was observed that
Material surface pattern is as shown in Figure 1.
Using embodiment 1 obtain nickel-cobalt-manganternary ternary anode material assembled battery and its physical parameter is measured, tie
Fruit is as shown in the table：
| Efficiency/% first | Positive pole gram volume mAh/g | Energy density Wh/kg |
| 83.56 | 160.58 | 190.46 |
Referring to Fig. 2, the battery assembled to the nickel-cobalt-manganternary ternary anode material that embodiment 1 obtains carries out cycle performance survey
Examination, as a comparison, prepares battery using identical method by existing conventional nickel-cobalt-manganternary ternary anode material and measures cycle performance.
As a result understand：The circulating battery that the nickel-cobalt-manganternary ternary anode material obtained using embodiment 1 is assembled is after 300 weeks, capability retention
For 95.67%, and under equal conditions, the circulating battery of existing conventional nickel-cobalt-manganternary ternary anode material assembling after 300 weeks, protect by capacity
Holdup is 89.17%.
In nickel-cobalt-manganternary ternary anode material preparation method provided by the invention, using nickle cobalt lithium manganate as matrix, surface
The aluminium element of specified quantitative is adulterated, and carries out sulfonic group cladding, by prepared by the raising of the synergy of aluminium ion and sulfonic acid group
The lithium ion diffusivity of nickel-cobalt-manganternary ternary anode material, cation mixing phenomenon is reduced, it is steady so as to improve the electrochemistry of material
It is qualitative.In addition, the preparation method technique is simple, is easy to industrialized production, the electricity of the nickel-cobalt-manganternary ternary anode material assembling of preparation
Pond has good cycle performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is to combine specific preferred embodiment to institute of the present invention
The further description of work, it is impossible to assert that the specific implementation of the present invention is confined to these explanations.It is all the present invention spirit and
All any modification, equivalent and improvement made within principle etc., should be included within the scope of the present invention.
Claims (10)
- A kind of 1. nickel-cobalt-manganternary ternary anode material preparation method, it is characterised in that：Comprise the following steps：1) certain density cobalt salt solution, manganese salt solution and nickel salt solution is respectively configured and above-mentioned three kinds of solution is mixed and mixed Cobalt, manganese, the molar ratio of three kinds of elements of nickel are 1 in solution afterwards：(1-3)：(2-5), and mixed solution is put into 60-90 DEG C water bath with thermostatic control in reaction generation sediment A；2) filter out the sediment A and washing, dry after be added in a certain amount of water, by adhesive, dispersant and AlCl3Add in the aqueous solution of the sediment A and make the binding agent, dispersant and AlCl3Molar concentration be respectively 2- 4mol/L, 2-4mol/L and 3-5mol/L, it is then placed in reaction generation sediment B in 60-90 DEG C of water bath with thermostatic control；3) filter out the sediment B and after washing, drying, the ratio of 0.5-0.8g sulfonate is corresponded to according to every gram of sediment B Example adds the sediment B and the sulfonate in 1-METHYLPYRROLIDONE solution, is then placed in 60-70 DEG C of water bath with thermostatic control Middle aging generates sediment C for a period of time；4) centrifuge out the sediment C and be heat-treated at a temperature of 600-800 DEG C, to obtain nickel-cobalt-manganese ternary just Pole material precursor；5) by lithium salts and the nickel-cobalt-manganternary ternary anode material presoma according to 1：After the molar ratio of (1-1.5) is well mixed It is calcined at a temperature of 800-900 DEG C, to obtain nickel-cobalt-manganternary ternary anode material.
- 2. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：In step 1), adopt respectively It is that the 2-5mol/L cobalt salt solution, the manganese salt are molten to be dissolved into cobalt salt, manganese salt and nickel salt in water and configure molar concentration Liquid and the nickel salt solution；The cobalt salt is soluble cobalt, preferably cobaltous sulfate, cobalt nitrate or cobalt chloride；The manganese salt For soluble manganese salt, preferably manganese sulfate, manganese nitrate or manganese chloride；The nickel salt is soluble nickel salt, preferably nickel sulfate, Nickel nitrate or nickel chloride.
- 3. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：In step 1), the cobalt It is put into after salting liquid, manganese salt solution and nickel salt solution mixing in water bath with thermostatic control, will by the way that ammoniacal liquor or sodium hydroxide solution is added dropwise PH value is controlled in 12-13.
- 4. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：Step 1) is to step 2) In, it is put into after the cobalt salt solution, manganese salt solution and nickel salt solution mixing in water bath with thermostatic control, stirring 6-8h, after standing 2-4h Filter out the sediment A.
- 5. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：In step 2), according to every Gram sediment A corresponds to the aqueous solution of sediment A described in the proportional arrangement of 100mL water；Described adhesive is preferably triethoxysilicane Alkane, polyvinyl alcohol, sodium carboxymethylcellulose, starch or dextrin；The dispersant is preferably salicylide or acetone.
- 6. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：Step 2) is to step 3) In, described adhesive, the dispersant and AlCl3It is put into water bath with thermostatic control, stirs after being added to the aqueous solution of the sediment A 6-8h, stand 2-4h and filter out the sediment B afterwards.
- 7. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：Step 3) is to step 4) In, the sediment B and the sulfonate are added to 1-METHYLPYRROLIDONE solution and are put into water bath with thermostatic control, stirs 5- The sediment C is centrifuged out after 6h, aging 12-24h.
- 8. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：The sulfonate is preferably Dodecyl sodium sulfate, neopelex, sodium xylene sulfonate, Amcide Ammate, sodium alkyl benzene sulfonate, benzene sulfonic acid, One or more in 4- cumene sodium sulfonates, benzene sulfinic acid sodium salt and benzenesulfinic acid zinc.
- 9. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：It is described heavy in step 4) The time that starch C is heat-treated at a temperature of 600-800 DEG C is 3-12h.
- 10. nickel-cobalt-manganternary ternary anode material preparation method as claimed in claim 1, it is characterised in that：In step 5), the lithium Salt carries out roasting after being mixed with the nickel-cobalt-manganternary ternary anode material presoma be in nitrogen protection atmosphere, and in 800- Roasting time at a temperature of 900 DEG C is 6-12h；The lithium salts is preferably lithium carbonate, lithium hydroxide or lithium chloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109244454A (en) * | 2018-11-06 | 2019-01-18 | 北京理工大学 | A kind of NCM tertiary cathode material with hierarchical structure |
| CN112164774A (en) * | 2020-09-08 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Composite high-nickel ternary cathode material and preparation method thereof |
| CN112479270A (en) * | 2020-12-02 | 2021-03-12 | 山东丰元化学股份有限公司 | Preparation method of ternary positive electrode material of lithium ion power battery |
| CN112479271A (en) * | 2020-12-09 | 2021-03-12 | 山东丰元化学股份有限公司 | Preparation method of high-nickel ternary cathode material |
| CN114573047A (en) * | 2022-03-08 | 2022-06-03 | 宜宾光原锂电材料有限公司 | High-power NCM precursor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109244454A (en) * | 2018-11-06 | 2019-01-18 | 北京理工大学 | A kind of NCM tertiary cathode material with hierarchical structure |
| CN112164774A (en) * | 2020-09-08 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Composite high-nickel ternary cathode material and preparation method thereof |
| CN112479270A (en) * | 2020-12-02 | 2021-03-12 | 山东丰元化学股份有限公司 | Preparation method of ternary positive electrode material of lithium ion power battery |
| CN112479271A (en) * | 2020-12-09 | 2021-03-12 | 山东丰元化学股份有限公司 | Preparation method of high-nickel ternary cathode material |
| CN114573047A (en) * | 2022-03-08 | 2022-06-03 | 宜宾光原锂电材料有限公司 | High-power NCM precursor and preparation method thereof |
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