CN117917787A - High-capacity nickel-based positive electrode material, preparation method thereof and lithium ion battery - Google Patents
High-capacity nickel-based positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN117917787A CN117917787A CN202211285749.6A CN202211285749A CN117917787A CN 117917787 A CN117917787 A CN 117917787A CN 202211285749 A CN202211285749 A CN 202211285749A CN 117917787 A CN117917787 A CN 117917787A
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- Prior art keywords
- positive electrode
- nickel
- electrode material
- complexing agent
- based positive
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 235
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 120
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 119
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000008139 complexing agent Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000012266 salt solution Substances 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000013067 intermediate product Substances 0.000 claims abstract description 23
- 238000000975 co-precipitation Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910019549 CoyMzO2 Inorganic materials 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 35
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 25
- -1 organic ester compounds Chemical class 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-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
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- DRAJWRKLRBNJRQ-UHFFFAOYSA-N Hydroxycarbamic acid Chemical compound ONC(O)=O DRAJWRKLRBNJRQ-UHFFFAOYSA-N 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates 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
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 23
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- 239000011572 manganese Substances 0.000 description 13
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
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- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
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- QQUZYDCFSDMNPX-UHFFFAOYSA-N ethene;4-methyl-1,3-dioxolan-2-one Chemical compound C=C.CC1COC(=O)O1 QQUZYDCFSDMNPX-UHFFFAOYSA-N 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
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- 239000000174 gluconic acid Substances 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- UKAUYVFTDYCKQA-UHFFFAOYSA-N homoserine Chemical compound OC(=O)C(N)CCO UKAUYVFTDYCKQA-UHFFFAOYSA-N 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
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- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
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- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- JEVFKQIDHQGBFB-UHFFFAOYSA-K tripotassium;2-[bis(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O JEVFKQIDHQGBFB-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium ion batteries, and discloses a high-capacity nickel-based positive electrode material, a preparation method thereof and a lithium ion battery. The nickel-based positive electrode material includes: a compound having a chemical composition of Li aNixCoyMzO2, an oxide containing T element supported on the compound; wherein M is at least one of VIIB group elements and IIIA group elements, T is at least one of IVB group elements, and the nickel-based positive electrode material contains Li-T-O chemical bonds. The preparation method of the nickel-based positive electrode material comprises the following steps: performing coprecipitation reaction on the metal salt solution, the precipitator solution and the complexing agent solution to obtain a precursor; mixing the precursor, the compound containing the T element, alcohol and water, filtering and drying to obtain an intermediate product; mixing the intermediate product with a lithium source and performing a solid phase reaction. The nickel-based positive electrode material provided by the invention has high specific discharge capacity and first-week coulomb efficiency.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a high-capacity nickel-based positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The world has faced tremendous energy and environmental challenges over the past three decades. The problems of global warming and ecological deterioration are caused by the large consumption of fossil energy and the emission of greenhouse gases. In view of this, researchers have been working on developing new energy technologies to address these issues. Among many chemical power sources, lithium ion batteries have been receiving attention because of their advantages of high energy density, long service life, small self-discharge degree, no memory effect, environmental protection, and the like. Since the first successful commercialization of lithium ion battery technology by sony corporation in 1991, lithium ion batteries have been used in large scale in consumer electronics such as cell phones, laptop computers, cameras, and the like. In recent years, with the strong pushing of electric vehicles, the explosive growth of power batteries is driven.
The energy density is a key index of the lithium ion battery, and the key of improving the energy density is to improve the specific capacity of the positive electrode material. The most commonly used positive electrode material in lithium ion batteries currently commercialized is LiCoO 2、LiMn2O4、LiFePO4, etc. In the charge and discharge process, liCoO 2 can undergo irreversible change from a hexagonal structure to a monoclinic structure, thereby resulting in low specific capacity and poor chemical stability. The reversible capacity of the positive electrode material LiMn 2O4 is very limited (about 120 mAh/g), and the problems of Mn 3+ dissolution and the like exist in the charge and discharge processes. LiFePO 4 also has the problems of low operating voltage (3.4V), low reversible capacity, etc. (about 160 mAh/g). The materials have limited specific capacity and lower first-week coulomb efficiency, and can not meet the requirements of large-scale energy storage and high endurance mileage of electric automobiles. Therefore, it is urgent to develop an alternative positive electrode material to improve the specific discharge capacity and the first-week coulombic efficiency of the positive electrode material.
Disclosure of Invention
The invention aims to solve the problems of limited specific capacity and low first-week coulomb efficiency of a positive electrode material in the prior art, and provides a high-capacity nickel-based positive electrode material, a preparation method thereof and a lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a nickel-based positive electrode material comprising: a compound having a chemical composition of Li aNixCoyMzO2, an oxide containing T element supported on the compound; wherein a is more than or equal to 0.9 and less than or equal to 1.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than 1, and x+y+z=1; and M is at least one of a VIIB group element and a IIIA group element, T is at least one of an IVB group element, and the nickel-based positive electrode material contains a Li-T-O chemical bond.
In a second aspect, the present invention provides a method for preparing a nickel-based positive electrode material, the method comprising the steps of:
(1) Performing coprecipitation reaction on the metal salt solution, the precipitator solution and the complexing agent solution to obtain a precursor;
(2) Mixing the precursor, the compound containing the T element, alcohol and water, filtering and drying to obtain an intermediate product;
(3) Mixing the intermediate product with a lithium source and performing solid phase reaction to obtain the nickel-based anode material;
Wherein the metal salt contains at least one of Ni, co and M elements, and M is at least one of VIIB group elements and IIIA group elements; the T element is at least one selected from IVB group elements.
In a third aspect, the present invention provides a nickel-based positive electrode material obtained by the method described in the second aspect.
A fourth aspect of the present invention provides a lithium ion battery comprising the nickel-based positive electrode material according to the first or third aspect.
Through the technical scheme, the invention can obtain the following beneficial effects:
The nickel-based positive electrode material provided by the invention is different from the existing positive electrode material in that the nickel-based positive electrode material has novel composition and structure, contains a chemical structure of Li-T-O, wherein T is selected from IVB group elements, the chemical structure of Li-T-O is a fast ion conductor, meanwhile, the conductivity of the Li-T-O compound is good, and the nickel-based positive electrode material can improve the migration rate of lithium ions and electrons in the positive electrode material and improve the electrochemical performance of a lithium battery when applied to the lithium ion battery.
The nickel-based positive electrode material prepared by the method provided by the invention has excellent electrochemical performance, and has higher specific discharge capacity and first-week coulombic efficiency. The specific discharge capacity at the 0.1C multiplying power can reach 216.3mAh/g, the first week coulomb efficiency can reach 93%, and the specific discharge capacity at the 1C multiplying power can reach 196.4mAh/g. The novel nickel-based positive electrode material provided by the invention can be used in high-energy-density lithium ion batteries.
Drawings
FIG. 1 is an SEM image of a nickel-based positive electrode material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a nickel-based positive electrode material prepared in example 1 of the present invention;
FIG. 3 is an enlarged view of XRD pattern (FIG. 2) of the nickel-based positive electrode material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the concentration of complexing agent in the coprecipitation reaction system according to example 1 of the present invention as a function of reaction time;
FIG. 5 is a charge-discharge curve of 0.1C rate for the nickel-based positive electrode material prepared in example 1 of the present invention;
fig. 6 is a charge-discharge curve of 1C magnification of the nickel-based positive electrode material prepared in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a nickel-based positive electrode material comprising: a compound having a chemical composition of Li aNixCoyMzO2, an oxide containing T element supported on the compound; wherein a is more than or equal to 0.9 and less than or equal to 1.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than 1, and x+y+z=1; and M is at least one of a VIIB group element and a IIIA group element, T is at least one of an IVB group element, and the nickel-based positive electrode material contains a Li-T-O chemical bond. The oxide containing the T element remarkably improves the discharge specific capacity and the first-week coulomb efficiency of the nickel-based positive electrode material.
In the present invention, the T element is at least one selected from the group consisting of group IVB elements, preferably at least one of Ti, zr, and Hf.
The nickel-based positive electrode material provided by the invention contains Li-T-O chemical bonds, and the Li-T-O chemical bonds are loaded on Li aNixCoyMzO2 in the form of Li-T-O compounds.
In the present invention, the Li-T-O chemical bond structure contained in the nickel-based positive electrode material can be confirmed by measuring an X-ray diffraction pattern (XRD) of the nickel-based positive electrode material. The XRD pattern of the nickel-based positive electrode material was measured by an X-ray diffractometer of model D8 ADVANCE SS of Bruce, germany. In a preferred embodiment, the XRD diffraction pattern of the nickel-based cathode material is shown in fig. 2, and it can be seen from the figure that the main diffraction peak of the nickel-based cathode material is consistent with α -NaFeO 2 of hexagonal structure, which indicates that a good layered crystal structure is formed, and the proportion of lithium-nickel mixed discharge in the nickel-based cathode material is 1.52% and the proportion of lithium-nickel mixed discharge is low by structural refinement. The XRD diffraction pattern of the nickel-based positive electrode material is shown in figure 3, and diffraction peaks belonging to Li-Hf-O can be clearly seen in the range of 20-30 degrees in addition to diffraction peaks of the layered structure, which indicates that the chemical structure of Li-Hf-O is contained in the nickel-based positive electrode material.
In a preferred embodiment of the present invention, the molar ratio of the oxide containing T element in terms of T element to the compound having a chemical composition of Li aNixCoyMzO2 in terms of (Ni+Co+M) is (0-0.1): 1, wherein the molar amount of the oxide containing T element is not 0. That is, when the molar amount of the compound having the chemical composition of Li aNixCoyMzO2 is 1, the molar amount of the oxide containing the T element may be any value in the range constituted by 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 and any two of these values.
In the invention, in the chemical composition Li aNixCoyMzO2, a is more than or equal to 0.9 and less than or equal to 1.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x+y+z is more than or equal to 0 and less than or equal to 1, preferably, a is more than or equal to 0.9 and less than or equal to 1.3,0.5 and less than or equal to 0.95, y is more than or equal to 0 and less than or equal to 0.5, and the values of x+y+z are more than or equal to 1, and x, y and z satisfy the electric neutrality principle.
In the present invention, M is at least one selected from the group consisting of group VIIB elements and group IIIA elements, and preferably Mn and/or Al. That is, preferably, the compound having the chemical composition Li aNixCoyMzO2 is Li aNixCoyMnzO2 and/or Li aNixCoyAlzO2.
In a preferred embodiment of the present invention, the nickel-based positive electrode material is a secondary microsphere formed by agglomeration of primary particles, and the particle size of the secondary microsphere is 1 to 30 μm, preferably 1 to 20 μm.
Preferably, the primary particles have a size of 20-800nm.
In the present invention, the size of the primary particles is not particularly limited, and may be nano-sized particles, submicron-sized particles, or micron-sized particles. The arrangement of the primary particles is not particularly limited, and may be irregular or radially distributed.
In the invention, the morphology of the nickel-based positive electrode material is characterized by a Scanning Electron Microscope (SEM), and the model of the adopted scanning electron microscope is ZEISS Merlin (ZEISS company, germany). In a preferred embodiment, the SEM image of the nickel-based cathode material is shown in fig. 1, from which it can be observed that the nickel-based cathode material provided by the present invention is a spherical particle, which is a secondary microsphere formed by the agglomeration of primary particles. The primary particles are between 20 and 800nm in size and the secondary microspheres are about 10.6 μm in size.
The inventors of the present invention have found through intensive studies on a nickel-based positive electrode material that, when a compound having a chemical composition of Li aNixCoyMzO2 and a metal oxide containing a group IVB element supported on the above compound are contained in the nickel-based positive electrode material, the nickel-based positive electrode material has a higher specific discharge capacity and initial cycle coulombic efficiency, and can be used in a lithium ion battery having a high energy density.
In a second aspect, the present invention provides a method for preparing a nickel-based positive electrode material, the method comprising the steps of:
(1) Performing coprecipitation reaction on the metal salt solution, the precipitator solution and the complexing agent solution to obtain a precursor;
(2) Mixing the precursor, the compound containing the T element, alcohol and water, filtering and drying to obtain an intermediate product;
(3) Mixing the intermediate product with a lithium source and performing solid phase reaction to obtain the nickel-based anode material;
Wherein the metal salt contains at least one of Ni, co and M elements, and M is at least one of VIIB group elements and IIIA group elements; the T element is at least one selected from IVB group elements.
The inventor of the invention finds that in the preparation process of the nickel-based positive electrode material, a positive electrode material precursor is prepared through coprecipitation reaction, then an intermediate product obtained by mixing the positive electrode material precursor with a compound containing a T element, alcohol and water is subjected to solid phase reaction with a lithium source, the prepared nickel-based positive electrode material comprises an oxide containing the T element, the nickel-based positive electrode material contains a chemical structure of Li-T-O, and the discharge specific capacity and the first week coulomb efficiency of the nickel-based positive electrode material are obviously improved.
In a preferred embodiment of the present invention, the coprecipitation reaction in step (1) includes: adding a metal salt solution, a precipitator solution and a complexing agent solution into a reaction kettle at the same time under the stirring state for reaction to obtain a reaction product; and then carrying out solid-liquid separation and drying on the reaction product to obtain a precursor.
In the present invention, the metal salt contains at least one of Ni, co and M, M is at least one selected from the group consisting of group VIIB elements and group IIIA elements, and preferably Mn and/or Al. Wherein the Ni, co and M elements are respectively in the form of nickel salt, cobalt salt and M salt.
In the present invention, the kinds of the nickel salt, cobalt salt and M salt are not particularly limited, and preferably the nickel salt, cobalt salt and M salt are selected from at least one of their sulfate, nitrate, acetate, oxalate and hydrochloride, and more preferably the nickel salt, cobalt salt and M salt are selected from at least one of nickel sulfate, nickel nitrate, cobalt acetate, cobalt oxalate, manganese sulfate, manganese nitrate, aluminum acetate and aluminum sulfate.
In a preferred embodiment of the present invention, the molar concentration of the metal salt solution is 0.01 to 5mol/L, for example, 0.01mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, and any value in the range of any two of these values, preferably 0.01 to 4mol/L, more preferably 0.5 to 4mol/L, in terms of the metal element.
In a preferred embodiment of the invention, the molar ratio of Ni, co and M in the metal salt solution is (0-1): 0-1, preferably (0.5-0.95): 0-0.5, wherein the molar amount of Ni is not 0.
In the present invention, the kind of the precipitant is not particularly limited as long as the precipitation reaction of the metal salt solution can be satisfied, and preferably the precipitant is at least one selected from the group consisting of hydroxides, carbonates and bicarbonates of alkali metals, preferably at least one selected from the group consisting of Na, K and Li; more preferably, the precipitant is selected from at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium hydroxide, lithium carbonate, and lithium bicarbonate. The embodiment of the invention is exemplified by sodium hydroxide, and the invention is not limited thereto.
In the present invention, the concentration of the precipitant solution is not particularly limited, and preferably the concentration of the precipitant solution is 0.01 to 16mol/L, for example, 0.01mol/L、0.02mol/L、0.1mol/L、0.5mol/L、1mol/L、2mol/L、3mol/L、4mol/L、5mol/L、6mol/L、7mol/L、8mol/L、9mol/L、10mol/L、11mol/L、12mol/L、13mol/L、14mol/L、15mol/L、16mol/L and any value in the range of any two of these values, preferably 2 to 12mol/L.
In the present invention, the kind of the complexing agent may be not particularly limited, and is a compound capable of forming a complex with Ni, co and M in an aqueous solution; preferably, the complexing agent is selected from at least one of an ammonium ion donor, an alcohol amine complexing agent, an aminocarboxylic acid complexing agent, a hydroxyamino carboxylic acid complexing agent, a carboxylate complexing agent, and a thiocyanate complexing agent.
In a preferred embodiment of the present invention, the ammonium ion donor is selected from at least one of ammonia water, ammonium oxalate, ammonium carbonate and ammonium hydroxide. The embodiment of the invention is exemplified by ammonia water, and the invention is not limited thereto.
In a preferred embodiment of the present invention, the alcohol amine complexing agent is selected from at least one of ethanolamine, diethanolamine, 2-dibutylamino ethanol, 2-diethylaminoethanol and N, N-diethylethanolamine.
In a preferred embodiment of the present invention, the aminocarboxylic acid complexing agent is selected from at least one of sodium Nitrilotriacetate (NTA), potassium nitrilotriacetate, ethylenediamine tetraacetic acid and its salts (EDTA) and diethylenetriamine pentaacetic acid (DTPA).
In a preferred embodiment of the present invention, the hydroxyaminocarboxylic acid-based complexing agent is selected from at least one of hydroxyethylenediamine tetraacetic acid (HEDTA) and salts thereof, ethyleneglycol bis (β -diaminoethyl) diethyl ether-N, N, N 'N' -tetraacetic acid (EGTA) and salts thereof, and dihydroxyglycine and salts thereof.
In a preferred embodiment of the present invention, the carboxylate-based complexing agent is selected from at least one of oxalic acid and salts thereof, tartaric acid and salts thereof, citric acid and salts thereof, gluconic acid and salts thereof, carboxymethyl hydroxy malonic acid (CMOM) and salts thereof, carboxymethyl hydroxy succinic acid (CMOS) and salts thereof, and hydroxyethyl amino acetic acid (DHEG) and salts thereof.
In a preferred embodiment of the present invention, the thiocyanate-based complexing agent is at least one selected from the group consisting of sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, calcium thiocyanate, and zinc thiocyanate.
In a preferred embodiment of the present invention, the concentration of the complexing agent solution may be not particularly limited, and preferably the concentration of the complexing agent solution is 0.01 to 16mol/L, for example, may be 0.01mol/L、0.1mol/L、0.5mol/L、1mol/L、2mol/L、3mol/L、4mol/L、5mol/L、6mol/L、7mol/L、8mol/L、9mol/L、10mol/L、11mol/L、12mol/L、13mol/L、14mol/L、15mol/L、16mol/L and any range between any two values, and further preferably 2 to 15mol/L.
In a preferred embodiment of the invention, the base solution is added to the reaction vessel prior to adding the metal salt solution, the precipitant solution and the complexing agent solution to the reaction vessel.
In a preferred embodiment of the invention, the base solution is an aqueous solution comprising a complexing agent; the volume of the base liquid is 0-100%, preferably 0-80%, and more preferably 10-60% of the volume of the reaction kettle. The concentration of the complexing agent in the base liquid is 0 to 1.8mol/L, preferably 0.05 to 1.5mol/L, and more preferably 0.1 to 1.0mol/L.
In a preferred embodiment of the invention, the concentration of complexing agent in the base liquid is at least 0.05mol/L, preferably at least 0.1mol/L lower than the concentration of complexing agent at the end of the reaction.
In a preferred embodiment of the present invention, the concentration of the complexing agent in the coprecipitation reaction system gradually increases, and the rate of change of the concentration of the complexing agent gradually decreases; preferably, the concentration of the complexing agent is varied at a rate of 1 mol/L.multidot.h or less, preferably from 0.001 to 1 mol/L.multidot.h, and more preferably from 0.001 to 0.5 mol/L.multidot.h.
In a preferred embodiment of the present invention, the total reaction time of coprecipitation is defined as R hours, and the concentration change rate of the complexing agent is not lower than 0.021 mol/L.h, preferably 0.021 to 1 mol/L.h, more preferably 0.021 to 0.5 mol/L.h, for example, 0.021 mol/L.h, 0.026 mol/L.h, 0.031 mol/L.h, 0.036 mol/L.h, 0.041 mol/L.h, 0.046 mol/L.h, 0.5 mol/L.h, and any value in the range constituted by any two of these values in the first 1/8R hours at the start of the reaction.
In the present invention, the "concentration change rate of the complexing agent" refers to the difference between the final concentration and the initial concentration of the complexing agent in the reaction system in any time period, and the present invention is calculated in each hour. The "the concentration change rate of the complexing agent in the coprecipitation reaction system gradually decreases" means that the concentration change rate of the complexing agent in the reaction system (as a whole) shows a tendency of gradually decreasing in the whole period from the time when the complexing agent is added to the coprecipitation reaction system to the end of the reaction, but one or more local intervals are allowed to exist; within this local interval, the concentration of complexing agent in the reaction system changes in a different manner (e.g., maintains a constant and/or gradually increasing and/or disordered state). Provided that the presence of such local intervals is unavoidable to the state of the art and does not affect the person skilled in the art in determining the rate of change of the concentration of the complexing agent in the reaction system over said whole period of time as still (overall) exhibiting a gradual decreasing trend. In addition, the presence of such local intervals does not affect the achievement of the intended purpose of the present invention, is acceptable and is also included in the scope of the present invention.
In a preferred embodiment of the present invention, the time from the addition of the complexing agent to the completion of the reaction to the concentration of 80% or more of the complexing agent in the precipitation reaction system is not more than 1/4R hours.
In a preferred embodiment of the invention, the concentration of the complexing agent at the end of the reaction is from 0.05 to 2mol/L, preferably from 0.05 to 1.2mol/L.
In the present invention, in order to promote the sufficient progress of the reaction of the metal salt solution, the precipitant solution and the complexing agent solution, the conditions of the precipitation reaction include: the temperature is 20-70deg.C, preferably 45-60deg.C; the pH value is 8-14, preferably 10-12; the reaction time is not less than 10 hours, preferably 12 to 96 hours, more preferably 12 to 48 hours; the precipitation reaction is carried out under stirring conditions at a stirring speed of 50-1200r/min, preferably 600-1200r/min.
It should be understood that the control of the pH may be to control a constant pH during the reaction time, or to vary the pH of the reaction process depending on the product object, but the range of pH variation should be within the above-mentioned reaction system, and in a further preferred embodiment, the pH of the reaction system is kept constant within the above-mentioned range.
In a preferred embodiment of the present invention, the coprecipitation reaction time is denoted as R hours, and the solid content of the precipitation reaction system is not more than 7wt%, preferably not more than 5wt%, for example, 0wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% and any value in the range constituted by any two of these values in the first 1/8R hours before the start of the reaction.
In the invention, the solid content of the coprecipitation reaction system is related to the addition amount of the metal salt solution, the complexing agent solution and the precipitant solution, and the addition amount is related to the flow rate and the concentration of each material, so that the control of the solid content of the coprecipitation reaction system can be realized by controlling the flow rate and the concentration of the metal salt solution, the complexing agent solution and the precipitant solution by a person skilled in the art.
The flow rates and the concentration selection ranges of the metal salt solution, the complexing agent solution and the precipitant solution are wide, and the flow rates and the concentrations of all materials can be controlled by a person skilled in the art according to requirements. In some preferred embodiments, in the case that the concentrations of the metal salt solution, the complexing agent solution and the precipitant solution are determined, the ratio of the initial volumetric flow rates of the metal salt solution and the complexing agent solution is set to be preferably 1-10, more preferably 2-6, and then the flow rate of the metal salt solution is kept unchanged, the concentration of the complexing agent in the coprecipitation reaction system and the change rate thereof are controlled within the above-defined range by controlling the flow rate of the complexing agent, and the pH of the precipitation reaction system is controlled to satisfy the above-mentioned range by controlling the flow rate of the precipitant solution, so that the regulation of the solid content of the coprecipitation reaction system can be realized.
In the present invention, the solid-liquid separation is not particularly limited as long as the reaction product obtained after the coprecipitation reaction can be separated, and for example, filtration or centrifugation can be used.
In the present invention, the product obtained by solid-liquid separation is preferably subjected to washing treatment, and the washing solvent is preferably water, more preferably hot water, at a temperature of 30 to 90 ℃.
In the present invention, the drying method may be a method conventional in the art, and for example, may be vacuum drying, freeze drying, air drying or oven drying. The present invention is preferably vacuum heat drying, and the drying temperature and time are not particularly required as long as the washed product can be dried, for example: the vacuum heating and drying temperature is 50-150 ℃ and the time is 4-24h.
In the present invention, step (2) includes: and mixing the precursor, the compound containing the T element, alcohol and water, filtering and drying to obtain an intermediate product.
In a preferred embodiment of the present invention, in step (2), the method of mixing comprises: firstly mixing the precursor, a compound containing a T element and alcohol to obtain a mixture; and then carrying out second mixing on the mixture and the alcohol-water mixed solution. By adopting the mixing mode, the discharge specific capacity and the first-week coulomb efficiency of the prepared nickel-based positive electrode material can be obviously improved.
In the present invention, the conditions of the first mixing are not particularly limited as long as the precursor, the T-element-containing compound and the alcohol are uniformly mixed.
In the present invention, the kind and amount of the alcohol used in the first mixing process are not particularly limited as long as the precursor and the T-element-containing compound can be dissolved. Preferably, the alcohol is selected from at least one of methanol, ethanol, ethylene glycol, propylene glycol, and glycerol. Preferably, the alcohol is used in an amount of 50-500mL during the first mixing process relative to 50g of the precursor.
In a preferred embodiment of the invention, the molar ratio of the compound containing the element T, calculated as element T, to the precursor, calculated as (Ni+Co+M), is (0-0.5): 1, preferably (0-0.1): 1, wherein the molar amount of the compound containing the element T is not 0.
In a preferred embodiment of the present invention, the T-element-containing compound is selected from T-element-containing organic ester compounds, preferably at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetramethyl zirconate, tetraethyl zirconate, tetrapropyl zirconate, tetrabutyl zirconate, tetramethyl hafnate, tetraethyl hafnate, tetrapropyl hafnate, and tetrabutyl hafnate.
In a preferred embodiment of the present invention, the conditions of the second mixing include: the stirring speed is 500-2000rpm.
In a preferred embodiment of the present invention, the mass ratio of the precursor to the aqueous alcohol mixture solution is 1 (0.2-10), preferably 1 (1-8).
According to a preferred embodiment of the present invention, the alcohol-water mixed solution has a volume ratio of alcohol to water of (0.1 to 10): 1, preferably (0.5 to 5): 1.
In the present invention, in the step (2), the drying may be performed by a method conventional in the art, and preferably, the drying conditions include: the temperature is 60-150 ℃ and the time is 4-24h.
In the present invention, step (3) includes: and mixing the intermediate product with a lithium source and performing solid phase reaction to obtain the nickel-based anode material.
In the present invention, the lithium source may be present in the form of a lithium salt, and the lithium salt is preferably at least one selected from the group consisting of lithium nitrate, lithium chloride, lithium carbonate, lithium hydroxide, lithium acetate, and hydrates thereof.
In a preferred embodiment of the invention, the molar ratio of the lithium source in terms of Li element to the precursor in terms of (Ni+Co+M) is (0.9-1.3): 1, for example 0.9, 0.95, 1.00, 1.05, 1.10, 1.15, 1.20, 1.30, and any value in the range consisting of any two of these values.
In the present invention, the mixing method of the positive electrode material precursor and the lithium source is not particularly limited as long as the mixing uniformity can be ensured. Preferably, the mixing can be achieved by a high-speed mixer, ball milling and the like.
In a preferred embodiment of the invention, the solid phase reaction comprises a calcination treatment. The method of the firing treatment may not be particularly limited, and preferably the firing treatment includes a first firing and a second firing. The adoption of the preferred embodiment can not only reduce the energy consumption of roasting, but also obtain the layered anode material with more complete crystal structure.
Wherein, preferably, the conditions of the first firing include: the firing temperature is 300 to 600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ and any value in the range of any two of these values, more preferably, the firing temperature is 450 to 550 ℃; preferably, the first calcination time is 1 to 10 hours, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, and any value in the range of any two of these values, and more preferably, the calcination time is 4 to 8 hours.
Wherein, preferably, the conditions of the second firing include: the firing temperature may be 600 to 1000 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃,1000 ℃ and any value in the range of any two of these values, more preferably 750 to 900 ℃; preferably, the first calcination time is 4 to 48 hours, for example, may be 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours, 48 hours, and any value in the range of any two of these values, more preferably, the calcination time is 8 to 24 hours.
According to the method provided by the present invention, the temperature rising rate of the temperature rising process to the temperatures of the first firing and the second firing is not particularly limited, and is preferably 0.5 to 10 ℃/min, for example, 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 3 ℃/min, 5 ℃/min, 10 ℃/min, and any value in the range constituted by any two of these values.
In the present invention, specifically, the mixed materials may be baked in an atmosphere furnace, and the baking atmosphere may be at least one of air, oxygen, and an inert atmosphere such as nitrogen.
In a third aspect, the present invention provides a nickel-based positive electrode material obtained by the method described in the second aspect. The properties of the nickel-based positive electrode material have been described in detail in the first aspect, and the description thereof will not be repeated.
A fourth aspect of the present invention provides a lithium ion battery comprising the nickel-based positive electrode material according to the first or third aspect. The inventor of the invention discovers in research that the nickel-based positive electrode material provided by the invention is used in a lithium ion battery, and can improve the discharge capacity and the first-week coulombic efficiency of the lithium ion battery.
The structure of the lithium ion battery provided by the invention can be known to those skilled in the art, and generally, the lithium ion battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm; the positive electrode and the negative electrode may be prepared by coating and drying a composite for forming a positive electrode-containing material and a composite for forming a negative electrode-containing material on respective current collectors.
In the present invention, the positive electrode composite may be prepared by a positive electrode material, a conductive agent, a binder, and a solvent.
In the present invention, the conductive agent used in the positive electrode composite is not particularly limited as long as it has conductivity and remains stable in the charge-discharge range. Preferably, the conductive agent is at least one selected from acetylene black, ketjen black, artificial graphite, natural graphite, carbon tube, graphene, superconducting carbon, carbon nanofiber, carbon dot, aluminum powder, nickel powder, titanium oxide, and conductive polymer.
In the present invention, the binder used in the positive electrode composite is not particularly limited as long as it provides adhesion of the positive electrode material, the conductive agent, and the current collector. Preferably, the binder is selected from at least one of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), aqueous acrylic resin, polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), ethylene-vinyl acetate (EVA), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoroethylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylic resin.
In the present invention, the positive electrode current collector is not particularly limited as long as it has appropriate conductivity. Preferably, the material of the positive electrode current collector may be aluminum, nickel, copper, titanium, silver, stainless steel or carbon material, and the positive electrode current collector may be processed into various forms such as foil, sheet, film, net, hole, non-woven fabric, etc.
In a preferred embodiment of the present invention, the solvent used in the positive electrode composite may be N-methylpyrrolidone.
In the present invention, the anode composite may be prepared by an anode material, a conductive agent, a binder, and a solvent.
In the present invention, the kind of the negative electrode material is not particularly limited, and one skilled in the art can select according to actual requirements. Preferably, the negative electrode material is selected from at least one of artificial graphite, natural graphite, soft carbon, hard carbon, mesophase microspheres (MCMB), carbon fiber, lithium metal, silicon oxide, lithium metal alloy, and lithium titanate.
In the present invention, the conductive agent and the binder used in the negative electrode composite are not particularly limited, and preferably, the conductive agent and the binder used in the negative electrode composite may be of the same type and content as those used in the preparation of the positive electrode composite.
In a preferred embodiment of the present invention, the solvent used in the negative electrode composite may be water.
In the present invention, the negative electrode current collector is not particularly limited as long as it has appropriate conductivity. Preferably, the material of the negative electrode current collector may be aluminum, nickel, copper, titanium, silver, stainless steel or carbon material, and the negative electrode current collector may be processed into various forms such as foil, sheet, film, net, hole, non-woven fabric, etc.
In the present invention, the electrolyte may be a solid electrolyte such as a polymer electrolyte, an inorganic solid electrolyte, or the like; or may be a liquid electrolyte containing a lithium salt and a solvent.
In a preferred embodiment of the present invention, the polymer electrolyte is selected from at least one of polyvinyl alcohol, phosphate polymer, polyvinylidene fluoride, polyoxyethylene derivative, polyoxypropylene derivative, polyethylene derivative and polyester sulfide.
In a preferred embodiment of the present invention, the inorganic solid electrolyte is selected from at least one of Li2S、Li2S-P2S5、LiI、Li-La-Zr-O、Li-Ge-V-O、Li3N、Li4SiO4、LiPON、LISION、Li-Al-Ti-P、Li3PO4-Li2S-SiS2、LiBH4、LiBH4-LiX(X＝Cl、Br or I), liBH 4-LiNH2、LiNH2、Li3AlH6、Li2 NH, and Li 2O-B2O3-P2O5.
In the present invention, the liquid electrolyte is a solution of a lithium salt in a solvent, which may be a nonaqueous solvent, preferably at least one selected from the group consisting of Ethylene Carbonate (EC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene Carbonate (PC), ethylene Propylene Carbonate (EPC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), methyl Formate (MF), ethyl formate (Eft), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), and propyl Butyrate (BP).
In a preferred embodiment of the present invention, the lithium salt is selected from at least one of lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium perchlorate (LiClO 4), lithium hexafluoroarsenate (LiAsF 6), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoro (lidaob) oxalato borate (lipob), lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiPO 2F2), lithium difluoro (LiDFOP) oxalato phosphate, and lithium tetrafluorooxalato borate (LiTFOP).
In the invention, in order to improve the performance of the lithium ion battery, additives can be optionally added into the electrolyte. The additive is preferably at least one selected from the group consisting of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), tris (trimethylsilane) phosphate (TMSP), sulfonate cyclic quaternary ammonium salt, ethylene sulfite (DTO), dimethyl sulfite (DMS), 1-propylene-1, 3-sultone (PST), 4-propylethylene sulfate (PEGLST), diethyl sulfite (DES), adiponitrile (ADN), succinonitrile (SN), 1, 3-propane sultone (1, 3-PS), vinyl sulfate (DTD) and 4-methyl ethylene sulfate (PCS).
In the invention, the diaphragm is arranged between the anode and the cathode to isolate the anode from the cathode. The separator may be various separators conventionally used in the art, and preferably, the separator may be polyolefin such as polyethylene, polypropylene, a composite of polyethylene and polypropylene, a sheet formed of glass fiber, nonwoven fabric, or the like. When a solid electrolyte is used, the solid electrolyte may also be used as a separator.
The preparation method of the lithium ion battery is not particularly limited, and can be prepared by adopting a method conventional in the art. Preferably, the preparation method of the lithium ion battery comprises the following steps: uniformly mixing a positive electrode material, a conductive agent, a binder and a solvent, coating on at least one surface of a positive electrode current collector, drying, rolling and slicing to obtain a positive electrode; uniformly mixing a negative electrode material, a conductive agent, a binder and a solvent, coating on at least one surface of a negative electrode current collector, drying, rolling and slicing to obtain a negative electrode; and assembling the positive electrode, the diaphragm and the negative electrode into a laminated or coiled battery cell, placing the battery cell in a shell, injecting electrolyte, and packaging to obtain the lithium ion battery.
In the present invention, the amounts of the positive and negative electrode materials, the conductive agent and the binder are not particularly limited, and preferably, the mass content of the positive electrode material or the negative electrode material is 50 to 99wt%, the mass content of the conductive agent is 0.5 to 25wt%, and the mass content of the binder is 0.5 to 25wt%, based on the solid content of the positive electrode or the negative electrode composite.
The present invention will be described in detail by examples. In the following examples and comparative examples,
Scanning Electron Microscopy (SEM) was obtained by scanning electron microscopy of the ZEISS Merlin model of ZEISS company, ZEISS, germany;
the X-ray diffraction pattern (XRD) was measured by an X-ray diffractometer model D8 ADVANCE SS of Bruce, germany;
In the following examples and comparative examples, all the materials involved are commercially available unless otherwise specified.
Example 1
This example is used to illustrate the preparation and evaluation methods of the nickel-based positive electrode material according to the present invention.
(1) Preparation of nickel-based positive electrode material
Preparing a metal salt solution, wherein the total metal concentration is 3mol/L, and the molar ratio of nickel, cobalt and manganese elements in the metal salt solution is 8:1:1, and nickel sulfate, cobalt sulfate and manganese sulfate are used in the preparation process; preparing NaOH solution with the concentration of 5 mol/L; preparing complexing agent ammonia water solution, wherein the concentration of ammonia water is 5mol/L.
An ammonia water solution accounting for 30 percent of the volume of the reaction kettle is added in advance, and the concentration is 0.5mol/L. The metal salt solution, the NaOH solution and the complexing agent solution are added into a reaction kettle at the same time to carry out precipitation reaction, the stirring speed is controlled to be 800rpm, and the reaction temperature is 55 ℃. The initial volume flow rate ratio of the metal salt solution to the complexing agent solution is controlled to be 4, then the flow rate of the metal salt solution is kept unchanged, and the feeding flow rate of the complexing agent is controlled, so that the concentration of the complexing agent in the system is gradually increased, the increasing rate of the concentration of the complexing agent is gradually reduced, and the change of the concentration of the complexing agent in the system along with the reaction time is shown in figure 4. The flow rate of the NaOH solution was controlled so that the pH of the reaction system was maintained around 11.6 throughout the reaction. Wherein the solid content of the reaction system at the 6 th hour is 4.8wt%, and the concentration of the ammonia water in the system at the end of the reaction is about 1.06mol/L. Stopping the reaction when the reaction time reaches the target particle size after about 48 hours, carrying out vacuum suction filtration on the slurry, washing 3 times by deionized water, and drying and dehydrating for 12 hours in a vacuum drying oven at 120 ℃ to obtain a positive electrode material precursor A1.
50G of the A1 precursor, 250mL of ethanol solution and tetrabutyl hafnate are taken, wherein the molar ratio of Hf (Ni+Co+Mn) is controlled to be 0.01, and the mixture B1 is obtained after uniform stirring.
300ML of a mixed solution of water and ethanol with a volume ratio of 1:1 was prepared, and the mixed solution of water and ethanol was slowly added dropwise to the mixture B1, while maintaining a stirring speed of 500rpm during the addition. Filtering after the dripping is finished, and drying and dehydrating for 12 hours in a vacuum drying oven at 120 ℃ to obtain an intermediate product C1.
Taking 10g of intermediate product C1, adding a lithium source LiOH H 2 O to ensure that the molar ratio of Li (Ni+Co+Mn) is 1.02:1, uniformly mixing the intermediate product C1 and LiOH H 2 O, and loading into a crucible for step-by-step sintering, wherein the method comprises the following steps: heating to 450 ℃ from room temperature at 5 ℃/min, preserving heat for 6 hours, and performing a second step: heating to 850 ℃ from 450 ℃ at 5 ℃/min, preserving heat for 12 hours, and naturally cooling to obtain the nickel-based anode material.
(2) Evaluation of Nickel-based Positive electrode Material
SEM characterization was performed on the nickel-based cathode material prepared as described above, as shown in fig. 1. As can be seen from the figure, the nickel-based positive electrode material with good sphericity can be obtained by adopting the preparation method provided by the invention, and the positive electrode material is a secondary microsphere formed by stacking primary particles. The primary particles are between 20 and 800nm in size and the secondary microspheres are about 10.6 μm in size.
As shown in the figure 2, the result of XRD characterization on the nickel-based positive electrode material prepared by the preparation method provided by the invention is that the main diffraction peak of the nickel-based positive electrode material prepared by the preparation method provided by the invention is consistent with the alpha-NaFeO 2 of a hexagonal structure, so that a good layered crystal structure is formed, the lithium-nickel mixed discharge proportion of the nickel-based positive electrode material is 1.52% through structural refinement, and the lithium-nickel mixed discharge proportion is low, thereby being beneficial to capacity exertion of the nickel-based positive electrode material. The XRD diffraction pattern of the nickel-based positive electrode material is shown in figure 3, and diffraction peaks belonging to Li-Hf-O can be clearly seen in the range of 20-30 degrees in addition to diffraction peaks of the layered structure, which indicates that the chemical structure of Li-Hf-O is contained in the nickel-based positive electrode material.
Taking the positive electrode material, acetylene black and polyvinylidene fluoride solution with the mass percent of 10%, and according to the positive electrode material: acetylene black: uniformly mixing polyvinylidene fluoride in a mass ratio of 90:5:5, coating the mixture on an aluminum foil, drying a solvent, slicing to obtain a positive electrode plate, using metallic lithium as a negative electrode plate, using a polypropylene diaphragm of CELLLGARD2400 as a diaphragm, using a liquid electrolyte as an electrolyte, using a mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1, and using lithium hexafluorophosphate LiPF 6 as a solute in a molar concentration of 1mol/L. The 2025 type button cell was assembled in an inert atmosphere glove box with moisture and oxygen contents below 0.1ppm.
The electrochemical performance of the nickel-based positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the charge-discharge curve at 0.1C multiplying power is shown in figure 5, the initial discharge specific capacity at 0.1C multiplying power is 216.3mAh/g, and the initial cycle coulomb efficiency reaches 93%; as shown in FIG. 6, the charge-discharge curve at 1C rate can reach 196.4mAh/g.
Example 2
This example is used to illustrate the preparation and evaluation methods of the nickel-based positive electrode material according to the present invention.
(1) Preparation of nickel-based positive electrode material
Preparing a metal salt solution, wherein the total metal concentration is 2mol/L, and the molar ratio of nickel, cobalt and aluminum elements in the metal salt solution is 8:1.5:0.5, and nickel sulfate, cobalt sulfate and aluminum sulfate are used in the preparation process; preparing NaOH solution with the concentration of 5 mol/L; preparing complexing agent ammonia water solution, wherein the concentration of ammonia water is 4mol/L.
An ammonia water solution accounting for 20 percent of the volume of the reaction kettle is added in advance, and the concentration of the ammonia water is 0.5mol/L. The metal salt solution, the NaOH solution and the complexing agent solution are added into a reaction kettle at the same time to carry out precipitation reaction, the stirring speed is controlled to be 1000rpm, and the reaction temperature is 50 ℃. The initial volume flow rate ratio of the metal salt solution to the complexing agent solution is controlled to be 4, then the flow rate of the metal salt solution is kept unchanged, and the feeding flow rate of the complexing agent is controlled, so that the change of the concentration of the complexing agent in the system along with the reaction time is the same as that of the embodiment 1. The flow rate of NaOH solution was controlled so that the pH during the reaction was maintained around 11.4. Wherein the solid content of the reaction system in the 6 th hour is 4.1wt%, the reaction is stopped when the target particle size is reached after the reaction time is about 48 hours, the slurry is subjected to vacuum suction filtration, and after washing for 3 times by deionized water, the slurry is dried and dehydrated in a vacuum drying oven at 120 ℃ for 12 hours, so that the positive electrode material precursor A2 is obtained.
50G of the A2 precursor, 250mL of ethanol solution and tetraethyl hafnate are taken, wherein the molar ratio of Hf (Ni+Co+Al) is controlled to be 0.01, and the mixture B2 is obtained after uniform stirring.
400ML of a mixed solution of water and ethanol with a volume ratio of 1:2 was prepared, and the mixed solution of water and ethanol was slowly added dropwise to the mixture B2, while maintaining a stirring speed of 500rpm during the addition. Filtering after the dripping is finished, and drying and dehydrating for 12 hours in a vacuum drying oven at 120 ℃ to obtain an intermediate product C2.
Taking 10g of intermediate product C2, adding a lithium source LiOH H 2 O to ensure that the molar ratio of Li (Ni+Co+Al) is 1.1:1, uniformly mixing the intermediate product C2 and LiOH H 2 O, and loading into a crucible for step-by-step sintering, wherein the method comprises the following steps: heating to 480 ℃ from room temperature at 10 ℃/min, preserving heat for 6 hours, and performing a second step: heating to 820 ℃ from 480 ℃ at 10 ℃/min, preserving heat for 12 hours, and naturally cooling to obtain the nickel-based anode material.
(2) Evaluation of Nickel-based Positive electrode Material
SEM and XRD tests were performed on the nickel-based positive electrode material obtained, and the SEM pattern was similar to fig. 1 and the XRD pattern was similar to fig. 2 and 3.
A lithium ion battery was prepared as described in example 1.
The electrochemical performance of the nickel-based positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the initial discharge specific capacity at 0.1C multiplying power is 215.9mAh/g, the initial cycle coulomb efficiency reaches 92.9%, and the discharge specific capacity at 1C multiplying power can also reach 195.8mAh/g.
Example 3
This example is used to illustrate the preparation and evaluation methods of the nickel-based positive electrode material according to the present invention.
(1) Preparation of nickel-based positive electrode material
A positive electrode material precursor A1 was obtained as in example 1.
50G of the A1 precursor, 250mL of ethylene glycol solution and tetrapropyl titanate are taken, wherein the molar ratio of Ti (Ni+Co+Mn) is controlled to be 0.01, and the mixture B3 is obtained after uniform stirring.
200ML of a mixed solution of water and ethylene glycol was prepared in a volume ratio of 2:1, and the mixed solution of water and ethylene glycol was slowly added dropwise to the mixture B3, while maintaining a stirring speed of 500rpm during the addition. Filtering after the dripping is finished, and drying and dehydrating for 12 hours in a vacuum drying oven at 120 ℃ to obtain an intermediate product C3.
Taking 10g of intermediate product C3, adding lithium source LiOH H 2 O to make the mole ratio of Li (Ni+Co+Mn) be 1.2:1, uniformly mixing intermediate product C3 and LiOH H 2 O, loading into a crucible, and sintering step by step, wherein the first step is as follows: heating to 500 ℃ from room temperature at 5 ℃/min, preserving heat for 7 hours, and performing a second step: heating to 800 ℃ from 500 ℃ at 5 ℃/min, preserving heat for 12 hours, and naturally cooling to obtain the nickel-based anode material.
(2) Evaluation of Nickel-based Positive electrode Material
SEM and XRD tests were performed on the nickel-based positive electrode material obtained, and the SEM pattern was similar to fig. 1 and the XRD pattern was similar to fig. 2 and 3.
A lithium ion battery was prepared as described in example 1.
The electrochemical performance of the positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the first discharge specific capacity at 0.1C multiplying power is 214.1mAh/g, the first week coulomb efficiency reaches 92.5%, and the discharge specific capacity at 1C multiplying power can also reach 193.4mAh/g.
Example 4
This example is used to illustrate the preparation and evaluation methods of the nickel-based positive electrode material according to the present invention.
(1) Preparation of nickel-based positive electrode material
A positive electrode material precursor A1 was obtained as in example 1.
50G of the A1 precursor, 250mL of propylene glycol solution and tetramethyl zirconate are taken, wherein the molar ratio of Zr (Ni+Co+Mn) is controlled to be 0.01, and the mixture B4 is obtained after uniform stirring.
250ML of a mixed solution of water and glycerol was prepared in a volume ratio of 1:1, and the whole mixed solution of water and glycerol was slowly added dropwise to the mixture B4, while maintaining a stirring speed of 500rpm during the addition. Filtering after the dripping is finished, and drying and dehydrating for 12 hours in a vacuum drying oven at 120 ℃ to obtain an intermediate product C4.
Taking 10g of intermediate product C4, adding lithium source LiOH H 2 O to make the molar ratio of Li (Ni+Co+Mn) be 0.95:1, uniformly mixing intermediate product C4 and LiOH H 2 O, loading into a crucible, and sintering step by step, wherein the first step is as follows: heating to 550 ℃ from room temperature at 5 ℃/min, preserving heat for 6 hours, and performing a second step: heating to 750 ℃ from 550 ℃ at 5 ℃/min, preserving heat for 18 hours, and naturally cooling to obtain the nickel-based anode material.
(2) Evaluation of Nickel-based Positive electrode Material
SEM and XRD tests were performed on the nickel-based positive electrode material obtained, and the SEM pattern was similar to fig. 1 and the XRD pattern was similar to fig. 2 and 3.
A lithium ion battery was prepared as described in example 1.
The electrochemical performance of the positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the first discharge specific capacity at 0.1C multiplying power is 213.2mAh/g, the first week coulomb efficiency reaches 91.8%, and the discharge specific capacity at 1C multiplying power can also reach 192.1mAh/g.
Example 5
(1) Preparation of nickel-based positive electrode material
A nickel-based cathode material was prepared in the same manner as in example 1 except that the molar ratio of Hf (Ni+Co+Mn) was 0.05.
(2) Evaluation of Nickel-based Positive electrode Material
SEM and XRD tests were performed on the nickel-based positive electrode material obtained, and the SEM pattern was similar to fig. 1 and the XRD pattern was similar to fig. 2 and 3.
A lithium ion battery was prepared as described in example 1.
The electrochemical performance of the positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the first discharge specific capacity at 0.1C multiplying power is 210.2mAh/g, the first week coulomb efficiency reaches 91.8%, and the discharge specific capacity at 1C multiplying power can also reach 191.2mAh/g.
Example 6
(1) Preparation of nickel-based positive electrode material
A nickel-based cathode material was prepared in the same manner as in example 1 except that the molar ratio of Hf (Ni+Co+Mn) was 0.002.
(2) Evaluation of Nickel-based Positive electrode Material
SEM and XRD tests were performed on the nickel-based positive electrode material obtained, and the SEM pattern was similar to fig. 1 and the XRD pattern was similar to fig. 2 and 3.
A lithium ion battery was prepared as described in example 1.
The electrochemical performance of the positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the first discharge specific capacity at 0.1C multiplying power is 212.5mAh/g, the first week coulomb efficiency reaches 92%, and the discharge specific capacity at 1C multiplying power can also reach 192.7mAh/g.
Example 7
(1) Preparation of nickel-based positive electrode material
A nickel-based cathode material was prepared as in example 1, except that intermediate C1 was prepared as follows:
50g of A1 precursor, 400mL of ethanol solution, 150mL of water and tetrabutyl hafnate were stirred at 500rpm for 4 hours to obtain a mixture, which was then filtered and dried in a vacuum oven at 120℃for 12 hours to obtain intermediate C1. Wherein the molar ratio of Hf (Ni+Co+Mn) is controlled to be 0.01.
(2) Evaluation of Nickel-based Positive electrode Material
SEM and XRD tests were performed on the nickel-based positive electrode material obtained, and the SEM pattern was similar to fig. 1 and the XRD pattern was similar to fig. 2 and 3.
A lithium ion battery was prepared as described in example 1.
The electrochemical performance of the positive electrode material is measured in the charge-discharge voltage range of 2.8-4.3V, the first discharge specific capacity at 0.1C multiplying power is 209.6mAh/g, the first week coulomb efficiency reaches 90.7%, and the discharge specific capacity at 1C multiplying power can also reach 189.5mAh/g.
In conclusion, the nickel-based positive electrode material prepared by the method provided by the invention has higher specific discharge capacity and first-week coulomb efficiency, and is obviously superior to that of the comparative example.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A nickel-based positive electrode material, characterized in that the nickel-based positive electrode material comprises: a compound having a chemical composition of Li aNixCoyMzO2, an oxide containing T element supported on the compound; wherein a is more than or equal to 0.9 and less than or equal to 1.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than 1, and x+y+z=1; and M is at least one of a VIIB group element and a IIIA group element, T is at least one of an IVB group element, and the nickel-based positive electrode material contains a Li-T-O chemical bond.
2. The nickel-based positive electrode material according to claim 1, wherein the T element is selected from at least one of Ti, zr, and Hf;
preferably, said M is selected from Mn and/or Al;
Preferably, the molar ratio of the oxide containing the T element in terms of the T element to the compound having the chemical composition Li aNixCoyMzO2 in terms of (Ni+Co+M) is (0-0.1): 1, wherein the molar amount of the oxide containing the T element is not 0;
Preferably, in the compound having the chemical composition Li aNixCoyMzO2, 0.9.ltoreq.a.ltoreq. 1.3,0.5.ltoreq.x.ltoreq.0.95, 0.ltoreq.y.ltoreq.0.5, 0.ltoreq.z.ltoreq.0.5, and x+y+z=1.
3. The nickel-based positive electrode material according to claim 1 or 2, wherein the nickel-based positive electrode material is a secondary microsphere formed by agglomeration of primary particles, the secondary microsphere having a particle size of 1-30 μm, preferably 1-20 μm.
4. A method of preparing a nickel-based positive electrode material, the method comprising the steps of:
(1) Performing coprecipitation reaction on the metal salt solution, the precipitator solution and the complexing agent solution to obtain a precursor;
(2) Mixing the precursor, the compound containing the T element, alcohol and water, filtering and drying to obtain an intermediate product;
(3) Mixing the intermediate product with a lithium source and performing solid phase reaction to obtain the nickel-based anode material;
Wherein the metal salt contains at least one of Ni, co and M elements, and M is at least one of VIIB group elements and IIIA group elements; the T element is at least one selected from IVB group elements.
5. The method of claim 4, wherein in step (2), the method of mixing comprises: firstly mixing the precursor, a compound containing a T element and alcohol to obtain a mixture; and then carrying out second mixing on the mixture and the alcohol-water mixed solution.
6. The method according to claim 5, wherein the mass ratio of the precursor to the alcohol-water mixed solution is 1 (0.2-10);
Preferably, the volume ratio of alcohol to water in the alcohol-water mixed solution is (0.1-10): 1, preferably (0.5-5): 1.
7. The method according to any one of claims 4 to 6, wherein the molar ratio of the T-containing compound in terms of T element to the precursor in terms of (ni+co+m) is (0-0.5): 1, preferably (0-0.1): 1, wherein the molar amount of the T-containing compound is not 0;
preferably, the T element is selected from at least one of Ti, zr, and Hf;
preferably, the T-element-containing compound is selected from T-element-containing organic ester compounds, preferably at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetramethyl zirconate, tetraethyl zirconate, tetrapropyl zirconate, tetrabutyl zirconate, tetramethyl hafnate, tetraethyl hafnate, tetrapropyl hafnate, and tetrabutyl hafnate;
Preferably, the alcohol is selected from at least one of methanol, ethanol, ethylene glycol, propylene glycol, and glycerol.
8. The method of any of claims 4-7, wherein the lithium source is selected from at least one of lithium nitrate, lithium chloride, lithium carbonate, lithium hydroxide, lithium acetate, and hydrates thereof;
Preferably, the molar ratio of the lithium source in terms of Li element to the precursor in terms of (Ni+Co+M) is (0.9-1.3): 1.
9. The method according to any one of claims 4 to 8, wherein in the step (3), the solid phase reaction includes a calcination treatment;
preferably, the firing treatment includes a first firing and a second firing;
preferably, the conditions of the first firing include: the temperature is 300-600deg.C, preferably 450-550deg.C; the time is 1-10h, preferably 4-8h;
Preferably, the conditions of the second firing include: the temperature is 600-1000 ℃, preferably 750-900 ℃; the time is 4-48 hours, preferably 8-24 hours.
10. The method according to any one of claims 4 to 9, wherein in the step (1), the concentration of the complexing agent in the coprecipitation reaction system gradually increases, and the rate of change of the concentration of the complexing agent gradually decreases;
Preferably, the concentration of the complexing agent is varied at a rate of 1 mol/L.multidot.h or less, preferably from 0.001 to 1 mol/L.multidot.h, more preferably from 0.001 to 0.5 mol/L.multidot.h;
preferably, the coprecipitation reaction time is recorded as R hours, and the concentration change rate of the complexing agent is not lower than 0.021 mol/L.h in the first 1/8R hours of the reaction;
preferably, the time from adding the complexing agent to 80% or more of the concentration of the complexing agent at the end of the reaction in the coprecipitation reaction system is not more than 1/4R hours;
Preferably, the concentration of complexing agent at the end of the reaction is from 0.05 to 2mol/L, preferably from 0.05 to 1.2mol/L.
11. The process according to any one of claims 4 to 10, wherein the coprecipitation reaction time is denoted R hours, and the solid content of the precipitation reaction system is not higher than 7wt%, preferably not higher than 5wt%, within the first 1/8R hours of the start of the reaction.
12. The method of any one of claims 4-11, wherein the conditions of the coprecipitation reaction include: the temperature is 20-70deg.C, preferably 45-60deg.C; the pH value is 8-14, preferably 10-12; the reaction time is not less than 10 hours, preferably 12-96 hours; the stirring speed is 50-1200r/min, preferably 600-1200r/min.
13. The process according to any one of claims 4 to 12, wherein the concentration of the metal salt solution is 0.01 to 5mol/L, preferably 0.01 to 4mol/L, in terms of metal element;
preferably, the concentration of the precipitant solution is 0.01-16mol/L, preferably 2-12mol/L;
preferably, the concentration of the complexing agent solution is 0.01-16mol/L, preferably 2-15mol/L;
Preferably, in the metal salt solution, the molar ratio of Ni, co and M is (0-1): 0-1, preferably (0.5-0.95): 0-0.5, wherein the molar amount of Ni is not 0;
preferably, said M is selected from Mn and/or Al;
Preferably, the complexing agent is selected from at least one of an ammonium ion donor, an alcohol amine complexing agent, an aminocarboxylic acid complexing agent, a hydroxyamino carboxylic acid complexing agent, a carboxylate complexing agent and a thiocyanate complexing agent;
preferably, the precipitant is selected from at least one of alkali metal hydroxide, carbonate and bicarbonate;
Preferably, the alkali metal is selected from at least one of Na, K and Li.
14. A nickel-based positive electrode material produced by the method of any one of claims 4 to 13.
15. A lithium ion battery, characterized in that it comprises the nickel-based positive electrode material according to any one of claims 1-3, 14.
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