CN116750809A - Modified ternary positive electrode material and preparation method thereof - Google Patents
Modified ternary positive electrode material and preparation method thereof Download PDFInfo
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- CN116750809A CN116750809A CN202310815604.0A CN202310815604A CN116750809A CN 116750809 A CN116750809 A CN 116750809A CN 202310815604 A CN202310815604 A CN 202310815604A CN 116750809 A CN116750809 A CN 116750809A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims description 30
- -1 aluminum dihydroxyglycolate Chemical compound 0.000 claims description 21
- 239000010405 anode material Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CYWDDBNPXTUVNN-UHFFFAOYSA-I 2-ethylhexanoate;niobium(5+) Chemical compound [Nb+5].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O CYWDDBNPXTUVNN-UHFFFAOYSA-I 0.000 claims description 4
- GIMXAEZBXRIECN-UHFFFAOYSA-J 2-hydroxyacetate;titanium(4+) Chemical compound [Ti+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O GIMXAEZBXRIECN-UHFFFAOYSA-J 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- HNGGTLCGILLNOV-UHFFFAOYSA-N [W].C1=CCCC=CCC1 Chemical compound [W].C1=CCCC=CCC1 HNGGTLCGILLNOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 2
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ASKHRHGGZBQNEA-UHFFFAOYSA-N dimethylazanide;niobium(5+) Chemical compound [Nb+5].C[N-]C.C[N-]C.C[N-]C.C[N-]C.C[N-]C ASKHRHGGZBQNEA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SLFNBFCWCWWIIB-UHFFFAOYSA-N 2-(dihydroxyamino)acetic acid Chemical compound ON(O)CC(O)=O SLFNBFCWCWWIIB-UHFFFAOYSA-N 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/32—Spheres
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- C01—INORGANIC CHEMISTRY
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a modified ternary positive electrode material and a preparation method thereof. The invention provides a preparation method of a modified low-residual-alkali ternary positive electrode material by adopting a wet coating mode in combination with a water washing process. The method can remove residual LiOH and Li on the ternary positive electrode material 2 CO 3 And lithium impurities are removed, the cycling stability of the ternary positive electrode material can be obviously improved, and the method has industrial production application prospects. The invention carries out surface modification while washing, metal oxide is obtained by high-temperature sintering metal-containing organic matters to form a coating layer, and metal ions can permeate and dope into the ternary positive electrode. Surface of the bodyThe modification not only reduces pulverization and breakage of NCM particles in circulation, but also can effectively stabilize the crystal structure of NCM, reduce cation mixing and discharge and generation of rock salt structure, thereby improving electrochemical stability of the electrode.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a modified ternary positive electrode material and a preparation method thereof.
Background
The lithium ion battery is a chemical energy storage device with high energy conversion efficiency, and is one of the most widely used chemical power supplies at present because of the advantages of high energy density, low self discharge, high voltage, no memory effect, long cycle life and the like. Among numerous lithium ion battery positive electrode materials, layered Nickel Cobalt Manganese (NCM) ternary positive electrode material LiNi with high specific discharge capacity and high discharge voltage x Co y M (1-x-y) O 2 The advantages of reversible capacity, efficiency capability, capital cost and the like quickly become the first choice of the high-energy-density battery.
In the ternary positive electrode material, nickel is the most main active element, and the higher the nickel content is, the higher the discharge specific capacity is, but a series of new problems such as unstable surface properties, lithium nickel mixed discharge, inter-crystal microcracks and the like are brought along with the increase of the nickel content.
Coating and doping are often employed in the prior art to effect modification of the ternary cathode material. During modification, ternary positive electrode material and nano metal oxide are mixed in a dry method, and then a coating layer is formed through high-temperature sintering, so that metal ions are doped into material lattices. The excellent coating material can effectively improve the structural stability of the ternary positive electrode material, prevent the bulk phase material from side reaction with electrolyte, and further improve the cycle performance and the multiplying power performance of the material. The doping of the ternary anode material can maintain the layered structure of the material in the charge-discharge process, so that the lithium-nickel mixed discharge is effectively reduced, and the cycle stability is further improved. However, the nano metal oxide has higher cost, and increases the production cost of the ternary positive electrode material.
In addition, with the increase of the nickel content, liOH and Li with higher electrode surface can be caused 2 CO 3 And residual alkaline lithium impurities. Higher LiOH on the surface of the material increases its pH, resulting in gel formation during electrode processing. In addition, li 2 CO 3 Gas is generated during the cycling process, which affects the cycle life and safety performance of the battery. Water washing is an effective method for removing residual alkali on the surface.However, since the nickel-rich ternary anode is very sensitive to water, the storage stability of the nickel-rich ternary anode is poor after water washing, and the clean surface is more easily corroded by electrolyte to form a litho-salt passivation structure.
In the prior art, a process method for improving the ternary cathode material is also disclosed, for example, chinese patent publication No. CN113488643A discloses a surface coating modification method for the ternary cathode material of a lithium ion battery, and the coating modification of the surface of the ternary cathode material of the lithium ion battery is realized by depositing an alumina film on the surface of a ternary cathode electrode plate of the lithium ion battery, and the method has the advantages of short preparation period, low energy consumption and the like, however, the capacity retention rate of the cathode material prepared by the patent after 1C multiplying power circulation is still to be improved.
Based on the method, the organic aluminum source is used as a coating agent to coat the ternary positive electrode material (such as NCM) of the lithium ion battery, and the electrochemical performance such as capacitance and the like of the prepared modified positive electrode material is improved by adjusting the raw material proportion, the technological parameters and the specific working procedures.
Disclosure of Invention
The invention aims to provide a preparation method of a modified low-residual-alkali ternary positive electrode material by adopting a wet coating mode in combination with a water washing process aiming at the defects in the prior art. The method can remove residual LiOH and Li on the ternary positive electrode material 2 CO 3 And the lithium impurities are removed, the cycling stability of the ternary positive electrode material can be obviously improved, and the method is simple in process, low in cost, convenient to operate and excellent in performance, and has industrial production application prospects. In addition, the wet coating combined with the water washing process can also combine the water washing and mixing processes in the traditional process, so that the process cost is reduced.
Furthermore, the invention also provides a method for preparing the modified ternary positive electrode material by dry coating, which comprises the steps of directly coating a coating agent on the surface of the ternary positive electrode material, and then carrying out high-temperature heat treatment to obtain the modified ternary positive electrode material so as to overcome the defect of poor cycling stability of the ternary positive electrode material.
Further, the application of the modified ternary positive electrode material in preparing lithium ion batteries is also provided.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for preparing a modified ternary positive electrode material by wet cladding comprises the following steps:
1) Preparing a coating agent solution;
2) Mixing the ternary positive electrode material with the coating agent solution in the step 1) according to a certain proportion, stirring and uniformly mixing, and then carrying out suction filtration and drying to obtain the ternary positive electrode material coated by the coating agent;
3) And (3) placing the ternary positive electrode material coated by the coating agent in the step (2) in an atmosphere furnace, and sintering in pure oxygen atmosphere to obtain the modified low-residual-alkali ternary positive electrode material.
Further, the coating agent in the step 1) is one or more of aluminum dihydroxyglycolate, titanium glycolate, zirconium polyglycolide, aminopolyethylene glycol silicon, tetracarbonyl (1, 5-cyclooctadiene) tungsten, penta (dimethylamino) niobium and niobium 2-ethylhexanoate, preferably aluminum dihydroxyglycolate.
Further, the concentration of the coating agent solution prepared in the step 1) is 0.05-10 mg/mL.
Further, the ternary positive electrode material in the step 2) is LiNi x Co y M (1-x-y) O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.30, M is one or two of Mn and Al elements, and preferably, the ternary positive electrode material in the step 1) is Li (Ni) 0.8 Co 0.1 Mn 0.1 )O 2 (abbreviated as NCM 811).
Further, the mass ratio of the ternary positive electrode material to the coating agent solution in the step 2) is 0.01-1:1.
Further, the stirring process in the step 2) is specifically that stirring is carried out for 0.5-500 min at the rotating speed of 200-600 rpm; preferably, stirring is carried out at 400rpm for 10min.
Further, the drying temperature in the step 2) is 50-200 ℃ and the drying time is 1-20 h.
Further, the sintering temperature in the step 3) is 200-900 ℃, and the heat preservation time is 1-10 h.
Further, the invention also provides a method for preparing the modified ternary cathode material by dry cladding, which comprises the following steps:
(1) Mixing a coating agent and a ternary positive electrode material according to a certain mass ratio to obtain a coated ternary positive electrode material;
(2) And (3) placing the coated ternary anode material in an atmosphere furnace, and sintering in pure oxygen atmosphere to obtain the modified ternary anode material.
Further, the coating agent in the step (1) is one or more of aluminum dihydroxyglycolate, titanium glycolate, zirconium polyglycolide, aminopolyethylene glycol silicon, tetracarbonyl (1, 5-cyclooctadiene) tungsten, penta (dimethylamino) niobium and niobium 2-ethylhexanoate, preferably aluminum dihydroxyglycolate.
Further, the ternary positive electrode material in the step (1) is LiNi x Co y M (1-x-y) O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.30, M is one or two of Mn and Al elements, and preferably, the ternary positive electrode material in the step (1) is Li (Ni) 0.8 Co 0.1 Mn 0.1 )O 2 (abbreviated as NCM 811).
Further, the mass ratio of the coating agent to the ternary positive electrode material in the step (1) is 0.001-0.1:1.
Further, in the step (2), the sintering temperature is 200-900 ℃, and the heat preservation time is 1-8 h.
Further, the method for preparing the modified ternary cathode material by dry coating further comprises the step of washing the ternary cathode material before the ternary cathode material is coated by the coating agent.
Specifically, the water washing step comprises the following steps:
mixing the ternary positive electrode material and deionized water according to the mass ratio of 0.01-1:1, stirring and washing for 0.5-500 min under the condition of 200-600 rpm, suction filtering, and finally vacuum drying for 1-20 h at the temperature of 50-200 ℃ to obtain the water-washed ternary positive electrode material.
Furthermore, the modified ternary anode material prepared by the wet coating preparation method or the dry coating preparation method has good capacitance and charge and discharge performance, and can be used for preparing lithium ion batteries.
Furthermore, based on a general inventive concept, the invention also provides application of the modified ternary cathode material in preparing lithium ion batteries.
Specifically, the modified ternary cathode material is used for preparing a lithium ion battery.
Compared with the prior art, the invention has the advantages that:
1) The wet coating method of the invention takes the aqueous solution of the coating agent as the detergent of the ternary positive electrode to remove the residual LiOH and Li in the ternary positive electrode 2 CO 3 And when lithium impurities are removed, compared with the conventional ternary positive electrode washed by the aqueous solution in industrial production, the coating agent provides an alkaline water washing environment, and protects the ternary positive electrode from being corroded by water, so that the generation of a surface disorder structure of the ternary positive electrode is reduced.
2) The wet coating method can combine two processes of water washing, coating and mixing in the traditional process, reduce the process flow and reduce the production cost. In the coating process, the coating agent is finally coated on the surface of the ternary positive electrode material through the procedures of aqueous solution washing, filtering, drying, coating and the like, so that the coating process is more uniform compared with the dry coating.
3) The invention carries out surface modification while washing, metal oxide is obtained by high-temperature sintering metal-containing organic matters to form a coating layer, and metal ions can permeate and dope into the ternary positive electrode. The surface modification not only reduces pulverization and breakage of NCM particles in circulation, but also can effectively stabilize the crystal structure of NCM, reduce cation mixing and discharge and generation of rock salt structure, thereby improving electrochemical stability of the electrode.
4) The dry coating method disclosed by the invention is simple in process, low in price of the aluminum dihydroxyaminoacetate and beneficial to large-scale production and application. In the dry coating method, after being sintered at high temperature, the dihydroxyglycine can form Li with the lithium residue on the surface 3 N has lithium supplementing effect on ternary positive electrode material, and is beneficial to positive and negativePolar matching and improved cycling stability.
5) The prior art shows that after high temperature treatment, al element can exist on the surface of the ternary positive electrode material in the form of oxide and simultaneously takes Al as the raw material 3+ Is osmotically doped into the ternary positive electrode material (NCM 811) lattice. Therefore, the dry coating method of the invention effectively reduces cation mixing after modification, forms a protective layer to prevent the reaction of the ternary anode and the electrolyte, and improves the electrochemical circulation stability.
Drawings
FIG. 1 shows NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) SEM images of (a);
FIG. 2 is an SEM image of pure water-washed NCM811 prepared in comparative example 2;
FIG. 3 is an SEM image of the aluminum dihydroxyglycolate wet coated NCM811 prepared in example 1, as it is not sintered;
FIG. 4 is an SEM image of the aluminum dihydroxyglycolate wet coated NCM811 prepared in example 1 after sintering;
FIG. 5 is a graph showing cycle performance of comparative example 1, comparative example 2, example 1, example 2, example 3, example 4 and example 5;
FIG. 6 is a graph of cycle performance for comparative example 1 and example 6;
fig. 7 is a cycle performance chart of comparative example 2 and example 7.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the accompanying drawings. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions, and the raw materials and reagents used are commercially available products without any particular explanation.
Comparative example and example both use Li (Ni) prepared by one sintering of a precursor, supplied commercially by Henan New Country Tianli energy Co., ltd 0.8 Co 0.1 Mn 0.1 )O 2 Ternary positiveThe electrode material is used as a starting material and is named as a sintered NCM811.
Comparative example 1
Comparative example 1 a ternary positive electrode material of one-bake NCM811 commonly used in the conventional industry was used as the positive electrode material without any treatment, and specifically, an SEM image of the ternary positive electrode material of one-bake NCM811 in comparative example 1 is shown in fig. 1, and it can be seen from fig. 1 that the surface of one-bake NCM811 is rough and has a large amount of residual lithium impurities.
Comparative example 2
Comparative example 2 a positive electrode material was prepared by washing a primary burned NCM811 ternary positive electrode material commonly used in the conventional industry with deionized water, and specifically comprises the following steps:
mixing the primary NCM811 ternary positive electrode material with deionized water according to the mass ratio of 0.2:1, stirring and washing for 2min at 400rpm, suction filtering, and finally vacuum drying for 10h at the temperature of 100 ℃ to obtain the primary NCM811 ternary positive electrode material subjected to water washing, wherein an SEM image of the primary NCM811 ternary positive electrode material prepared in comparative example 2 is shown in FIG. 2, and as can be seen from FIG. 2, the NCM811 surface is smoother, and no residual lithium impurities are observed.
Example 1
Example 1 provides a preparation method of a modified ternary cathode material, which adopts a wet coating mode and takes aluminum dihydroxyaminoacetate as a coating agent to prepare the modified ternary cathode material, and comprises the following specific steps:
1) Adding aluminum dihydroxyaminoacetate into deionized water, and stirring and dissolving to obtain an aluminum dihydroxyaminoacetate solution with the concentration of 1.2 mg/mL;
2) Mixing the primary-burned NCM811 ternary positive electrode material with the aluminum dihydroxyglycolate solution in the step 1) according to the mass ratio of 0.2:1, stirring and uniformly mixing for 10min under the condition of 400rpm, carrying out suction filtration, and carrying out vacuum drying at the temperature of 100 ℃ for 10h to obtain the aluminum dihydroxyglycolate coated NCM811 ternary positive electrode material;
3) And (3) placing the NCM811 ternary anode material coated by the aluminum dihydroxyglycolate in the step (2) in an atmosphere furnace, and sintering for 4 hours at 700 ℃ in pure oxygen atmosphere to obtain the modified low-residual-alkali NCM811 ternary anode material.
The aluminum dihydroxyglycolate coated NCM811 ternary positive electrode material prepared in step 2) of example 1 is shown in FIG. 3 as an SEM image when not sintered, and is shown in FIG. 4 as an SEM image after 700 ℃ sintering. As can be seen in fig. 3, the unsintered NCM811 has a slightly roughened surface with a layer of residue on the surface. As can be seen in fig. 4, the surface of the NCM811 after sintering is smoother.
Example 2
Example 2 provides a preparation method of a modified ternary cathode material, which adopts a wet coating mode and takes aluminum dihydroxyaminoacetate as a coating agent, wherein the difference between example 2 and example 1 is that the concentration of the aluminum dihydroxyaminoacetate solution prepared in step 1) is 0.5mg/mL.
Example 3
Example 3 provides a preparation method of a modified ternary cathode material, which adopts a wet coating mode and takes aluminum dihydroxyaminoacetate as a coating agent, wherein the difference between example 3 and example 1 is that the concentration of the aluminum dihydroxyaminoacetate solution prepared in the step 1) is 0.7mg/mL.
Example 4
Example 4 provides a method for preparing a modified ternary cathode material, which uses aluminum dihydroxyaminoacetate as a coating agent in a wet coating manner, and the difference between example 4 and example 1 is that the concentration of the aluminum dihydroxyaminoacetate solution prepared in step 1) is 1.0mg/mL.
Example 5
Example 4 provides a method for preparing a modified ternary cathode material, which uses aluminum dihydroxyaminoacetate as a coating agent in a wet coating manner, and the difference between example 4 and example 1 is that the concentration of the aluminum dihydroxyaminoacetate solution prepared in step 1) is 1.5mg/mL.
Performance test 1
The surface residual lithium content of the products prepared in comparative examples 1 to 5 and comparative example 1 was measured by a potentiometric titration method (the measurement method is described in patent document CN109917070a, the method for measuring the residual free lithium content in ternary cathode material), and the measurement results are shown in table 1.
Table 1 titration data for residual lithium content of ternary cathode materials of comparative example 1, example 2, example 3, example 4 and example 5.
As can be seen from Table 1, comparative example 1 has a higher content of residual lithium on the surface, and the mass fractions of residual lithium are respectively Li 2 CO 3 (0.711%), liOH (1.034%), in comparison with examples 1-5, the surface residual lithium content was low, li 2 CO 3 The content is less than 0.45%, and the content of LiOH is less than 0.4%. The results in Table 1 show that the wet coating method of the present invention can make the surfaces LiOH and Li of NCM811 2 CO 3 The content is obviously reduced.
The products prepared in comparative examples 1 to 5 and comparative example 1 were tested for cycle performance by constant current charge and discharge between 3 and 4.8V by assembling CR2032 button cell, and the specific preparation method is as follows:
according to the active material (modified ternary positive electrode material prepared): conductive agent (Super P): uniformly mixing the binder (PVDF) with N-methylpyrrolidone (NMP) as a solvent in a mass ratio of 8:1:1, coating, and vacuum drying at 120 ℃ for 12 hours to obtain a pole piece, wherein the pole piece is used as a working electrode, a metal lithium piece is used as a counter electrode, a polypropylene film is used as a diaphragm, and 1M LiPF is used as a cathode 6 And (3) performing constant-current charge and discharge test on the CR2032 button cell assembled by the electrolyte with the ratio of EC to DMC=1:1:1.
The results are shown in table 1 and fig. 5, fig. 5 is a cycle performance curve at a 1C rate, and the initial specific power generation capacity at a corresponding 1C rate and the coulombic efficiency after 200 cycles in fig. 5 are shown in table 1.
As can be seen from Table 1 and FIG. 5, comparative example 1 had an initial discharge specific capacity of 162.38mAh/g and a capacity retention of 91.50% after 200 cycles. Comparative example 2 did not change significantly in initial discharge specific capacity from comparative example 1, but the capacity retention after 200 cycles was only 9.44%.
Examples 1 to 5 have a large improvement in initial discharge specific capacity as compared with comparative examples 1 and 2. After 200 cycles, the specific discharge capacities of examples 1 to 5 were all much higher than that of comparative example 2, and in particular, the capacity retention ratios in examples 1 and 5 exceeded that of comparative example 1. The results show that the wet coating method can remove residual lithium salt and improve the cycle stability of NCM811 electrodes.
Example 6
Example 6 provides a preparation method of a modified ternary cathode material, which adopts a dry coating mode and takes aluminum dihydroxyaminoacetate as a coating agent to prepare the modified ternary cathode material, and comprises the following specific steps:
(1) Mixing aluminum dihydroxyglycolate and a primary sintered NCM811 ternary positive electrode material according to the mass ratio of 0.006:1, and stirring and uniformly mixing for 2 hours under the condition of 300rpm to obtain an aluminum dihydroxyglycolate coated NCM811 ternary positive electrode material;
(2) And (3) placing the NCM811 ternary anode material coated by the aluminum dihydroxyglycolate in the step (1) in an atmosphere furnace, and sintering for 4 hours at 700 ℃ in pure oxygen atmosphere to obtain the modified low-residual-alkali NCM811 ternary anode material.
Example 7
Embodiment 7 provides a preparation method of a modified ternary cathode material, which adopts a dry coating mode and takes aluminum dihydroxyaminoacetate as a coating agent to prepare the modified ternary cathode material, and comprises the following specific steps:
(1) Mixing the primary sintered NCM811 ternary positive electrode material with deionized water according to the mass ratio of 0.2:1, stirring and uniformly mixing for 2min under the condition of 400rpm, carrying out suction filtration, and finally carrying out vacuum drying at the temperature of 100 ℃ for 10h to obtain the water-washed primary sintered NCM811 ternary positive electrode material;
(2) The primary calcined NCM811 ternary anode material after water washing in the step (1) and aluminum dihydroxyaminoacetate are mixed according to the following ratio of 1: mixing the materials according to the mass ratio of 0.006, and stirring and uniformly mixing the materials for 3 hours under the condition of 300rpm to obtain an NCM811 ternary positive electrode material coated by aluminum dihydroxyglycolate;
(3) And (3) placing the NCM811 ternary anode material coated by the aluminum dihydroxyglycolate in the step (2) in an atmosphere furnace, and sintering for 4 hours at 700 ℃ in pure oxygen atmosphere to obtain the modified low-residual-alkali NCM811 ternary anode material.
Performance test 2
The cycle performance of the products prepared in comparative examples 6 to 7 and comparative example 1 was measured by constant current charge and discharge between 3 and 4.8V (see performance test 1 for preparation method) by assembling CR2032 button cell, and the results are shown in table 2 and fig. 6 and 7.
Table 2 initial specific capacity at cycle 1C and capacity retention at 200 cycles for comparative example 1, comparative example 2, example 6, example 7.
The cycle performance of comparative example 6 and comparative example 1, and the cycle performance curve at 1C magnification are shown in fig. 6. The initial specific power generation capacity at the corresponding 1C magnification and the coulombic efficiency after 200 cycles in fig. 6 are shown in table 2.
Comparative example 1 has an initial specific discharge capacity of 162.38mAh/g, which is lower than 173.39mAh/g of example 6. The capacity retention after 200 cycles was 91.50% for comparative example 1 and 100% for example 6. The result shows that the method of adopting the dry coating method of the aluminum dihydroxyglycine can effectively improve the circulation stability of NCM811.
The cycle performance of comparative example 7 and comparative example 2, and the cycle performance curve at 1C magnification are shown in fig. 7. The initial specific power generation capacity at the corresponding 1C magnification and the coulombic efficiency after 200 cycles in fig. 7 are shown in table 2.
Comparative example 2 has an initial specific discharge capacity of 177.87mAh/g, which is slightly lower than 182.39mAh/g of example 7. Example 7 has a capacity retention of 97.26% after 200 cycles, well above 9.44% for example 2. The results show that the dry coating of the aluminum dihydroxyglycolate can greatly promote the improvement of the circulation stability of the water-washed NCM811.
The preparation method adopted by the modified ternary positive electrode material not only simplifies the preparation method of the ternary positive electrode material in the prior art, but also improves the overall performance of the ternary positive electrode material, has good application value, and is suitable for technological popularization and application.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The method for preparing the modified ternary cathode material by wet cladding is characterized by comprising the following steps of:
1) Preparing a coating agent solution;
2) Mixing the ternary positive electrode material with the coating agent solution in the step 1) according to a certain proportion, stirring and uniformly mixing, and then carrying out suction filtration and drying to obtain the ternary positive electrode material coated by the coating agent;
3) And (3) placing the ternary positive electrode material coated by the coating agent in the step (2) in an atmosphere furnace, and sintering in pure oxygen atmosphere to obtain the modified low-residual-alkali ternary positive electrode material.
2. The method of claim 1, wherein the coating agent of step 1) is one or more of aluminum dihydroxyglycolate, titanium glycolate, zirconium polyhydroxyacetate, aminopolyethylene glycol silicon, tungsten tetracarbonyl (1, 5-cyclooctadiene), niobium penta (dimethylamino) and niobium 2-ethylhexanoate; the concentration of the coating agent solution prepared in the step 1) is 0.05-10 mg/mL.
3. The method of claim 1, wherein the mass ratio of the ternary cathode material to the coating agent solution in step 2) is 0.01-1:1.
4. The method of claim 1, wherein the sintering temperature in step 3) is 200-900 ℃ and the holding time is 1-10 hours.
5. A method for preparing a modified ternary positive electrode material by dry cladding comprises the following steps:
(1) Mixing a coating agent and a ternary positive electrode material according to a certain mass ratio to obtain a coated ternary positive electrode material;
(2) And (3) placing the coated ternary anode material in an atmosphere furnace, and sintering in pure oxygen atmosphere to obtain the modified ternary anode material.
6. The method of claim 5, wherein the coating agent of step (1) is one or more of aluminum dihydroxyglycolate, titanium glycolate, zirconium polyglycolide, aminopolyethylene glycol silicon, tetracarbonyl (1, 5-cyclooctadiene) tungsten, niobium penta (dimethylamino) and niobium 2-ethylhexanoate; and (3) the mass ratio of the coating agent to the ternary positive electrode material in the step (1) is 0.001-0.1:1.
7. The method of claim 5, wherein the sintering temperature in step (2) is 200-900 ℃ and the holding time is 1-8 hours.
8. The method of claim 5, wherein the dry coating process for preparing the modified ternary cathode material further comprises washing the ternary cathode material with water prior to coating the ternary cathode material with the coating agent; the water washing step comprises the following steps:
mixing the ternary positive electrode material and deionized water according to a mass ratio of 0.01-1:1, stirring and washing for 0.5-500 min under the condition of 200-600 rpm, suction filtering, and finally vacuum drying for 1-20 h at the temperature of 50-200 ℃ to obtain the water-washed ternary positive electrode material.
9. The modified ternary cathode material is prepared by adopting the method of any one of claims 1-8.
10. The use of the modified ternary cathode material of claim 9 in the preparation of a lithium ion battery.
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