CN115537906A - Modified single crystal ternary cathode material, preparation method thereof and lithium ion battery - Google Patents
Modified single crystal ternary cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 83
- 239000010406 cathode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 147
- 238000005245 sintering Methods 0.000 claims abstract description 76
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000004970 Chain extender Substances 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
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- 238000000576 coating method Methods 0.000 claims abstract description 23
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 239000010703 silicon Substances 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 116
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- NIZHERJWXFHGGU-UHFFFAOYSA-N isocyanato(trimethyl)silane Chemical group C[Si](C)(C)N=C=O NIZHERJWXFHGGU-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical group COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- -1 alcohol compound Chemical class 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002641 lithium Chemical class 0.000 claims 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 7
- 239000010405 anode material Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/04—After-treatment of single crystals or homogeneous polycrystalline material with defined structure using electric or magnetic fields or particle radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a modified single crystal ternary cathode material, a preparation method thereof and a lithium ion battery. The preparation method comprises the following steps: s1, in an oxygen-containing atmosphere, a single crystal type ternary positive electrode precursor Ni is included x Co y Mn 1‑x‑y (OH) 2 Mixing the materials of lithium source, silicon source and coupling agent, and sintering once to obtain the final productTo a neutralizing agent; s2, reacting raw materials including first isocyanate, alcohol compounds containing nitrogen and/or phosphorus, a first chain extender, a second chain extender and a neutralizer, and drying to obtain a pre-sintered material; s3, performing secondary sintering on the pre-sintered material to obtain a phosphorus-nitrogen-silicon co-doped carbon layer coating material, and bombarding the coating material by adopting a nitrogen ion beam to obtain a modified material; and S4, mechanically stirring and mixing the modified material and second isocyanate, and then carrying out heat treatment to obtain the modified single crystal ternary cathode material, so that the corresponding battery has higher discharge capacity and cycling stability under high cut-off voltage.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a modified single crystal ternary cathode material, a preparation method thereof and a lithium ion battery.
Background
The single crystal type nickel cobalt lithium manganate ternary positive electrode material is a new line of research interest in academia and industry because the comprehensive indexes of performance and cost are superior to those of traditional lithium cobaltate and lithium iron phosphate.
With the accelerated development of new energy automobiles, the lithium ion battery for the automobile has a more severe requirement on the driving mileage. The endurance mileage of the power battery is improved, and the most common method at present is to improve the cut-off voltage of a battery system. However, under high cut-off voltage, the side reactions on the surface of the electrode are increased correspondingly, so that the discharge capacity and the cycle performance of the single crystal type nickel cobalt lithium manganate anode material are greatly reduced, and the aim of the high-mileage lithium ion battery for the vehicle can not be achieved. Although a plurality of coating modified single crystal type ternary positive electrode materials exist in the prior art, a common coating material has no electrochemical activity, and although the coating modification can improve the performance of the material, the polarization of the material is increased, and the capacity and rate performance are reduced. Therefore, it is highly desirable to develop a single crystal type ternary cathode material with long cycling and high discharge capacity at high cut-off voltage.
Disclosure of Invention
The invention mainly aims to provide a modified single crystal ternary cathode material, a preparation method thereof and a lithium ion battery, and aims to solve the problem that the lithium ion battery in the prior art has poor performances such as the retention rate of the cycle capacity under high cut-off voltage.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing a modified single crystal ternary cathode materialThe preparation method comprises the following steps: s1, in an oxygen-containing atmosphere, a single crystal type ternary positive electrode precursor Ni is included x Co y Mn 1-x-y (OH) 2 Mixing the materials of the lithium source, the silicon source and the coupling agent, and then sintering for the first time to obtain a neutralizer; s2, reacting raw materials including first isocyanate, alcohol compounds containing nitrogen and/or phosphorus, a first chain extender, a second chain extender and a neutralizer, and drying to obtain a pre-sintered material; step S3, in N 2 Under the protection of atmosphere or inert gas atmosphere, carrying out secondary sintering on the pre-sintered material to obtain a phosphorus-nitrogen-silicon co-doped carbon layer coating material, and bombarding the coating material by adopting a nitrogen ion beam to obtain a modified material; s4, mechanically stirring and mixing the modified material and second isocyanate, and then carrying out heat treatment to obtain a modified single crystal ternary cathode material; wherein x is more than or equal to 0.8 and less than or equal to 1,0 and more than or equal to y is less than or equal to 0.15.
Further, the step S1 includes: mechanically stirring and mixing a lithium source, a silicon source, a coupling agent and ethanol, and then performing ball milling and drying to obtain modified lithium hydroxide, wherein the ball milling time is preferably 60-90 min, and the drying temperature is preferably 80-100 ℃; in an oxygen-containing atmosphere, ni is a single-crystal ternary positive electrode precursor x Co y Mn 1-x-y (OH) 2 Carrying out primary sintering on the raw material of the modified lithium hydroxide to obtain a silicon-doped sintering material; crushing and sieving the silicon-doped sintering material, and standing for 30-60 min to obtain a neutralizing agent; the mass ratio of the lithium source, the silicon source, the coupling agent and the ethanol is 1.11-0.23; preferably, the lithium source is lithium hydroxide, the silicon source is silicon dioxide, and the coupling agent is selected from any one or more of vinyltris (beta-methoxyethoxy) silane, gamma-aminopropyltriethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
Further, the single crystal type ternary positive electrode precursor Ni x Co y Mn 1-x-y (OH) 2 The mass ratio of the modified lithium hydroxide to the modified lithium hydroxide is 1.16-2.32; the process of the preferred primary sintering comprises: single crystal form ternary positive electrode precursorNi x Co y Mn 1-x-y (OH) 2 The mixture of the modified lithium hydroxide and the modified lithium hydroxide is heated to 300 to 350 ℃ and is kept warm for 1 to 5 hours, and then the mixture is heated to 800 to 900 ℃ and is kept warm for 10 to 15 hours.
Further, the particle size distribution of the neutralizing agent is between 2 and 3 μm; preferably, standing is carried out at the relative humidity of air of 40-95% and the temperature of 40-80 ℃; preferably, the neutralizing agent contains 0.1 to 0.5% of LiOH.
Further, the step S2 includes: mechanically stirring first isocyanate and alcohol compounds containing nitrogen and/or phosphorus to react for 1-3 h at 80-94 ℃ to obtain a prepolymer; adding a first chain extender and a second chain extender into the prepolymer for continuous reaction for 0.5 to 1 hour to obtain a polymerization product; adding the polymerization product and a neutralizer into water, dispersing for 10-20 min at a speed of 800-1000 r/min, and drying to obtain a pre-sintered material; preferably, the mass ratio of the first isocyanate, the alcohol compound containing nitrogen and/or phosphorus, the first chain extender, the second chain extender and the neutralizing agent is 1.3-1.6; preferably the first isocyanate is lysine diisocyanate and/or 1,5-naphthalene diisocyanate; preferably, the alcohol compound containing nitrogen and/or phosphorus is phosphorus-containing trihydric alcohol, and the preferable phosphorus-containing trihydric alcohol is obtained by the reaction of trimethyl phosphate and 1,4-butanediol; preferably, the first chain extender is dimethylolpropionic acid and/or 1,2-propylene glycol-3-sodium sulfonate; preferably the second chain extender is a trimethylsilyl isocyanate.
Further, the temperature of the secondary sintering is 500-700 ℃, and the heat preservation time of the secondary sintering is preferably 2-5 h; the thickness of the phosphorus-nitrogen-silicon co-doped carbon layer is preferably between 15 and 40 nm.
Further, the technological parameters of the bombardment are as follows: the flow rate is 30-60 sccm, the linear ion beam current is 0.1-0.4A, the matrix bias voltage is-100 to-70V, and the bombardment time is 3-8 min.
Further, in the step S4, the mass ratio of the modifier to the second isocyanate is 15 to 20:1; preferably the second isocyanate is toluene diisocyanate and/or hexamethylene diisocyanate; the temperature of the heat treatment is preferably 40 to 60 ℃, and the time of the heat treatment is preferably 10 to 30min.
According to another aspect of the application, a modified single crystal ternary cathode material is provided, and the modified single crystal ternary cathode material is prepared by the preparation method.
According to another aspect of the application, a lithium ion battery is provided, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode comprises the modified single crystal ternary positive electrode material prepared by the preparation method or the modified single crystal ternary positive electrode material.
By applying the technical scheme of the application, the preparation method of the application is applied to the single crystal LiNi x Co y Mn 1-x-y O 2 Silicon is doped in the crystal lattice of the anode material, and a silicon-phosphorus-nitrogen co-doped carbon layer coated with diisocyanate trimer modification is obtained on the surface of the silicon-doped anode material; through the double modification effects, the low tortuosity of the prepared electrode is cooperatively realized, the uneven electrochemical reaction among the anode particles is effectively optimized, and the generation of microcracks and lattice distortion in the crystal structure of the anode material in the circulating process are inhibited, so that the stability of the material structure is maintained, the expansion degree of the unit cell volume of the material under high cut-off voltage is effectively reduced, the collapse of the crystal structure is inhibited, and the discharge capacity and the cyclic discharge stability of the lithium ion battery applied to the material under the high cut-off voltage are further improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows an SEM microtopography of a modified single crystal ternary cathode material provided in accordance with example 1 of the present invention;
FIG. 2 shows an SEM micro-topography of a modified single crystal ternary cathode material provided in accordance with comparative example 1 of the present invention;
fig. 3 shows a first charge-discharge curve diagram of the modified single-crystal ternary cathode materials provided in example 1 and comparative example 1 according to the present invention;
fig. 4 shows discharge capacity at different rates and 50-cycle discharge capacity curves of example 1 according to the present invention from comparative example 1.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art of the present application, in order to solve the problem of poor performance such as cycle capacity retention rate at high cut-off voltage of a lithium ion battery in the prior art, the present application provides a modified single crystal ternary cathode material, a preparation method thereof, and a lithium ion battery.
In an exemplary embodiment of the present application, there is provided a method of preparing a modified single crystal ternary positive electrode material, the method comprising: s1, in an oxygen-containing atmosphere, preparing a single-crystal ternary anode precursor Ni x Co y Mn 1-x-y (OH) 2 Mixing materials of a lithium source, a silicon source and a coupling agent, and then sintering for the first time to obtain a neutralizer; s2, reacting raw materials including first isocyanate, alcohol compounds containing nitrogen and/or phosphorus, a first chain extender, a second chain extender and a neutralizer, and drying to obtain a pre-sintered material; step S3, in N 2 Under the protection of atmosphere or inert gas atmosphere, carrying out secondary sintering on the pre-sintered material to obtain a phosphorus-nitrogen-silicon co-doped carbon layer coating material, and bombarding the coating material by adopting a nitrogen ion beam to obtain a modified material; s4, mechanically stirring and mixing the modified material and second isocyanate, and then carrying out heat treatment to obtain a modified single crystal ternary cathode material; wherein x is more than or equal to 0.8 and less than 1, and y is more than 0 and less than or equal to 0.15.
The above preparation method of the present application is to single crystal form LiNi x Co y Mn 1-x-y O 2 Silicon is doped in the crystal lattice of the anode material, and a silicon-phosphorus-nitrogen co-doped carbon layer coated with diisocyanate trimer modification is obtained on the surface of the silicon-doped anode material (hereinafter referred to as a substrate material); through the dual modification effects, the low tortuosity of the prepared electrode is cooperatively realized, the nonuniform electrochemical reaction among positive electrode particles is effectively optimized, and the crystal junction of the positive electrode material in the circulation process is inhibitedThe generation of intractructural microcracks and lattice distortion maintain the stability of the material structure, effectively reduce the expansion degree of unit cell volume of the material under high cut-off voltage, inhibit the collapse of the crystal structure, and further improve the discharge capacity and the cyclic discharge stability of the lithium ion battery applied by the material under the high cut-off voltage.
In an embodiment of the present application, the step S1 includes: mechanically stirring and mixing a lithium source, a silicon source, a coupling agent and ethanol, and then performing ball milling and drying to obtain modified lithium hydroxide, wherein the ball milling time is preferably 60-90 min, and the drying temperature is preferably 80-100 ℃; in an oxygen-containing atmosphere, ni is a single crystal type ternary positive electrode precursor x Co y Mn 1-x-y (OH) 2 Carrying out primary sintering on the raw material of the modified lithium hydroxide to obtain a silicon-doped sintered material; crushing and sieving the silicon-doped sintering material, and standing for 30-60 min to obtain a neutralizing agent; the mass ratio of the lithium source, the silicon source, the coupling agent and the ethanol is 1.11-0.23; preferably, the lithium source is lithium hydroxide, the silicon source is silicon dioxide, and the coupling agent is selected from any one or more of vinyltris (beta-methoxyethoxy) silane, gamma-aminopropyltriethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
According to the method, the lithium source and the silicon source with different particle sizes are selected, the lithium hydroxide is uniformly and effectively coated by the silicon source under the modification effect of the coupling agent, and finally, the modified lithium hydroxide with the required particle size is obtained through wet ball milling and drying; on one hand, modified lithium hydroxide is beneficial to the single crystal type ternary anode precursor Ni x Co y Mn 1-x-y (OH) 2 The uniform coating is beneficial to the silicon in the single crystal type ternary anode precursor Ni in the primary sintering process x Co y Mn 1-x-y (OH) 2 The interior of the material lattice is uniformly doped, so that the uniform growth of particles is realized, the silicon-doped sintering material with narrow particle size distribution is obtained by crushing, and the neutralizer with uniform surface residual alkali distribution is obtained.
In order to further improve the performance of the neutralizer, the single-crystal ternary positive electrode precursor Ni is preferably selected x Co y Mn 1-x-y (OH) 2 The mass ratio of the modified lithium hydroxide to the modified lithium hydroxide is 1.16-2.32; the process of the preferred primary sintering comprises: single crystal form ternary positive electrode precursor Ni x Co y Mn 1-x-y (OH) 2 The mixture of the modified lithium hydroxide and the modified lithium hydroxide is heated to 300-350 ℃, and is kept warm for 1-5 h, and then is heated to 800-900 ℃ and is kept warm for 10-15 h, thereby being beneficial to improving the efficiency of one-time sintering.
The particle size distribution of the neutralizer is preferably between 2 and 3 mu m; preferably, standing is carried out at the relative humidity of air of 40-95% and the temperature of 40-80 ℃; the narrow particle size range is cooperated with proper environmental conditions, so that LiOH can be rapidly and uniformly generated on the surface of the silicon-doped sintering material, and the neutralizing capacity of a neutralizing agent is improved; the neutralizer preferably contains 0.1-0.5% of LiOH, can neutralize a polymerization product (obtained by polymerization reaction of a first isocyanate, a nitrogen and/or phosphorus-containing alcohol compound, a first chain extender and a second chain extender) more fully, and can ensure that the polymerization product is coated on the surface of a base material more uniformly after emulsification so as to ensure that a phosphorus-nitrogen-silicon co-doped carbon layer generated by secondary sintering is coated uniformly.
In an embodiment of the present application, the step S2 includes: mechanically stirring first isocyanate and alcohol compounds containing nitrogen and/or phosphorus to react for 1-3 h at 80-94 ℃ to obtain a prepolymer; adding a first chain extender and a second chain extender into the prepolymer for continuous reaction for 0.5 to 1 hour to obtain a polymerization product; adding the polymerization product and a neutralizer into water, dispersing for 10-20 min at a speed of 800-1000 r/min, and drying to obtain a pre-sintered material; preferably, the mass ratio of the first isocyanate, the alcohol compound containing nitrogen and/or phosphorus, the first chain extender, the second chain extender and the neutralizing agent is 1.3-1.6; preferably the first isocyanate is lysine diisocyanate and/or 1,5-naphthalene diisocyanate; preferably, the alcohol compound containing nitrogen and/or phosphorus is phosphorus-containing trihydric alcohol, and the preferable phosphorus-containing trihydric alcohol is obtained by the reaction of trimethyl phosphate and 1,4-butanediol; preferably, the first chain extender is dimethylolpropionic acid and/or 1,2-propylene glycol-3-sodium sulfonate; preferably the second chain extender is a trimethylsilyl isocyanate.
And S2, obtaining a carbon-doped precursor containing phosphorus and nitrogen elements in the main chain and silicon elements in the side chain through polymerization, and uniformly coating the phosphorus-nitrogen-silicon co-doped carbon layer coating material on the surface of the base material after the carbon-doped precursor and a neutralizing agent are subjected to neutralization reaction and secondary sintering. The control of the above conditions is advantageous for increasing the efficiency of the polymerization reaction and the neutralization reaction involved in step S2, and in particular the mass ratio of the first isocyanate, the nitrogen and/or phosphorus-containing alcohol compound, the first chain extender, the second chain extender and the neutralizing agent is more advantageous for the synergistic cooperation between the components.
In order to improve the efficiency and the effect of the secondary sintering, the temperature of the secondary sintering is preferably 500-700 ℃, and the heat preservation time of the secondary sintering is preferably 2-5 h; the thickness of the phosphorus-nitrogen-silicon co-doped carbon layer is preferably between 15 and 40nm, so that the modification effect on the matrix material is favorably improved.
In one embodiment of the present application, the process parameters of the bombardment are: the flow rate is 30-60 sccm, the linear ion beam current is 0.1-0.4A, the matrix bias voltage is-100 to-70V, and the bombardment time is 3-8 min.
Through bombardment of nitrogen ion beams on the material coated with the phosphorus-nitrogen-silicon co-doped carbon layer, ammonia or imino and other polar groups are formed on the surface of the material, and the preferred technological parameters of the bombardment are favorable for more rapidly forming the ammonia or imino and other polar groups on the surface of the phosphorus-nitrogen-silicon co-doped carbon layer. After the groups are compounded with second isocyanate, the second isocyanate is catalyzed to be self-polymerized to modify a phosphorus-nitrogen-silicon co-doped carbon layer coating material, so that the modified single crystal ternary cathode material is obtained.
In an embodiment of the present application, in the step S4, the mass ratio of the modifier to the second isocyanate is 15 to 20:1; preferably the second isocyanate is toluene diisocyanate and/or hexamethylene diisocyanate; the temperature of the heat treatment is preferably 40 to 60 ℃, and the time of the heat treatment is preferably 10 to 30min.
Under the conditions, the efficiency of the heat treatment is improved, so that the second isocyanate is more fully polymerized under the action of the modifier.
In another exemplary embodiment of the present application, a modified single crystal ternary cathode material is provided, which is prepared by the above preparation method.
The modified single crystal ternary cathode material obtained by the preparation method has the advantages that silicon is doped in the crystal lattice, and a diisocyanate trimer modified silicon-phosphorus-nitrogen co-doped carbon layer is coated outside the crystal lattice; through the double modification effects, the low tortuosity of the prepared electrode is cooperatively realized, the uneven electrochemical reaction among the anode particles is effectively optimized, and the generation of microcracks and lattice distortion in the crystal structure of the anode material in the circulating process are inhibited, so that the stability of the material structure is maintained, the expansion degree of the unit cell volume of the material under high cut-off voltage is effectively reduced, the collapse of the crystal structure is inhibited, and the discharge capacity and the cyclic discharge stability of the lithium ion battery applied to the material under the high cut-off voltage are further improved.
In another exemplary embodiment of the present application, a lithium ion battery is provided, which includes a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode includes the modified single crystal ternary positive electrode material prepared by the preparation method or the modified single crystal ternary positive electrode material.
The lithium ion battery comprising the modified single crystal ternary cathode material has excellent structural stability, realizes low tortuosity of prepared electrodes as the cathode material of the battery, effectively optimizes uneven electrochemical reaction among cathode particles, and can greatly improve the electrical properties of the applied battery such as capacity and cycle capacity retention rate under high cut-off voltage.
The advantageous effects of the present application will be further described below with reference to examples.
Example 1
Mechanically stirring lithium hydroxide, silicon dioxide, vinyl tri (beta-methoxyethoxy) silane and ethanol uniformly according to a mass ratio of 1; wherein the D50 of lithium hydroxide is 25 μm and the D50 of silicon dioxide is 15nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and modified lithium hydroxide according to the mass ratio of 1.16, and then sintering in an oxygen-containing atmosphere; the primary sintering procedure was as follows: heating to 350 ℃, preserving heat for 1h, heating to 800 ℃, preserving heat for 15h, and cooling to room temperature to obtain the silicon-doped sintering material.
Crushing and sieving the silicon-doped sintering material to obtain a material with the particle size distribution of 2-3 mu m, and then placing the material in an environment with the relative humidity of air of 95% and the temperature of 40 ℃ for 60min to obtain a neutralizer; wherein the neutralizing agent contains 0.5% LiOH.
Reacting lysine diisocyanate and phosphorus-containing trihydric alcohol at 94 ℃ for 3 hours under mechanical stirring to obtain a prepolymer; adding dimethylolpropionic acid and trimethylsilyl isocyanate into the prepolymer to continue reacting for 0.5h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 1000r/min for 20min, and drying to obtain a pre-sintered material; wherein, the mass ratio of the lysine diisocyanate, the phosphorus-containing trihydric alcohol, the dimethylolpropionic acid, the trimethylsilyl isocyanate to the neutralizing agent is 1.3.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 700 ℃, and preserving the temperature for 5h to obtain the phosphorus-nitrogen-silicon co-doped carbon layer coating material with the thickness of 40 nm.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 60sccm, the linear ion beam current is 0.4A, the substrate bias voltage is-100V, and the bombardment time is 8min.
Mixing the modified material and toluene diisocyanate according to a mass ratio of 15:1, mechanically stirring and mixing, and then carrying out heat treatment at 60 ℃ for 30min to obtain the modified single crystal ternary cathode material.
Example 2
Mechanically stirring lithium hydroxide, silicon dioxide, gamma-aminopropyltriethoxysilane and ethanol uniformly according to a ratio of 1.23; wherein the D50 of lithium hydroxide is 40 μm and the D50 of silica is 5nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and modified lithium hydroxide according to the mass ratio of 1:2.22, and then sintering in an oxygen-containing atmosphere; the primary sintering procedure was as follows: heating to 300 ℃, preserving heat for 5h, heating to 840 ℃, preserving heat for 10h, and cooling to room temperature to obtain the silicon-doped sintering material.
Crushing and sieving the silicon-doped sintering material to obtain a material with the particle size distribution of 2-3 mu m, and then placing the material in an environment with the relative humidity of air of 40% and the temperature of 80 ℃ for 30min to obtain a neutralizer; wherein the neutralizing agent is contained in an amount of 0.1%.
Reacting 1,5-naphthalene diisocyanate and phosphorus-containing triol at 88 ℃ for 1h under mechanical stirring to obtain a prepolymer; adding dimethylolpropionic acid and trimethylsilyl isocyanate into the prepolymer to continue reacting for 1h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 800r/min for 10min, and drying to obtain a pre-sintered material; wherein, the mass ratio of 1,5-naphthalene diisocyanate, phosphorus-containing triol, dimethylolpropionic acid, trimethylsilyl isocyanate and neutralizing agent is 1.6.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 500 ℃, and preserving the heat for 3h to obtain the phosphorus-nitrogen-silicon co-doped carbon layer coating material with the thickness of 30 nm.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 30sccm, the linear ion beam current is 0.1A, the substrate bias voltage is-70V, and the bombardment time is 3min.
Mixing the modified material and hexamethylene diisocyanate in a mass ratio of 20:1, mechanically stirring and mixing, and then carrying out heat treatment at 40 ℃ for 20min to obtain the modified single crystal ternary cathode material.
Example 3
Mechanically stirring lithium hydroxide, silicon dioxide, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and ethanol uniformly according to a ratio of 1; wherein the D50 of lithium hydroxide is 30 μm and the D50 of silica is 10nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and modified lithium hydroxide according to the mass ratio of 1; the primary sintering procedure was as follows: heating to 320 ℃, preserving heat for 4h, heating to 860 ℃, preserving heat for 12h, and cooling to room temperature to obtain the silicon-doped sintering material.
Crushing and sieving the silicon-doped sintering material to obtain a material with the particle size distribution of 2-3 mu m, and then placing the material in an environment with the relative humidity of air of 60% and the temperature of 60 ℃ for 40min to obtain a neutralizer; wherein the neutralizing agent contains 0.5% LiOH.
Reacting 1,5-naphthalene diisocyanate and phosphorus-containing triol at 92 ℃ for 1h under mechanical stirring to obtain a prepolymer; adding 1,2-propanediol-3-sodium sulfonate and trimethylsilyl isocyanate into the prepolymer to continue reacting for 0.8h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 850r/min for 15min, and drying to obtain a pre-sintered material; wherein, the mass ratio of 1,5-naphthalene diisocyanate, phosphorus-containing triol, 1,2-propanediol-3-sodium sulfonate, trimethylsilyl isocyanate and neutralizer is 1.6.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 700 ℃, and preserving the temperature for 2h to obtain the phosphorus-nitrogen-silicon co-doped carbon layer coating material with the thickness of 15nm.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 40sccm, the linear ion beam current is 0.3A, the substrate bias voltage is-90V, and the bombardment time is 5min.
According to the mass ratio of 18:1, weighing the modified material, mechanically stirring and mixing the modified material and hexamethylene diisocyanate, and then carrying out heat treatment for 10min at 50 ℃ to obtain the modified single crystal ternary cathode material.
Example 4
Mechanically stirring lithium hydroxide, silicon dioxide, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and ethanol uniformly according to a ratio of 1 to 0.3, placing the mixture in a ball mill for ball milling for 80min, taking out the mixture after the ball milling is finished, and placing the mixture in a drying box for drying at 88 ℃ to obtain modified lithium hydroxide with the D50 of 10 mu m; wherein the D50 of lithium hydroxide is 30 μm and the D50 of silica is 12nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and the modified lithium hydroxide according to the mass ratio of 1; the primary sintering procedure was as follows: heating to 340 ℃, preserving heat for 2h, heating to 820 ℃, preserving heat for 10h, and cooling to room temperature to obtain the silicon-doped sintering material.
Crushing and sieving the silicon-doped sintering material to obtain a material with the particle size distribution of 2-3 mu m, and then placing the material in an environment with the relative humidity of air of 80% and the temperature of 70 ℃ for 50min to obtain a neutralizer; wherein the neutralizing agent contains 0.4% LiOH.
Reacting lysine diisocyanate and phosphorus-containing trihydric alcohol at 80 ℃ for 2 hours under mechanical stirring to obtain a prepolymer; adding dimethylolpropionic acid and trimethylsilyl isocyanate into the prepolymer to continue reacting for 0.6h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 900r/min for 12min, and drying to obtain a pre-sintered material; wherein, the mass ratio of the lysine diisocyanate, the phosphorus-containing trihydric alcohol, the dimethylolpropionic acid, the trimethylsilyl isocyanate to the neutralizing agent is 1.4.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 600 ℃, and preserving the temperature for 4h to obtain the phosphorus-nitrogen-silicon co-doped carbon layer coating material with the thickness of 20 nm.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 50sccm, the linear ion beam current is 0.2A, the substrate bias voltage is-80V, and the bombardment time is 6min.
Mixing the modified material and hexamethylene diisocyanate in a mass ratio of 16:1, mechanically stirring and mixing, and then carrying out heat treatment at 45 ℃ for 30min to obtain the modified single crystal ternary cathode material.
Example 5
Mechanically stirring lithium hydroxide, silicon dioxide, gamma-aminopropyltriethoxysilane and ethanol uniformly according to a ratio of 1.11; wherein the D50 of lithium hydroxide is 25 μm and the D50 of silicon dioxide is 5nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the powder with modified lithium hydroxide according to the mass ratio of 1:2.16, and then carrying out primary sintering in an oxygen-containing atmosphere; the primary sintering procedure was as follows: heating to 300 ℃, preserving heat for 1h, heating to 800 ℃, preserving heat for 10h, and cooling to room temperature to obtain the silicon-doped sintering material.
Crushing and sieving the silicon-doped sintering material to obtain a material with the particle size distribution of 2-3 microns, and then placing the material in an environment with the relative humidity of air of 40% and the temperature of 40 ℃ for 30min to obtain a neutralizer; wherein the neutralizing agent contains 0.1% LiOH.
Reacting lysine diisocyanate and phosphorus-containing trihydric alcohol at 80 ℃ for 1h under mechanical stirring to obtain a prepolymer; adding dimethylolpropionic acid and trimethylsilyl isocyanate into the prepolymer to continue reacting for 0.5h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 800r/min for 10min, and drying to obtain a pre-sintered material; wherein the mass ratio of the lysine diisocyanate, the phosphorus-containing triol, the dimethylolpropionic acid, the trimethylsilyl isocyanate to the neutralizing agent is 1.4.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 500 ℃, and preserving the temperature for 2h to obtain the phosphorus-nitrogen-silicon co-doped carbon layer coating material with the thickness of 15nm.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 30sccm, the linear ion beam current is 0.1A, the substrate bias voltage is-100V, and the bombardment time is 3min.
Mixing the modified material and toluene diisocyanate according to a mass ratio of 15:1, mechanically stirring and mixing, and then carrying out heat treatment at 40 ℃ for 10min to obtain the modified single crystal ternary cathode material.
Example 6
Uniformly mechanically stirring lithium hydroxide, silicon dioxide, a coupling agent N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and ethanol according to a ratio of 1; wherein the D50 of lithium hydroxide is 40 μm and the D50 of silica is 15nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and modified lithium hydroxide according to the mass ratio of 1; the primary sintering procedure was as follows: heating to 350 ℃, preserving heat for 5h, heating to 900 ℃, preserving heat for 15h, and cooling to room temperature to obtain the silicon-doped sintering material.
Crushing and sieving the silicon-doped sintering material to obtain a material with the particle size distribution of 2-3 mu m, and then placing the material in an environment with the relative humidity of air of 95% and the temperature of 80 ℃ for 60min to obtain a neutralizer; wherein the neutralizing agent contains 0.5% LiOH.
Reacting 1,5-naphthalene diisocyanate and phosphorus-containing triol at 94 ℃ for 3 hours under mechanical stirring to obtain a prepolymer; adding 1,2-propylene glycol-3-sodium sulfonate and trimethylsilyl isocyanate into the prepolymer to continue reacting for 1h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 1000r/min for 20min, and drying to obtain a pre-sintered material; wherein, the mass ratio of 1,5-naphthalene diisocyanate, phosphorus-containing triol, 1,2-propanediol-3-sodium sulfonate, trimethylsilyl isocyanate and neutralizer is 1.6.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 700 ℃, and preserving the heat for 5 hours to obtain the material coated with the phosphorus-nitrogen-silicon co-doped carbon layer with the thickness of 40 nm.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 60sccm, the linear ion beam current is 0.4A, the substrate bias voltage is-70V, and the bombardment time is 8min.
And (2) mixing the modified material with hexamethylene diisocyanate according to the mass ratio of 20:1, mechanically stirring and mixing, and then carrying out heat treatment at 60 ℃ for 30min to obtain the modified single crystal ternary cathode material.
Example 7
The difference from the embodiment 1 is that the modified ternary cathode material is prepared by mixing lithium hydroxide, silicon dioxide, vinyl tri (beta-methoxyethoxy) silane and ethanol according to the mass ratio of 1.
Example 8
The difference from the embodiment 1 is that the modified ternary cathode material is prepared by mixing lithium hydroxide, silicon dioxide, vinyl tri (beta-methoxyethoxy) silane and ethanol according to the mass ratio of 1.
Example 9
The difference from the embodiment 1 is that the modified ternary cathode material is prepared by mixing lithium hydroxide, silicon dioxide, vinyl tri (beta-methoxyethoxy) silane and ethanol according to the mass ratio of 1.
Example 10
The difference from the embodiment 1 is that the mass ratio of the lysine diisocyanate, the phosphorus-containing trihydric alcohol, the dimethylolpropionic acid, the trimethylsilyl isocyanate and the neutralizing agent is 1.6.
Example 11
The difference from the embodiment 1 is that the mass ratio of the lysine diisocyanate, the phosphorus-containing trihydric alcohol, the dimethylolpropionic acid, the trimethylsilyl isocyanate and the neutralizing agent is 1.2.
Example 12
The difference from the example 1 is that the mass ratio of the modifier to the toluene diisocyanate is 20: and 1, finally preparing the modified ternary cathode material.
Example 13
The difference from the example 1 is that the mass ratio of the modifier to the toluene diisocyanate is 25: and 1, finally preparing the modified ternary cathode material.
Example 14
The difference from example 1 is that single crystal form Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 And finally preparing the modified ternary cathode material by the precursor and the modified lithium hydroxide according to the mass ratio of 1.
Example 15
The difference from example 1 is that single crystal form Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 And finally preparing the modified ternary cathode material by the precursor and the modified lithium hydroxide according to the mass ratio of 1.
Comparative example 1
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and lithium hydroxide according to the mass ratio of 1:2.16, and then carrying out primary sintering in an oxygen-containing atmosphere; the primary sintering procedure was as follows: heating to 800 ℃, preserving heat for 15h, and cooling to room temperature to obtain the sintering material.
Crushing and sieving the sintered material to obtain a material with the D50 of 3 microns, and placing the material in an environment with the relative humidity of air of 95% and the temperature of 40 ℃ for 60min to obtain a neutralizer; wherein the neutralizing agent contains 0.5% LiOH.
Reacting lysine diisocyanate and phosphorus-containing trihydric alcohol for 3 hours at 94 ℃ under mechanical stirring to obtain a prepolymer; adding dimethylolpropionic acid and trimethylsilyl isocyanate into the prepolymer to continue reacting for 0.5h to obtain a polymerization product; finally, adding the polymerization product and a neutralizing agent into deionized water, dispersing at a high speed of 1000r/min for 20min, and drying to obtain a pre-sintered material; wherein, the mass ratio of the lysine diisocyanate, the phosphorus-containing trihydric alcohol, the dimethylolpropionic acid, the trimethylsilyl isocyanate to the neutralizing agent is 1.3.
And (2) carrying out secondary sintering on the pre-sintered material in a nitrogen atmosphere, wherein the secondary sintering process comprises the following steps: heating to 700 ℃, and preserving the temperature for 5h to obtain the phosphorus-nitrogen-silicon co-doped carbon layer coating material.
And bombarding the coated material by adopting a nitrogen ion beam to obtain a modified material, wherein the bombardment parameters are as follows: the flow rate is 60sccm, the linear ion beam current is 0.4A, the substrate bias voltage is-100V, and the bombardment time is 8min.
Mixing the modified material and toluene diisocyanate according to a mass ratio of 15:1, mechanically stirring and mixing, and then carrying out heat treatment at 60 ℃ for 30min to obtain the single crystal ternary cathode material which can be directly used as the ternary cathode material.
Comparative example 2
Mechanically stirring lithium hydroxide, silicon dioxide, gamma-aminopropyltriethoxysilane and ethanol uniformly according to a ratio of 1.23; wherein the D50 of lithium hydroxide is 40 μm and the D50 of silica is 5nm.
Single crystal form of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor and modified lithium hydroxide according to the mass ratio of 1:2.22, and then sintering in an oxygen-containing atmosphere; the primary sintering procedure was as follows: heating to 300 ℃, preserving heat for 5h, heating to 840 ℃, preserving heat for 10h, and cooling to room temperature to obtain a silicon-doped sintering material; and crushing and sieving the sintered material to obtain a material with the particle size distribution of 2-3 mu m, and directly using the material as a ternary cathode material.
Comparative example 3
Weighing single crystal Ni according to the mass ratio of 1 0.8 Co 0.1 Mn 0.1 (OH) 2 Mixing the precursor with lithium hydroxide and then carrying out primary sintering in an oxygen-containing atmosphere; the primary sintering procedure was as follows: heating to 860 ℃, preserving heat for 12h, and cooling to room temperature to obtain a sintering material; and crushing and sieving the sintered material to obtain a material with the D50 of 4.5 mu m, and directly using the material as a ternary cathode material.
Comparative example 4
The difference from the embodiment 1 is that the phosphorus-nitrogen-silicon co-doped carbon layer coating material is directly used as a ternary cathode material without adopting a nitrogen ion beam to bombard the coating material.
The performance of the positive electrode materials prepared in examples 1 to 15 and comparative examples 1 to 4 was measured by a conventional method.
1. The powder resistance was measured using a four-electrode powder resistance meter, and the powder resistance was measured at 25 ℃ and under different pressures, respectively.
2. The materials prepared in the examples and the comparative examples, a conductive agent carbon black and a binder polyvinylidene fluoride are uniformly mixed with N-methyl pyrrolidone as a dispersing agent according to a mass ratio of 90. Taking the prepared positive electrode wafer as a working electrode, a metal lithium sheet as a counter electrode and 1mol/L LiPF 6 Dissolved in a mixed solution of ethylene carbonate and dimethyl carbonate (wt% = 1:1)) Is an electrolyte. And assembling a 2032 type button cell in a glove box, performing a first charge-discharge test at 0.2C within the range of cut-off voltage of 3.5-4.5V, performing a cyclic charge-discharge test at 1C multiplying power, and recording the capacity retention rate after 200 cycles.
The results of the above tests are shown in Table 1.
TABLE 1
As can be seen from FIGS. 1 and 2, the diisocyanate trimer modified silicon-phosphorus-nitrogen co-doped carbon layer prepared by the invention is uniformly and effectively coated on the silicon-doped single crystal LiNi x Co y Mn 1-x-y O 2 The surface of the material.
The combination of table 1 shows that, compared with the comparative example, the powder resistivity of the modified single crystal type ternary cathode material prepared by the invention is far lower than that of the comparative example, the discharge capacity is obviously improved at 4.5V and 0.2C multiplying power, and the 1C cycle retention rate is far higher than that of the comparative example.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the above preparation method of the present application is to single crystal form LiNi x Co y Mn 1-x-y O 2 The lattice is doped with silicon, and a silicon-phosphorus-nitrogen co-doped carbon layer coated with diisocyanate trimer modification is obtained on the surface of the base material; through the double modification effects, the low tortuosity of the prepared electrode is cooperatively realized, the uneven electrochemical reaction among positive electrode material particles is effectively optimized, and the generation of microcracks and lattice distortion in the crystal structure of the positive electrode material in the circulation process are inhibited, so that the stability of the material structure is maintained, the expansion degree of the unit cell volume of the material under high cut-off voltage is effectively reduced, the collapse of the crystal structure is inhibited, and the discharge capacity and the cycle discharge stability of the lithium ion battery applied to the material under the high cut-off voltage are further improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified single crystal ternary cathode material is characterized by comprising the following steps:
s1, in an oxygen-containing atmosphere, a single crystal type ternary positive electrode precursor Ni is included x Co y Mn 1-x-y (OH) 2 Mixing materials of a lithium source, a silicon source and a coupling agent, and then sintering for the first time to obtain a neutralizer;
s2, reacting raw materials including first isocyanate, alcohol compounds containing nitrogen and/or phosphorus, a first chain extender, a second chain extender and the neutralizer, and drying to obtain a pre-sintered material;
step S3, in N 2 Under the protection of atmosphere or inert gas atmosphere, carrying out secondary sintering on the pre-sintered material to obtain a phosphorus-nitrogen-silicon co-doped carbon layer coating material, and bombarding the coating material by adopting a nitrogen ion beam to obtain a modified material;
s4, mechanically stirring and mixing the modified material and second isocyanate, and then carrying out heat treatment to obtain the modified single crystal ternary cathode material;
wherein x is more than or equal to 0.8 and less than 1,0 and less than or equal to 0.15.
2. The method according to claim 1, wherein the step S1 includes:
mechanically stirring and mixing the lithium source, the silicon source, the coupling agent and ethanol, and then performing ball milling and drying to obtain a modified lithium source, wherein the ball milling time is preferably 60-90 min, and the drying temperature is preferably 80-100 ℃;
in an oxygen-containing atmosphere, ni is used as a precursor of the single crystal type ternary positive electrode x Co y Mn 1-x-y (OH) 2 Carrying out primary sintering on the raw material of the modified lithium source to obtain a silicon-doped sintering material;
crushing and sieving the silicon-doped sintering material, and standing for 30-60 min to obtain a neutralizing agent;
the mass ratio of the lithium source, the silicon source, the coupling agent and the ethanol is 1.11-0.23, preferably the D50 of the lithium source is 25-40 μm, preferably the D50 of the silicon source is 5-15 nm, and preferably the D50 of the modified lithium source is 8-12 μm;
preferably, the lithium source is lithium hydroxide, the silicon source is silicon dioxide, and the coupling agent is selected from any one or more of vinyltris (beta-methoxyethoxy) silane, gamma-aminopropyltriethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
3. The method according to claim 2, wherein the single-crystal ternary positive electrode precursor Ni is Ni x Co y Mn 1-x-y (OH) 2 The mass ratio of the modified lithium hydroxide to the modified lithium hydroxide is 1.16-2.32;
preferably, the primary sintering process comprises:
the single crystal type ternary positive electrode precursor Ni x Co y Mn 1-x-y (OH) 2 The mixture with the modified lithium hydroxide is heated to 300-350 ℃, and is kept warm for 1-5 h, and then is heated to 800-900 ℃ and is kept warm for 10-15 h.
4. The method according to claim 2, wherein the particle size distribution of the neutralizing agent is between 2 and 3 μm;
preferably, the standing is carried out at 40-80 ℃ and at 40-95% relative humidity of air;
preferably, the neutralizing agent contains 0.1 to 0.5% of LiOH.
5. The method according to claim 2, wherein the step S2 includes:
mechanically stirring the first isocyanate and the alcohol compound containing nitrogen and/or phosphorus to react for 1-3 h at 80-94 ℃ to obtain a prepolymer;
adding the first chain extender and the second chain extender into the prepolymer to continue reacting for 0.5 to 1 hour to obtain a polymerization product;
adding the polymerization product and the neutralizer into water, dispersing for 10-20 min at a speed of 800-1000 r/min, and drying to obtain the pre-sintered material;
preferably, the mass ratio of the first isocyanate, the nitrogen and/or phosphorus-containing alcohol compound, the first chain extender, the second chain extender and the neutralizing agent is 1.3 to 1.6;
preferably the first isocyanate is lysine diisocyanate and/or 1,5-naphthalene diisocyanate;
preferably, the alcohol compound containing nitrogen and/or phosphorus is phosphorus-containing trihydric alcohol, and the phosphorus-containing trihydric alcohol is obtained by reacting trimethyl phosphate with 1,4-butanediol;
preferably, the first chain extender is dimethylolpropionic acid and/or 1,2-propanediol-3-sodium sulfonate;
preferably, the second chain extender is trimethylsilyl isocyanate.
6. The preparation method according to claim 2, characterized in that the temperature of the secondary sintering is 500-700 ℃, and the holding time of the secondary sintering is preferably 2-5 h;
the thickness of the phosphorus-nitrogen-silicon co-doped carbon layer is preferably between 15 and 40 nm.
7. The method of claim 2, wherein the process parameters of the bombardment are: the flow rate is 30-60 sccm, the linear ion beam current is 0.1-0.4A, the matrix bias voltage is-100 to-70V, and the bombardment time is 3-8 min.
8. The preparation method according to claim 2, wherein in the step S4, the mass ratio of the modifying material to the second isocyanate is 15 to 20:1;
preferably, the second isocyanate is toluene diisocyanate and/or hexamethylene diisocyanate;
the temperature of the heat treatment is preferably 40 to 60 ℃, and the time of the heat treatment is preferably 10 to 30min.
9. A modified single crystal ternary cathode material, which is prepared by the preparation method of any one of claims 1 to 8.
10. A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the positive electrode comprises the modified single crystal ternary positive electrode material prepared by the preparation method of any one of claims 1 to 8 or the modified single crystal ternary positive electrode material of claim 9.
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