CN114671469B - Carbonate grafted oxide type positive electrode material precursor and preparation method and application thereof - Google Patents
Carbonate grafted oxide type positive electrode material precursor and preparation method and application thereof Download PDFInfo
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- CN114671469B CN114671469B CN202210330351.3A CN202210330351A CN114671469B CN 114671469 B CN114671469 B CN 114671469B CN 202210330351 A CN202210330351 A CN 202210330351A CN 114671469 B CN114671469 B CN 114671469B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 123
- 239000002243 precursor Substances 0.000 title claims abstract description 103
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011572 manganese Substances 0.000 claims abstract description 60
- 239000002002 slurry Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 214
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 71
- 150000005323 carbonate salts Chemical class 0.000 claims description 30
- 150000005324 oxide salts Chemical class 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 150000001868 cobalt Chemical class 0.000 claims description 16
- 150000002696 manganese Chemical class 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 239000010405 anode material Substances 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- 230000001276 controlling effect Effects 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 21
- 238000005086 pumping Methods 0.000 description 20
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 241000080590 Niso Species 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 230000002572 peristaltic effect Effects 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- -1 oxide Chemical compound 0.000 description 7
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013188 LiBOB Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910011324 LiNi0.6Co0.4O2 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 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
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a carbonate grafted oxide type positive electrode material precursor, which has the structural formula of ACO 3 ‑R‑BO x A and B are Ni 1‑a‑b Co a Mn b Z c Wherein a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1; a+b is more than 0 and less than or equal to 1; c is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 4, the molar ratio of nickel, cobalt and manganese in A is different from the molar ratio of nickel, cobalt and manganese in B, and Z is at least one of Al, mg, ti, B, zr, bi, mo, P and rare earth elements; r is a grafting agent comprising at least one element of Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and rare earth elements. Compared with the prior art, the precursor is grafted at the precursor end, so that the aim of uniformly mixing different types of materials is fulfilled, and the problems of uneven slurry dispersion, poor pole piece uniformity and inconsistent electrochemical performance of the materials existing in the existing mixed anode material are solved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a carbonate grafted oxide type positive electrode material precursor, a preparation method and application thereof.
Background
Lithium ion batteries are increasingly used in everyday life. Currently, the positive electrode materials of lithium ion batteries mainly comprise lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate and the like. Different types of positive electrode materials have different electrochemical performances and are matched with different application scenes.
Along with the continuous expansion of application scenes of lithium ion batteries, the lithium ion batteries manufactured by a single positive electrode material have difficulty in meeting the requirements of various subdivision fields in terms of performance and cost. The mixing of multiple positive electrode materials (typically two) generally achieves a balance of cost control and performance requirements. The current common method is to directly mix several positive electrode materials according to different proportions according to the requirements. However, this method still has the following problems: 1) A slurry mixing process problem of the mixed material; 2) The dispersion uniformity of the anode material in the pole piece is improved; 3) The lithium removal and insertion behaviors of different materials under the same voltage in the charge and discharge process have the influence on the stability of the pole piece structure and the consistency of macroscopic electrical performance of the battery.
In view of the foregoing, it is necessary to provide a solution to the above-mentioned problems.
Disclosure of Invention
One of the objects of the present invention is: the precursor of the carbonate grafted oxide type positive electrode material is provided to solve the problems of uneven slurry dispersion, poor uniformity of a pole piece and inconsistent electrochemical performance of the material when a plurality of positive electrode materials are mixed and used in the application process of the lithium ion battery at present.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A carbonate grafted oxide type positive electrode material precursor has a structural formula of ACO 3 -R-BO x A and B are Ni 1-a- b Co a Mn b Z c Wherein a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1; a+b is more than 0 and less than or equal to 1; c is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 4, the molar ratio of nickel, cobalt and manganese in A is different from the molar ratio of nickel, cobalt and manganese in B, and Z is at least one of Al, mg, ti, B, zr, bi, mo, P and rare earth elements; r is a grafting agent comprising at least one element of Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and rare earth elements.
Preferably, the mass of R is ACO 3 And BO (BO) x 1 to 10 percent of the sum of the mass.
Preferably, ACO 3 And BO (BO) x The mass ratio of (2) is 1:99-99:1.
PreferablyIn the formula (I), R is (M) x N y )CO 3 Or (M) x N y )(OH) 2 X is more than 0 and less than 1; y is more than 0 and less than 1; x+y is more than 0 and less than or equal to 1; m and N are selected from different elements, and are at least one element of Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and rare earth elements.
The second object of the present invention is: the preparation method of the carbonate grafted oxide type positive electrode material precursor comprises the following steps:
s1, mixing an aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt with a carbonate aqueous solution for reaction, controlling the pH value of the solution in the reaction process to be 6-9, aging, and suction-filtering to obtain carbonate salt ACO 3 ；
S2, mixing an aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt with an aqueous solution of carbonate to react, controlling the pH of the solution in the reaction process to be 6-9, aging, filtering, drying, burning at 500-900 ℃ and grinding to obtain oxide salt BO x ；
S3, preparing the carbonate salt ACO 3 With oxide salts BO x Mixing at 25-70 deg.c to prepare slurry; adding a solution for liquid phase reaction to form a grafting agent R into the slurry, stirring and reacting for 30-90 min, washing and drying to obtain a carbonate grafted oxide type positive electrode material precursor ACO 3 -R-BO x 。
Preferably, in step S1, the carbonate salt ACO 3 The preparation method of (2) comprises the following steps: adding aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt and carbonate aqueous solution into a reactor containing water at a speed of 1-2 mL/min respectively, continuously stirring and reacting at 30-80 ℃ in an inert atmosphere, controlling the pH of the solution in the reaction process to be 6-9, continuously stirring and aging for 10-36 h after the addition, and vacuum filtering to obtain carbonate salt ACO 3 。
Preferably, in step S2, the oxide salt BO x The preparation method of (2) comprises the following steps: adding aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt and carbonate aqueous solution into a reactor containing water at a speed of 1-2 mL/min respectively, continuously stirring and reacting at 30-80 ℃ in inert atmosphere, and controlling the solution in the reaction process The pH value of (2) is 6-9, the mixture is continuously stirred and aged for 10-36 hours after the addition, the mixture is filtered and dried in vacuum, and the mixture is burned for 5-12 hours at the temperature of 500-900 ℃ to obtain oxide salt BO x 。
Preferably, in step S3, the solution for forming the grafting agent R by the liquid phase reaction includes a first solution and a second solution, wherein the first solution is a mixed solution of cobalt salt and manganese salt, the second solution is sodium bicarbonate solution or sodium hydroxide solution, and the first solution and the second solution form the grafting agent R by the liquid phase reaction to form the carbonate salt ACO 3 With oxide salts BO x Grafting is performed.
Preferably, in step S3, the first solution and the second solution are pumped into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively for pre-reaction, and then the rest of the first solution and the second solution are pumped into the slurry for continuous stirring reaction, and washed and dried to obtain the carbonate grafted oxide type positive electrode material precursor ACO 3 -R-BO x 。
The third object of the present invention is to provide a preparation method of the grafted positive electrode material, wherein the carbonate grafted oxide positive electrode material precursor is mixed with lithium salt, sintered for 6-24 hours at 750-950 ℃, cooled and ground to obtain the grafted positive electrode material.
Preferably, the sintering conditions are: firstly, heating to 750-800 ℃ at the speed of 5-7 ℃/min, and preserving heat for 2-6 h; then heating to 900-950 ℃ at the speed of 2-6 ℃/min, and preserving heat for 10-24 h.
The fourth object of the present invention is to provide a grafted positive electrode material prepared by the above-mentioned preparation method of a grafted positive electrode material.
The fifth object of the present invention is to provide a positive electrode sheet comprising the above-mentioned graft type positive electrode material.
The invention aims at providing a lithium ion battery, which comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate, wherein the positive plate is the positive plate.
Compared with the prior art, the invention has the beneficial effects that: the oxide type salt grafted carbonate type salt positive electrode material precursor provided by the invention achieves the aim of uniformly mixing different types of materials through a precursor end grafting mode, namely, the carbonate type salt positive electrode material precursor and the oxide type salt positive electrode material precursor are coupled together through a chemical method under the action of a grafting agent, and are fused to form a brand new and stable positive electrode material precursor. In the cathode material prepared by the grafting type precursor, two different types of cathode materials are fused and grown into a whole to form the grafting type cathode material, so that the problem of uneven dispersion of mixed components in the process of preparing slurry by the grafting type cathode material is avoided, the problem of segregation of the mixed components in a pole piece does not exist, and the electrochemical potential is the same, thereby solving the problems of uneven dispersion of slurry, poor uniformity of the pole piece and inconsistent electrochemical performance of the material in the application process of the lithium ion battery when the mixed cathode materials are mixed and used in the current lithium ion battery application. Meanwhile, as different types of positive electrode materials have different electrochemical properties, the preparation method of the grafted precursor can design and prepare the positive electrode material with specific properties.
Drawings
Fig. 1 is an SEM image of a grafted cathode material precursor according to example 1 of the present invention.
Fig. 2 is an XRD pattern of a grafted positive electrode material precursor of example 1 of the present invention.
Fig. 3 is an SEM image of the graft type cathode material of example 1 of the present invention.
Fig. 4 is an XRD pattern of the graft type cathode material of example 1 of the present invention.
Detailed Description
1. Carbonate grafted oxide type positive electrode material precursor
The first aspect of the present invention is to provide a carbonate grafted oxide type positive electrode material precursor, which has the structural formula of ACO 3 -R-BO x A and B are Ni 1-a-b Co a Mn b Z c Wherein a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1; a+b is more than 0 and less than or equal to 1; c is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 4, and the mole ratio of nickel, cobalt and manganese in A is different from BThe molar ratio of nickel, cobalt and manganese in the alloy is Al, mg, ti, B, zr, bi, mo, P and at least one of rare earth elements; r is a grafting agent comprising at least one element of Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and rare earth elements.
Wherein, the mole ratio of nickel, cobalt and manganese in A includes but is not limited to 1:1: 1. 5:2: 3. 6:2: 2. 8:1: 1. 6:1:3, the specific adjustment can also be carried out according to the requirement, such as 55:15:30. the doping amount of the element Z in the A can be adjusted according to the weight ratio of the A by selecting at least one of Al, mg, ti, B, zr, bi, mo, P, F and rare earth elements according to the requirement, and is preferably less than 1% of the weight of the A, and more preferably 0.05-0.5% of the weight of the A.
Likewise, the molar ratio of nickel, cobalt, manganese in B includes, but is not limited to, 1:1: 1. 5:2: 3. 6:2: 2. 8:1: 1. 6:1:3, the specific adjustment can also be carried out according to the requirement, such as 55:15:30. the doping amount of the element Z in the B can be adjusted according to the weight ratio of the B by selecting at least one of Al, mg, ti, B, zr, bi, mo, P, F and rare earth elements according to the requirement, and is preferably less than 1% of the weight of the B, and more preferably 0.05-0.5% of the weight of the B.
Specifically, the carbonate grafted oxide type positive electrode material precursor may be (Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -R-(Ni 1/3 Co 1/3 Mn 1/3 )O x 、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -R-Co 3 O 4 、(Ni 0.6 Co 0.2 Mn 0.2 )CO 3 -R-Co 3 O 4 、(Ni 0.6 Co 0.2 Mn 0.2 )CO 3 -R-(Ni 1/3 Co 1/3 Mn 1/3 )O x 、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -R-(Ni 0.6 Mn 0.4 O) x 、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -R-(Ni 0.5 Co 0.2 Mn 0.3 )O x Or CoCO 3 -R-(Ni 0.5 Co 0.2 Mn 0.3 )O x 。
The grafting agent R can be at least one of carbonate, oxide, phosphate and hydroxide. I.e. at least one of the carbonate, oxide, phosphate, hydroxide, ni, co, mn, al, mg, ti, B, zr, bi, mo, P, rare earth elements, such as CoCO 3 、MnPO 4 Etc.
Preferably, the grafting agent R is (M x N y )CO 3 Or (M) x N y )(OH) 2 X is more than 0 and less than 1; y is more than 0 and less than 1; x+y is more than 0 and less than or equal to 1; m and N are selected from different elements, and are at least one element of Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and rare earth elements. Specifically included but not limited to (Co 0.5 Mn 0.5 )CO 3 、(Ni 0.5 Mn 0.5 )CO 3 、(Co 0.5 Mn 0.5 )(OH) 2 And (Ni) 0.5 Mn 0.5 )(OH) 2 . With grafting agent (Co) 0.5 Mn 0.5 )CO 3 And (Ni) 0.5 Mn 0.5 )CO 3 For example, the corresponding grafted positive electrode material precursor may be (Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -(Co 0.5 Mn 0.5 )CO 3 -(Ni 1/3 Co 1/3 Mn 1/3 )O x 、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 、(Ni 0.6 Co 0.2 Mn 0.2 )CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 、(Ni 0.6 Co 0.2 Mn 0.2 )CO 3 -(Ni 0.5 Mn 0.5 )CO 3 -(Ni 1/3 Co 1/3 Mn 1/3 )O x 、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -(Ni 0.5 Mn 0.5 )CO 3 -(Ni 0.6 Mn 0.4 O) x 、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 -(Ni 0.5 Mn 0.5 )CO 3 -(Ni 0.5 Co 0.2 Mn 0.3 )O x Or CoCO 3 -(Co 0.5 Mn 0.5 )CO 3 -(Ni 0.5 Co 0.2 Mn 0.3 )O x 。
The invention preferentially achieves the aim of uniformly mixing different types of positive electrode material precursors in a mode of grafting at a precursor end, adopts the grafted precursor to prepare the positive electrode material for fusion growth of different types of positive electrode materials, ensures the consistency of the positive electrode material particles in electrochemical performance, such as the same potential and the like, and ensures the excellent effects of the subsequently obtained lithium ion battery in polarization resistance, cycle stability, high temperature performance and safety performance.
The grafting agent adopted by the invention is a component part of the positive electrode material, and can be used as a functional doping agent, so that the grafting agent with proper dosage does not negatively influence the structure and the performance of the final positive electrode material.
The grafted positive electrode material precursor provided by the invention is easier to realize the secondary ball grafted single-crystal positive electrode material.
In some embodiments, the mass of R is ACO 3 And BO (BO) x 1 to 10 percent of the sum of the mass. The quality of the grafting agent R is controlled within the range, so that on one hand, the situation that a grafting precursor cannot be obtained due to the fact that the grafting agent R surrounds the grafting materials A and B too much is avoided, and on the other hand, the situation that the coupling fusion of the grafting materials A and B cannot be guaranteed due to the fact that the grafting agent R is too little is avoided. Preferably, the mass of R is ACO 3 And BO (BO) x The total mass is 2-5%, specifically 2%, 2.5%, 3%, 3.5%, 4%, 4.5% and 5%. The grafting agent with 2-5% can couple the grafting material A and the grafting material B together well through chemical method, so as to obtain the positive electrode material precursor with stable structure, which can be shown in figures 1-2.
In some embodiments, ACO 3 And BO (BO) x The mass ratio of (2) is 1:99-99:1. The specific adjustment can be carried out according to actual demands. Preferably, the carbonate salt ACO 3 With oxide salts BO x The mass ratio of (2) can be 20:80-80:20. In particular, the method comprises the steps of,carbonate salt ACO 3 With oxide salts BO x The mass ratio of (c) may be 20:80, 30:70, 40:60, 50:50, 60:40, 70:30 or 80:20, such as in 100g mass, carbonate salt ACO 3 Is 80g in mass, oxide salt BO x Is 20g; carbonate salt ACO 3 Is 60g in mass, oxide salt BO x Mass of 40g, etc.
The second aspect of the present invention is directed to a method for preparing the carbonate grafted oxide type positive electrode material precursor, comprising the steps of:
s1, mixing an aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt with a carbonate aqueous solution for reaction, controlling the pH value of the solution in the reaction process to be 6-9, aging, and suction-filtering to obtain carbonate salt ACO 3 ；
S2, mixing an aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt with an aqueous solution of carbonate to react, controlling the pH of the solution in the reaction process to be 6-9, aging, filtering, drying, burning at 500-900 ℃ and grinding to obtain oxide salt BO x ；
S3, preparing the carbonate salt ACO 3 With oxide salts BO x Mixing at 25-70 deg.c to prepare slurry; adding a solution for liquid phase reaction to form a grafting agent R into the slurry, stirring and reacting for 30-90 min, washing and drying to obtain a carbonate grafted oxide type positive electrode material precursor ACO 3 -R-BO x 。
According to the preparation method provided by the invention, carbonate salt particles and oxide salt particles are prepared respectively, then the carbonate salt particles and the oxide salt particles are mixed to prepare slurry, and the slurry are mixed at the temperature of 25-70 ℃ so as to be more beneficial to uniform mixing of the carbonate salt particles and the oxide salt particles; then adding a solution for liquid phase reaction to form grafting agent R into the slurry (the added solution can be used for generating grafting agent R through liquid phase reaction), controlling the reaction time to ensure that carbonate type salt particles and oxide type salt particles are connected to the grafting agent under the action of the grafting agent, thereby forming ACO 3 -R-BO x The structure is a novel positive electrode material precursor with a grafted structure.
In some embodiments, in step S1, the carbonate salt ACO 3 The preparation method of (2) comprises the following steps: adding aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt and carbonate aqueous solution into a reactor containing water at a speed of 1-2 mL/min respectively, continuously stirring and reacting at 30-80 ℃ in an inert atmosphere, controlling the pH of the solution in the reaction process to be 6-9, continuously stirring and aging for 10-36 h after the addition, and vacuum filtering to obtain carbonate salt ACO 3 。
In some embodiments, in step S2, the oxide salt BO x The preparation method of (2) comprises the following steps: adding aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt and carbonate aqueous solution into a reactor containing water at a speed of 1-2 mL/min respectively, continuously stirring and reacting at 30-80 ℃ in an inert atmosphere, controlling the pH of the solution in the reaction process to be 6-9, continuously stirring and aging for 10-36 h after the addition, vacuum filtering and drying, and burning for 5-12 h at 500-900 ℃ to obtain oxide salt BO x 。
In some embodiments, in step S3, the solution for liquid phase reaction to form the grafting agent R comprises a first solution that is a mixed solution of cobalt salt and manganese salt and a second solution that is a sodium bicarbonate solution or sodium hydroxide solution, which are reacted by liquid phase reaction to form the grafting agent R to ACO the carbonate salt 3 With oxide salts BO x Grafting is performed. The second solution mainly enables cobalt and manganese in the first solution to perform coprecipitation reaction, so that a product grafting agent R is obtained through the reaction, and the grafting material A and the grafting material B are coupled together through bridging action of the grafting agent R. Preferably, the molar ratio of cobalt salt to manganese salt in the first solution is 1:1, and the grafting is performed by adopting a mixed grafting agent solution, so that the experiment proves that the grafting material A and the grafting material B have better coupling effect.
In some embodiments, in step S3, the first solution and the second solution are pumped into the slurry at a rate of 0.5mL/min and 3.5mL/min, respectively, to perform a pre-reaction, and then the remaining first solution and second solution are pumped into the slurry to continue stirring and reacting, and washing and drying are performed, thereby obtaining the grafted cathode material precursor ACO 3 -R-BO x . First control flowAnd (3) pumping a part of solution to perform a pre-grafting reaction, pumping the rest of grafted solution into the slurry to stir and react, and further ensuring the grafting effect of carbonate salt and oxide salt so as to ensure the consistency of the electrochemical performance of the subsequent positive electrode material.
2. Grafted positive electrode material
The third aspect of the invention aims to provide a preparation method of a grafted positive electrode material, which comprises the steps of mixing a carbonate grafted oxide positive electrode material precursor with lithium salt, sintering for 6-24 hours at 750-950 ℃, cooling, and grinding to obtain the grafted positive electrode material.
In some embodiments, the sintering conditions are: firstly, heating to 750-800 ℃ at the speed of 5-7 ℃/min, and preserving heat for 2-6 h; then heating to 900-950 ℃ at the speed of 2-6 ℃/min, and preserving heat for 10-24 h. Preferably, the sintering conditions are: firstly, heating to 760 ℃ at the speed of 6 ℃/min, and preserving heat for 4 hours; then heating to 950 ℃ at the speed of 3 ℃/min, and preserving heat for 12 hours.
A fourth aspect of the present invention is directed to providing a grafted positive electrode material, such as LiNi, prepared by the method for preparing a grafted positive electrode material 0.5 Co 0.2 Mn 0.3 O 2 -LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiCoO 2 。
3. Positive plate
A fifth aspect of the present invention is directed to a positive electrode sheet comprising the above-described graft type positive electrode material.
The positive plate comprises a positive current collector and a positive active layer coated on at least one surface of the positive current collector, wherein the positive active material in the positive active layer is the grafted positive material. The grafted positive electrode material is mixed with a binder and a conductive agent to prepare slurry, and then the slurry is coated on a positive electrode current collector, and the positive electrode plate is obtained after drying.
4. Lithium ion battery
The sixth aspect of the present invention is directed to a lithium ion battery, which includes a positive electrode sheet, a negative electrode sheet, and a separator spaced between the positive electrode sheet and the negative electrode sheet, where the positive electrode sheet is the positive electrode sheet described above.
The active material coated on the negative electrode sheet can be one or more of graphite, soft carbon, hard carbon, carbon fiber, mesophase carbon microsphere, silicon-based material, tin-based material, lithium titanate or other metals capable of forming alloy with lithium. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon oxygen compound, silicon carbon compound and silicon alloy; the tin-based material can be selected from one or more of elemental tin, tin oxide and tin alloy. While the negative current collector used for the negative electrode sheet is generally a structure or a part for collecting current, the negative current collector may be various materials suitable for use as a negative current collector of a lithium ion battery in the field, for example, the negative current collector may be a metal foil, etc., and more specifically may include a copper foil, etc.
And the separator may be a variety of materials suitable for lithium ion battery separators in the art, for example, may be a combination of one or more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fibers, and the like.
The lithium ion battery also includes an electrolyte comprising an organic solvent, an electrolyte lithium salt, and an additive. Wherein the electrolyte lithium salt can be LiPF used in high-temperature electrolyte 6 And/or LiBOB; liBF used in the low-temperature electrolyte may be used 4 、LiBOB、LiPF 6 At least one of (a) and (b); liBF used in the overcharge-preventing electrolyte may also be used 4 、LiBOB、LiPF 6 At least one of LiTFSI; liClO may also be 4 、LiAsF 6 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 At least one of them. And the organic solvent may be a cyclic carbonate, including PC, EC; chain carbonates, including DFC, DMC, or EMC; carboxylic esters, including MF, MA, EA, MP, and the like, are also contemplated. To addAgents include, but are not limited to, film forming additives, conductive additives, flame retardant additives, overcharge prevention additives, and control of H in electrolytes 2 At least one of an additive for O and HF content, an additive for improving low temperature performance, and a multifunctional additive.
In order to make the technical scheme and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation method of carbonate grafted oxide type positive electrode material with structural formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiCoO 2 Wherein the structural formula of the precursor is NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 。
The preparation method of the carbonate grafted oxide type positive electrode material precursor comprises the following steps:
S1、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 (i.e., NCM523-CO 3 ) Precursor preparation: preparing NiSO according to a molar ratio of 5:2:3 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum to obtain carbonate salt NCM523-CO 3 ；
S2、Co 3 O 4 Precursor preparation: preparation of 2mol x L -1 CoSO of (2) 4 500mL of aqueous solution, labeled solution 1; formulation of 4mol L -1 NH of (C) 4 HCO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum and dried, burned for 6 hours in the air atmosphere at 650 ℃, ground and sieved to obtain oxide salt Co 3 O 4 ；
S3, preparing a precursor: 80g of NCM523-CO was weighed 3 And 20g Co 3 O 4 Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio 1: 1) At a concentration of 2mol/L, where CoSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 5 percent, and the second solution NaHCO 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-CO 3 Grafted Co 3 O 4 Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 (4:1)。
The obtained grafted positive electrode material precursor is used for preparing a positive electrode material, and the preparation steps are as follows:
s4, obtaining NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 (4:1) and Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 920 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; solid phase sinteringThen cooling to room temperature along with the furnace, grinding to obtain the grafted anode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiCoO 2 。
Example 2
Unlike example 1, the preparation step S3 of the carbonate grafted oxide type positive electrode material precursor.
S3, preparing a precursor: 60g NCM523-CO is weighed 3 And 40g Co 3 O 4 Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio 1: 1) At a concentration of 2mol/L, where CoSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 5 percent, and the second solution NaHCO 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-CO 3 Grafted Co 3 O 4 Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 (1.5:1)。
The remainder is the same as embodiment 1 and will not be described here again.
Example 3
Unlike example 1, the preparation step S3 of the carbonate grafted oxide type positive electrode material precursor.
S3, preparing a precursor: weighing 50g of NCM523-CO 3 And 50g Co 3 O 4 Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio 1: 1) At a concentration of 2mol/L, where CoSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 5 percent, and the second solution NaHCO 3 The concentration is 1mol/L; simultaneously pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively for reactionAfter 30min, pumping the residual first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-CO 3 Grafted Co 3 O 4 Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 (1:1)。
The remainder is the same as embodiment 1 and will not be described here again.
Example 4
Unlike example 1, the preparation step S3 of the carbonate grafted oxide type positive electrode material precursor.
S3, preparing a precursor: 40g of NCM523-CO was weighed 3 And 60g Co 3 O 4 Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio 1: 1) At a concentration of 2mol/L, where CoSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 5 percent, and the second solution NaHCO 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-CO 3 Grafted Co 3 O 4 Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -Co 3 O 4 (1:1.5)。
The remainder is the same as embodiment 1 and will not be described here again.
Example 5
Preparation method of carbonate grafted oxide type positive electrode material with structural formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiNi 1/3 Co 1/3 Mn 1/3 O 2 . Wherein the structural formula of the precursor is NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -NCM111-O x 。
S1、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 (i.e., NCM523-CO 3 ) Precursor preparation: preparing NiSO according to a molar ratio of 5:2:3 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum to obtain carbonate salt NCM523-CO 3 ；
S2、(Ni 1/3 Co 1/3 Mn 1/3 ) O (i.e. NCM111-O x ) Precursor preparation: preparing NiSO according to a molar ratio of 1:1:1 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum and dried, burned for 6 hours in the air atmosphere at 650 ℃, and grinded and sieved to obtain oxide type salt NCM111-O x 。
S3, preparing a precursor: 80g of NCM523-CO was weighed 3 And 20gNCM111-O x Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio of1: 1) At a concentration of 2mol/L, where CoSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 5 percent, and the second solution NaHCO 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-CO 3 Grafted NCM111-O x Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -NCM111-O x (4:1)。
The obtained grafted positive electrode material precursor is used for preparing a positive electrode material, and the preparation steps are as follows:
S4, obtaining NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -NCM111-O x (4:1) and Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 920 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a grafted anode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiNi 1/3 Co 1/3 Mn 1/3 O 2 。
Example 6
Unlike example 5, the preparation step S3 of the carbonate grafted oxide type positive electrode material precursor.
S3, preparing a precursor: 60g NCM523-CO is weighed 3 And 40g NCM111-O x Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio 1: 1) At a concentration of 2mol/L, naHCO as a second solution 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washingWashing, filtering and drying the slurry to obtain a grafted positive electrode material precursor NCM523-CO 3 Grafted NCM111-O x Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -NCM111-O x (1.5:1)。
The remainder is the same as embodiment 5 and will not be described here again.
Example 7
Unlike example 5, the preparation step S3 of the carbonate grafted oxide type positive electrode material precursor.
S3, preparing a precursor: weighing 50g of NCM523-CO 3 And 50g NCM111-O x Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (CoSO 4 ：MnSO 4 Molar ratio 1: 1) At a concentration of 2mol/L, naHCO as a second solution 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a grafted positive electrode material precursor NCM523-CO 3 Grafted NCM111-O x Is marked as NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -NCM111-O x (1:1)。
The remainder is the same as embodiment 5 and will not be described here again.
Example 8
Preparation method of carbonate grafted oxide type positive electrode material with structural formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiNi 0.6 Co 0.4 O 2 . Wherein the structural formula of the precursor is NCM523-CO 3 -(Co 0.5 Mn 0.5 )CO 3 -(Ni 0.6 Co 0.4 )O x 。
The preparation method of the carbonate grafted oxide type positive electrode material precursor comprises the following steps:
S1、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 (i.e., NCM523-CO 3 ) Precursor preparation: is prepared according to the mol ratio of 5:2:3NiSO 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum to obtain carbonate salt NCM523-CO 3 ；
S2、(Ni 0.6 Co 0.4 )O x (i.e. NiCo-O) x ) Precursor preparation: preparing NiSO according to a molar ratio of 6:4 4 、CoSO 4 Is (Ni) 2+ 、Co 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum and dried, burned for 6 hours in the air atmosphere at 650 ℃, ground and sieved to obtain oxide salt NiCo-O x 。
S3, preparing a precursor: 80g of NCM523-CO was weighed 3 And 20g of NiCo-O x Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (NiSO 4 ：MnSO 4 Molar ratio 1: 1) The concentration is 2mol/L, wherein, niSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 5 percent,second solution NaHCO 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-CO 3 Grafted NiCo-O x Is marked as NCM523-CO 3 -(Ni 0.5 Mn 0.5 )CO 3 -(Ni 0.6 Co 0.4 )O x (4:1)。
The obtained grafted positive electrode material precursor is used for preparing a positive electrode material, and the preparation steps are as follows:
s4, obtaining NCM523-CO 3 -(Ni 0.5 Mn 0.5 )CO 3 -(Ni 0.6 Co 0.4 )O x (4:1) and Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 920 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a grafted anode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 -LiNi 0.6 Co 0.4 O 2 。
Example 9
A process for preparing the carbonate grafted oxide type positive electrode material with LiCoO structural formula 2 -LiNi 0.5 Co 0.2 Mn 0.3 O 2 . Wherein the structural formula of the precursor is CoCO 3 -(Ni 0.5 Mn 0.5 )CO 3 -NCM523-O x 。
S1、CoCO 3 Precursor preparation: preparation of 2mol x L -1 CoSO of (2) 4 500mL of aqueous solution, labeled solution 1; formulation of 4mol L -1 NH of (C) 4 HCO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring speed at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum to obtain carbonate salt CoCO 3 。
S2、NCM523-O x Precursor preparation: preparing NiSO according to a molar ratio of 5:2:3 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered and dried in vacuum, burned for 6 hours in the air atmosphere at 650 ℃, and grinded and sieved to obtain oxide salt NCM523-O x 。
S3, preparing a precursor: 50g of CoCO was weighed out 3 And 50gNCM523-O x Dispersing in 100g deionized water, and stirring at 60 ℃ to prepare slurry; preparing a solution (for generating grafting agent R by liquid phase reaction): comprises a first solution (NiSO 4 ：MnSO 4 Molar ratio 1: 1) The concentration is 2mol/L, wherein, niSO 4 And MnSO 4 The sum of the mass of the precursor of the positive electrode material is 3 percent, and the second solution NaHCO 3 The concentration is 1mol/L; pumping the first solution and the second solution into the slurry at the rates of 0.5mL/min and 3.5mL/min respectively, reacting for 30min, pumping the rest first solution and the second solution into the slurry, continuously stirring and reacting for 30min, washing, filtering and drying the slurry to obtain a positive electrode material precursor NCM523-O x Grafting CoCO 3 Is denoted as CoCO 3 -(Ni 0.5 Mn 0.5 )CO 3 -NCM523-O x (1:1)。
The obtained grafted positive electrode material precursor is used for preparing a positive electrode material, and the preparation steps are as follows:
s4, obtaining the CoCO 3 -(Ni 0.5 Mn 0.5 )CO 3 -NCM523-O x (1:1) and Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 920 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a grafted positive electrode material LiCoO 2 -LiNi 0.5 Co 0.2 Mn 0.3 O 2 。
Comparative example 1
The preparation method of the positive electrode material comprises the following steps:
S1、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 (i.e., NCM523-CO 3 ) Precursor preparation: preparing NiSO according to a molar ratio of 5:2:3 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum to obtain carbonate salt NCM523-CO 3 ；
S2, NCM523-CO 3 With Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 900 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a first anode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 ；
S3、Co 3 O 4 Precursor preparation: preparation of 2mol x L -1 CoSO of (2) 4 500mL of aqueous solution, labeled solution 1; formulation of 4mol L -1 NH of (C) 4 HCO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum and dried, burned for 6 hours in the air atmosphere at 650 ℃, ground and sieved to obtain oxide salt Co 3 O 4 ；
S4, co 3 O 4 With Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 920 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a second anode material LiCoO 2 ；
S5, mixing the first positive electrode material and the second positive electrode material according to a mass ratio of 80: and 20, mechanically and uniformly mixing to obtain the composite anode material.
Comparative example 2
The preparation method of the positive electrode material comprises the following steps:
S1、(Ni 0.5 Co 0.2 Mn 0.3 )CO 3 (i.e., NCM523-CO 3 ) Precursor preparation: preparing NiSO according to a molar ratio of 5:2:3 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were passed through peristaltic pumps at about 1The mixture is added into a five-mouth flask reactor with 100mL of deionized water at the speed of mL/min for stirring reaction, and N is introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum to obtain carbonate salt NCM523-CO 3 ；
S2, NCM523-CO 3 With Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05, mechanically mixing, loading the obtained mixture into a sagger, putting the sagger into a muffle furnace, heating to 760 ℃ at a speed of 6 ℃/min under the air atmosphere, and preserving heat for 2 hours; heating to 900 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a first anode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 ；
S3、(Ni 1/3 Co 1/3 Mn 1/3 )O x (i.e., NCM 111-O) x ) Precursor preparation: preparing NiSO according to a molar ratio of 1:1:1 4 、CoSO 4 、MnSO 4 Is (Ni) 2+ 、Co 2+ 、Mn 2+ Is 2 mol.L -1 ) 500mL, labeled solution 1; formulation of 4mol L -1 Na of (2) 2 CO 3 500mL of solution, labeled solution 2; solution 1 and solution 2 were fed into a five-neck flask reactor with 100mL of deionized water at a rate of about 1mL/min by a peristaltic pump and reacted with stirring, and N was introduced during the reaction 2 Protecting and keeping the reaction temperature at 30-80 ℃ and stirring at 500rpm/min; simultaneously controlling the pH value of the solution in the reaction process to be 6-9 by dropwise adding ammonia water; continuing stirring for 24 hours after the addition of the solution 1 and the solution 2 is finished so as to age; after the aging is finished, the obtained precipitate is filtered in vacuum and dried, and is burned for 6 hours in the air atmosphere at 650 ℃ to obtain oxide type salt NCM111-O x ；
S4, NCM111-O x With Li 2 CO 3 According to a metal/Li molar ratio of 1:1.05 mechanical mixing, placing the obtained mixture into a sagger, placing into a muffle furnace, and under air atmosphere, mixing with waterHeating to 760 ℃ at the speed of 6 ℃/min, and preserving heat for 2h; heating to 920 ℃ at a speed of 3 ℃/min, and preserving heat for 12 hours; cooling to room temperature along with a furnace after solid-phase sintering, and grinding to obtain a second anode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 ；
S5, mixing the first positive electrode material and the second positive electrode material according to a mass ratio of 80: and 20, mechanically and uniformly mixing to obtain the composite anode material.
The above positive electrode material component ingredients were finished as shown in table 1 below.
TABLE 1
| Carbonate salt | Oxide salts | |
| Example 1 | 80g NCM523-CO 3 | 20g Co 3 O 4 |
| Example 2 | 60g NCM523-CO 3 | 40g Co 3 O 4 |
| Example 3 | 50g NCM523-CO 3 | 50g Co 3 O 4 |
| Example 4 | 40g NCM523-CO 3 | 60g Co 3 O 4 |
| Example 5 | 80g NCM523-CO 3 | 20g NCM111-O x |
| Example 6 | 60g NCM523-CO 3 | 40g NCM111-O x |
| Example 7 | 50g NCM523-CO 3 | 50g NCM111-O x |
| Example 8 | 80g NCM523-CO 3 | 20g NiCo-O x |
| Example 9 | 50g CoCO 3 | 50g NCM523-O x |
The grafted positive electrode material precursor obtained in example 1 was subjected to electron microscopic examination and X-ray diffraction analysis, see SEM and XRD patterns shown in fig. 1 to 2. As can be seen from fig. 1 to 2, the grafted positive electrode material precursor provided by the invention has successfully completed grafting of carbonate type salt and oxide type salt, and the grafted precursor structure is not destroyed, so that the grafting effect is good.
In addition, electron microscopic examination and X-ray diffraction analysis were also performed on the grafted cathode material obtained in example 1. As can be seen from SEM and XRD patterns of fig. 3 to 4, the grafted cathode material obtained in the present invention is converted into a cathode material after sintering, and has a layered structure.
The grafted positive electrode materials obtained in examples 1 to 9 and comparative example 1 were used in positive electrode sheets, and the preparation method was as follows: and mixing the grafted positive electrode material with super P and PVDF binder according to the mass ratio of 95:2:3 to prepare slurry, so as to obtain the positive electrode plate, wherein the mass of the grafted positive electrode material is 500g, and the specific preparation method can be seen in the preparation of the existing positive electrode plate.
Preparing the obtained positive plate into a full battery, testing the cycle performance, taking natural graphite as a negative electrode material, and taking 1mol/L LiPF as electrolyte 6 EC, DMC, EMC (volume ratio 1:1:1) of (with additives), the separator was a celgard2400 polypropylene film, and a soft-pack full cell (404050) was made. The additives in the electrolyte can be referred to as conventional electrolyte additive settings, and will not be described herein.
Performance test:
1) Capacity exertion test a: (4.2-2.75V, RT, 0.2C/0.2C): charging the formed 0.2C constant current to a cut-off voltage of 4.2V, and stopping constant voltage until the current is less than 0.05C; the 0.2C constant current discharges to a cut-off voltage of 2.75V. And multiplying the constant current discharge time by the discharge current and dividing the discharge current by the mass of the positive electrode material to obtain the capacity exertion.
Capacity exertion test B: (4.35-2.75V, RT, 0.2C/0.2C): charging the formed 0.2C constant current to a cut-off voltage of 4.35V, and stopping constant voltage until the current is less than 0.05C; the 0.2C constant current discharges to a cut-off voltage of 2.75V. And multiplying the constant current discharge time by the discharge current and dividing the discharge current by the mass of the positive electrode material to obtain the capacity exertion.
2) Cycle performance test a: at 25+ -2deg.C, the lithium ion secondary battery is charged to 4.2V at a constant current of 1C, then charged to 0.05C at a constant voltage of 4.2V, left for 5min, and then discharged to 2.75V at a constant current of 1C, which is a charge-discharge cycle process, and the discharge capacity at this time is the discharge capacity of the first cycle. The battery was subjected to a cyclic charge-discharge test according to the above method, and the discharge capacity per cycle was recorded.
Cycle performance test B: at 55+ -2deg.C, the lithium ion secondary battery is charged to 4.35V at a constant current of 1C, then charged to 0.05C at a constant voltage of 4.35V, left for 5min, and then discharged to 2.75V at a constant current of 1C, which is a charge-discharge cycle process, and the discharge capacity at this time is the discharge capacity of the first cycle. The battery was subjected to a cyclic charge-discharge test according to the above method, and the discharge capacity per cycle was recorded.
3) Overcharge resistance test: at room temperature, each group of 10 cells was discharged to 3.0V at 0.5C, and then subjected to a 1C/10V overcharge test. A thermocouple and a temperature acquisition instrument (HIOKI, LR 8501) are added on the battery core, the positive electrode and the negative electrode of the battery core are connected with a constant current and constant voltage source (Agilent, 34410A), the current is regulated to 1C, the voltage is 10V until the current is reduced to 0A, and the temperature change and the swelling condition of the battery core are monitored in the overcharging process.
The test results are shown in Table 2 below.
TABLE 2
From the test results, the positive electrode material of the carbonate type salt grafted oxide type salt provided by the invention is applied to a battery, and the cycle performance, high-temperature cycle performance, charging and other safety performances of the battery are effectively improved. The invention is mainly because the carbonate salt and the oxide salt are coupled together by a chemical grafting method through a precursor end grafting mode, so that the aim of uniformly mixing different types of materials is fulfilled, the problems of uneven slurry dispersion and poor pole piece uniformity in the application process of the existing direct-mixed positive electrode material in a lithium ion battery are effectively solved, more importantly, the problem of unbalanced local potential of different types of materials in the charging and discharging processes is solved, the electrochemical performance of the positive electrode material in the battery is improved, and the final grafted positive electrode material realizes larger improvement of the comprehensive performance.
In addition, as can be seen from the comparison of examples 1 to 9, the precursor is prepared by different methods and different contents, and the finally obtained positive electrode material has different effects on the normal temperature cycle performance, the high temperature cycle performance, the charging safety performance and the like of the lithium ion battery. For example, when the mass ratio of carbonate type salt to oxide type salt couple is 4: and 1, preparing the precursor, and obtaining better normal temperature cycle performance, high temperature cycle performance, charging safety performance and the like.
In summary, the positive electrode material precursor of the carbonate salt grafted oxide salt solves the problems of uneven slurry dispersion, poor pole piece uniformity and inconsistent electrochemical performance of the material in the application process of the lithium ion battery of the current mixed positive electrode material, and effectively improves the cycle performance of the battery.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. A carbonate grafted oxide type positive electrode material precursor is characterized in that the structural formula is ACO 3 R-BO x, A and B are Ni 1-a-b Co a Mn b Z c Wherein a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1; a+b is more than 0 and less than or equal to 1; c is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 4, the molar ratio of nickel, cobalt and manganese in A is different from the molar ratio of nickel, cobalt and manganese in B, and Z is at least one of Al, mg, ti, B, zr, bi, mo, P and rare earth elements; r is a grafting agent comprising Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and at least one element of rare earth elements;
wherein R is (M) x N y )CO 3 Or (M) x N y )(OH) 2 X is more than 0 and less than 1; y is more than 0 and less than 1; x+y is more than 0 and less than or equal to 1; m and N are selected from different elements, and are at least one element of Ni, co, mn, al, mg, si, ti, B, zr, bi, mo, P and rare earth elements; the mass of R is ACO 3 And BO (BO) x 1 to 1 of the sum of the masses0％。
2. The carbonate grafted oxide positive electrode material precursor according to claim 1, wherein ACO 3 And BO (BO) x The mass ratio of (2) is 1:99-99:1.
3. A method for preparing a carbonate grafted oxide type positive electrode material precursor according to any one of claims 1 to 2, comprising the steps of:
s1, mixing an aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt with a carbonate aqueous solution for reaction, controlling the pH value of the solution in the reaction process to be 6-9, aging, and suction-filtering to obtain carbonate salt ACO 3 ；
S2, mixing an aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt with an aqueous solution of carbonate to react, controlling the pH of the solution in the reaction process to be 6-9, aging, filtering, drying, burning at 500-900 ℃ and grinding to obtain oxide salt BO x ；
S3, preparing the carbonate salt ACO 3 With oxide salts BO x Mixing at 25-70 deg.c to prepare slurry; adding a solution for liquid phase reaction to form a grafting agent R into the slurry, stirring and reacting for 30-90 min, washing and drying to obtain a carbonate grafted oxide type positive electrode material precursor ACO 3 -R-BO x 。
4. The method for preparing a carbonate-grafted oxide type positive electrode material precursor according to claim 3, wherein in step S1, the carbonate-type salt ACO 3 The preparation method of (2) comprises the following steps: adding aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt and carbonate aqueous solution into a reactor containing water at a speed of 1-2 mL/min respectively, continuously stirring and reacting at 30-80 ℃ in an inert atmosphere, controlling the pH of the solution in the reaction process to be 6-9, continuously stirring and aging for 10-36 h after the addition, and vacuum filtering to obtain carbonate salt ACO 3 。
5. The carbonate-grafted oxide cathode material according to claim 3A method for producing a precursor, characterized in that in step S2, the oxide salt BO x The preparation method of (2) comprises the following steps: adding aqueous solution containing nickel salt, cobalt salt, manganese salt and Z salt and carbonate aqueous solution into a reactor containing water at a speed of 1-2 mL/min respectively, continuously stirring and reacting at 30-80 ℃ in an inert atmosphere, controlling the pH of the solution in the reaction process to be 6-9, continuously stirring and aging for 10-36 h after the addition, vacuum filtering and drying, and burning for 5-12 h at 500-900 ℃ to obtain oxide salt BO x 。
6. The method for preparing a carbonate-grafted oxide positive electrode material precursor according to claim 3, wherein in step S3, the solution for forming the grafting agent R by the liquid phase reaction comprises a first solution and a second solution, the first solution is a mixed solution of cobalt salt and manganese salt, the second solution is a sodium bicarbonate solution or sodium hydroxide solution, and the first solution and the second solution form the grafting agent R by the liquid phase reaction to ACO the carbonate-type salt 3 With oxide salts BO x Grafting is performed.
7. A preparation method of a grafted positive electrode material, which is characterized in that the carbonate grafted oxide positive electrode material precursor according to any one of claims 1-2 is mixed with lithium salt, sintered for 6-24 hours at 750-950 ℃, cooled and ground to obtain the grafted positive electrode material.
8. A grafted positive electrode material prepared by the method for preparing a grafted positive electrode material according to claim 7.
9. A positive electrode sheet comprising the grafted positive electrode material of claim 8.
10. A lithium ion battery comprising a positive plate, a negative plate and a diaphragm spaced between the positive plate and the negative plate, wherein the positive plate is the positive plate of claim 9.
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| CN106532006A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method of cobaltous oxide coated ternary anode material |
| CN113044891A (en) * | 2021-03-09 | 2021-06-29 | 高点(深圳)科技有限公司 | Preparation method of surface grafting type high-voltage lithium cobaltate, surface grafting type high-voltage lithium cobaltate and application thereof |
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| JP6427921B2 (en) * | 2013-06-28 | 2018-11-28 | 日亜化学工業株式会社 | Cathode active material for non-aqueous secondary battery and method for producing the same |
| US10050313B2 (en) * | 2016-06-19 | 2018-08-14 | GM Global Technology Operations LLC | Lithium ion battery |
| CN106532029A (en) * | 2016-12-28 | 2017-03-22 | 四川富骅新能源科技有限公司 | High-voltage ternary positive electrode material for lithium-ion battery and preparation method of high-voltage ternary positive electrode material |
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| CN106532006A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method of cobaltous oxide coated ternary anode material |
| CN113044891A (en) * | 2021-03-09 | 2021-06-29 | 高点(深圳)科技有限公司 | Preparation method of surface grafting type high-voltage lithium cobaltate, surface grafting type high-voltage lithium cobaltate and application thereof |
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