CN114388779B - Composite ternary positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Composite ternary positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN114388779B CN114388779B CN202210030579.0A CN202210030579A CN114388779B CN 114388779 B CN114388779 B CN 114388779B CN 202210030579 A CN202210030579 A CN 202210030579A CN 114388779 B CN114388779 B CN 114388779B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- equal
- inner core
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 46
- 239000010410 layer Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 6
- 239000002019 doping agent Substances 0.000 claims abstract description 5
- 230000005496 eutectics Effects 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002344 surface layer Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000012792 core layer Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 15
- 238000005253 cladding Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- 229910052759 nickel Inorganic materials 0.000 description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000011265 semifinished product Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000002479 acid--base titration Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010280 constant potential charging Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- -1 argon ion Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
-
- 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 discloses a composite ternary positive electrode material, which is provided with a first inner core-a second inner core-a first coating layer-a second coating layer multi-layer composite structure, wherein the chemical formula of the first inner core is LiNi x1 Co y1 Mn z1 O 2 Wherein x1 is more than or equal to 0.7 and less than 1, y1 is more than or equal to 0.05 and less than or equal to 0.2,0.03, and z1 is more than or equal to 0.2; the chemical formula of the second inner core is LiNi x2 Co y2 Mn z2 La m O 2 Wherein x2 is more than or equal to 0.5 and less than or equal to 0.7, y2 is more than or equal to 0.05 and less than or equal to 0.3,0.05, z2 is more than or equal to 0.3, and m is more than 0 and less than or equal to 0.01; the content of the dopant La gradually increases from the particle core to the surface, and is enriched on the surface layer, and a composite oxide containing lithium lanthanum is formed on the surface as a first coating layer; the second coating layer is Al 2 O 3 With LaPO 4 A point-surface composite network structure formed by partial melting eutectic. The invention also discloses a preparation method of the ternary positive electrode material. The ternary positive electrode material prepared by the invention is assembled into a battery, and has high discharge specific capacity, rate capability, cycle performance and safety performance. The method has simple process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to a composite high-nickel ternary positive electrode material and a preparation method thereof, in particular to a ternary positive electrode material with a first inner core-second inner core-first coating layer-second coating layer multilayer composite structure and a preparation method thereof, and the ternary positive electrode material is used for preparing lithium ion batteries, and belongs to the field of lithium ion batteries.
Background
The layered NCA or NCM composite ternary positive electrode material has the advantages of low cost, high discharge capacity, good cycle performance, good thermal stability, stable structure and the like, and has been developed into one of the novel lithium ion battery positive electrode materials with the most development prospect. Of these, high nickel ternary is most competitive in the lithium ion battery field, e.g., liNi 0.8 Co 0.1 Mn 0.1 O 2 Has excellent energy density, but Ni when charged to a high lithium removal state 3+ 、Ni 2+ Oxidized to Ni with strong oxidizing property 4+ The decomposition of the electrolyte can be accelerated, so that the dissolution of the metal elements of the ternary material and the structural damage are caused, the safety performance and the cycle performance of the battery are further deteriorated, and meanwhile, the precipitation of crystal lattice O is caused by excessive lithium ion release, so that the safety performance of the battery is deteriorated.
Aiming at the defects of poor circularity and safety of high-nickel materials, a plurality of patents at present disclose related solutions, and main strategies comprise doping treatment, surface coating treatment, synthesizing concentration gradient materials and the like on the anode materials. According to the invention patent CN201810178272.9, a precursor, a doping agent and a lithium source are mixed and sintered to obtain a sintered material, and then cobalt hydroxide and a B source oxide are coated to obtain the Y/La doped Co/B Co-coated nickel-cobalt-manganese ternary anode material. The invention patent CN 109950498A prepares a high nickel anode material with a uniform coating layer by mixing with a lithium source and a nano coating. The invention patent CN201911396665.8 discloses a concentration gradient material, which is prepared by mixing a precursor with an element concentration gradient structure and an additive after high-speed fusion with lithium hydroxide, and the high-nickel ternary positive electrode material with gradient distribution of transition metal element concentration. The method can stabilize the material structure to a certain extent, improve the cycle performance of the material, but along with the cycleIncreased number of times, li + Can be inevitably separated out from the positive electrode material and is enriched on the surface of the positive electrode to form inert Li 2 O and further with H in air 2 O and CO 2 React to form Li 2 CO 3 LiOH, hinder Li + The circulation performance of the material is reduced, and the battery is decomposed under the initiation of high voltage and electrolyte to cause the gas production of the battery, so that the battery has serious potential safety hazard and the circulation performance is obviously deteriorated. Meanwhile, in long-time charge and discharge cycles, the surface coating can be dissipated, so that the ternary material can be in direct contact with the electrolyte, the thermal stability is reduced, and the cycle life is reduced.
To solve the problem, doping elements are introduced and a flexible surface regeneration layer is designed, so that the structure of the material is more stable, and Li is reduced + Precipitation and simultaneous formation of Li 2 O can be converted into active substances which are favorable for lithium ion transmission, and the corrosion of electrolyte in the long-cycle process of the material is reduced, so that the long-cycle stability and the safety performance of the material can be improved, and the method is one of the problems focused by a plurality of manufacturers and scientific research institutions.
Disclosure of Invention
The invention aims to provide a composite ternary positive electrode material and a preparation method thereof, wherein the composite ternary positive electrode material has an egg-like structure, and has excellent ploidy, structural stability and long cycle life.
In order to achieve the above object, the present invention is as follows:
in one aspect of the present invention, the present invention provides a composite ternary cathode material having a first core-second core-first cladding-second cladding multilayer composite structure, wherein:
the chemical formula of the first inner core is LiNi x1 Co y1 Mn z1 O 2 Wherein x1 is more than or equal to 0.7 and less than 1, y1 is more than or equal to 0.05 and less than or equal to 0.2,0.03, and z1 is more than or equal to 0.2;
the chemical formula of the second inner core is LiNi x2 Co y2 Mn z2 La m O 2 Wherein x2 is more than or equal to 0.5 and less than or equal to 0.7, y2 is more than or equal to 0.05 and less than or equal to 0.3,0.05, z2 is more than or equal to 0.3, and m is more than or equal to 0≤0.01；
The content of the dopant La gradually increases from the particle core to the surface, and is enriched on the surface layer, and a first coating layer containing lithium lanthanum composite oxide is formed on the surface;
the second coating layer is Al 2 O 3 With LaPO 4 A point-surface composite network structure formed by partial melting eutectic;
the first cladding layer is coated on at least a portion of the surface of the second core, and the second cladding layer is coated on at least a portion of the surface of the first cladding layer.
The particle size of the positive electrode material is 1 to 18. Mu.m, preferably 8 to 13. Mu.m.
The thickness of the first core is 0.5 to 11 μm, preferably 2 to 10 μm.
The thickness of the second core is 0.5 to 7 μm, preferably 1 to 4 μm.
The first coating layer contains Li 2 O-La 2 O 3 -P 2 O 5 The heterostructure, which is a flexible surface-regenerating layer, has a thickness which increases with the number of charge and discharge, and is in the range of 1 to 300nm, preferably 1 to 100nm.
The thickness of the second coating layer is 1 to 500nm, preferably 1 to 100nm.
Al 2 O 3 The mass fraction of the active material of the positive electrode of the lithium ion battery is 0.01-0.5%, preferably 0.05-0.2%.
The mass fraction of La in the second inner core, the first coating layer and the second coating layer is respectively 0.1-1%, 0.01-0.3% and 0.01-0.3% of the positive electrode active material; preferably 0.2% -0.6%, 0.03% -0.15% and 0.03% -0.2% respectively.
The mass fraction of La in the second inner core, the first coating layer and the second coating layer, which accounts for the positive electrode active material, satisfies the following relation I and the relation II:
more preferably
The invention also provides a preparation method of the composite positive electrode material, which comprises the steps of preparing precursor powder, and then mixing the precursor powder with a lithium source and LaPO 4 Sintering to obtain high nickel ternary primary sintered product, and mixing the primary sintered product with LaPO 4 With nano Al 2 O 3 And (5) mixing and sintering to obtain a high-nickel ternary finished product. Preferably, the method comprises the following steps:
(1) Preparing a positive electrode material precursor: according to the stoichiometric ratio of Ni to Co to Mn=x2 to y2 to z2, adding soluble nickel salt, soluble cobalt salt and soluble manganese salt into deionized water together to prepare a solution with metal concentration of 1-3 mol/L, uniformly stirring, and dropwise adding H 2 SO 4 The pH value of the solution is regulated to about 2 to obtain a second inner core layer solution, wherein x2 is more than or equal to 0.5 and less than or equal to 0.7, y2 is more than or equal to 0.05 and less than or equal to 0.3,0.05, z2 is more than or equal to 0.3, and m is more than or equal to 0 and less than or equal to 0.01;
further, according to the stoichiometric ratio of Ni to Co to Mn=x1 to y1 to z1, dissolving soluble nickel salt, soluble cobalt salt and soluble manganese salt in water to prepare a solution with metal concentration of 1-3 mol/L, so as to obtain a first inner core layer solution, wherein x1 is more than or equal to 0.7 and less than 1, y1 is more than or equal to 0.05 and less than or equal to 0.2,0.03 and z1 is more than or equal to 0.2;
further, stirring the first kernel solution by using a magnetic stirrer, adding the second kernel layer solution into the first kernel layer solution at a dropping speed of 0.5-1.5 mL/min, and simultaneously adding a precipitant and a complexing agent to enable the second kernel layer to be deposited on the surface of the first kernel layer, and controlling the pH value of the reaction to be 11-12; the precipitant is selected from NaOH and Na 2 CO 3 The complexing agent is one or more selected from ammonia water, citric acid and glycine, and the concentration of the complexing agent is controlled to be kept between 0.45 and 0.55mol/L; wherein, the solute mass ratio of the second inner core layer to the solute mass ratio of the first inner core layer is 1: (3-30).
Preferably, the solute mass ratio of the second inner core solute to the first inner core layer is 1: (5-10).
Further, the reaction temperature is controlled to be stabilized at 50-60 ℃, the pH is stabilized at about 11-12, and the reaction is aged for 50-60 hours after the completion of the dripping reaction. Filtering, washing and drying the precipitate, wherein the drying temperature is 80-100 ℃ and the time is 18-30 h, and obtaining the dried ternary cathode material precursor.
(2) Preparation of a baked product: the obtained precursor, a lithium source and LaPO are mixed 4 Mixing materials for 1-2 h by a high mixer according to the mol ratio of Li (Ni+Co+Mn+La) =1.0:1-1.2:1, wherein the rotating speed is 800-1000 r/min; the lithium source is one or more of LiOH and Li2CO 3.
Preferably, the molar ratio of Li (Ni+Co+Mn+La) is 1.02:1 to 1.05:1.
Preferably, the lithium source is micro powder LiOH.H 2 O。
Further, sintering the mixture under air or oxygen atmosphere, wherein the sintering is to sinter the precursor, the lithium source and LaPO 4 The mixed powder is kept at 400-700 ℃ for 2-6 hours to remove bound water, and is heated to 700-900 ℃ to be sintered for 4-15 hours;
preferably, the sintering temperature is 800-850 ℃ and the sintering time is 10-15 h.
Further, naturally cooling the sintered product to room temperature, and then crushing and sieving to obtain a high-nickel ternary primary sintered product with a first inner core-second inner core-first coating layer;
(3) Preparing a positive electrode material finished product: high nickel ternary primary sintered product and Al 2 O 3 With LaPO 4 Coating under the action of high-speed shearing to obtain a coated semi-finished product, mixing by a high-speed mixer for 1-2 h at a rotating speed of 800-1000 r/min;
further, sintering the coated semi-finished product for 5-10 hours at 300-700 ℃ in air or oxygen atmosphere.
Preferably, the sintering time is 400-550 ℃ and the sintering time is 6-8 h.
And further, naturally cooling the sintered product to room temperature, and sieving to obtain the target product.
The invention has the beneficial effects that:
(1) The second core layer is doped by La element, so that the high-nickel ternary material has higher structural stability, high mechanical stability and higher ionic and electronic conductivity, and can effectively reduce the problem of particle pulverization of the ternary material due to the existence of lattice stress in the circulating process, so that the high-nickel ternary material has excellent circulating and multiplying power performance while exerting high capacity;
(2) The first coating layer in the invention can not only have the capacity of absorbing the inert layer, but also play a role of isolating electrolyte. With increasing cycle number, li + Precipitation phenomenon gradually increases, and Li is enriched and formed on the surface of the positive electrode 2 O, hinder Li in the cathode material + Is transported by the dopant LaPO 4 La produced by decomposition 2 O 3 And P 2 O 5 With Li 2 O reacts with and forms Li 2 O-La 2 O 3 -P 2 O 5 Heterogeneous regeneration structure. The structure ensures Li in the process of multiple charge and discharge + The electrolyte can be isolated at the same time of the rapid transmission;
(3) The second coating layer adopts a point-surface combination mode, so that the corrosion of electrolyte can be effectively prevented, and the safety performance of the material is improved. LaPO (LaPO) 4 Some melting is carried out in the coating process, the coating is carried out in a surface distribution mode, and meanwhile, PO 4 3- The strong covalent bond with metal ions and the strong P≡O bond can stabilize the electrode surface, thereby improving the thermal stability of the material and the corrosion resistance to the electrolyte. Al (Al) 2 O 3 As a common coating, al is coated on the surface of the positive electrode material in the form of dot distribution 2 O 3 With LaPO 4 Co-cladding will produce aThe fixed eutectic structure and the network structure combined by the point and the surface are coated on the surface of the anode material, so that the lithium removal structure can be effectively stabilized, and the circulation stability is improved.
The preparation process of the positive electrode active material is simple, the operation is simple and convenient, and the preparation process is suitable for large-scale industrial production and application.
Drawings
Fig. 1 is an SEM image of the material obtained in example 1 of the present invention.
FIG. 2 is a cross-sectional view of the material obtained in example 1 of the present invention after argon ion polishing.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
Experiments the electrochemical performance of the invention will be studied using a C2032 type button cell and a 4085118 type soft pack ion cell.
The lithium ion battery cathode materials in examples and comparative examples were used as active materials to prepare lithium ion button cells according to a method comprising the steps of: dispersing active substances, a conductive agent Super P and a binder PVDF in N-methyl pyrrole ketone (NMP) according to the mass ratio of 95:2:3, wherein the solid content is 70%, and ball milling to form uniform anode slurry; coating the positive slurry on the rough surface of clean aluminum foil by using a coater, and then placing the positive slurry into a vacuum oven to be dried for 12 hours at 120 ℃ in vacuum to prepare a pole piece; the prepared pole piece is adopted, a lithium piece is taken as a counter electrode, celgard2400 is taken as a diaphragm, and the pole piece is assembled into a 2032 button cell in an argon glove box; the electrolyte used in assembling 2032 button cell is LiPF 6 LiPF obtained by dissolving in a mixed solvent of Ethyl Carbonate (EC) and diethyl carbonate (DMC) (volume ratio EC: dmc=1:1) 6 Is 1 mol/L.
The button cell of this patent was tested on a New Wei blue electric tester (model: CT-4008Tn-5V20 mA-164). The method specifically comprises the following steps: 1) Firstly, standing each prepared C2032 button battery at room temperature for one night, then carrying out constant-current charging to a charging cutoff voltage at a rate of 0.2C, then carrying out constant-current discharging to a discharging cutoff voltage at a rate of 0.2C after constant-voltage charging to 0.05mA, and obtaining a first-round discharge capacity of 0.2C after standing for 5 min; 2) Then, constant-current and constant-voltage charging is carried out at 0.33C, constant-current discharge is carried out at 0.5C, 1C, 2C and 3C multiplying power respectively, and 0.5C, 1C, 2C and 3C discharge capacities are respectively obtained, wherein the capacity retention rate of 3C/0.2C is=3C discharge capacity/0.2C first-cycle discharge capacity is 100%; 3) Finally, constant-current constant-voltage charging is carried out at 0.33C, charging and discharging cycle test is carried out at 1C discharging multiplying power, and the capacity retention rate of 100 cycles of cycle = 1C after 100 cycles of discharge capacity/1C first cycle discharge capacity is 100%; all tests were performed at room temperature, with a voltage range between 3 and 4.3V for the charge and discharge test.
The lithium ion battery positive electrode materials in examples and comparative examples were used as active materials to prepare lithium ion pouch batteries according to a method comprising the steps of: the active substance, the CNT, the conductive agent Super P and the binder PVDF are dispersed in N-methyl pyrrole ketone (NMP) according to the mass ratio of 96:0.5:1.5:2, the solid content is 70%, and the uniform positive electrode slurry is formed by ball milling and uniformly coated on the Al foil. Deionized water is used as a solvent for the negative electrode, and the graphite and the SBR, CMC, SP =96.3:1.7:1:1 are prepared into slurry with the solid content of 45 percent, and the slurry is uniformly coated on the Cu foil. Vacuum drying in a vacuum oven at 120deg.C for 12 hr to obtain positive and negative pole pieces; the positive electrode pole piece and the negative electrode pole piece are rolled and cut into pieces, then are wound into a battery core together with a diaphragm, and are subjected to main procedures of shell entering, top sealing, liquid injection, formation, forming, detection and the like to prepare the 4085118 type [email protected] soft package battery.
The soft package battery of the patent is tested on a Xinwei charge-discharge machine (model: CT-4008T-5V 12A-S1). The method specifically comprises the following steps: 1) Firstly, standing each 4085118 soft-package battery at room temperature for one night, then carrying out constant-current charging to a charging cut-off voltage at a rate of 0.33 ℃, then carrying out constant-current discharging to a discharging cut-off voltage at a rate of 0.33 ℃ after standing for 5min, and obtaining a discharge capacity at 25 ℃; 2) Then, constant-current and constant-voltage charging is carried out at 0.33 ℃, after standing for 8 hours, constant-current discharging is carried out at-10 ℃ at a rate of 1C until discharge cut-off voltage is reached, and discharge capacity at-10 ℃ is obtained, and the capacity retention rate at-10 ℃ is= -10 ℃ discharge capacity/25 ℃ discharge capacity is 100%; 3) Constant-current constant-voltage charging is carried out on a 4085118 soft-package battery according to the step 1), the constant-current discharging is carried out at 25 ℃ to a discharge cut-off voltage at a 1C multiplying power, a first-cycle discharge capacity at 25 ℃ is obtained, the repeated charging and discharging for 500 cycles are carried out according to the procedure, and a circulating discharge capacity is obtained, wherein the circulating capacity retention rate at 25 ℃ is equal to the circulating discharge capacity/the first-cycle discharge capacity which is equal to 100%; 4) The DCR (direct current internal resistance) test was conducted at a temperature of 25℃and 4C to 20%, 50% and 90% SOC, and was conducted according to GB/T31486-2015.
Example 1
1. Calculating and weighing sulfate of Ni, co and Mn according to the molar ratio of Ni to Co to Mn=0.65 to 0.15 to 0.2, adding the sulfate into deionized water together to prepare a solution with the metal concentration of 2mol/L, uniformly stirring, and dropwise adding H 2 SO 4 Adjusting the pH value to about 2 to obtain a second inner core layer solution;
2. calculating and weighing sulfate of Ni, co and Mn according to the molar ratio of Ni to Mn=0.83:0.12:0.05, adding the sulfate into deionized water together, and mixing to prepare a first core layer solution with the metal concentration of 2 mol/L;
3. stirring the first kernel layer solution by a magnetic stirrer at a stirring speed of 1000rpm, measuring the second kernel layer solution according to a solute mass ratio of 1:8 in the second kernel layer and the first kernel layer solution, and adding the second kernel layer solution into the first kernel layer solution at a dripping speed of 1 mL/min;
4. simultaneously, the reaction temperature is regulated to 60 ℃, ammonia water is injected to keep the ammonia concentration at 0.5mol/L, a 2mol/L NaOH solution is injected to regulate the pH value to be about 11.5, and after the reaction is completed after the dripping is finished, the mixture is aged for 60 hours. After complete precipitation, filtering, washing and drying the precipitate, wherein the drying temperature is 100 ℃ and the time is 24 hours, so as to obtain a dried positive electrode material precursor;
5. the obtained precursor and LiOH H are mixed 2 O and LaPO 4 Mixing (1) (Ni+Co+Mn): la=0.997:0.003 and (2) Ni:Co:Mn=0.65:0.15:0.2 with Li (Ni+Co+Mn+La) =1.03) for 2h at 800r/min, loading the materials into a sagger, sintering in a roller kiln, preserving heat at 500 ℃ for 3h,then the temperature rising speed is 3 ℃/min, the temperature rises to 800 ℃ and the sintering is carried out for 14 hours, then the temperature is reduced to the room temperature, and the whole sintering process ensures O 2 The concentration is more than or equal to 95 percent. The material is crushed and sieved to obtain a high-nickel ternary primary sintered product of the first inner core, the second inner core and the first coating layer;
6. according to Al 2 O 3 With LaPO 4 Weighing Al with the mass ratio of 0.1% of the positive electrode material 2 O 3 With LaPO 4 Mixing the first burned product with a high-speed mixer for 1h at a rotating speed of 800r/min to obtain a coated semi-finished product;
7. sintering the coated semi-finished product for 8 hours at 550 ℃ in air or oxygen atmosphere;
8. and naturally cooling the sintered product to room temperature, and sieving to obtain the target product.
The grain diameter of the obtained target product is 13 mu m, wherein the thickness of the first inner core is 8-10 mu m, the thickness of the second inner core is 2-3 mu m, the thickness of the first coating layer is 15-20 nm, the thickness of the second coating layer is 20-40 nm, and the mass ratio of La in the second inner core layer is 0.36% and the mass ratio of La in the first coating layer is 0.07% according to the calculation of the residual alkali content tested by an acid-base titration method.
Example 2
1. In example 1, S5 was changed to LiOH.H, which was obtained as described above 2 O and LaPO 4 Mixing (1) (Ni+Co+Mn): la=0.9985:0.0015 and (2) Ni:Co:Mn=0.65:0.15:0.2 with Li (Ni+Co+Mn+La) =1.03) according to the molar ratio of each element for 2h, loading the materials into a sagger, sintering in a roller kiln at a heating rate of 3 ℃/min, heating to 800 ℃ for 14 hours, cooling to room temperature, and ensuring O in the whole sintering process 2 The concentration is more than or equal to 95 percent. The material is crushed and sieved to obtain a high-nickel ternary primary sintered product of the first inner core, the second inner core and the first coating layer;
2. in example 1S 6 was modified to be according to Al 2 O 3 With LaPO 4 Weighing Al with the mass ratio of 0.05% of the positive electrode material 2 O 3 With LaPO 4 And mixing the first burned product by a high-speed mixer to obtain a coated semi-finished product;
3. the other implementation steps are consistent with the steps 1-4 and the steps 7-8 in the embodiment, and the target finished product is obtained.
The grain diameter of the obtained target product is 13 mu m, wherein the thickness of the first inner core is 8-10 mu m, the thickness of the second inner core is 2-3 mu m, the thickness of the first coating layer is 5-10 nm, the thickness of the second coating layer is 10-20 nm, and the mass ratio of La in the second inner core layer is 0.19% and the mass ratio of La in the first coating layer is 0.03% according to the calculation of the residual alkali content tested by an acid-base titration method.
Example 3
1. In example 1, S1 is changed to be calculated according to the mole ratio of Ni to Co to Mn=0.7 to 0.1 to 0.2 of each element, sulfate of Ni, co and Mn is weighed, the above substances are added into deionized water together to prepare a solution with metal concentration of 2mol/L by mixing, the solution is stirred uniformly, and H is added dropwise 2 SO 4 Adjusting the pH value to about 2 to obtain a second inner core layer solution;
2. in the embodiment 1, S3 is changed to stirring a kernel solution by a magnetic stirrer at a stirring speed of 1000rpm, measuring the second kernel layer solution according to a solute mass ratio of 1:6 in the second kernel layer and the first kernel layer solution, and adding the second kernel layer solution into the first kernel layer solution at a dropping speed of 1 mL/min;
3. in example 1, S5 was changed to LiOH.H, which was obtained as described above 2 O and LaPO 4 Mixing (1) (Ni+Co+Mn): la=0.995:0.005 and (2) Ni:Co:Mn=0.7:0.1:0.2 with Li (Ni+Co+Mn+La) =1.03) for 2h by a high-mixing machine, loading the materials into a sagger, sintering in a roller kiln at a heating rate of 3 ℃/min, heating to 800 ℃ for 14 h, cooling to room temperature, and ensuring O in the whole sintering process 2 The concentration is more than or equal to 95 percent. The material is crushed and sieved to obtain a high-nickel ternary primary sintered product of the first inner core, the second inner core and the first coating layer;
4. the other implementation steps are consistent with the step 2, the step 4 and the steps 6 to 8 in the embodiment, and the target finished product is obtained.
The grain diameter of the obtained target product is 11 mu m, wherein the thickness of the first inner core is 6-8 mu m, the thickness of the second inner core is 2-3 mu m, the thickness of the first coating layer is 20-30 nm, the thickness of the second coating layer is 20-40 nm, and the mass ratio of La in the second inner core layer is 0.6% and the mass ratio of La in the first coating layer is 0.12% according to the calculation of the residual alkali content tested by an acid-base titration method.
Example 4
1. In the embodiment 1, S3 is changed to stirring a kernel solution by a magnetic stirrer at a stirring speed of 1000rpm, measuring the second kernel layer solution according to a solute mass ratio of 1:6 in the second kernel layer and the first kernel layer solution, and adding the second kernel layer solution into the first kernel layer solution at a dropping speed of 1 mL/min;
2. in example 1, S5 was changed to LiOH.H, which was obtained as described above 2 O and LaPO 4 Mixing (1) (Ni+Co+Mn): la=0.998:0.002 and (2) Ni:Co:Mn=0.65:0.15:0.2 with Li (Ni+Co+Mn+La) =1.03) for 2h by a high-mixing machine, loading the materials into a sagger, sintering in a roller kiln at a heating rate of 3 ℃/min, heating to 800 ℃ for 14 h, cooling to room temperature, and ensuring O in the whole sintering process 2 The concentration is more than or equal to 95 percent. The material is crushed and sieved to obtain a high-nickel ternary primary sintered product of the first inner core, the second inner core and the first coating layer;
3. in example 1S 6 was modified to be according to Al 2 O 3 With LaPO 4 Weighing Al with the mass ratio of 0.1% of the positive electrode material 2 O 3 With LaPO 4 And mixing the first burned product by a high-speed mixer to obtain a coated semi-finished product;
4. the other implementation steps are consistent with the steps 1-4 and the steps 6-8 in the embodiment 1, and the target finished product is obtained.
The grain diameter of the obtained target product is 13 mu m, wherein the thickness of the first inner core is 6-9 mu m, the thickness of the second inner core is 3-5 mu m, the thickness of the first coating layer is 10-15 nm, the thickness of the second coating layer is 10-15 nm, and the mass ratio of La in the second inner core layer is 0.25% and the mass ratio of La in the first coating layer is 0.04% according to the calculation of the residual alkali content tested by an acid-base titration method.
Comparative example 1
1. S5 modification in example 1To obtain the precursor and LiOH H 2 Mixing O with Li (Ni+Co+Mn) =1.03 for 2 hr, loading the mixture into sagger, sintering in roller kiln at 3 deg.c/min to 800 deg.c for 14 hr, cooling to room temperature, and sintering to ensure O 2 The concentration is more than or equal to 95 percent. The material is crushed and sieved to obtain a high-nickel ternary primary sintered product of the first inner core and the second inner core;
2. the other implementation steps are consistent with the steps 1-4 and the steps 6-8 in the embodiment 1, and the target finished product is obtained.
The grain diameter of the obtained target product is 13 mu m, wherein the thickness of the first inner core is 8-10 mu m, the thickness of the second inner core is 2-3 mu m, the first coating layer is not arranged, and the thickness of the second coating layer is 20-40 nm.
Comparative example 2
1. The high nickel ternary one-shot materials of the first core-second core-first cladding layer were prepared according to steps 1 to 5 in example 1, except that the second cladding layer cladding was not performed, and the remaining steps were identical to steps 7 to 8 in example 1. Obtaining a target finished product.
The grain diameter of the obtained target product is 13 mu m, wherein the thickness of the first inner core is 8-10 mu m, the thickness of the second inner core is 2-3 mu m, the thickness of the first coating layer is 15-20 nm, no second coating layer exists, the mass ratio of La in the second inner core layer is 0.36% and the mass ratio of La in the first coating layer is 0.07% according to the calculation of the residual alkali content tested by an acid-base titration method.
The comparative examples 1 to 4 and comparative examples 1 to 2 show the button cell performance and the all-electric soft pack performance in Table 1.
Table 1 comparison of lithium ion battery performances of examples 1 to 4 and comparative examples 1 to 2
As is apparent from the results of table 1, the positive electrode material prepared in the examples of the present invention has a high capacity and cycle retention rate as compared with the comparative examples, and has a lower DCR (direct current resistance) value at the time of assembly into a full power, and a better low-temperature discharge performance, which means that a high-nickel positive electrode material excellent in cycle performance and rate performance can be obtained by designing the material structure and introducing a regeneration layer capable of absorbing inert substances.
Claims (18)
1. A composite ternary positive electrode material is characterized by comprising a first inner core-a second inner core-a first coating layer-a second coating layer multi-layer composite structure, wherein the chemical formula of the first inner core is LiNi x1 Co y1 Mn z1 O 2 Wherein x1 is more than or equal to 0.7 and less than 1, y1 is more than or equal to 0.05 and less than or equal to 0.2,0.03, and z1 is more than or equal to 0.2; the chemical formula of the second core is
LiNi x2 Co y2 Mn z2 La m O 2 Wherein x2 is more than or equal to 0.5 and less than or equal to 0.7, y2 is more than or equal to 0.05 and less than or equal to 0.3,0.05, z2 is more than or equal to 0.3, and m is more than 0 and less than or equal to 0.01;
the content of the dopant La gradually increases from the particle core to the surface, and is enriched on the surface layer, and a first coating layer containing lithium lanthanum composite oxide is formed on the surface; the second coating layer is Al 2 O 3 With LaPO 4 A point-surface composite network structure formed by partial melting eutectic; the first cladding layer is coated on at least a portion of the surface of the second core, and the second cladding layer is coated on at least a portion of the surface of the first cladding layer.
2. The positive electrode material according to claim 1, wherein the positive electrode material has a particle diameter of 1 to 18 μm.
3. The positive electrode material according to claim 2, wherein the positive electrode material has a particle diameter of 8 to 13 μm.
4. The positive electrode material according to claim 1, wherein the thickness of the first inner core is 0.5 to 11 μm.
5. The positive electrode material according to claim 4, wherein the thickness of the first inner core is 2 to 10 μm.
6. The positive electrode material according to claim 1, wherein the thickness of the second core is 0.5 to 7 μm.
7. The positive electrode material according to claim 6, wherein the thickness of the second core is 1 to 4 μm.
8. The positive electrode material according to any one of claims 1 to 7, wherein the first coating layer contains Li 2 O-La 2 O 3 -P 2 O 5 The heterostructure, which is a flexible surface regeneration layer, has a thickness that increases with increasing charge and discharge times, and varies from 1 to 300 nm.
9. The positive electrode material according to any one of claims 1 to 7, wherein the thickness of the second coating layer is 1 to 500nm; and/or Al 2 O 3 The mass fraction of the active material of the positive electrode is 0.01-0.5%.
10. The positive electrode material according to claim 9, wherein Al 2 O 3 The mass fraction of the active material of the positive electrode is 0.05-0.2%.
11. The positive electrode material according to any one of claims 1 to 7, wherein the amount of La in the second core, the first coating layer, and the second coating layer is in the range of 0.1% to 1%, 0.01% to 0.3%, and 0.01% to 0.3%, respectively, by mass of the positive electrode active material.
12. The positive electrode material according to claim 11, wherein the amount of La in the second core, the first coating layer, and the second coating layer is in the range of 0.2% to 0.6%, 0.03% to 0.15%, and 0.03% to 0.2% by mass, respectively, of the positive electrode active material.
13. The positive electrode material according to claim 11, wherein the La content satisfies the following relation I and relation II, as follows:
14. the positive electrode material according to claim 13, wherein the La content satisfies the following relation I and relation II, as follows:
15. the method for producing a composite ternary cathode material according to any one of claims 1 to 14, comprising the steps of: (1) preparation of a positive electrode material precursor: according to the stoichiometric ratio of Ni to Co to Mn=x2 to y2 to z2, dissolving soluble nickel salt, soluble cobalt salt and soluble manganese salt in water to obtain a second inner core layer precursor solution; according to the stoichiometric ratio of Ni to Co to Mn=x1 to y1 to z1, dissolving soluble nickel salt, soluble cobalt salt and soluble manganese salt in water to obtain a first inner core layer solution; mixing the first inner core layer solution, the precipitator, the complexing agent and the second inner core layer solution to obtain mixed suspension, so that Ni x2 Co y2 Mn z2 (OH) 2 Depositing on the surface of the first inner core layer particles, and obtaining a precursor material by a coprecipitation method; (2) preparation of a baked product: mixing the precursor material with Li source and LaPO 4 Uniformly mixing, sintering, grinding, crushing and sieving to obtain a composite ternary positive electrode material-sintered product; (3) Positive electrode materialPreparing a finished product: sintering the composite ternary positive electrode material 4 Al and Al 2 O 3 Mixing, sintering and sieving to obtain the positive electrode material finished product.
16. The preparation method according to claim 15, wherein in the step (2), the mixed powder is kept at 400-700 ℃ for 2-6 hours to remove the bound water; heating to 700-900 deg.c and sintering for 4-15 hr.
17. The method according to claim 15, wherein in the step (3), sintering is performed at 300 to 700 ℃ for 5 to 10 hours under an air or oxygen atmosphere.
18. A lithium ion battery comprising a composite ternary cathode material according to claim 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210030579.0A CN114388779B (en) | 2022-01-12 | 2022-01-12 | Composite ternary positive electrode material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210030579.0A CN114388779B (en) | 2022-01-12 | 2022-01-12 | Composite ternary positive electrode material, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114388779A CN114388779A (en) | 2022-04-22 |
| CN114388779B true CN114388779B (en) | 2024-02-02 |
Family
ID=81202143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210030579.0A Active CN114388779B (en) | 2022-01-12 | 2022-01-12 | Composite ternary positive electrode material, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114388779B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115810757B (en) * | 2023-02-09 | 2023-05-05 | 中创新航科技股份有限公司 | Positive electrode active material and lithium ion battery containing same |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752713A (en) * | 2013-12-30 | 2015-07-01 | 北京当升材料科技股份有限公司 | Lithium ion battery composite anode material and preparation method thereof |
| WO2017096525A1 (en) * | 2015-12-08 | 2017-06-15 | 北京当升材料科技股份有限公司 | Lithium-ion battery positive electrode material, preparation method therefor, lithium-ion battery positive electrode, and lithium-ion battery |
| KR20180077081A (en) * | 2016-12-28 | 2018-07-06 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery including the same |
| CN108269970A (en) * | 2016-12-31 | 2018-07-10 | 北京当升材料科技股份有限公司 | A kind of new type lithium ion battery gradient anode material and preparation method thereof |
| CN109461893A (en) * | 2017-12-29 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of Olivine-type Cathode Material in Li-ion Batteries and preparation method thereof |
| CN109461891A (en) * | 2017-11-02 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of high voltage lithium cobalt oxide anode and preparation method thereof |
| CN110970601A (en) * | 2018-09-28 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Double-gradient coated high-nickel ternary cathode material and preparation method thereof |
| CN111422926A (en) * | 2020-04-10 | 2020-07-17 | 浙江帕瓦新能源股份有限公司 | Core-shell structure Al/L a co-doped high-nickel ternary precursor, preparation method thereof and anode material |
| WO2021068448A1 (en) * | 2019-10-10 | 2021-04-15 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery |
| CN113629241A (en) * | 2021-08-06 | 2021-11-09 | 合肥国轩高科动力能源有限公司 | Preparation method of core-shell structure cathode material, cathode material and lithium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102268079B1 (en) * | 2017-11-21 | 2021-06-23 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same |
-
2022
- 2022-01-12 CN CN202210030579.0A patent/CN114388779B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752713A (en) * | 2013-12-30 | 2015-07-01 | 北京当升材料科技股份有限公司 | Lithium ion battery composite anode material and preparation method thereof |
| WO2017096525A1 (en) * | 2015-12-08 | 2017-06-15 | 北京当升材料科技股份有限公司 | Lithium-ion battery positive electrode material, preparation method therefor, lithium-ion battery positive electrode, and lithium-ion battery |
| KR20180077081A (en) * | 2016-12-28 | 2018-07-06 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery including the same |
| CN108269970A (en) * | 2016-12-31 | 2018-07-10 | 北京当升材料科技股份有限公司 | A kind of new type lithium ion battery gradient anode material and preparation method thereof |
| CN109461891A (en) * | 2017-11-02 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of high voltage lithium cobalt oxide anode and preparation method thereof |
| CN109461893A (en) * | 2017-12-29 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of Olivine-type Cathode Material in Li-ion Batteries and preparation method thereof |
| CN110970601A (en) * | 2018-09-28 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Double-gradient coated high-nickel ternary cathode material and preparation method thereof |
| WO2021068448A1 (en) * | 2019-10-10 | 2021-04-15 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery |
| CN111422926A (en) * | 2020-04-10 | 2020-07-17 | 浙江帕瓦新能源股份有限公司 | Core-shell structure Al/L a co-doped high-nickel ternary precursor, preparation method thereof and anode material |
| CN113629241A (en) * | 2021-08-06 | 2021-11-09 | 合肥国轩高科动力能源有限公司 | Preparation method of core-shell structure cathode material, cathode material and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| Promoting the electrochemical performance of LiNi0.8Co0.1Mn0.1O2 cathode via LaAlO3 coating;Yong-Chun Li et al.;《Journal of Alloys and Compounds》;第766卷;546-555 * |
| 梯度包覆镍酸锂材料Li[Ni_(0.92)Co_(0.04)Mn_(0.04)]O_2的合成与研究;杜柯 等;无机化学学报;第29卷(第5期);1031-1036 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114388779A (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210367233A1 (en) | Ternary positive electrode material and preparation method therefor, and lithium-ion battery | |
| US20190386293A1 (en) | Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery | |
| CN104201366B (en) | A kind of preparation method of high security high compacted density nickle cobalt lithium manganate NCM523 ternary material | |
| CN107665983B (en) | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery | |
| EP4024519A1 (en) | Positive electrode material, preparation method therefor and lithium ion battery | |
| CN110867573A (en) | Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile | |
| CN108493435B (en) | Lithium ion battery anode material Li (Ni)0.8Co0.1Mn0.1)1-xYxO2And preparation method | |
| CN106025208A (en) | Preparation method for carbon-coated ternary positive electrode material | |
| CN109390553B (en) | Composite positive electrode material, positive plate and all-solid-state lithium battery | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN115939336A (en) | Positive electrode material of sodium ion battery, positive plate and secondary battery | |
| CN113353995A (en) | Cathode material with low cobalt content and preparation method and application thereof | |
| CN110649230B (en) | Nanometer rivet core-shell structure anode material and preparation method thereof | |
| CN110863245A (en) | Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile | |
| KR20230139299A (en) | Positive electrode material, battery, and electronic device | |
| CN110459764A (en) | A kind of anode material for lithium-ion batteries and the preparation method and application thereof | |
| CN113571679A (en) | Spinel oxide coated lithium-rich manganese-based positive electrode material | |
| CN115732661A (en) | Positive active material and application thereof | |
| CN115571927A (en) | Composite in-situ coated high-nickel single crystal positive electrode material and preparation method thereof | |
| CN116031380A (en) | Polycrystalline sodium ion-like positive electrode material, and preparation method and application thereof | |
| CN114388779B (en) | Composite ternary positive electrode material, preparation method thereof and lithium ion battery | |
| CN105958061A (en) | Preparation method for nickel-cobalt-aluminum ternary positive electrode material | |
| CN114031123A (en) | Ternary precursor with core-shell structure and preparation method thereof, and quaternary anode material and preparation method thereof | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof | |
| CN111916713A (en) | High-voltage lithium nickel manganese oxide positive electrode material with core-multilayer shell structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |