CN117936757A - Lithium supplementing material, lithium supplementing diaphragm and preparation method of lithium supplementing diaphragm - Google Patents
Lithium supplementing material, lithium supplementing diaphragm and preparation method of lithium supplementing diaphragm Download PDFInfo
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- CN117936757A CN117936757A CN202410332419.0A CN202410332419A CN117936757A CN 117936757 A CN117936757 A CN 117936757A CN 202410332419 A CN202410332419 A CN 202410332419A CN 117936757 A CN117936757 A CN 117936757A
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- lithium
- lithium supplementing
- supplementing
- shell
- diaphragm
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 174
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 158
- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims description 36
- 239000011258 core-shell material Substances 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910011763 Li2 O Inorganic materials 0.000 claims description 2
- 229910011777 Li2 S Inorganic materials 0.000 claims description 2
- 229910014333 LiNi1-x-yCoxMyO2 Inorganic materials 0.000 claims description 2
- 229910014832 LiNi1−x−yCoxMyO2 Inorganic materials 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 239000011247 coating layer Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- 230000006870 function Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000005611 electricity Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011257 shell material Substances 0.000 description 32
- 239000010410 layer Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012528 membrane Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910018068 Li 2 O Inorganic materials 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229940053662 nickel sulfate Drugs 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of batteries. The invention provides a lithium supplementing material, a lithium supplementing diaphragm and a preparation method thereof, wherein the lithium supplementing material takes a lithium supplementing agent as an inner core, and ternary or quaternary active materials (such as NCM, NCA and the like) as a coating layer, so that the coating layer can conduct electricity and ions, not only enhances the conductivity of the lithium supplementing material, but also can provide active Li ions to have sufficient lithium supplementing amount, thereby realizing excellent and stable lithium supplementing effect. When the obtained lithium supplementing material is applied to the diaphragm to form a coating diaphragm, the risk of short circuit caused by introducing an inactive conductive carbon substance can be avoided, the normal play of the basic function of the diaphragm can be ensured, and the functions of lithium supplementing and lithium ion conduction can effectively improve the performance of the battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a lithium supplementing material, a lithium supplementing diaphragm and a preparation method thereof.
Background
Along with the development of science and technology, the lithium ion battery is widely applied in a plurality of fields due to the advantages of high energy density, high rated voltage, no memory effect, long cycle life and the like. The lithium ion battery mainly comprises an anode, a cathode, electrolyte and a diaphragm. Among them, the separator plays a critical role as a critical inner layer component.
The separator of the lithium ion battery has the main functions of separating the positive electrode from the negative electrode, preventing the positive electrode and the negative electrode from contacting to cause the short circuit of the battery, and simultaneously allowing free passage of lithium ions to conduct the lithium ions. The safety of the battery is ensured, and the high-efficiency operation of the battery is ensured. Therefore, the performance of the separator directly affects the discharge capacity, cycle life, and safety of the lithium ion battery.
According to different preparation materials and processes, the lithium ion battery diaphragm is mainly divided into a substrate diaphragm and a coating diaphragm, wherein the substrate diaphragm mainly comprises a polyolefin diaphragm, an inorganic ceramic diaphragm, a composite diaphragm and the like. And the surface of the substrate membrane is coated with a thin coating layer to enhance the properties of the membrane, such as pore size, distribution, mechanical strength, chemical stability, etc. of the membrane. Currently, common coating materials are inorganic coatings such as alumina coatings and silicon nitride coatings, organic coatings such as polymer coatings, inorganic-organic composite coatings, and the like. The coating can not only improve the high temperature resistance, mechanical strength, chemical stability and the like of the diaphragm, but also improve the migration efficiency of lithium ions, thereby improving the electrochemical performance of the battery.
However, most of the existing coatings are chemically inert materials, which affect the electrochemical performance of the anode and cathode of the battery to some extent. Therefore, there is still a need to develop a new solution for coating the separator to ensure the basic function of the separator and to effectively improve or enhance the performance of the battery.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a lithium supplementing material, a lithium supplementing diaphragm and a preparation method thereof, wherein the lithium supplementing material is provided with a lithium supplementing agent inner core and a ternary or quaternary active material outer shell, a lithium supplementing layer is formed on a diaphragm base material by the lithium supplementing material to obtain the lithium supplementing diaphragm, and the lithium supplementing diaphragm can not only ensure the basic function of the diaphragm to be exerted, but also slowly release lithium to effectively improve and promote the performance of a battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium supplementing material, the lithium supplementing material has a core-shell structure, the core comprises a lithium supplementing agent, the shell comprises LiNi 1-x-yCoxMyO2, x is more than 0 and less than or equal to 0.5, y is more than 0 and less than or equal to 0.5, x+y is less than 1, and M comprises Mn and/or Al.
The lithium supplementing material takes the lithium supplementing agent as the inner core and takes the ternary or quaternary active materials (such as NCM, NCA and the like) as the coating layer, so that the coating layer can conduct electricity and ions, not only enhances the conductivity of the lithium supplementing material, but also provides active Li ions, thereby having sufficient lithium supplementing amount and realizing excellent and stable lithium supplementing effect. In the prior art, the non-active conductive carbon is often added in the coating slurry, and when the obtained lithium supplementing material is applied to the membrane to form the coating membrane, the risk of short circuit caused by introducing non-active conductive carbon substances can be avoided, normal play of basic functions of the membrane can be ensured, and the performance of the battery can be effectively improved due to the effects of lithium supplementing and lithium ion conduction.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the lithium supplementing agent is at least one of Li 2O、Li2 S, LFO, LNO and a compound Li 2S/Co、Li2 O/Co.
The particle diameter of the lithium-supplementing material is preferably 20nm to 20 μm, for example, 20nm, 60nm, 100nm, 300nm, 600nm, 800nm, 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, 15 μm, 18 μm or 20 μm, etc., and preferably 100nm to 1 μm, but not limited to the listed values, and other values not listed in the above-mentioned numerical ranges are applicable.
The thickness of the shell is preferably 2 to 2000nm, for example 2nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm or 2000nm, and more preferably 2 to 1000nm, but is not limited to the values listed, and other values not listed in the above-mentioned value range are equally applicable.
In a second aspect, the present invention provides a method for preparing the lithium supplementing material according to the first aspect, where the preparation method includes:
and mixing the lithium supplementing agent precursor with the shell raw material to form a core-shell coating, and mixing and sintering the core-shell coating and a lithium source to obtain the lithium supplementing material.
The preparation method of the lithium supplementing material is simple, has low cost, is compatible with the existing preparation equipment and production line, is suitable for mass production, and can be widely applied to process production.
As a preferable technical scheme of the invention, the preparation method comprises the following steps: firstly mixing and stirring a lithium supplementing agent precursor and a solvent, then adding a shell raw material, mixing and stirring, then adding a mixed solution of ammonia water and strong alkali, mixing and stirring, and titrating out the shell precursor through the mixed solution, so that the shell precursor simultaneously coats the lithium supplementing agent precursor, and after the core-shell coating is obtained, washing and drying the core-shell coating, and then mixing and sintering the core-shell coating with a lithium source.
Preferably, the shell material comprises a soluble Ni salt, a soluble Co salt, and a soluble M salt.
Preferably, the mass ratio of the soluble Ni salt to the lithium-supplementing agent precursor is (1-9): (10-90), such as 1:10、3:10、5:10、7:10、9:10、1:25、3:25、5:25、7:25、9:25、1:50、3:50、5:50、7:50、9:50、1:75、3:75、5:75、7:75、9:75、1:90、3:90、5:90、7:90 or 8:90, but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the core-shell coating is also in a core-shell structure, wherein the core of the core-shell coating is a lithium supplementing agent precursor, and the shell is the shell precursor; the shell precursor is Ni 1-x-yCoxMy(OH)2, x is more than 0 and less than or equal to 0.5, y is more than 0 and less than or equal to 0.5, x+y is less than 1, and M comprises Mn and/or Al.
Preferably, the drying temperature is 50 to 120 ℃, such as 50 ℃, 55 ℃, 60 ℃, 65 ℃,70 ℃,75 ℃,80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, and the drying time is 1 to 3 hours, such as1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours or the like, but the drying temperature is not limited to the recited values, and other non-recited values within the above-recited values are equally applicable.
Preferably, the sintering temperature is 600 to 1200 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or the like, and the sintering time is 3 to 7 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, or 6 hours, but not limited to the recited values, and other non-recited values within the above-recited value range are equally applicable.
Preferably, the lithium-compensating agent precursor is mixed with a solvent, including but not limited to water, under agitation.
Preferably, the amount of the lithium source and the core-shell coating is controlled according to the molar ratio of the lithium element to the nickel element of (10-100): (3-9), for example 10:3、20:3、20:5、20:5.3、20:5.5、20:5.8、20:6、20:6.2、20:6.5、20:6.8、20:7、20:7.3、20:7.5、20:7.8、20:8、20:8.3、20:8.5、20:8.8 or 20:9, but the invention is not limited to the listed values, and other non-listed values in the above-mentioned value range are equally applicable.
In a third aspect, the invention provides a lithium-supplementing separator, which comprises a separator and a lithium-supplementing layer arranged on the separator, wherein the lithium-supplementing layer contains the lithium-supplementing material in the first aspect or contains the lithium-supplementing material obtained by the preparation method in the second aspect.
The lithium supplementing diaphragm can supplement the loss of active lithium in the process of generating the SEI film in the first circulation process, so that the lithium supplementing layer is preferably arranged on one side of the diaphragm base material facing the positive electrode. Active lithium can be provided by the inner core and the outer shell of the lithium supplementing material in the lithium supplementing layer, and the electronic conductivity of an internal lithium compound is improved by the coating layer formed by the ternary or quaternary active material, so that the performance of a battery can be effectively improved by using the lithium supplementing diaphragm. The lithium supplementing material and the lithium supplementing diaphragm provided by the invention have good compatibility with the current commercial anode and cathode, and the electrolyte and the battery manufacturing process do not need to be adjusted and redesigned, so that the lithium supplementing material and the lithium supplementing diaphragm are very suitable for the current secondary lithium ion battery.
As a preferable embodiment of the present invention, the lithium supplementing layer is disposed on a side of the separator facing the positive electrode.
Preferably, the lithium supplementing layer further contains a binder.
Preferably, the binder accounts for 0.5% -20% of the mass of the lithium supplementing layer, for example, 0.5%, 0.8%, 1%, 1.5%, 2%, 3%, 5%, 8%, 10%, 12%, 14%, 16%, 18% or 20%, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the binder comprises a conductive polymer.
Preferably, the conductive polymer comprises at least one of polyacetylene, polypyrrole, polyaniline, polythiophene, or polyfuran.
In the preparation of the lithium supplementing diaphragm, the conductive polymer is preferably used as a binder to construct the lithium supplementing layer together with the lithium supplementing material, and the conductive polymer can not only increase the cohesiveness to enable the lithium supplementing material to be combined with the diaphragm base material, but also construct a conductive network structure to enable conduction between the lithium supplementing material and the positive electrode material and formation of potential difference between the positive electrode material and the negative electrode, so that the performance of the battery is improved, and the influence caused by using a conventional non-electric conductive binder (such as polyvinylidene fluoride (PVDF)) is avoided.
In a fourth aspect, the present invention provides a method for preparing the lithium-compensating separator according to the third aspect, the method comprising:
preparing lithium supplementing layer slurry, and coating the obtained lithium supplementing layer slurry on the diaphragm to form a lithium supplementing layer to obtain the lithium supplementing diaphragm.
It should be noted that the specific selection of the separator is not limited in the present invention, and the separator that can be applied to the battery in the prior art is suitable for constructing the lithium-supplementing separator according to the present invention, and should be reasonably selected and adjusted according to actual needs. Illustratively, the membrane comprises a PE membrane (polyethylene membrane).
As a preferred embodiment of the present invention, the solvent for preparing the slurry of the lithium supplementing layer includes at least one of N-methylpyrrolidone, acetone, dimethyl carbonate (DMC) and absolute ethyl alcohol, and typical, but non-limiting combinations include, for example, a combination of N-methylpyrrolidone and acetone, a combination of N-methylpyrrolidone and dimethyl carbonate, a combination of N-methylpyrrolidone and absolute ethyl alcohol, a combination of acetone and dimethyl carbonate, a combination of acetone and absolute ethyl alcohol, and the like.
Preferably, the lithium supplementing material accounts for 20% -70%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70% by mass, the binder accounts for 0.5% -20%, such as 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 7%, 8%, 10%, 13%, 15%, 18% or 20% by mass, and the solvent accounts for 10% -70%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70% by mass, based on 100% by mass of the lithium supplementing layer slurry, but the present invention is not limited to the above-mentioned values, and other non-cited values in the above-mentioned numerical ranges are applicable.
In a fifth aspect, the present invention provides a lithium ion energy storage device, which contains the lithium supplementing material according to the first aspect or contains the lithium supplementing separator according to the third aspect.
Preferably, the lithium ion energy storage device comprises a lithium ion battery.
Compared with the prior art, the invention has at least the following beneficial effects:
According to the lithium supplementing material, the lithium supplementing agent is used as the inner core, and the ternary or quaternary active material is used as the coating layer, so that the coating layer can conduct electricity and ions, the conductivity of the lithium supplementing material is enhanced, and the lithium supplementing material can provide active Li ions to have sufficient lithium supplementing amount, so that an excellent and stable lithium supplementing effect can be realized.
When the obtained lithium supplementing material is applied to the diaphragm to form a coating diaphragm, the loss of active lithium in the process of generating an SEI film in the first circulation process can be supplemented, the normal play of the basic function of the diaphragm can be ensured, the risk of short circuit caused by introducing an inactive conductive carbon substance is avoided, and the provided lithium supplementing and lithium ion conduction effects can effectively improve the performance of the battery.
The conductive polymer is used as a binder to construct the lithium supplementing layer together with the lithium supplementing material, and can not only increase the cohesiveness to enable the lithium supplementing material to be combined with the diaphragm base material, but also construct a conductive network structure to enable conduction between the lithium supplementing material and the positive electrode material and formation of potential difference between the positive electrode material and the negative electrode, so that the performance of the battery is improved, and the influence caused by using a conventional non-electric conductive binder (such as polyvinylidene fluoride (PVDF)) is avoided.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium supplementing material, and the preparation method of the lithium supplementing material comprises the following steps:
1) Li 2CO3 is taken as a precursor of the lithium supplementing agent and is put into a stirring tank with water; then, the shell raw material is also put into a stirring tank, so that the lithium-supplementing agent precursor, the shell raw material and solvent water are stirred and mixed, wherein the shell raw material is nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 8:1:1, and the mass ratio of the lithium-supplementing agent precursor to the nickel sulfate is controlled to be 5:1;
2) Titrating a mixed solution of ammonia water and strong alkali NaOH (molar ratio of 1:1) into a stirring tank so that a Ni 0.8Co0.1Mn0.1(OH)2 particle coating layer (shell precursor) is generated on the surface layer of Li 2CO3 to form a core-shell coating;
3) Washing and drying the substances in the stirring tank obtained in the step 2), wherein the drying temperature is 80 ℃ and the drying time is 2 hours; mixing the mixture with a lithium source LiOH after drying, controlling the mole ratio of Ni element in the core-shell coating and Li in the lithium source to be 8:10, and then sintering at 800 ℃ for 5 hours to obtain a lithium supplementing material, wherein the core of the lithium supplementing material is Li 2 O, and the chemical formula of the lithium supplementing material is as follows: liNi 0.8Co0.1Mn0.1O2.
In the lithium supplementing material obtained in the embodiment, the particle size of the lithium supplementing agent is 500nm; the thickness of the shell of the lithium supplementing material was 50nm.
Example 2
The embodiment provides a lithium supplementing material, and the preparation method of the lithium supplementing material comprises the following steps:
1) Fe 2O3 is taken as a precursor of the lithium supplementing agent and is put into a stirring tank with water; then, the shell raw material is also put into a stirring tank, so that the lithium-supplementing agent precursor, the shell raw material and solvent water are stirred and mixed, wherein the shell raw material is nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 8:1:1, and the mass ratio of the lithium-supplementing agent precursor to the nickel sulfate is controlled to be 5:1;
2) Titrating a mixed solution (molar ratio of 1:1) with strong alkali NaOH into a stirring tank so as to generate a Ni 0.8Co0.1Mn0.1(OH)2 particle coating layer (shell precursor) on the surface layer of Fe 2O3 to form a core-shell coating;
3) Washing and drying the substances in the stirring tank obtained in the step 2), wherein the drying temperature is 80 ℃ and the drying time is 2 hours; mixing the mixture with lithium source LiOH after drying, controlling the mole ratio of Ni in the core-shell coating and Li in the lithium source to be 8:20, and then sintering at 800 ℃ for 5 hours to obtain a lithium supplementing material, wherein the core of the lithium supplementing material is LFO, and the chemical formula of the lithium supplementing material is as follows: liNi 0.8Co0.1M0.1O2.
In the lithium supplementing material obtained in the embodiment, the particle size of the lithium supplementing agent is 800nm; the thickness of the shell of the lithium supplementing material was 60nm.
Example 3
The embodiment provides a lithium supplementing material, and the preparation method of the lithium supplementing material is to adjust a lithium supplementing agent precursor from Li 2CO3 to simple substance S.
1) Taking simple substance S as a precursor of the lithium supplementing agent, and putting the precursor into a stirring tank with water; then, the shell raw material is also put into a stirring tank, so that the lithium-supplementing agent precursor, the shell raw material and solvent water are stirred and mixed, wherein the shell raw material is nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 5:2:3, and the mass ratio of the lithium-supplementing agent precursor to the nickel sulfate is controlled to be 10:1;
2) Titrating a mixed solution of ammonia water and strong alkali NaOH (the molar ratio is 1:1) into a stirring tank so as to generate a Ni 0.5Co0.2Mn0.3(OH)2 particle coating layer (shell precursor) on the surface layer of the simple substance S, thereby forming a core-shell coating;
3) Washing and drying the substances in the stirring tank obtained in the step 2), wherein the drying temperature is 80 ℃ and the drying time is 2 hours; mixing the mixture with a lithium source Li 2 O after drying, controlling the mole ratio of Ni in the core-shell coating to Li in the lithium source to be 8:20, and then sintering at 800 ℃ for 5 hours to obtain a lithium supplementing material, wherein the core of the lithium supplementing material is L 2 S, and the chemical formula of the lithium supplementing material is as follows: liNi 0.5Co0.2Mn0.3O2.
In the lithium supplementing material obtained in the embodiment, the particle size of the lithium supplementing agent is 600nm; the thickness of the shell of the lithium supplementing material was 70nm.
Comparative example 1
This comparative example uses only the lithium supplementing agent in example 1 as the lithium supplementing material.
Comparative example 2
This comparative example uses only the shell material in example 1, i.e., ternary active material LiNi 0.8Co0.1Mn0.1O2, as a lithium supplementing material.
Comparative example 3
This comparative example provides a lithium supplementing material having a core-shell structure, and the only difference from example 1 is that the shell of this comparative example is a carbon coating layer having the same thickness as the shell layer of example 1.
Comparative example 4
The comparative example provides a lithium supplementing material, and the preparation method of the lithium supplementing material comprises the following steps:
Li 2CO3 is used as a lithium supplementing agent precursor, mixed with Ni 0.8Co0.1Mn0.1(OH)2 powder, and the mass of Li 2CO3 and Ni 0.8Co0.1Mn0.1(OH)2 powder is controlled to be 6.7:1; and (3) mixing the lithium supplementing agent precursor and the shell precursor dry powder, and then calcining at 800 ℃ for 5 hours to form the particle mixture of the lithium supplementing material Li 2 O and LiNi 0.8Co0.1Mn0.1O2.
In comparative example 4, the powder quality conversion is consistent with that in example 1, the ternary material precursor is coated on the surface of Li 2CO3 through in-situ growth by the synthesis process of the ternary material precursor, the inner core is Li 2 O after calcination synthesis, the outer shell is coated LiNi 0.8Co0.1Mn0.1O2 material, comparative example 4 is consistent with that of the traditional ternary material composite lithium supplementing agent, li 2CO3 and Ni 0.8Co0.1Mn0.1(OH)2 are mixed and sintered, an in-situ coated core-shell structure cannot be generated, and only the particle mixture of Li 2 O and LiNi 0.8Co0.1Mn0.1O2 cannot effectively improve the conductivity of Li 2 O.
Application example 1
The application example provides a lithium supplementing diaphragm, and the method for preparing the lithium supplementing diaphragm comprises the following steps:
Preparing lithium supplementing material, a binder PEDOT (poly 3, 4-ethylenedioxythiophene) and a solvent NMP in the mass ratio of 50:1:49 into lithium supplementing layer slurry, coating one side surface of a PE membrane substrate with the lithium supplementing layer slurry, wherein the coating thickness is 3 mu m, and drying in an oven at 85 ℃ for 10min to obtain the lithium supplementing membrane.
Application example 2
The present application example provides a lithium-supplementing separator, and the method for preparing the lithium-supplementing separator is that the lithium-supplementing material of example 1 is replaced by the lithium-supplementing material of example 2, and the amount of binder is reduced, so that the mass ratio of the lithium-supplementing material, the binder and the solvent is adjusted from 50:1:49 to 50:0.497:49, and other conditions are exactly the same as those of application example 1.
Application example 3
The present application example provides a lithium-supplementing separator, and the method for preparing the lithium-supplementing separator is that the lithium-supplementing material of example 1 is replaced by the lithium-supplementing material of example 3, and the amount of binder is increased, so that the mass ratio of the lithium-supplementing material, the binder and the solvent is adjusted from 50:1:49 to 50:24.75:49, and other conditions are exactly the same as in application example 1.
Application example 4
The application example provides a lithium supplementing diaphragm, and the method for preparing the lithium supplementing diaphragm is to replace a binder PEDOT with polyvinylidene fluoride PVDF, and the usage amount of the binder is kept unchanged, except that other conditions are identical to those of the application example 1.
Comparative examples 1 to 4 were used
The application of comparative examples 1 to 4 provides a separator, respectively, which is prepared by replacing the lithium supplementing material of example 1 with the lithium supplementing material of comparative examples 1 to 4, respectively, except that the other conditions are exactly the same as in application example 1.
Comparative example 5 was used
The present application comparative example uses the PE separator substrate in example 1 as a separator.
The separator obtained in the application example and the application comparative example was tested:
(1) The internal resistance of the separator was tested by the method of GB/T36363-2018 and the results are recorded in Table 1;
(2) Preparing the diaphragms obtained in the application examples and the application comparative examples into a lithium iron phosphate soft package battery with the design capacity of 5Ah, wherein the positive electrode is LFP, PVDF, SP=96:1.8:2.2, and the current collector is aluminum foil; the negative electrode is graphite: CMC sbr=97:1.2:1.8, current collector is copper foil; the partial capacity formation voltage interval is 2.0-4.3V. First effect test charges to 4.3V at 0.1C and discharges to 2.0V at 0.1C; the ratio of the discharge capacity to the charge capacity was calculated. The capacity retention rate of 500 cycles was calculated by performing a cycle charge/discharge performance test with a 1C current at a cycle voltage interval of 2.0 to 3.65v, and the results are recorded in table 1.
TABLE 1
From the above, it can be seen that: in application examples 1-4, compared with other diaphragms coated with coatings, the lithium supplementing agent coated with the high-nickel LiNi 0.8Co0.1M0.1O2 in application examples 1-2 can effectively reduce the internal resistance of the diaphragm, simultaneously has better lithium supplementing effect, improves the first effect and prolongs the service life. The lithium-supplementing coating diaphragm prepared by the invention has excellent lithium ion conductivity, and has obvious improvement effect on the cycle performance of the battery core.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (11)
1. A lithium supplementing material is characterized by having a core-shell structure, wherein a core comprises a lithium supplementing agent, a shell comprises LiNi 1-x-yCoxMyO2, x is more than 0 and less than or equal to 0.5, y is more than 0 and less than or equal to 0.5, x+y is less than 1, and M comprises Mn and/or Al.
2. The lithium supplementing material according to claim 1, wherein the lithium supplementing agent is at least one of Li 2O、Li2 S, LFO, LNO and a compound Li 2S/Co、Li2 O/Co.
3. The lithium supplementing material according to claim 1, wherein the particle size of the lithium supplementing material is 20nm to 20 μm.
4. The lithium supplementing material according to claim 1, wherein the thickness of the shell is 2 to 2000nm.
5. A method of preparing a lithium-supplementing material according to any one of claims 1 to 4, comprising:
And mixing the lithium supplementing agent precursor with a shell raw material to form a core-shell coating, and mixing and sintering the core-shell coating and a lithium source to obtain the lithium supplementing material.
6. The method for preparing a lithium supplementing material according to claim 5, wherein said method for preparing comprises: firstly mixing and stirring a lithium supplementing agent precursor and a solvent, then adding a shell raw material, mixing and stirring, then adding a mixed solution of ammonia water and strong alkali, mixing and stirring, and titrating out the shell precursor through the mixed solution, so that the shell precursor simultaneously coats the lithium supplementing agent precursor to obtain the core-shell coating, and mixing and sintering the core-shell coating with a lithium source after washing and drying the core-shell coating.
7. The method for producing a lithium supplementing material according to claim 6, wherein said shell raw material comprises a soluble Ni salt, a soluble Co salt and a soluble M salt; the mass ratio of the soluble Ni salt to the lithium supplementing agent precursor is (1-9) (10-90); the shell precursor is Ni 1-x-yCoxMy(OH)2, x is more than 0 and less than or equal to 0.5, y is more than 0 and less than or equal to 0.5, x+y is less than 1, and M comprises Mn and/or Al.
8. The method for producing a lithium-supplementing material according to any one of claims 5 to 7, wherein the amounts of the lithium source and the core-shell coating are controlled in such a manner that the molar ratio of the lithium element to the nickel element is (10 to 100): (3 to 9).
9. A lithium supplementing separator, comprising a separator and a lithium supplementing layer arranged on the separator, wherein the lithium supplementing layer contains the lithium supplementing material according to any one of claims 1 to 4 or the lithium supplementing material obtained by the preparation method according to any one of claims 5to 8.
10. The lithium-compensating separator of claim 9, wherein the lithium-compensating layer is disposed on a side of the separator facing the positive electrode; the lithium supplementing layer also contains a binder; the binder accounts for 0.5% -20% of the mass of the lithium supplementing layer; the binder comprises a conductive polymer; the conductive polymer includes at least one of polyacetylene, polypyrrole, polyaniline, polythiophene, and polyfuran.
11. A method of making the lithium-compensating separator of claim 9 or 10, comprising:
Preparing lithium supplementing layer slurry, wherein the mass of the lithium supplementing material accounts for 20% -70%, the mass of the binder accounts for 0.5% -20%, the mass of the solvent accounts for 10% -70% of the mass of the lithium supplementing layer slurry, and coating the obtained lithium supplementing layer slurry on the diaphragm to form a lithium supplementing layer, so that the lithium supplementing diaphragm is obtained.
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