CN110034280B - In-situ composite lithium battery negative electrode material and preparation method and application thereof - Google Patents
In-situ composite lithium battery negative electrode material and preparation method and application thereof Download PDFInfo
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- CN110034280B CN110034280B CN201810244052.1A CN201810244052A CN110034280B CN 110034280 B CN110034280 B CN 110034280B CN 201810244052 A CN201810244052 A CN 201810244052A CN 110034280 B CN110034280 B CN 110034280B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 67
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 100
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 86
- 239000010406 cathode material Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 34
- 230000004927 fusion Effects 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000002210 silicon-based material Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 18
- 229910052715 tantalum Inorganic materials 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 239000003570 air Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 8
- 229910021385 hard carbon Inorganic materials 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 8
- 229910021384 soft carbon Inorganic materials 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 230000001788 irregular Effects 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 239000002228 NASICON Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002001 electrolyte material Substances 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 239000007833 carbon precursor Substances 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000006182 cathode active material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011257 shell material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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 an in-situ composite lithium battery cathode material and a preparation method and application thereof, wherein the in-situ composite lithium battery cathode material is of a core-shell structure, has a particle size of 2nm-100um and comprises a core and a shell layer; the inner core is formed by compounding a negative active material and a solid electrolyte material, wherein the mass ratio of the negative active material to the solid electrolyte material is 0.001-1000; the structure of the kernel specifically includes: the solid electrolyte material is coated on the surface of the negative electrode active material, the negative electrode active material is coated on the surface of the solid electrolyte material, the solid electrolyte material is dispersed and distributed in the negative electrode active material, and the negative electrode active material is dispersed and distributed in one or more of the solid electrolyte materials.
Description
Technical Field
The invention relates to the technical field of materials, in particular to an in-situ composite lithium battery negative electrode material and a preparation method and application thereof.
Background
The lithium ion battery has the characteristics of high output voltage, high energy density, long cycle life, good safety performance, no memory effect and the like, and is successfully applied to the field of mobile power sources as a main energy storage device. In order to further meet the requirements of power grid energy storage, electric vehicles and consumer electronic products on energy storage devices, electrode materials and lithium battery systems with longer cycle life, better safety and higher energy density become research hotspots. The conventional lithium ion battery adopts an electrolytic liquid system which is an organic liquid dissolved with lithium salt, the electrolyte generates heat due to overcharge, internal circuits and other abnormalities, and the danger of spontaneous combustion or explosion exists.
The development and preparation of solid electrode materials and pole pieces are particularly important for quasi-solid, semi-solid and all-solid batteries. Particularly in quasi-solid, semi-solid and all-solid batteries, the cathode material is not in direct contact with the electrolyte, so that a surface solid electrolyte layer is avoided, the first-cycle coulomb efficiency is increased, and the energy density of the battery is greatly improved. In addition, the solid electrolyte has a wide electrochemical window, does not react with the lithium metal or has a slow reaction speed, so that the lithium metal can be used as a negative electrode of a lithium battery.
In the development process of the solid-state anode material, the interface contact state between the solid-state electrolyte and the anode active material is one or more of point-to-point contact, point-to-surface contact, and surface-to-surface contact. The poor contact between the solid electrolyte and the electrode active material increases the contact resistance between the solid electrolyte and the electrode active material, which leads to overlarge internal resistance of the whole battery, lithium ions cannot shuttle between the cathode material and the electrolyte material well, reduces the battery capacity, and causes lower durability and higher interface impedance.
In the existing technical scheme of the solid-state negative electrode material, a negative electrode active material, a solid-state electrolyte material, a binder, a conductive additive and the like are mechanically mixed, or the negative electrode active material and the solid-state electrolyte material are mechanically mixed and then sintered at high temperature for coating. However, the technical scheme often has the problems that the contact between the negative electrode active material and the solid electrolyte material is poor, the contact mode is point-to-point contact, and the negative electrode active material and the solid electrolyte material are separated due to the expansion of the negative electrode active material in the circulation process.
Disclosure of Invention
The invention provides an in-situ composite lithium battery cathode material and a preparation method and application thereof. The in-situ composite lithium battery cathode material can be used in liquid, semi-solid and all-solid batteries, and improves the cycle life, rate capability, safety performance and first cycle efficiency of the battery.
In a first aspect, an embodiment of the present invention provides an in-situ composite lithium battery negative electrode material, which has a core-shell structure, has a particle size of 10nm to 100um, and includes a core and a shell;
the inner core is formed by compounding a negative electrode active material and a solid electrolyte material, wherein the mass ratio of the negative electrode active material to the solid electrolyte material is 0.001-1000; the structure of the kernel specifically includes: the solid electrolyte material is coated on the surface of the negative electrode active material, the negative electrode active material is coated on the surface of the solid electrolyte material, the solid electrolyte material is dispersed in the negative electrode active material, and the negative electrode active material is dispersed in the solid electrolyte material;
the particle size of the negative active material is between 2nm and 100um, and the shape of the negative active material is one or a mixture of spherical, ellipsoidal, polygonal and irregular shapes;
the granularity of the solid electrolyte material is between 1nm and 10um, and the appearance is one or a mixture of spherical, polygonal and irregular shapes;
the shell layer is a single-layer film formed by carbon materials, and the thickness of the shell layer is 1nm-2 um.
Preferably, the negative active material for a lithium battery includes:
the material comprises natural graphite, artificial graphite, lithium titanate, soft carbon, hard carbon and silicon-based materials, and one or more of the materials obtained by modifying the natural graphite, the artificial graphite, the lithium titanate, the soft carbon, the hard carbon and the silicon-based materials;
the silicon-based material comprises one or a mixture of a plurality of materials of a silicon protoxide material, a nano silicon carbon material, a micron silicon material, a film silicon, a columnar silicon material and a rod-shaped silicon material.
Preferably, the solid electrolyte material includes:
one of garnet-type solid electrolyte material, NASICON-type solid electrolyte material, L ISICON-type solid electrolyte material, perovskite-type solid electrolyte material, and derivatives thereof;
wherein the L ISICON type solid electrolyte is L i14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, B is one or more of Si, S and P, and the NASICON type solid electrolyte is L i1+xAxB2+x(PO4)3Wherein x is 0.01-0.5, A is one or more of Al, Y, Ga, Cr, In, Fe, Se and L a, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and hafnium Hf metal, and the perovskite type solid electrolyte is L i3xA2/3-xBO3Wherein x is 0.01-0.5, A is one or more of L a, Al, Mg, Fe and Ta, B is one or more of Ti, Nb, Sr and Pr, and the garnet solid electrolyte is L i7A3B2O12Wherein A is one or more of L a, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and metal hafnium Hf.
In a second aspect, an embodiment of the present invention provides a method for preparing an in-situ composite lithium battery anode material according to the first aspect, including:
weighing a lithium battery negative electrode active substance and a solid electrolyte synthetic raw material as required, and fully mixing to obtain a mixture, wherein the solid electrolyte synthetic raw material comprises oxide, hydroxide, carbonate, phosphate or ammonium salt of L i, A and B elements with the particle size of 10-1000 nm, wherein A is one or more of Zr, Cr and Sn, B is one or more of Si, S and P, or A is one or more of Al, Y, Ga, Cr, In, Fe, Se and L a, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and Hf, or A is one or more of L a, Al, Mg, Fe and Ta, B is one or more of Ti, Nb, Sr and Pr, or A is one or more of L a, Ca, Sr, Ba and K, and B is one or more of Zr, Mg, Fe and Ta and Hf, or B is one or more of Ti, Nb and Hf, the natural negative electrode active substance comprises one or more of hard graphite, silicon-based carbon, silicon-based lithium titanate and silicon-based modified carbon, silicon-based lithium titanate and silicon-based lithium titanate;
mechanically fusing the mixture to obtain a primary coating material;
performing heat treatment on the primary coating material to obtain a secondary coating material with a solid electrolyte material coated in situ on the surface of the lithium battery negative active material;
and carrying out carbon coating treatment on the secondary coating material to obtain the in-situ composite lithium battery cathode material.
Preferably, the mixing is liquid phase mixing or solid phase mixing;
the liquid phase mixing comprises: dispersing the negative active material of the lithium battery and a solid electrolyte synthetic raw material in a solvent according to a mass ratio, fully mixing and drying to obtain a mixture;
the solid phase mixing comprises: and weighing the lithium battery negative electrode active material and the solid electrolyte synthetic raw material according to the mass ratio, and putting the raw materials into a mixing device for fully mixing to obtain the mixture.
Preferably, the mechanofusion comprises:
and adding the mixture into a fusion machine, and fusing under the conditions that the rotating speed is 500-6000 rpm, the cutter gap width is 0.01-1 cm, the fusion time is 10-60 mins, the fusion temperature is room temperature-100 ℃, and the fusion atmosphere is dry air, nitrogen or argon.
Preferably, the heat treatment comprises:
placing the primary coating material in heat treatment equipment, heating to 300-1400 ℃ at a heating rate of 1-20 ℃/min in the atmosphere of argon, air or nitrogen, and preserving heat for 0.5-1000 hours;
wherein the heat treatment apparatus comprises: tube furnaces, box furnaces, rotary furnaces, roller kilns, tunnel kilns and pusher kilns.
Preferably, the carbon coating treatment comprises a solid phase method and/or a gas phase method;
the solid phase method comprises the following steps: mixing a carbon precursor with the secondary coating material, and carrying out high-temperature 400-1500 ℃ heat treatment in an inert atmosphere; wherein the precursor of carbon comprises: saccharides, asphaltic substances, polymer precursors;
the gas phase process comprises: selecting one or a combination of several of acetylene, methane, ethylene and toluene, and carrying out gas phase coating treatment on the secondary coating material at 800-1200 ℃.
In a third aspect, an embodiment of the present invention provides a negative electrode sheet prepared by using the in-situ composite lithium battery negative electrode material described in the first aspect.
In a fourth aspect, the embodiment of the present invention provides a secondary battery including the negative electrode tab of the third aspect; the secondary battery comprises a liquid state, a semi-solid state and a solid state lithium ion battery and a metal lithium battery.
According to the in-situ composite lithium battery cathode material provided by the embodiment of the invention, the cathode active material and the solid electrolyte material have good contact, a good channel is provided for lithium ion transmission, and meanwhile, the expansion caused by the volume change of the cathode material in the process of lithium intercalation and deintercalation of the cathode can be relieved to a great extent. The in-situ composite lithium battery cathode material can be used in a liquid battery, can avoid side reactions caused by direct contact of electrolyte and a cathode active material, and greatly improves the cycle life, rate capability, safety performance and first-cycle efficiency of the battery. The in-situ composite lithium battery cathode material provided by the invention can be used for liquid lithium ion batteries, semi-solid lithium ion batteries and all-solid lithium ion batteries.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a schematic structural diagram of an in-situ composite lithium battery anode material provided in an embodiment of the invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of an in-situ composite lithium battery negative electrode material provided by an embodiment of the present invention;
fig. 3 is a flowchart of a method for preparing an in-situ composite lithium battery anode material according to an embodiment of the present invention;
fig. 4 is a graph comparing the cycle performance of half cells prepared in examples 1 and 2 of the present invention and comparative example.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
The embodiment of the invention provides an in-situ composite lithium battery cathode material which has a core-shell structure, has a particle size of 10nm-100um and comprises a core and a shell layer;
the inner core is formed by compounding a negative electrode active material and a solid electrolyte material of the lithium battery, wherein the mass ratio of the negative electrode active material to the solid electrolyte material is 0.001-1000.
The structure of the kernel specifically includes: the solid electrolyte material is coated on the surface of the negative electrode active material, the negative electrode active material is coated on the surface of the solid electrolyte material, the solid electrolyte material is dispersed in the negative electrode active material, and the negative electrode active material is dispersed in the solid electrolyte material;
the granularity of the negative active material is between 2nm and 100um, and the shape of the negative active material is one or a mixture of spherical, ellipsoidal, polygonal and irregular shapes; the negative active material includes: the material comprises natural graphite, artificial graphite, lithium titanate, soft carbon, hard carbon, silicon-based materials and the like, and one or more of the materials obtained by modifying the natural graphite, the artificial graphite, the lithium titanate, the soft carbon, the hard carbon, the silicon-based materials and the like. The silicon-based material comprises one or more of silicon oxide SiOx (0< x <2), nano silicon material, nano silicon carbon material, micron silicon material, thin film silicon, columnar silicon material and rod-like silicon material.
The solid electrolyte material has a particle size of 1nm-10um and is one or a mixture of spherical, polygonal and irregular shapes, wherein the solid electrolyte material comprises one of garnet type solid electrolyte material, NASICON type solid electrolyte material, L ISICON solid electrolyte material, perovskite type solid electrolyte material and derivative materials thereof;
l solid electrolyte of ISICON type is L i14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, and B is one or more of Si, S and P;
the NASICON type solid electrolyte is specifically L i1+xAxB2+x(PO4)3Wherein x is 0.01-0.5, A is one or more of Al, Y, Ga, Cr, In, Fe, Se and L a, and B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and metal hafnium Hf;
the perovskite type solid electrolyte is specifically L i3xA2/3-xBO3X is 0.01-0.5, A is one or more of L a, Al, Mg, Fe and Ta, and B is one or more of Ti, Nb, Sr and Pr;
the garnet solid electrolyte is specifically L i7A3B2O12Wherein A is one or more of L a, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and metal hafnium Hf.
The shell layer is a single-layer film formed by carbon materials, and the thickness is 1nm-2 um.
Fig. 1 is a schematic structural diagram of an in-situ composite lithium battery negative electrode material according to an embodiment of the present invention. The Scanning Electron Microscope (SEM) image of the in-situ composite lithium battery negative electrode material provided by the embodiment of the invention is shown in fig. 2, and the in-situ composite lithium battery negative electrode material is in a random polygon shape.
According to the in-situ composite lithium battery cathode material provided by the embodiment of the invention, the cathode active material and the solid electrolyte material have good contact, a good channel is provided for lithium ion transmission, and meanwhile, the expansion caused by the volume change of the cathode material in the process of lithium intercalation and deintercalation of the cathode can be relieved to a great extent. The in-situ composite lithium battery cathode material can be used in a liquid battery, can avoid side reaction caused by direct contact of electrolyte and a cathode active material, and greatly improves the first cycle efficiency of the battery. The in-situ composite lithium battery cathode material provided by the invention can be used for liquid lithium ion batteries, semi-solid lithium ion batteries and all-solid lithium ion batteries.
The following describes a method for preparing an in-situ composite lithium battery negative electrode material provided by the embodiment of the invention.
The preparation method of the in-situ composite lithium battery negative electrode material provided by the embodiment includes the steps as shown in fig. 3, including:
specifically, the mixing may be liquid phase mixing or solid phase mixing.
The specific process of liquid phase mixing comprises the following steps: dispersing a negative active material of a lithium battery and a solid electrolyte synthetic raw material in a solvent according to a mass ratio, fully mixing, and performing blast drying, vacuum drying, spray drying and other means to obtain a mixture;
the solid phase mixing process comprises the following steps: weighing the negative active material of the lithium battery and the solid electrolyte synthetic raw material according to the mass ratio, and fully mixing the raw materials in mixing equipment such as a ball mill, a high-speed mixer and the like to obtain a mixture.
Wherein the solid electrolyte synthesis raw material comprises oxide, hydroxide, carbonate, phosphate or ammonium salt of L i, A and B with particle size of 10nm-1000nm, and in a preferred example, the particle size of the solid electrolyte synthesis raw material is 10nm-100nm, more preferably 10nm-20 nm.
Wherein A is one or more of Zr, Cr and Sn, B is one or more of Si, S and P, and is used for preparing L ISICON type solid electrolyte;
or A is one or more of Al, Y, Ga, Cr, In, Fe, Se and L a, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and metal hafnium (Hf) and is used for preparing the NASICON type solid electrolyte;
or A is L a, one or more of Al, Mg, Fe and Ta, B is one or more of Ti, Nb, Sr and Pr, and the perovskite solid electrolyte is prepared;
or A is one or more of L a, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and Hf, and is used for preparing the garnet-type solid electrolyte.
The negative active material for a lithium battery includes: the material comprises natural graphite, artificial graphite, lithium titanate, soft carbon, hard carbon, silicon-based materials and the like, and one or more of the materials obtained by modifying the natural graphite, the artificial graphite, the lithium titanate, the soft carbon, the hard carbon and the silicon-based materials.
specifically, the mixture can be added into a fusion machine, and fusion is carried out under the conditions that the rotating speed is 500-6000 rpm, the width of a cutter gap is 0.01-1 cm, the fusion time is 10-60 mins, the fusion temperature is room temperature to 100 ℃, and the fusion atmosphere is dry air, nitrogen or argon.
specifically, the heat treatment process specifically includes: placing the primary coating material in a heat treatment device such as a tube furnace, a box furnace, a rotary furnace, a roller kiln, a tunnel kiln, a pushed slab kiln and the like, heating to 300-1400 ℃ at a heating rate of 1-20 ℃/min in the atmosphere of argon, air or nitrogen, and preserving heat for 0.5-1000 hours.
And 240, carrying out carbon coating treatment on the secondary coating material to obtain the in-situ composite lithium battery cathode material.
Specifically, the carbon coating treatment may be performed by one or both of a solid phase method and a gas phase method.
The gas phase method specifically comprises the following steps: selecting one or a combination of several of acetylene, methane, ethylene and toluene, and carrying out gas phase coating treatment on the secondary coating material prepared in the step 230 at the temperature of 800-1200 ℃.
The solid phase method comprises the following specific steps: mixing carbon precursors such as saccharides, pitch substances, polymer precursors and the like with the secondary coating material prepared in the step 230, and performing high-temperature heat treatment at 400-1500 ℃ in an inert atmosphere.
In addition, the high-temperature heat treatment process using the solid phase method may be performed after step 210 or step 220, that is, the mixture or the primary coating material may be carbon-coated and then subjected to the fusion process. I.e., the introduction of the carbon material in the shell material, may be carried out at any step after the synthesis of the solid electrolyte material.
The technical solution of the present invention will be described in further detail by specific examples.
Example 1
Mixing a silica material with a solid electrolyte material L i7La3Zr2O12(LL ZO) mixing a synthetic raw material lithium carbonate (the average particle size is 100nm and the purity is 99.8%), zirconium oxide (the average particle size is 100nm and the purity is 99.99%), aluminum oxide (the average particle size is 50nm and the purity is 99.9%) and lanthanum oxide (the average particle size is 100nm and the purity is 99.9%) in a high-speed VC machine, rotating speed is 400rpm and time is 2 hours, a dispersing solvent is isopropanol, after uniform mixing, baking is carried out in an oven at 80 ℃ for 24 hours, adding the uniformly mixed and baked materials into a fusion machine, adjusting the rotating speed to 300rpm, the width of a cutter gap to be 0.5cm, fusion time to be 60mins, fusion temperature to be 100 ℃ and fusion atmosphere to be dry air, carrying out fusion to obtain a fusion product, placing the fusion product in a box furnace, heating from room temperature to 900 ℃ at a heating rate of 3 ℃/min under argon atmosphere, keeping the temperature for 5 hours, and processing to obtain a sample, namely the in-situ composite lithiumA battery negative electrode material.
Assembling conditions are as follows: the material prepared in example 1 was mixed with a conductive agent, a binder and a thickener, and then pulped and coated. And the metal lithium is used as a counter electrode and is assembled into a half cell.
This was assembled into a half cell for cycle performance testing and the results are shown in figure 4.
Example 2
Mixing a synthetic raw material lithium carbonate (the average particle size is 100nm and the purity is 99.8%) of a silicon oxide material and LL ZO solid electrolyte material, zirconium oxide (the average particle size is 100nm and the purity is 99.99%), aluminum oxide (the average particle size is 100nm and the purity is 99.9%), tantalum oxide (the average particle size is 100nm and the purity is 99.9%) by using a planetary ball mill, rotating at 300rpm for 24 hours, using isopropanol as a dispersing solvent, and mixing at room temperature, baking at 80 ℃ for 24 hours in an oven, adding the uniformly mixed and baked material into a fusion machine, adjusting the rotating speed to 600rpm, the width of a cutter gap to be 0.1cm, the fusion time to be 30mins, the fusion temperature to be 100 ℃ and the fusion atmosphere to be dry air, and obtaining a fusion product, placing the fusion product into a box furnace, heating the room temperature to 900 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and carrying out heat treatment on the material in a tube furnace, using toluene as a precursor, carrying out a carbon coating reaction, and obtaining a lithium battery coating in-situ composite material after heat treatment at 5 hours.
It was assembled into a half cell using the same assembly conditions as in example 1 above and subjected to cycle performance testing, and the results are shown in fig. 4.
Example 3
Mixing a silica material with a solid electrolyte material L i1.4Al0.4Ti1.6(PO4)3(L ATP) Synthesis of raw Material lithium carbonate (average particle diameter 100nm, purity 99.8%) titanium oxide (average particle diameter 100nm, purity 99.99%), alumina (average particle diameter 50nm, purity 99.9%), ammonium dihydrogen phosphate (average particle diameter 500nm, purity 98%) was mixed by a tumbling ball mill at 300rpm for 24 hours with a dispersion solvent of 100 hoursWater, after mixing well, baking in an oven at 120 ℃ for 24 hours. And adding the uniformly mixed materials into a fusion machine, adjusting the rotating speed to 600rpm, adjusting the width of a cutter gap to 0.1cm, fusing for 30mins at the room temperature of 100 ℃, and fusing under the condition that the fusion atmosphere is dry air to obtain a fusion product. And (3) placing the fusion product in a box-type furnace, wherein the reaction atmosphere is air, raising the temperature from room temperature to 900 ℃ at the heating rate of 3 ℃/min, and preserving the temperature for 5 hours. And obtaining a sample which is the in-situ composite lithium battery cathode material after treatment.
Comparative example:
mixing the nano LL ZO powder in a high-speed VC machine at the rotating speed of 400rpm for 2 hours, uniformly mixing the isopropanol serving as a dispersing solvent, drying the mixture in an oven at the temperature of 80 ℃ for 24 hours, putting the product in a box-type furnace, heating the product to 900 ℃ from room temperature at the heating rate of 3 ℃/min in the presence of argon, preserving the temperature for 5 hours, and carrying out heat treatment to obtain the material taking the sample as the comparative example.
It was assembled into a half cell using the same assembly conditions as in examples 1 and 2 above and subjected to a cycle performance test, and the results are shown in fig. 4.
As can be seen from fig. 4, the cell performance of example 2 and example 1 is significantly better than that of comparative example 1, wherein the cell performance of example 2 is better than that of comparative example 1. This shows that the in-situ composite lithium battery cathode material has excellent battery performance.
According to the in-situ composite lithium battery cathode material provided by the embodiment of the invention, the cathode active material and the solid electrolyte material have good contact, a good channel is provided for lithium ion transmission, and meanwhile, the expansion caused by the volume change of the cathode material in the process of lithium intercalation and deintercalation of the cathode can be relieved to a great extent. The in-situ composite lithium battery cathode material can be used in a liquid battery, can avoid side reactions caused by direct contact of electrolyte and a cathode active material, and greatly improves the cycle life, rate capability, safety performance and first-cycle efficiency of the battery. The in-situ composite lithium battery cathode material provided by the invention can be used for preparing a cathode pole piece and is applied to liquid lithium ion batteries, semi-solid lithium ion batteries and all-solid lithium ion batteries.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The in-situ composite lithium battery cathode material is characterized in that the in-situ composite lithium battery cathode material is of a core-shell structure, has a particle size of 2nm-100um and comprises a core and a shell layer;
the inner core is formed by compounding a negative electrode active material and a solid electrolyte material, wherein the mass ratio of the negative electrode active material to the solid electrolyte material is 0.001-1000; the structure of the kernel specifically includes: the solid electrolyte material is coated on the surface of the negative electrode active material, the negative electrode active material is coated on the surface of the solid electrolyte material, the solid electrolyte material is dispersed in the negative electrode active material, and the negative electrode active material is dispersed in the solid electrolyte material;
the particle size of the negative active material is between 2nm and 100um, and the shape of the negative active material is one or a mixture of spherical, ellipsoidal, polygonal and irregular shapes;
the granularity of the solid electrolyte material is between 1nm and 10um, and the appearance is one or a mixture of spherical, polygonal and irregular shapes;
the shell layer is a single-layer film formed by carbon materials, and the thickness of the shell layer is 1nm-2 um.
2. The in-situ composite lithium battery negative electrode material as claimed in claim 1, wherein the lithium battery negative electrode active material comprises:
the material comprises natural graphite, artificial graphite, lithium titanate, soft carbon, hard carbon and silicon-based materials, and one or more of the materials obtained by modifying the natural graphite, the artificial graphite, the lithium titanate, the soft carbon, the hard carbon and the silicon-based materials;
the silicon-based material comprises one or a mixture of a plurality of materials of a silicon protoxide material, a nano silicon carbon material, a micron silicon material, a film silicon, a columnar silicon material and a rod-shaped silicon material.
3. The in-situ composite lithium battery negative electrode material of claim 1, wherein the solid state electrolyte material comprises:
one of garnet-type solid electrolyte material, NASICON-type solid electrolyte material, L ISICON-type solid electrolyte material, perovskite-type solid electrolyte material, and derivatives thereof;
wherein the L ISICON type solid electrolyte is L i14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, B is one or more of Si, S and P, and the NASICON type solid electrolyte is L i1+xAxB2+x(PO4)3Wherein x is 0.01-0.5, A is one or more of Al, Y, Ga, Cr, In, Fe, Se and L a, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and hafnium Hf metal, and the perovskite type solid electrolyte is L i3xA2/3-xBO3Wherein x is 0.01-0.5, A is one or more of L a, Al, Mg, Fe and Ta, B is one or more of Ti, Nb, Sr and Pr, and the garnet solid electrolyte is L i7A3B2O12Wherein A is one or more of L a, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and metal hafnium Hf.
4. A method for preparing the in-situ composite lithium battery negative electrode material according to any one of claims 1 to 3, wherein the method comprises:
weighing a lithium battery negative electrode active substance and a solid electrolyte synthetic raw material as required, and fully mixing to obtain a mixture, wherein the solid electrolyte synthetic raw material comprises oxide, hydroxide, carbonate, phosphate or ammonium salt of L i, A and B elements with the particle size of 10-1000 nm, wherein A is one or more of Zr, Cr and Sn, B is one or more of Si, S and P, or A is one or more of Al, Y, Ga, Cr, In, Fe, Se and L a, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and Hf, or A is one or more of L a, Al, Mg, Fe and Ta, B is one or more of Ti, Nb, Sr and Pr, or A is one or more of L a, Ca, Sr, Ba and K, and B is one or more of Zr, Mg, Fe and Ta and Hf, or B is one or more of Ti, Nb and Hf, the natural negative electrode active substance comprises one or more of hard graphite, silicon-based carbon, silicon-based lithium titanate and silicon-based modified carbon, silicon-based lithium titanate and silicon-based lithium titanate;
mechanically fusing the mixture to obtain a primary coating material;
performing heat treatment on the primary coating material to obtain a secondary coating material with a solid electrolyte material coated in situ on the surface of the lithium battery negative active material;
and carrying out carbon coating treatment on the secondary coating material to obtain the in-situ composite lithium battery cathode material.
5. The method for preparing the in-situ composite lithium battery negative electrode material as claimed in claim 4, wherein the mixing is liquid phase mixing or solid phase mixing;
the liquid phase mixing comprises: dispersing the negative active material of the lithium battery and a solid electrolyte synthetic raw material in a solvent according to a mass ratio, fully mixing and drying to obtain a mixture;
the solid phase mixing comprises: and weighing the lithium battery negative electrode active material and the solid electrolyte synthetic raw material according to the mass ratio, and putting the raw materials into a mixing device for fully mixing to obtain the mixture.
6. The method for preparing the in-situ composite lithium battery negative electrode material as claimed in claim 4, wherein the mechanical fusion comprises:
and adding the mixture into a fusion machine, and fusing under the conditions that the rotating speed is 500-6000 rpm, the cutter gap width is 0.01-1 cm, the fusion time is 10-60 mins, the fusion temperature is room temperature-100 ℃, and the fusion atmosphere is dry air, nitrogen or argon.
7. The method for preparing the in-situ composite lithium battery anode material as claimed in claim 4, wherein the heat treatment comprises:
placing the primary coating material in heat treatment equipment, heating to 300-1400 ℃ at a heating rate of 1-20 ℃/min in the atmosphere of argon, air or nitrogen, and preserving heat for 0.5-1000 hours;
wherein the heat treatment apparatus comprises: tube furnaces, box furnaces, rotary furnaces, roller kilns, tunnel kilns and pusher kilns.
8. The method for preparing the in-situ composite lithium battery anode material as claimed in claim 4, wherein the carbon coating treatment comprises a solid phase method and/or a gas phase method;
the solid phase method comprises the following steps: mixing a carbon precursor with the secondary coating material, and carrying out high-temperature 400-1500 ℃ heat treatment in an inert atmosphere; wherein the precursor of carbon comprises: saccharides, asphaltic substances, polymer precursors;
the gas phase process comprises: selecting one or a combination of several of acetylene, methane, ethylene and toluene, and carrying out gas phase coating treatment on the secondary coating material at 800-1200 ℃.
9. A negative pole piece prepared by using the in-situ composite lithium battery negative pole material as claimed in any one of claims 1 to 3.
10. A secondary battery comprising the negative electrode tab of claim 9; the secondary battery comprises a liquid state, a semi-solid state and a solid state lithium ion battery and a metal lithium battery.
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| CN111430676B (en) * | 2019-09-29 | 2022-06-21 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery and preparation method thereof |
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| CN110880593B (en) * | 2019-11-28 | 2021-03-09 | 江苏大学 | Solid electrolyte modified lithium titanate negative electrode material and preparation method thereof |
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| CN112151777B (en) * | 2020-09-03 | 2021-12-10 | 浙江锋锂新能源科技有限公司 | Negative pole piece and preparation method thereof |
| CN115133011A (en) * | 2021-03-19 | 2022-09-30 | 比亚迪股份有限公司 | Negative electrode material, preparation method thereof and all-solid-state lithium battery |
| WO2023039750A1 (en) * | 2021-09-15 | 2023-03-23 | 宁德新能源科技有限公司 | Negative electrode composite material and use thereof |
| WO2023052836A1 (en) * | 2021-09-28 | 2023-04-06 | Vidyasirimedhi Institute Of Science And Technology (Vistec) | Cathode active material for lithium-ion battery and method for preparing said active material, and cathode comprising said active material and method for preparing said cathode |
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