CN114628651A - Preparation method and application of high-first-efficiency long-cycle SiO/C composite negative electrode material - Google Patents
Preparation method and application of high-first-efficiency long-cycle SiO/C composite negative electrode material Download PDFInfo
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- CN114628651A CN114628651A CN202111135283.7A CN202111135283A CN114628651A CN 114628651 A CN114628651 A CN 114628651A CN 202111135283 A CN202111135283 A CN 202111135283A CN 114628651 A CN114628651 A CN 114628651A
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- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000012265 solid product Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000007784 solid electrolyte Substances 0.000 claims description 69
- 229920000642 polymer Polymers 0.000 claims description 46
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims description 24
- 125000004386 diacrylate group Chemical group 0.000 claims description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000003825 pressing Methods 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 239000002135 nanosheet Substances 0.000 claims description 18
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 11
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 2
- 238000005554 pickling Methods 0.000 claims 2
- 239000011883 electrode binding agent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052799 carbon Inorganic materials 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000010406 cathode material Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 142
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000006230 acetylene black Substances 0.000 description 7
- 238000006138 lithiation reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000005570 vertical transmission Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery cathode materials, and discloses a preparation method and application of a high-first-efficiency long-circulation SiO/C composite cathode material, which comprises the following steps: mixing SiO, carbonate and metal lithium by ball milling in an inert atmosphere, sintering the mixture at 700-900 ℃ in an oxygen-free manner, and preserving heat for 10-100 hours; and cooling and then acid-washing the obtained sintered solid product to obtain the pre-lithiated SiO/C composite negative electrode material. According to the invention, the SiO is pre-lithiated by using metal lithium, and carbon coating of the pre-lithiated SiO is realized by reducing carbonate, so that the first effect is improved by changing the silicon oxygen of the SiO material, and further the controllable preparation of the carbon coating is realized; the used equipment is low in requirement and energy consumption, easy to operate, safe and pollution-free, and can realize industrial large-scale production and application; the solid battery prepared from the SiO/C composite negative electrode material shows high first-efficiency and long-cycle stability.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a preparation method and application of a high-first-efficiency long-circulation SiO/C composite cathode material.
Background
With the development of the lithium power battery industry, the requirements on the energy density of the lithium ion battery are continuously improved. Graphite is used as a cathode material of a traditional lithium ion battery, and the theoretical lithium storage capacity of the graphite can not meet the increasing energy density requirement. The SiO has high lithium storage capacity theoretically, and the synthesized raw materials have rich reserves and low price, so the SiO is one of the materials which are most hopeful to improve the performance of the current lithium ion negative electrode material. However, due to the presence of oxygen, SiO has a low electronic conductivity and a large number of first irreversible phases, resulting in a low conductivity and a high capacity loss. In addition, the large volume expansion of SiO during the lithium desorption/intercalation process has a negative impact on cycle life, limiting its commercial application.
Based on the method, carbon coating and pre-lithiation of SiO are common improvement methods, and the first cycle capacity and efficiency can be improved on the basis of ensuring the cycle performance of the SiO negative electrode material. The Chinese patent with publication number CN110212183A discloses a powder pre-lithiation silicon-based negative electrode material and a preparation method and application thereof, wherein in the high-temperature sintering process, lithium ions which are not completely reacted in a lithium-containing carborane cluster compound react with silicon monoxide through a liquid phase method, so that by-products such as lithium metasilicate, lithium silicate and lithium oxide are further formed to realize pre-lithiation, and further, a uniform and compact carbon layer is formed on the surface of the material through chemical vapor deposition. The method has the disadvantages that potential safety hazards exist in the large-scale preparation process of the organic liquid used by the liquid phase method, and the cost for realizing carbon coating by chemical vapor deposition is high, so that the method is not beneficial to large-scale industrial use.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-first-efficiency long-circulation SiO/C composite negative electrode material, so that a safe and environment-friendly negative electrode material with high first-efficiency and long circulation is obtained, and the first-cycle capacity and efficiency are improved on the basis of ensuring the circulation performance of the SiO negative electrode material.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the invention provides a preparation method of a high-first-efficiency long-cycle SiO/C composite negative electrode material, which comprises the following steps: mixing SiO, carbonate and metal lithium by ball milling in an inert atmosphere, sintering the mixture at 700-900 ℃ in an oxygen-free manner, and preserving heat for 10-100 hours; and cooling and then acid-washing the obtained sintered solid product to obtain the pre-lithiated SiO/C composite negative electrode material.
The pre-lithiation carbon-coated SiO negative electrode material is prepared through simple mixing and sintering reactions, only carbon, lithium carbonate and other solid impurities which can be removed simply are generated in the reaction process, the whole reaction step is simple, the operation is easy, and large-scale production and application can be realized. The ball milling under the inert atmosphere can avoid the side reaction of reactants and water vapor or carbon dioxide in the air, ensure the full progress of the positive and negative reaction and improve the reaction efficiency.
On one hand, the reducing metal lithium pre-lithiates SiO to adjust the silicon-oxygen ratio of the SiO surface, the SiO is used as an electrode active material of a lithium ion battery, and Li is firstly generated in the material preparation process2O、Li4SiO4Thus, in the charging and discharging process, lithium ions are not consumed or are rarely consumed, and Li generated in the first cycle of the lithium ion battery can be remarkably reduced2O、Li4SiO4The lithium ion consumption in the process obviously improves the first cycle reversible capacity and efficiency of the lithium ion battery, and can effectively buffer the volume expansion effect of the cathode material. On the other hand, the metal lithium can reduce carbonate to realize carbon coating of the pre-lithiated SiO, and is different from other organic carbon coating materials, toxic and harmful gas is not generated when the carbonate is used for carbon coating, only soluble impurities are generated, and the method is environment-friendly and pollution-free. Meanwhile, metal lithium and carbonate are used for reaction, so that the first effect of the SiO material can be improved while carbon coating is realized.
Within the sintering temperature range of 700-900 ℃, the reaction energy barrier of metal lithium, calcium carbonate and SiO can be better reached, the pre-lithiation and carbon coating double reaction is promoted, and the reaction efficiency is improved. And the sufficient and thorough forward reaction can be ensured by controlling the heat preservation time.
Preferably, the molar ratio of the SiO to the carbonate to the lithium metal is 1: 0.1-1: 0.1 to 1. If the metal lithium is too small, the pre-lithiation is not a component, and redundant metal lithium cannot be provided to react with calcium carbonate to form a carbon coating layer; too much carbon may remain, which is not favorable for the stability of the battery slurry, thus affecting the preparation of the battery, and too much carbon coating may also have side reactions with the electrolyte.
Preferably, the carbonate is calcium carbonate, and the particle size is 100-1000 nm. The particle size of calcium carbonate affects the morphology of carbon coating, too small a particle size tends to be porous, and too large a particle size hinders reaction kinetics.
Preferably, the particle size of the SiO is 100-1000 nm. Too large a particle hinders the reaction kinetics and too small a particle increases the raw material cost.
Preferably, the ball-material ratio of the ball mill is 10-100: 1, the time is 10-100 h, the temperature is-10-300 ℃, and the rotating speed is 100-500 r/min. If the ball-material ratio is too small, the material mixing is not uniform; if the ball-to-material ratio is too large, the ball milling efficiency is low and the metal impurities are more. The ball milling parameters are controlled to promote the uniform mixing of the lithium metal, the calcium carbonate and the SiO, and the side reaction of the material at a certain temperature can be inhibited by properly adjusting the temperature.
Preferably, the oxygen-free sintering is sintering in an inert atmosphere or in vacuum; the temperature rise rate of the oxygen-free sintering is 0.5-20 ℃/min. By properly adjusting the temperature rise rate, the side reaction of the material at a lower temperature can be inhibited.
Preferably, the acid solution used for acid washing is one or more of hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, acetic acid and phosphoric acid, and the acid washing time is 10-100 h; the concentration of the acid solution is 0.01-10 mol/L; the mass ratio of the sintered solid product to the acid solution is 1: 0.1 to 20. Solid impurities are removed by acid washing.
In a second aspect, the present invention also provides a solid-state battery, including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte; the negative plate is obtained by pressing the SiO/C composite negative material, the negative binder and the conductive agent; the solid electrolyte is a polymer composite solid electrolyte; the solid battery is prepared by respectively pressing a positive plate and a negative plate on two sides of the polymer composite solid electrolyte.
The negative plate obtained by pressing the SiO/C composite negative material is used as a lithium ion battery negative electrode, high first-effect and long-cycle stability can be shown, and the consumption of positive lithium ions can be reduced in the subsequent battery cycle process. The battery obtained by using the polymer composite solid electrolyte can reduce the interface resistance between the solid electrolyte layer and the anode, form a flexible, stable and rapid CEI film, and improve the stability and safety. And the SiO/C composite negative electrode material and the polymer composite solid electrolyte both have high ionic conductivity and mechanical property, and can prolong the cycle life of the battery.
Preferably, the preparation method of the polymer composite solid electrolyte comprises the following steps:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550-; after cooling to room temperature, the second sintering is sintering at 600-650 ℃ for 2-4h at the speed of 3-6 ℃/min; cooling to room temperature again, and repeating the second sintering; cooling, taking out and ball milling to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate in acetonitrile to form a mixed solution, then sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate, stirring, and then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalate) borate; performing ultraviolet crosslinking on the obtained slurry in inert gas atmosphere at the wavelength of 365nm and the intensity of 5-9mW/cm2Exposing the polymer composite solid electrolyte on an ultraviolet lamp for 5-8 times, wherein each exposure time is 5-10s, and each exposure interval is 10-15 min, so as to obtain the polymer composite solid electrolyte.
Adding g-C3N4Can reduce the crystallinity of polymer solid electrolyte, form lithium ion transmission network in polymer matrix, effectively improve ion conductivity, and simultaneously g-C3N4The surface has rich nitrogen atoms, and the nitrogen atoms can interact with lithium salt to increase the dissociation degree of the lithium salt. The nano-sheet can form a porous structure by adopting a three-step high-temperature aerobic sintering method, has a high specific surface area and a larger interaction area with a polymer, and polymer chains are not easy to relatively slip under the action of external force, so that the mechanical strength of the polymer solid electrolyte is improved. Surface defects generated by sintering can be used as potential channels for vertical transmission of lithium ionsFurther improving the transmission capability of lithium ions. g-C can be prepared by adopting a three-step high-temperature sintering method3N4The method has the advantages that a more uniform and abundant porous structure is formed, the specific surface area is improved, certain surface defects are formed, the dissociation degree and the lithium ion transmission capability of lithium salt can be increased, and the formation of a CEI film is accelerated.
The lithium bis (oxalato) borate can form a flexible, stable and rapid lithium ion Conductive (CEI) film on the surface of the positive active particle, so that the thermal stability and the high-voltage performance are improved, and the generation of non-conductive side reaction products and cracks of the high-voltage layered ternary positive particle in the circulation process can be effectively inhibited. The ultraviolet crosslinking method is used for structural crosslinking of the polymer solid electrolyte, so that the crystallinity of the polymer solid electrolyte is reduced, and the ionic conductivity and the mechanical property are improved.
Preferably, in the step (2), the molar ratio of vinyl groups of the polyethylene glycol diacrylate to lithium ions is 10 to 25: 1; the mass fraction of the polyethylene glycol diacrylate in the mixed solution is 30-60%; the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate is 0.5-1.0: 1.0-2.0.
Preferably, the mass ratio of the 2, 2-dimethoxy-2-acetophenone to the pentaerythritol tetra-3-mercaptopropionate is 1-3: 50-60 parts of; porous g-C in the step (1)3N4The molar ratio of the nanosheets, the lithium bis (oxalato) borate to the LiTFSI is 0.1-0.3: 0.2-0.5: 1.0-1.3.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method has low equipment requirement and energy consumption, is easy to operate, is safe and pollution-free, and can realize industrial large-scale production and application;
(2) the method comprises the following steps of carrying out pre-lithiation on SiO by using metal lithium, reducing carbonate to realize carbon coating on the pre-lithiated SiO, and improving the first effect by changing silicon oxygen of an SiO material so as to realize controllable preparation of the carbon coating;
(3) the solid battery prepared by taking the SiO/C composite negative electrode material as the lithium ion battery negative electrode shows high first efficiency and long cycle stability.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
general examples
Preparation of SiO/C composite cathode material
Mixing a mixture of 1: 0.1-1: 0.1-1% of SiO, calcium carbonate and metal lithium are mixed by ball milling in an inert atmosphere, the particle size of the SiO is 100-1000 nm, the particle size of the calcium carbonate is 100-1000 nm, the ball-to-material ratio of ball milling is 10-100: 1, the time is 10-100 h, the temperature is-10-300 ℃, and the rotating speed is 100-500 r/min; carrying out oxygen-free sintering on the mixture at 700-900 ℃ in an inert atmosphere or vacuum at a heating rate of 0.5-20 ℃/min, and carrying out heat preservation for 10-100 hours; and cooling the obtained sintered solid product, then carrying out acid washing to remove impurities, wherein an acid solution used for acid washing is one or more of hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, acetic acid and phosphoric acid, the acid washing time is 10-100 h, the concentration of the acid solution is 0.01-10 mol/L, and the mass ratio of the obtained sintered solid product to the acid solution is 1: 0.1 to 20 parts; and obtaining the pre-lithiated SiO/C composite negative electrode material.
2. Solid battery
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from 86-95 mass percent: 2-5: 2-4 parts of high-nickel ternary positive electrode material, conductive carbon black and PVDF are pressed under 50-80 standard atmospheric pressures, the negative electrode piece is obtained by pressing the prepared SiO/C composite negative electrode material, PVDF and acetylene black in a mass ratio of 70-85: 10-15 under 50-80 standard atmospheric pressures, the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 100-300 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under the standard atmospheric pressure of 90-100 to prepare the solid battery.
The preparation method of the polymer composite solid electrolyte comprises the following steps:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550-; after cooling to room temperature, the second sintering is sintering at 600-650 ℃ for 2-4h at the speed of 3-6 ℃/min; thenCooling to room temperature, and repeating the second sintering; cooling, taking out and ball milling to obtain porous g-C3N4A nanosheet;
(2) dissolving polyethylene glycol diacrylate in acetonitrile to form a mixed solution of the polyethylene glycol diacrylate with the mass fraction of 30-60%, then sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate, and stirring, wherein the molar ratio of vinyl to lithium ions of the polyethylene glycol diacrylate is 10-25: 1, the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate is 0.5-1.0: 1.0-2.0, wherein the mass ratio of 2, 2-dimethoxy-2-acetophenone to pentaerythritol tetra-3-mercaptopropionate is 1-3: 50-60 parts of; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate, wherein the porous g-C in the step (1)3N4The molar ratio of the nanosheets, the lithium bis (oxalato) borate to the LiTFSI is 0.1-0.3: 0.2-0.5: 1.0-1.3; performing ultraviolet crosslinking on the obtained slurry in inert gas atmosphere at a wavelength of 365nm and an intensity of 5-9mW/cm2Exposing the polymer composite solid electrolyte on an ultraviolet lamp for 5-8 times, wherein each exposure time is 5-10s, and each exposure interval is 10-15 min, so as to obtain the polymer composite solid electrolyte.
Example 1
Preparation of SiO/C composite cathode material
Mixing a mixture of 1: 0.1: 0.1 of SiO, calcium carbonate and metal lithium are mixed by ball milling in nitrogen atmosphere, the grain diameter of the SiO is 500nm, the grain diameter of the calcium carbonate is 500nm, the ball-to-material ratio of ball milling is 100:1, the time is 10h, the temperature is 150 ℃, and the rotating speed is 100 r/min; sintering the mixture at 800 deg.C under vacuum in the absence of oxygen at a heating rate of 20 deg.C/min, and maintaining the temperature for 100 hr; cooling the obtained sintered solid product, and then carrying out acid washing and impurity removal for 10 hours by using 5mol/L hydrochloric acid, wherein the mass ratio of the obtained sintered solid product to the acid solution is 1: and 2, obtaining the pre-lithiated SiO/C composite negative electrode material.
2. Solid battery
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from the following components in percentage by mass in a ratio of 91: 5: 4, the negative plate is obtained by pressing the prepared SiO/C composite negative electrode material, PVDF and acetylene black in a mass ratio of 75:10:15 under 70 standard atmospheric pressures, the thickness of the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 250 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under 100 standard atmospheric pressures to prepare the solid battery.
The preparation method of the polymer composite solid electrolyte comprises the following steps:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550 ℃, and the speed is 2 ℃/min; after cooling to room temperature, the second sintering is sintering at 600 ℃ for 3h at the speed of 4 ℃/min; cooling to room temperature again, and repeating the second sintering; cooling, taking out and ball milling to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate in acetonitrile to form a mixed solution of the polyethylene glycol diacrylate with the mass fraction of 30-60%, then sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate, and stirring, wherein the molar ratio of vinyl to lithium ions of the polyethylene glycol diacrylate is 18: 1, the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate was 0.6: 1, the mass ratio of 3, 2, 2-dimethoxy-2-acetophenone to pentaerythritol tetra-3-mercaptopropionate is 2: 55; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate, wherein the porous g-C in the step (1)3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.2: 0.3: 1.1; carrying out ultraviolet crosslinking on the obtained slurry in an inert gas atmosphere at the wavelength of 365nm and the intensity of 8mW/cm2The polymer composite solid electrolyte was obtained by exposing the substrate to ultraviolet light for 7 times, each exposure time was 5 seconds, and each exposure interval was 10 min.
Example 2
The difference from example 1 is that:
preparation of SiO/C composite cathode material
Mixing the components in a molar ratio of 1: 0.3: 0.3 of SiO, calcium carbonate and metal lithium are mixed by ball milling in nitrogen atmosphere, the grain diameter of the SiO is 800nm, the grain diameter of the calcium carbonate is 200nm, the ball-to-material ratio of ball milling is 60:1, the time is 25h, the temperature is 100 ℃, and the rotating speed is 300 r/min; sintering the mixture at 800 deg.C under vacuum in the absence of oxygen at a heating rate of 15 deg.C/min, and maintaining the temperature for 60 hr; cooling the obtained sintered solid product, and then carrying out acid washing and impurity removal for 20 hours by using 3mol/L sulfuric acid, wherein the mass ratio of the obtained sintered solid product to the acid solution is 1: and 3, obtaining the pre-lithiated SiO/C composite negative electrode material.
2. Solid battery
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from the following components in percentage by mass in a ratio of 91: 5: 4, the negative plate is obtained by pressing the prepared SiO/C composite negative electrode material, PVDF and acetylene black in a mass ratio of 75:10:15 under 70 standard atmospheric pressures, the thickness of the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 250 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under 100 standard atmospheric pressures to prepare the solid battery.
Example 3
The difference from example 1 is that:
preparation of SiO/C composite cathode material
Mixing a mixture of 1: 1: 1, mixing SiO, calcium carbonate and metal lithium in an inert atmosphere by ball milling, wherein the particle size of the SiO is 600nm, the particle size of the calcium carbonate is 800nm, the ball-to-material ratio of ball milling is 30:1, the time is 30h, the temperature is 50 ℃, and the rotating speed is 50 r/min; sintering the mixture at 800 deg.c in vacuum at 10 deg.c/min for 30 hr; cooling the obtained sintered solid product, and then carrying out acid washing impurity removal for 30 hours by using 2mol/L nitric acid, wherein the mass ratio of the obtained sintered solid product to the acid solution is 1: and 4, obtaining the pre-lithiated SiO/C composite negative electrode material.
2. Solid battery
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from the following components in percentage by mass 91: 5: 4, pressing the high-nickel ternary positive electrode material, the conductive carbon black and the PVDF under 70 standard atmospheric pressures to obtain the negative electrode piece, wherein the negative electrode piece is obtained by pressing the prepared SiO/C composite negative electrode material, the PVDF and the acetylene black in a mass ratio of 75:10:15 under 70 standard atmospheric pressures, the thickness of the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 250 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under 100 standard atmospheric pressures to prepare the solid battery.
Example 4
The difference from example 1 is that:
preparation of SiO/C composite cathode material
Mixing a mixture of 1: 1: 1, mixing SiO, calcium carbonate and metal lithium in an inert atmosphere by ball milling, wherein the particle size of SiO is 100nm, the particle size of calcium carbonate is 100nm, the ball-material ratio of ball milling is 10:1, the time is 100h, the temperature is 20 ℃, and the rotating speed is 500 r/min; sintering the mixture at 800 deg.C under vacuum in the absence of oxygen at a heating rate of 5 deg.C/min, and maintaining the temperature for 10 hr; cooling the obtained sintered solid product, and then carrying out acid washing and impurity removal for 40h by using 1mol/L hydrochloric acid, wherein the mass ratio of the obtained sintered solid product to the acid solution is 1: and 5, obtaining the pre-lithiated SiO/C composite negative electrode material.
2. Solid battery
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from the following components in percentage by mass in a ratio of 91: 5: 4, the negative plate is obtained by pressing the prepared SiO/C composite negative electrode material, PVDF and acetylene black in a mass ratio of 75:10:15 under 70 standard atmospheric pressures, the thickness of the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 250 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under 100 standard atmospheric pressures to prepare the solid battery.
Example 5
The difference from example 1 is that:
preparation of SiO/C composite cathode material
Mixing a mixture of 1: 0.1: 0.1 of SiO, calcium carbonate and metal lithium are mixed by ball milling in nitrogen atmosphere, the grain diameter of the SiO is 500nm, the grain diameter of the calcium carbonate is 500nm, the ball-to-material ratio of ball milling is 100:1, the time is 10h, the temperature is 150 ℃, and the rotating speed is 100 r/min; sintering the mixture at 900 deg.C under vacuum in the absence of oxygen at a heating rate of 15 deg.C/min, and maintaining the temperature for 40 hr; cooling the obtained sintered solid product, and then carrying out acid washing and impurity removal for 50h by using a mixed solution of 1mol/L hydrochloric acid and carbonic acid, wherein the mass ratio of the obtained sintered solid product to the acid solution is 1: and 10, obtaining the pre-lithiated SiO/C composite negative electrode material.
2. Solid battery
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from the following components in percentage by mass in a ratio of 91: 5: 4, the negative plate is obtained by pressing the prepared SiO/C composite negative electrode material, PVDF and acetylene black in a mass ratio of 75:10:15 under 70 standard atmospheric pressures, the thickness of the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 250 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under 100 standard atmospheric pressures to prepare the solid battery.
Example 6
The difference from example 1 is that:
the preparation method of the polymer composite solid electrolyte comprises the following steps:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550 ℃, and the speed is 3 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 2h at a speed of 3 ℃/min; cooling to room temperature again, and repeating the second sintering; cooling, taking out and ball milling to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate in acetonitrile to form a mixed solution of which the mass fraction of the polyethylene glycol diacrylate is 45%, sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate, and stirring, wherein the molar ratio of vinyl to lithium ions of the polyethylene glycol diacrylate is 15:1, the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate was 0.5: 1.0, 2, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate in a mass ratio of 3: 50; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate, wherein the porous g-C in the step (1)3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.1: 0.5: 1.0; performing ultraviolet crosslinking on the obtained slurry in inert gas atmosphere at a wavelength of 365nm and an intensity of 5-9mW/cm2The polymer composite solid electrolyte was obtained by exposing 5 times to ultraviolet light, each exposure time was 13 seconds, and each exposure interval was 10 min.
Comparative example 1
The difference from example 1 is that: pure SiO negative electrode material is used to replace SiO/C composite negative electrode material, and the grain diameter of SiO is 500 nm.
The lithium ion battery comprises a positive plate, a negative plate and solid electrolyte, wherein the positive plate is prepared from the following components in percentage by mass in a ratio of 91: 5: 4, the negative plate is obtained by pressing a pure SiO negative material, PVDF and acetylene black in a mass ratio of 75:10:15 under 70 standard atmospheric pressures, the thickness of the solid electrolyte is polymer composite solid electrolyte, and the thickness of the solid electrolyte is 250 mu m. And respectively pressing the positive plate and the negative plate on two sides of the polymer composite solid electrolyte under 100 standard atmospheric pressures to prepare the solid battery.
Comparative example 2
The difference from example 1 is that: the preparation method of the polymer composite solid electrolyte does not add porous g-C3N4Nanosheets and lithium bis (oxalato) borate.
The preparation method comprises the following steps:
dissolving polyethylene glycol diacrylate in acetonitrile to form a mixed solution of the polyethylene glycol diacrylate with the mass fraction of 30-60%, then sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate, and stirring, wherein the molar ratio of vinyl to lithium ions of the polyethylene glycol diacrylate is 18: 1, the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate was 0.6: the mass ratio of 3, 2, 2-dimethoxy-2-acetophenone to pentaerythritol tetra-3-mercaptopropionate is 2: 55; the obtained slurry is subjected to ultraviolet crosslinking in an inert gas atmosphere and the ultraviolet crosslinking is carried out at the wavelength365nm and 8mW/cm of intensity2The polymer composite solid electrolyte is obtained by exposing the polymer composite solid electrolyte on an ultraviolet lamp for 7 times, wherein each exposure time is 5s, and each exposure interval is 10 min.
And (3) performance testing:
the test conditions of each group of solid batteries are as follows: constant temperature 25 deg.C, first charge and discharge I0.1C, cycle I0.1C, voltage range 0.005-1.5V vs Li/Li+。
TABLE 1 electrochemical Properties of solid-State batteries under different conditions
As can be seen from the data in table 1, in combination with examples 1 to 6 and comparative example 1, the pre-lithiated SiO/C composite negative electrode material prepared in the present invention has advantages of high capacity, high coulombic efficiency, good cycle performance, and the like, compared with commercial SiO negative electrode materials, and a solid battery prepared by using the SiO/C composite negative electrode material as a negative electrode of a lithium ion battery exhibits high first efficiency and long cycle stability, and has excellent electrochemical performance. The invention uses metal lithium to pre-lithiate SiO, reduces carbonate to realize carbon coating of the pre-lithiated SiO, and improves the first effect by changing the silicon oxygen of the SiO material, thereby realizing controllable preparation of the carbon coating. Combining example 1 and comparative example 2, porous g-C was added to the polymer solid electrolyte3N4The two-dimensional nanosheet can remarkably improve the mechanical property and lithium ion transmission conductivity of the polymer composite solid electrolyte, and can improve the interface stability of the polymer solid electrolyte and a positive electrode after lithium bis (oxalato) borate (LiBOB) is added, so that the cycle life of a solid battery is prolonged.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-first-efficiency long-cycle SiO/C composite negative electrode material is characterized by comprising the following steps:
mixing SiO, carbonate and metal lithium by ball milling in an inert atmosphere, carrying out oxygen-free sintering on the mixture at 700-900 ℃, and carrying out heat preservation for 10-100 hours; and cooling and then acid-washing the obtained sintered solid product to obtain the pre-lithiated SiO/C composite negative electrode material.
2. The method for preparing the high-first-efficiency long-cycle SiO/C composite negative electrode material of claim 1, wherein the molar ratio of SiO to carbonate to lithium metal is 1: 0.1-1: 0.1 to 1.
3. The preparation method of the high-first-efficiency long-circulation SiO/C composite negative electrode material as claimed in claim 1 or 2, wherein the carbonate is calcium carbonate, and the particle size is 100-1000 nm; the particle size of the SiO is 100-1000 nm.
4. The preparation method of the high-first-efficiency long-circulation SiO/C composite negative electrode material as claimed in claim 1, wherein the ball-to-material ratio of the ball mill is 10-100: 1, the time is 10-100 h, the temperature is-10-300 ℃, and the rotating speed is 100-500 r/min.
5. The preparation method of the high-first-efficiency long-cycle SiO/C composite anode material of claim 1, wherein the oxygen-free sintering is sintering in an inert atmosphere or vacuum; the temperature rise rate of the oxygen-free sintering is 0.5-20 ℃/min.
6. The preparation method of the high-first-efficiency long-circulation SiO/C composite anode material as claimed in claim 1, wherein the acid solution used for pickling is one or more of hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, acetic acid and phosphoric acid, and the pickling time is 10-100 h; the concentration of the acid solution is 0.01-10 mol/L; the mass ratio of the sintered solid product to the acid solution is 1: 0.1 to 20.
7. A solid battery comprising a positive electrode sheet, a negative electrode sheet and a solid electrolyte, wherein the negative electrode sheet is obtained by pressing the SiO/C composite negative electrode material according to any one of claims 1 to 6, a negative electrode binder and a conductive agent; the solid electrolyte is a polymer composite solid electrolyte; the solid battery is prepared by respectively pressing a positive plate and a negative plate on two sides of the polymer composite solid electrolyte.
8. The solid-state battery according to claim 7, wherein the method for producing the polymer composite solid electrolyte comprises the steps of:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550-; after cooling to room temperature, the second sintering is sintering at 600-650 ℃ for 2-4h at the speed of 3-6 ℃/min; cooling to room temperature again, and repeating the second sintering; cooling, taking out and ball milling to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate in acetonitrile to form a mixed solution, then sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone and pentaerythritol tetra-3-mercaptopropionate, stirring, and then adding the porous g-C in the step (1)3N4Stirring the nanosheets and the lithium bis (oxalate) borate; performing ultraviolet crosslinking on the obtained slurry in inert gas atmosphere at a wavelength of 365nm and an intensity of 5-9mW/cm2Exposing the polymer composite solid electrolyte on an ultraviolet lamp for 5-8 times, wherein each exposure time is 5-10s, and each exposure interval is 10-15 min, so as to obtain the polymer composite solid electrolyte.
9. The solid-state battery according to claim 8, wherein in the step (2), the polyethylene glycol diacrylate has a vinyl group to lithium ion molar ratio of 10-25: 1; the mass fraction of the polyethylene glycol diacrylate in the mixed solution is 30-60%; the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate is 0.5-1.0: 1.0-2.0.
10. As claimed in claimThe solid-state battery of 8 or 9, wherein in the step (2), the mass ratio of the 2, 2-dimethoxy-2-acetophenone to the pentaerythritol tetra-3-mercaptopropionate is 1-3: 50-60 parts of; porous g-C in the step (1)3N4The molar ratio of the nanosheet to the lithium bis (oxalato) borate to the LiTFSI is 0.1-0.3: 0.2-0.5: 1.0-1.3.
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