CN117352640A - High-performance silicon-based composite anode material and preparation method and application thereof - Google Patents
High-performance silicon-based composite anode material and preparation method and application thereof Download PDFInfo
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- CN117352640A CN117352640A CN202311511394.2A CN202311511394A CN117352640A CN 117352640 A CN117352640 A CN 117352640A CN 202311511394 A CN202311511394 A CN 202311511394A CN 117352640 A CN117352640 A CN 117352640A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 70
- 239000010703 silicon Substances 0.000 title claims abstract description 70
- 239000010405 anode material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000002734 clay mineral Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910001919 chlorite Inorganic materials 0.000 claims description 2
- 229910052619 chlorite group Inorganic materials 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052900 illite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 239000002210 silicon-based material Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 125000004122 cyclic group Chemical group 0.000 description 10
- 239000002153 silicon-carbon composite material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WRSVIZQEENMKOC-UHFFFAOYSA-N [B].[Co].[Co].[Co] Chemical compound [B].[Co].[Co].[Co] WRSVIZQEENMKOC-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002620 silicon nanotube Substances 0.000 description 2
- 229910021430 silicon nanotube Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a high-performance silicon-based composite anode material, a preparation method and application thereof, and belongs to the technical field of lithium ion battery anode materials. The invention discloses a preparation method of a high-performance silicon-based composite anode material, which comprises the following steps: (1) Preparing clay mineral powder, aluminum powder and aluminum trichloride powder into a nano silicon material; (2) The silicon-based composite material prepared by the method can be used as a negative electrode material of a lithium ion battery, has excellent electrochemical performance, greatly improves the overall conductivity due to the load of the high-conductivity boride amorphous alloy, and effectively improves the multiplying power performance of the battery; wherein the boride loading effectively inhibits the volume expansion of silicon, and the cycle life is advantageously improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a high-performance silicon-based composite anode material, and a preparation method and application thereof.
Background
With the rapid development of modern industry, the social problems such as the aggravation of the shortage of fossil energy and the like need to be solved. In many energy storage and conversion devices, lithium ion batteries are widely used in portable electronic devices and power automobiles due to the advantages of high energy density, long cycle life and the like. However, the current commercialized lithium ion battery cathode material graphite cannot meet the requirement of a lithium ion battery with high performance at the future date due to low theoretical capacity (372 mAh/g). In order to further improve the energy density of the battery, searching for a high-capacity anode material becomes a research hot spot in the field of lithium ion batteries.
The silicon material has the characteristics of high theoretical capacity (4200 mAh/g), lower working potential (less than 0.4Vvs. Li/Li+), and the like, and is a cathode material with great development potential at present. However, the commercialization of silicon in the current stage is hindered by its own characteristics, and besides low intrinsic conductivity, silicon has a large volume change in the lithium ion deintercalation process, and these two disadvantages make the electrochemical polarization of the silicon anode material large, are unfavorable for rapid charge and discharge, and the large volume change can cause cracking and destruction of the active material.
In the prior art, CN116454256a describes a preparation method of a silicon-carbon composite material, in-situ compounding is directly performed by using nano silicon and nano carbon as raw materials, and a layer of carbon material is coated to reduce the possibility of the silicon-carbon composite material reacting with air or water in the storage process; and the micron-sized silicon-carbon composite material is obtained by slurry spray granulation, so that the surface area of the material is reduced. Compared with pure silicon nano material, the silicon-carbon composite material prepared by the method is beneficial to the carbon coating, and the conductivity and the cycle performance of the silicon-carbon composite material are effectively improved. The method adopts silane gas and hydrocarbon gas as raw materials of nano silicon and nano carbon, has higher cost, and the preparation of the silicon-carbon composite material needs three steps of heat treatment, and has long preparation time consumption, low yield, high production cost and other problems in the industrialized process.
Disclosure of Invention
The invention provides a high-performance silicon-based composite anode material, a preparation method and application thereof, which can solve the problems of low intrinsic conductivity, huge volume change in the charge and discharge process and the like of the silicon-based anode material.
In a first aspect, the invention provides a preparation method of a high-performance silicon-based composite anode material, which comprises the following steps:
step S1, mixing a silicon source material, aluminum powder and aluminum trichloride powder to obtain a first mixture, and carrying out high-temperature reaction on the first mixture to obtain a first product;
s2, carrying out acid washing and mixed solution treatment on the first product to obtain a nano silicon material;
s3, after the nano silicon material and the hydrated chloride are co-dissolved, dropwise adding a reducing agent in an inert gas atmosphere for reaction to obtain a second product;
and S4, freeze-drying the second product in a vacuum environment to obtain the product.
Further, the silicon source material is clay mineral powder after cleaning and drying, and the mass fraction of silicon element in the silicon source material is 55-60%; the silicon source material is at least one selected from halloysite, montmorillonite, attapulgite, kaolinite, chlorite and illite.
In the invention, clay minerals are used for providing a silicon source and are a kind of layered silicate formed by silicon oxygen tetrahedra and aluminum oxygen octahedra.
Further, the mass ratio of the silicon source material to the aluminum powder to the aluminum trichloride powder is 10:3-5:30-50.
Further, the high-temperature reaction environment is an inert gas environment, the high-temperature reaction temperature is 250-300 ℃, the time is 10-15 h, and the heating rate is 2-6 ℃/min.
Further, the inert gas in the invention is argon.
Further, the pickling time is 4-8 hours, and the pickling lotion is 1-3 mol/L hydrochloric acid;
the mixed solution comprises hydrofluoric acid and ethanol with volume fractions of 3-5% and 6-10% respectively.
Further, the product treated by the mixed solution is required to be centrifugally dried by deionized water to obtain the nano silicon material, wherein the centrifugal time is 10-20 min, and the speed is 3000-5000 r/min.
In the invention, the particle size range of the prepared nano silicon material is 10-150 nm.
Further, the hydrated chloride is one of cobalt chloride hexahydrate, nickel chloride hexahydrate and ferrous chloride tetrahydrate, and the mass ratio of the hydrated chloride to the nano silicon material is 2-4:1.
In the present invention, the purpose of the hydrated chloride is to provide a metal source for the post-synthesis of boride, and the metal source that can be used for the overall conductivity of the reinforcing material of the present invention includes only iron, nickel and cobalt, and the effect cannot be achieved by the remaining metals.
Further, the reducing agent is a mixed solution, and comprises 0.4-0.5% of sodium borohydride by mass and 0.04-0.05% of sodium hydroxide by mass.
Further, the freeze-drying temperature in the step S4 is-40 ℃ to-20 ℃, and the freeze-drying time is 6-10 hours.
In a second aspect, the invention provides a high-performance silicon-based composite anode material prepared by adopting the preparation method of the high-performance silicon-based composite anode material.
In a third aspect, the invention provides an application of a high-performance silicon-based composite anode material in preparing a lithium ion battery.
Compared with the prior art, the technical scheme provided by the embodiment of the application has at least the following advantages:
the invention discloses a high-performance silicon-based composite anode material, which is synthesized by taking low-cost natural pollution-free clay minerals as templates, wherein the nano structure can effectively inhibit the volume expansion of silicon in the charge and discharge process and is beneficial to improving the structural stability of the silicon in the circulation process;
the amorphous boride alloy material is loaded on the nano silicon, and the introduction of boride effectively enhances the overall conductivity of the material, is beneficial to charge transfer, and improves the overall multiplying power performance and coulombic efficiency of the material. In addition, the coating of boride (iron boride, cobalt boride or nickel boride) further inhibits the volume expansion of silicon, and greatly increases the stability of silicon in the charge and discharge processes.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a transmission electron microscope image of a one-dimensional silicon nanotube prepared in example 1;
fig. 2 is a scanning electron microscope image of a silicon-based composite anode material prepared in example 2.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
The principles and features of the present invention are described below in connection with the following examples, which are set forth to illustrate, but are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment discloses a nanotube-shaped silicon material, which is prepared by the following method:
(1) The halloysite powder was rinsed with deionized water and dried in an oven at 60 ℃. Uniformly grinding and mixing 1.2g of dried halloysite powder, 0.5g of aluminum powder and 5.0g of aluminum trichloride powder to obtain a mixture, transferring the mixture into a reaction kettle under the argon atmosphere of a glove box, and placing the reaction kettle into a blast drying box for reaction, wherein the reaction temperature is 280 ℃, the reaction time is 13h, and the heating rate is 5 ℃/min.
(2) And (3) pickling the obtained sintered product in 2mol/L hydrochloric acid for 6 hours to remove sintering byproducts, excessive aluminum powder and other impurities.
(3) And (3) cleaning the acid-washed product obtained in the step (2) in mixed liquid of hydrofluoric acid and ethanol with volume fractions of 5% and 10% respectively for 20min to remove silicon dioxide.
(4) Washing the product obtained in the step (3) with deionized water and centrifugally separating, wherein the centrifugal time is 10min, and the centrifugal speed is 5000r/min. Finally, drying for 4 hours in a baking oven at 60 ℃ to obtain the nanotube-shaped silicon material. The transmission electron microscope image is shown in fig. 1, and the appearance of the hollow nano tube is shown, and the appearance of structural fracture does not appear.
The nano-tubular silicon material obtained in the embodiment is used as an active substance, acetylene black and sodium carboxymethyl cellulose are respectively used as a conductive agent and a binder to assemble a half cell, and the mass ratio of the silicon material to the acetylene black to the sodium carboxymethyl cellulose is 8:1:1.
Mixing the three materials with proper amount of ethanol and deionized water to form slurry, uniformly coating the slurry on a copper foil to prepare the electrode, and drying the electrode for 18 hours in a vacuum environment. LiPF with lithium sheet as negative electrode, polyethylene film as diaphragm, and 1mol/L 6 (EC: DEC: dmc=1:1:1) button cells were assembled for the electrolyte in an argon filled glove box. At 500mA/g of electricityThe specific capacity of the assembled battery can reach 1372.31mAh/g when the battery is charged and discharged in a voltage range of 0.001-2.000V, and the capacity is kept at 901.89mAh/g after 300 times of cyclic charge and discharge.
Example 2
The embodiment provides a high-performance silicon-based composite anode material, which is prepared from the nano tubular silicon material in embodiment 1, and specifically comprises the following steps:
(1) The nano-tube-shaped silicon material obtained in the above example 1, 0.3g and 0.6g of ferrous chloride tetrahydrate were dissolved in 100mL of deionized water, and uniformly stirred on a magnetic stirrer for 30min to obtain a mixed solution.
(2) The mixed solution was transferred to a three-necked flask, and argon was introduced into the solution.
(3) The mixed solutions of sodium borohydride and sodium hydroxide with mass fractions of 0.5% and 0.05% respectively were added dropwise to a three-necked flask until no more vigorous bubbles were generated, and the resulting black precipitate was centrifuged.
(4) And (3) freeze-drying the black product in the step (3) for 8 hours in a vacuum environment to obtain the high-performance silicon-based composite anode material, wherein a scanning electron microscope image of the high-performance silicon-based composite anode material is shown in figure 2, and iron boride nano particles can be uniformly wrapped around a silicon nanotube to form a composite material with a core-shell structure.
The electrochemical performance test method of the high-performance silicon-based composite anode material prepared by the embodiment is the same as that of the embodiment 1. At a current density of 500mA/g, the capacity can reach 1511.25mAh/g; when the current density is increased to 5000mA/g, the capacity of the silicon-based composite anode material can still reach 831.27mAh/g, and excellent rate capability is shown; the capacity of the silicon-based composite anode material is kept at 1256.35mAh/g after 300 times of cyclic charge and discharge under the current density of 500mA/g, and the silicon-based composite anode material has excellent cyclic stability.
Example 3
The embodiment provides a nano sheet-shaped silicon material, which is prepared by the following method:
(1) The montmorillonite powder was washed with deionized water and dried in an oven at 60 ℃. Uniformly grinding and mixing 1.2g of dried montmorillonite powder, 0.5g of aluminum powder and 5.0g of aluminum trichloride powder to obtain a mixture, transferring the mixture into a reaction kettle under the argon atmosphere of a glove box, and placing the reaction kettle into a blast drying box for reaction at the reaction temperature of 280 ℃ for 13h at the heating rate of 5 ℃/min.
(2) And (3) pickling the obtained sintered product in 2mol/L hydrochloric acid for 6 hours to remove sintering byproducts, excessive aluminum powder and other impurities.
(3) And (3) cleaning the product obtained after the acid washing in the step (2) in mixed liquid of hydrofluoric acid and ethanol with volume fractions of 5% and 10% respectively for 20min to remove silicon dioxide.
(4) Washing the product in the step (3) by deionized water and centrifugally separating, wherein the centrifugal time is 10min, and the centrifugal speed is 5000r/min. Finally, drying for 4 hours in a baking oven at 60 ℃ to obtain the nano sheet-shaped silicon material.
The electrochemical performance test method of the half cell assembled by using the nano sheet-shaped silicon material prepared in the present example as an active material is the same as that of example 1. At a current density of 500mA/g, the capacity can reach 1220.42mAh/g; the capacity of the battery is kept at 750.68mAh/g after 300 times of cyclic charge and discharge at a current density of 500 mA/g.
Example 4
The embodiment provides a silicon-based composite anode material, which is prepared from a nano flaky silicon material prepared in embodiment 3, and specifically comprises the following steps:
(1) The nanosheet-shaped silicon material obtained in example 3, 0.3g and 0.6g of ferrous chloride tetrahydrate, were dissolved in 100mL of deionized water, and uniformly stirred on a magnetic stirrer for 30min to obtain a mixed solution.
(2) The above mixed solution was transferred to a three-necked flask, and argon was introduced into the solution.
(3) The mixed solutions of sodium borohydride and sodium hydroxide with mass fractions of 0.5% and 0.05% respectively were added dropwise to a three-necked flask until no more vigorous bubbles were generated, and the resulting black precipitate was centrifuged.
(4) And (3) freeze-drying the black product in the step (3) for 8 hours in a vacuum environment to obtain the silicon-based composite anode material.
The method for testing the electrochemical performance of the half cell assembled by using the silicon-based composite anode material prepared in the embodiment as an active material is the same as that of the embodiment 1. At a current density of 500mA/g, the capacity can reach 1410.54mAh/g; when the current density is increased to 5000mA/g, the capacity of the silicon-based composite anode material can still reach 681.57mAh/g; the capacity of the battery is kept at 1107.70mAh/g after 300 times of cyclic charge and discharge under the current density of 500 mA/g.
Example 5
The embodiment provides a nanorod-shaped silicon material, which is prepared by the following method:
(1) Cleaning attapulgite powder with deionized water, and drying in oven at 60deg.C. Uniformly grinding and mixing 1.2g of dried attapulgite powder, 0.5g of aluminum powder and 5.0g of aluminum trichloride powder to obtain a mixture, transferring the mixture into a reaction kettle under the argon atmosphere of a glove box, and placing the reaction kettle into a blast drying box for reaction at the reaction temperature of 280 ℃ for 13h at the heating rate of 5 ℃/min.
(2) And (3) pickling the obtained sintered product in 2mol/L hydrochloric acid for 6 hours to remove sintering byproducts, excessive aluminum powder and other impurities.
(3) And (3) cleaning the product obtained after the acid washing in the step (2) in mixed liquid of hydrofluoric acid and ethanol with volume fractions of 5% and 10% respectively for 20min to remove silicon dioxide.
(4) Washing the product in the step (3) by deionized water and centrifugally separating, wherein the centrifugal time is 10min, and the centrifugal speed is 5000r/min. Finally, drying for 4 hours in an oven at 60 ℃ to obtain the nanorod-shaped silicon material.
The electrochemical performance test method of the half cell was the same as in example 1, using the nanorod-shaped silicon material obtained in this example as an active material. At a current density of 500mA/g, the capacity can reach 1298.13mAh/g; the capacity of the battery is kept at 819.51mAh/g after 300 times of cyclic charge and discharge at a current density of 500 mA/g.
Example 6
This example provides a silicon-based composite anode material prepared by the nanorod-shaped silicon material prepared in example 5, comprising the steps of:
(1) The nanorod-shaped silicon material obtained in example 5 was dissolved with 0.3g and 0.6g of ferrous chloride tetrahydrate in 100mL of deionized water, and uniformly stirred on a magnetic stirrer for 30min to obtain a mixed solution.
(2) The mixed solution was transferred to a three-necked flask, and argon was introduced into the solution.
(3) The mixed solutions of sodium borohydride and sodium hydroxide with mass fractions of 0.5% and 0.05% respectively were added dropwise to a three-necked flask until no more vigorous bubbles were generated, and the resulting black precipitate was centrifuged.
(4) And (3) freeze-drying the black product in the step (3) for 8 hours in a vacuum environment to obtain the silicon-based composite anode material.
The method for testing the electrochemical performance of the half cell assembled by taking the silicon-based composite anode material obtained in the embodiment as an active ingredient is the same as that of the embodiment 1. At a current density of 500mA/g, the capacity can reach 1453.71mAh/g; when the current density is increased to 5000mA/g, the capacity of the silicon-based composite anode material can still reach 734.12mAh/g; the capacity of the battery is kept at 1163.69mAh/g after 300 times of cyclic charge and discharge under the current density of 500 mA/g.
Example 7
This example provides a silicon-based composite anode material, the method of preparation of which differs from that of example 2 in that 0.6g of ferrous chloride tetrahydrate is replaced by 0.6g of cobalt chloride hexahydrate, the remaining steps being the same.
The half cell assembled by the silicon-based composite anode material according to the same method has the capacity of 1473.28mAh/g under the current density of 500 mA/g; when the current density is increased to 5000mA/g, the capacity of the silicon-based composite anode material can still reach 769.90mAh/g; the capacity of the battery is kept at 1197.63mAh/g after 300 times of cyclic charge and discharge at a current density of 500 mA/g.
Example 8
This example provides a silicon-based composite anode material, which is prepared by a method different from example 2 in that 0.6g of ferrous chloride tetrahydrate is replaced by 0.6g of nickel chloride hexahydrate, and the rest steps are the same.
The half cell assembled by the silicon-based composite anode material according to the same method has the capacity of 1466.31mAh/g under the current density of 500 mA/g; when the current density is increased to 5000mA/g, the capacity of the silicon-based composite anode material can still reach 750.72mAh/g; the capacity of the battery is kept at 1171.29mAh/g after 300 times of cyclic charge and discharge at a current density of 500 mA/g.
Comparative example 1
The comparative example provides a half cell made of silicon material, which is prepared by the following method:
(1) Commercial silica powder was rinsed with deionized water and dried in an oven at 60 ℃. 1.2g of dried silicon dioxide powder, 0.5g of aluminum powder and 5.0g of aluminum trichloride powder are uniformly ground and mixed to obtain a mixture, the mixture is transferred into a reaction kettle under the argon atmosphere of a glove box, and the reaction kettle is placed into a blast drying box for reaction, wherein the reaction temperature is 280 ℃, the reaction time is 13h, and the heating rate is 5 ℃/min.
(2) And (3) pickling the obtained sintered product in 2mol/L hydrochloric acid for 6 hours to remove sintering byproducts, excessive aluminum powder and other impurities.
(3) And (3) cleaning the product after the acid washing in the step (2) in mixed liquid of hydrofluoric acid and ethanol with volume fractions of 5% and 10% respectively for 20min to remove silicon dioxide.
(4) Washing the product in the step (3) with deionized water and centrifugally separating, wherein the centrifugal time is 10min, and the centrifugal speed is 5000r/min. Finally, drying in an oven at 60 ℃ for 4 hours to obtain the silicon material.
(5) The electrochemical performance of the half cell assembled from the silicon material prepared in (4) as an active material was tested in the same manner as in example 1. At a current density of 500mA/g, the capacity can reach 1077.69mAh/g; the capacity of the battery is kept at 433.99mAh/g after 300 times of cyclic charge and discharge at a current density of 500 mA/g.
Table 1 lithium ion battery test results of examples 1-8 and comparative example 1
As can be seen from the electrical property comparison results of examples 1-8 and comparative example 1 in Table 1, the silicon-based composite anode material prepared by the invention has excellent electrochemical properties, the load of the high-conductivity boride amorphous alloy greatly improves the overall conductivity, the rate performance of the battery is effectively improved, in addition, the load of the boride effectively inhibits the volume expansion of silicon, and the cycle life is beneficially improved. It can also be seen that although cobalt boride and nickel boride also act as iron boride, the best effect is an iron boride material.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the high-performance silicon-based composite anode material is characterized by comprising the following steps of:
step S1, mixing a silicon source material, aluminum powder and aluminum trichloride powder to obtain a first mixture, and carrying out high-temperature reaction on the first mixture to obtain a first product;
s2, carrying out acid washing and mixed solution treatment on the first product to obtain a nano silicon material;
s3, after the nano silicon material and the hydrated chloride are co-dissolved, dropwise adding a reducing agent in an inert gas atmosphere for reaction to obtain a second product;
and S4, freeze-drying the second product in a vacuum environment to obtain the product.
2. The preparation method of the high-performance silicon-based composite anode material according to claim 1, wherein the silicon source material is clay mineral powder after cleaning and drying, and the mass fraction of silicon element in the silicon source material is 55-60%; the silicon source material is at least one selected from halloysite, montmorillonite, attapulgite, kaolinite, chlorite and illite.
3. The method for preparing a high-performance silicon-based composite anode material according to claim 1 or 2, wherein the mass ratio of the silicon source material to the aluminum powder to the aluminum trichloride powder is 10:3-5:30-50.
4. The method for preparing the high-performance silicon-based composite anode material according to claim 1, wherein the high-temperature reaction environment is an inert gas environment, the high-temperature reaction temperature is 250-300 ℃, the time is 10-15 h, and the heating rate is 2-6 ℃/min.
5. The method for preparing the high-performance silicon-based composite anode material according to claim 1, wherein the pickling time is 4-8 hours, and the pickling lotion is 1-3 mol/L hydrochloric acid;
the mixed solution comprises hydrofluoric acid and ethanol with volume fractions of 3-5% and 6-10% respectively.
6. The preparation method of the high-performance silicon-based composite anode material according to claim 1, wherein the hydrated chloride is one of cobalt chloride hexahydrate, nickel chloride hexahydrate and ferrous chloride tetrahydrate, and the mass ratio of the hydrated chloride to the nano silicon material is 2-4:1.
7. The preparation method of the high-performance silicon-based composite anode material according to claim 1, wherein the reducing agent is a mixed solution, and comprises 0.4-0.5% by mass of sodium borohydride and 0.04-0.05% by mass of sodium hydroxide.
8. The method for preparing a high-performance silicon-based composite anode material according to claim 1, wherein the freeze-drying temperature in the step S4 is-40 ℃ to-20 ℃ and the freeze-drying time is 6-10 h.
9. A high-performance silicon-based composite anode material prepared by the method for preparing the high-performance silicon-based composite anode material according to any one of claims 1 to 8.
10. The use of the high-performance silicon-based composite anode material according to claim 9 in the preparation of lithium ion batteries.
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