CN113611844B - Silicon-carbon composite material and preparation method and application thereof - Google Patents
Silicon-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN113611844B CN113611844B CN202110887321.8A CN202110887321A CN113611844B CN 113611844 B CN113611844 B CN 113611844B CN 202110887321 A CN202110887321 A CN 202110887321A CN 113611844 B CN113611844 B CN 113611844B
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 243
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 95
- 239000006260 foam Substances 0.000 claims abstract description 87
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 85
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 238000011065 in-situ storage Methods 0.000 claims abstract description 59
- 239000012745 toughening agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 78
- 239000007789 gas Substances 0.000 claims description 74
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 69
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 47
- 229910052742 iron Inorganic materials 0.000 claims description 39
- 239000002409 silicon-based active material Substances 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 229910052786 argon Inorganic materials 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000011068 loading method Methods 0.000 claims description 24
- 239000002134 carbon nanofiber Substances 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 11
- 239000003345 natural gas Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000006262 metallic foam Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010981 drying operation Methods 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000008239 natural water Substances 0.000 claims description 6
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 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 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000006261 foam material Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 239000002210 silicon-based material Substances 0.000 description 8
- 239000000306 component Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000002074 nanoribbon Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001595 contractor effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a silicon-carbon composite material and a preparation method and application thereof, which adopts a chemical vapor deposition method to prepare a graphene foam body with a carbon nano tube growing on the surface and toughened in situ by a carbon nano toughening agent, and then uses Si powder or SiO powder with a carbon nano tube or carbon nano sheet growing on the surfacexThe powder is loaded in the graphene foam body to prepare the flexible electrode based on the silicon-carbon composite material with a novel structure, so that the flexible electrode can be used as a cathode of a semi-solid, quasi-solid or all-solid battery. The silicon-carbon composite material prepared by the invention has the characteristics of high capacity and high cycle stability, has excellent interface wettability, stability and ion/electron conductivity with a solid electrolyte, does not need a current collector, and obviously improves the energy density and power density of a solid battery.
Description
Technical Field
The invention relates to the technical field of intersection of lithium ion batteries and graphene materials, in particular to a silicon-carbon composite material and a preparation method and application thereof.
Background
The lithium ion battery is widely applied to the product fields of mobile phones, digital products, 3C and the like as a secondary battery with high energy density. In recent years, in order to get rid of the problems of excessive dependence on petroleum energy structures, active response to environmental pollution and the like, China strongly supports and encourages the development of electric automobiles, and lithium ion batteries are vigorously developed as power core components of the electric automobiles. However, in order to achieve a higher driving range of the electric vehicle, the safety, energy density, and power density of the lithium ion battery need to be improved. The electrode material is taken as a key factor for determining the performance of the battery, and the existing graphite cathode material is difficult to meet the requirement of the lithium ion battery for realizing higher energy density, so that the research and development of a next-generation novel cathode material with high capacity and controllable cost have very important scientific research value and application prospect.
Silicon is due to its ultra-high theoretical capacity (4200mA h g)-1，Li22Si5) Abundant earth reserves, no toxicity and pollution, and the discharge platform similar to graphite becomes the next generation with the most potentialA lithium ion battery cathode material. However, the severe volume expansion and contraction effects of Si during charging and discharging can cause material pulverization, which leads to the active material falling off from the current collector, and the capacity is rapidly attenuated, thereby limiting the commercial application of Si. In addition, another disadvantage of silicon-based negative electrode materials is poor conductivity, which is not conducive to electron transport and lithium ion diffusion, thereby impairing the rate capability and cycling stability of the materials.
In recent years, researchers find that graphene foam has a connected three-dimensional porous structure, a developed pore structure, a large specific surface area and strong flexibility, and the graphene foam is most hopefully developed into a flexible electrode substrate material with strong conductivity. However, graphene foam has low mechanical strength and smooth surface, so that other materials are easy to fall off, break and the like when loaded on the surface.
Therefore, the problem to be solved by those skilled in the art is how to provide a composite material that utilizes the combination of graphene foam and silicon matrix and has high mechanical strength and strong interface stability.
Disclosure of Invention
In view of the above, the present invention provides a silicon-carbon composite material, and a preparation method and an application thereof, wherein a chemical vapor deposition method is adopted to prepare a graphene foam body with a carbon nanotube growing on the surface and toughened in situ by a carbon nano-toughening agent, and then Si powder or SiO powder with a carbon nanotube or a carbon nano-sheet growing on the surface is addedxThe powder is loaded in the graphene foam body to prepare the flexible electrode based on the silicon-carbon composite material with a novel structure, so that the flexible electrode can be used as a cathode of a semi-solid, quasi-solid or all-solid battery.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a silicon-carbon composite material comprises the following steps:
the method comprises the following steps: metal foam pretreatment
Soaking the metal foam body in 0.1-3M hydrochloric acid, ultrasonically cleaning for 10-30min at 50-100W, and then cleaning with deionized water to remove residual hydrochloric acid;
step two: loading of carbon nano toughener
Dispersing the carbon nano flexibilizer in the concentrationForming a solution A with the concentration of the carbon nano toughener of 0.1-0.5g/L in a surfactant aqueous solution of 0.1-5g/L, then uniformly coating the solution A on the metal foam body treated in the step one, and then drying for 4-8h under the condition of-0.1 MPa, wherein the loading amount of the carbon nano toughener on the metal foam body is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing inert gas into the foam obtained in the step two in a tubular furnace under the condition of-0.1-0.15 MPa, heating to 800-;
step four: foam etch
Soaking the foam in situ toughened by the carbon nano toughener obtained in the step three in an etching solution, keeping the temperature at 40-80 ℃ for continuously etching for 12-48h, then cleaning with deionized water until the pH is neutral, and finally drying at 80-120 ℃ for 2-4h to obtain the graphene foam in situ toughened by the carbon nano toughener;
step five: preparing a catalyst;
adding metal organic salt and benzyl ether into polyhydric alcohol according to the mass volume ratio of 1g (200-2000) mL, adding a surfactant after uniformly stirring, and refluxing for 20-30min at the temperature of 150-250 ℃ to obtain a catalyst solution;
step six: catalyst loading
Coating 1-10ml of catalyst solution on the surface of the graphene foam in-situ toughened by the carbon nano flexibilizer prepared in the fourth step, drying for 5-20min at 40-80 ℃, repeating the coating and drying operations for 3-5 times, then calcining for 1-3h in an atmosphere furnace at 250-400 ℃ under the air condition, and finally naturally cooling to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foam loaded in the sixth step into a constant temperature area of a CVD atmosphere furnace, firstly introducing inert gas, then heating to 600-900 ℃ at the speed of 10-20 ℃/min, then introducing carbon source gas to carry out CVD growth of the carbon nano tube, continuing the growth for 10-60min, and naturally cooling to room temperature to obtain the graphene foam with the surface in-situ grown carbon nano tube and subjected to in-situ toughening by the carbon nano toughening agent;
step eight: preparation of silicon-based active materials
Placing Si powder or SiOx powder in a constant-temperature area of a vacuum atmosphere furnace, introducing inert gas for 0.5h, heating to 800-1300 ℃, then continuously introducing a mixed gas of carbon source gas and hydrogen for 0.3-2h, and then switching to inert gas to naturally cool to room temperature to obtain the silicon-based active material with the carbon nano tube or the carbon nano sheet growing on the surface;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and the binder into slurry according to the mass ratio of (1-9) to 1, coating the slurry on the graphene foam material prepared in the step seven, drying the slurry at the constant temperature of 80 ℃ for 4-12h, and then compacting the slurry under the mechanical pressure of 1-15MPa to prepare the silicon-carbon composite material.
Preferably, the metal foam body in the first step is one of nickel foam, copper foam, aluminum foam or iron foam, the thickness is 0.1-5.0mm, and the bulk density is 0.1-10.0g/cm3The purity is more than or equal to 90 percent.
Preferably, the carbon nano flexibilizer in the step two is one of a carbon nano tube, a graphene nano belt or a carbon nano fiber, the diameter of the carbon nano flexibilizer is 10-50nm, the length of the carbon nano flexibilizer is 1-50 mu m, and the carbon content is more than or equal to 95 percent;
the surfactant is one of cetyl trimethyl ammonium bromide, lauryl sodium sulfate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and sodium dodecyl benzene sulfonate.
Preferably, the inert gas in the third step, the seventh step and the eighth step is one or two of argon, high-purity nitrogen, helium or radon;
in the third step, the carbon source gas is one or two of methane, ethylene, acetylene, natural gas or water gas.
Preferably, the etching solution in the fourth step is hydrochloric acid: ferric chloride: deionized water according to the mol volume ratio of (0.1-3) mol: 1 mol: (0.1-10) L.
Preferably, in the fifth step, the metal organic salt is one or a mixture of two of ferric acetylacetonate, nickel acetylacetonate and cobalt acetylacetonate, and the mixing mass ratio of the two is 1: (1-5);
the polyalcohol is one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and ethylene glycol monomethyl ether;
the surfactant is one or a mixture of two of oleylamine and oleic acid, and the volume ratio of the surfactant to the dibenzyl ether is (0.2-1.0): (200-2000).
Preferably, in the seventh step, the carbon source gas is one or a mixture of two or more of methane, acetylene, ethylene, natural gas and water gas, and the flow rate is 2-30 mL/min;
the obtained graphene foam is few-layer graphene, and the number of graphene layers is 2-10; the diameter of the carbon nano tube grown on the surface in situ is 3-10nm, and the length is 1-10 μm.
Preferably, in the eighth step, the carbon source gas is a mixed gas of one or two or more of methane, ethane, acetylene, ethylene, natural gas and water gas, and the volume flow ratio of the carbon source gas to the hydrogen gas is (1:1) - (1: 30).
The average grain diameter of the Si powder or SiOx powder is 0.01-30 mu m;
the diameter of the carbon nano tube on the surface of the obtained silicon-based active material is 3-20nm, and the length of the carbon nano tube is 1-5 mu m; the plane size of the carbon nano-sheet is 5-50nm, and the thickness is 1-10 nm.
Preferably, the binder in the ninth step is one of sodium carboxymethylcellulose, polytetrafluoroethylene, polyvinylidene fluoride or styrene-butadiene latex;
the silicon-carbon composite material comprises the following components in percentage by mass: 10-95% of graphene foam and 5-90% of silicon-based active material.
The invention also provides an application of the silicon-carbon composite material prepared by the technical scheme in the preparation of a solid-state battery, wherein the solid-state battery is a semi-solid-state battery, a quasi-solid-state battery or an all-solid-state battery, the solid-state battery comprises a shell, a positive electrode and a negative electrode which are positioned in the shell, and a solid electrolyte positioned between the positive electrode and the negative electrode, and the negative electrode material is the silicon-carbon composite material prepared by the scheme.
According to the technical scheme, compared with the prior art, the invention discloses a silicon-carbon composite material and a preparation method and application thereof, and the silicon-carbon composite material has the following beneficial effects:
according to the invention, a chemical vapor deposition method is adopted to generate a C-C chemical covalent bond with the carbon nano flexibilizer in the process of vapor phase growth of the graphene foam, so that the effects of in-situ toughening and mechanical strength improvement are realized. In addition, the carbon nano tube is grown on the surface of the graphene foam in situ, so that the combination compactness and the conductivity of the graphene foam and other materials can be improved, and the impregnation property with a solid electrolyte and the interface stability can be improved. In order to improve the electrochemical reaction activity and the cycling stability of the silicon-based material, the invention adopts a chemical vapor deposition method to grow the carbon nano tube or the carbon nano sheet on the surface of the silicon-based material in situ so as to enhance the surface conductivity of the silicon-based material and inhibit the pulverization of the silicon-based material. In order to improve the energy density and the power density of a solid battery and improve the stability and the impregnability of an interface between a negative electrode and a solid electrolyte, a silicon-based material with a carbon nano tube or a carbon nano sheet growing on the surface is loaded on a graphene foam body with a carbon nano toughening agent growing on the surface and toughened in situ, so that a flexible electrode based on a silicon-carbon composite material with a novel structure is constructed, the conductivity of the silicon-based material is obviously enhanced, and the volume expansion effect of the silicon-based material is inhibited. Meanwhile, the impregnation property and the interface stability between the negative electrode and the solid electrolyte can be obviously improved by utilizing the carbon nano tube or the carbon nano sheet on the surface of the silicon-based material and the carbon nano tube on the surface of the graphene foam, so that the service life of the solid battery is prolonged, and the energy/power density is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of in situ grown carbon nanotubes on the surface of graphene foam in the embodiment 1;
FIG. 2 is a scanning electron micrograph of the carbon nanotubes grown in situ on the surface of the silicon powder in the embodiment 1;
fig. 3 is an electron microscope photograph of graphene foam in-situ toughened with carbon nano toughener in the scheme of example 1 under uniaxial stretching.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the silicon-carbon composite material comprises the following steps:
the method comprises the following steps: foam nickel pretreatment
The thickness is 2mm, and the volume density is 5g/cm3Soaking foamed nickel with the purity of more than or equal to 90 percent in 2M hydrochloric acid, ultrasonically cleaning for 20min at 100W, and then cleaning residual hydrochloric acid by using deionized water;
step two: loading of carbon nano toughener
Dispersing carbon nano tubes with the diameter of 10-50nm, the length of 1-50 mu m and the carbon content of more than or equal to 95 percent in cetyl trimethyl ammonium bromide aqueous solution with the concentration of 3g/L to form solution A with the concentration of 3g/L of the carbon nano tubes, then evenly coating the solution A on the foamed nickel treated in the step one, drying the solution A for 6 hours under the pressure of-0.1 MPa, wherein the loading capacity of the carbon nano tubes on the foamed nickel is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing argon gas into the foamed nickel obtained in the step two at-0.1-0.15 MPa in a tubular furnace, heating to 800-1200 ℃, keeping constant temperature, then introducing hydrogen gas to remove impurities on the surface of the foamed nickel, then introducing a mixed gas of methane and hydrogen gas, wherein the flow rate of the mixed gas is 25sccm, the gas flow ratio of the mixed gas to the hydrogen gas is 1:15, continuously keeping constant temperature for growth for 25min, finally introducing argon gas, and cooling to room temperature at the speed of 100 ℃/min to obtain the foamed nickel with the in-situ toughened carbon nano tube;
step four: foamed nickel etching
And (3) soaking the foamed nickel subjected to in-situ toughening by the carbon nano tube obtained in the step three in hydrochloric acid: ferric chloride: deionized water according to a molar volume ratio of 1 mol: 1 mol: 1L of etching solution prepared according to the proportion, keeping the temperature at 60 ℃ for continuously etching for 30h, then cleaning with deionized water until the pH is neutral, and finally drying at 100 ℃ for 3h to obtain the graphene foamed nickel with the in-situ toughened carbon nano tube;
step five: preparing a catalyst;
adding ferric acetylacetonate and benzyl ether into glycol dimethyl ether according to the mass-volume ratio of 1g:1000mL, uniformly stirring, adding oleylamine, and refluxing for 22min at 200 ℃ to obtain a catalyst solution, wherein the volume ratio of oleylamine to benzyl ether is 1: 2000;
step six: catalyst loading
Coating 5ml of catalyst solution on the surface of the graphene foam nickel prepared in the step four, drying for 15min at 60 ℃, repeating the coating and drying operations for 4 times, then placing the obtained product in an atmosphere furnace at 350 ℃ and calcining for 2h under the air condition, and finally naturally cooling to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foamed nickel loaded in the sixth step into a constant-temperature area of a CVD atmosphere furnace, firstly introducing argon, then heating to 750 ℃ at the speed of 10 ℃/min, then introducing methane at the speed of 20mL/min to perform CVD growth of carbon nanotubes, continuing the growth for 20min, and naturally cooling to room temperature to obtain graphene foamed nickel subjected to in-situ toughening of the carbon nanotubes with the surfaces growing the carbon nanotubes in situ, wherein the number of graphene layers is 2-10; the diameter of the carbon nano tube growing on the surface in situ is 3-10nm, and the length is 1-10 mu m;
step eight: preparation of silicon-based active materials
Placing Si powder with the average grain diameter of 0.01-30 mu m in a constant temperature area of a vacuum atmosphere furnace, introducing argon for 0.5h, heating to 1000 ℃, and then continuously introducing a mixed gas of methane and hydrogen for 1h, wherein the volume flow ratio of the methane to the hydrogen is 1:15, switching to argon gas, and naturally cooling to room temperature to obtain the silicon-based active material with the carbon nano tube growing on the surface, wherein the diameter of the carbon nano tube is 3-20nm, and the length of the carbon nano tube is 1-5 mu m;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and sodium carboxymethylcellulose into slurry according to the mass ratio of 6:1, coating the slurry on the graphene foamed nickel material prepared in the step seven, drying at the constant temperature of 80 ℃ for 8 hours, and then compacting under the mechanical pressure of 10MPa to prepare the silicon-carbon composite material, wherein the silicon-carbon composite material comprises the following components in percentage by mass: 95% of graphene foam and 5% of silicon-based active material.
Example 2
The preparation method of the silicon-carbon composite material comprises the following steps:
the method comprises the following steps: copper foam pretreatment
The thickness is 2mm, and the volume density is 5g/cm3Soaking foamy copper with the purity of more than or equal to 90% in 2M hydrochloric acid, ultrasonically cleaning for 20min at 100W, and then cleaning residual hydrochloric acid with deionized water;
step two: loading of carbon nano toughener
Dispersing graphene nanoribbons with the diameter of 10-50nm, the length of 1-50 microns and the carbon content of more than or equal to 95% in lauryl sodium sulfate aqueous solution with the concentration of 3g/L to form a solution A with the concentration of 2g/L of the graphene nanoribbons, then uniformly coating the solution A on the foamy copper treated in the step one, and drying the foamy copper for 5 hours under the pressure of-0.1 MPa, wherein the loading capacity of the graphene nanoribbons on the foamy copper is 2mg/cm2；
Step three: CVD grown graphene foam
Introducing argon gas into the foamy copper obtained in the step two at-0.1-0.15 MPa in a tubular furnace, heating to 800-1200 ℃, keeping constant temperature, then introducing hydrogen gas to remove impurities on the surface of the foamy copper, then introducing mixed gas of ethylene and hydrogen gas, wherein the flow rate of the mixed gas is 25sccm, the gas flow ratio of the mixed gas to the hydrogen gas is 1:15, continuously keeping constant temperature for growth for 25min, finally introducing argon gas, and cooling to room temperature at the speed of 100 ℃/min to obtain graphene nanoribbon in-situ toughened foamy copper;
step four: blister copper etching
And C, soaking the foam copper subjected to in-situ toughening by the graphene nanoribbon obtained in the step three in hydrochloric acid: ferric chloride: deionized water according to a molar volume ratio of 1.5 mol: 1 mol: keeping the temperature at 60 ℃ in 3L of etching solution prepared according to the proportion, continuously etching for 30h, then cleaning with deionized water until the pH is neutral, and finally drying for 3h at 100 ℃ to obtain graphene copper foam with in-situ toughened graphene nanoribbons;
step five: preparing a catalyst;
adding nickel acetylacetonate and dibenzyl ether into diethylene glycol dimethyl ether according to the mass-volume ratio of 1g:1000mL, uniformly stirring, adding oleic acid, and refluxing for 22min at 200 ℃ to obtain a catalyst solution, wherein the volume ratio of the oleic acid to the dibenzyl ether is 1: 2000;
step six: catalyst loading
Coating 5ml of catalyst solution on the surface of the graphene copper foam prepared in the step four, drying for 15min at 60 ℃, repeating the coating and drying operations for 4 times, then placing the obtained product in an atmosphere furnace, calcining for 2h at 350 ℃ under the air condition, and finally naturally cooling to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foamy copper loaded in the sixth step into a constant temperature area of a CVD atmosphere furnace, firstly introducing argon, then heating to 750 ℃ at the speed of 15 ℃/min, then introducing acetylene at the speed of 20mL/min for CVD growth of the carbon nano tube, continuing the growth for 30min, and naturally cooling to room temperature to obtain graphene foamy copper with the surface in-situ grown carbon nano tube and subjected to in-situ toughening of the graphene nano strip, wherein the number of graphene layers is 2-10; the diameter of the carbon nano tube growing on the surface in situ is 3-10nm, and the length is 1-10 mu m;
step eight: preparation of silicon-based active materials
SiO with an average particle diameter of 0.01-30 μmxPlacing the powder in a constant temperature area of a vacuum atmosphere furnace, introducing argon for 0.5h, heating to 1000 ℃, and continuously introducing mixed gas of ethane and hydrogen for 1h, wherein the volume flow ratio of the ethane to the hydrogen is 1: 18, switching to argon gas, and naturally cooling to room temperature to obtain the silicon-based active material with the carbon nano tube growing on the surface, wherein the diameter of the carbon nano tube is 3-20nm, and the length of the carbon nano tube is 1-5 mu m;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and polytetrafluoroethylene into slurry according to the mass ratio of 6:1, coating the slurry on the graphene foam copper material prepared in the step seven, drying the slurry at the constant temperature of 80 ℃ for 8 hours, and then compacting the slurry under the mechanical pressure of 10MPa to prepare the silicon-carbon composite material, wherein the silicon-carbon composite material comprises the following components in percentage by mass: 90% of graphene foam and 10% of silicon-based active material.
Example 3
The preparation method of the silicon-carbon composite material comprises the following steps:
the method comprises the following steps: foam iron pretreatment
The thickness is 5mm, the volume density is 5g/cm3Soaking the foamed iron with the purity of more than or equal to 90% in 2M hydrochloric acid, ultrasonically cleaning for 20min at 100W, and then cleaning the residual hydrochloric acid by using deionized water;
step two: loading of carbon nano toughener
Dispersing carbon nanofibers with the diameter of 10-50nm, the length of 1-50 microns and the carbon content of more than or equal to 95% in a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer aqueous solution with the concentration of 3g/L to form a solution A with the concentration of 3g/L of the carbon nanofibers, then uniformly coating the solution A on the foamed iron treated in the step one, and drying the foamed iron at-0.1 MPa for 6 hours, wherein the loading capacity of the carbon nanofibers on the foamed iron is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing argon gas into the foamed iron obtained in the step two under-0.1-0.15 MPa in a tubular furnace, heating to 800-1200 ℃, keeping constant temperature, then introducing hydrogen gas to remove impurities on the surface of the foamed iron, then introducing a mixed gas of acetylene and hydrogen gas, keeping the flow rate of the mixed gas at 25sccm and the gas flow ratio of the mixed gas to the hydrogen gas at 1:15, continuously keeping constant temperature for growth for 25min, finally introducing argon gas, and cooling to room temperature at the speed of 100 ℃/min to obtain the carbon nanofiber in-situ toughened foamed iron;
step four: foamed iron etching
And C, soaking the foamed iron subjected to the in-situ toughening by the carbon nano fibers obtained in the step three in hydrochloric acid: ferric chloride: deionized water according to a molar volume ratio of 3 mol: 1 mol: keeping the temperature at 60 ℃ in 10L of etching solution prepared according to the proportion, continuously etching for 30h, then cleaning with deionized water until the pH is neutral, and finally drying at 100 ℃ for 3h to obtain the carbon nanofiber in-situ toughened graphene foam iron;
step five: preparing a catalyst;
adding cobalt acetylacetonate and dibenzyl ether into triethylene glycol dimethyl ether according to the mass volume ratio of 1g:1000mL, uniformly stirring, adding oleylamine, and refluxing for 22min at 200 ℃ to obtain a catalyst solution, wherein the volume ratio of oleylamine to dibenzyl ether is 0.1: 100;
step six: catalyst loading
Coating 5ml of catalyst solution on the surface of the graphene foam iron prepared in the fourth step, drying the graphene foam iron at 60 ℃ for 15min, repeating the coating and drying operations for 4 times, then calcining the graphene foam iron in an atmosphere furnace at 350 ℃ for 2h under the air condition, and finally naturally cooling the graphene foam iron to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foam iron loaded in the sixth step into a constant-temperature area of a CVD atmosphere furnace, firstly introducing argon, then heating to 750 ℃ at the speed of 20 ℃/min, then introducing ethylene at the speed of 20mL/min for CVD growth of the carbon nano tube, continuing the growth for 40min, and naturally cooling to room temperature to obtain graphene foam iron with the surface in-situ grown carbon nano tube and subjected to in-situ toughening by carbon nano fibers, wherein the number of graphene layers is 2-10; the diameter of the carbon nano tube growing on the surface in situ is 3-10nm, and the length is 1-10 mu m;
step eight: preparation of silicon-based active materials
Placing Si powder with the average grain diameter of 0.01-30 mu m in a constant temperature area of a vacuum atmosphere furnace, introducing argon for 0.5h, heating to 1000 ℃, and then continuously introducing a mixed gas of methane and hydrogen for 1h, wherein the volume flow ratio of the methane to the hydrogen is 1:30, then switching into argon gas, and naturally cooling to room temperature to obtain the silicon-based active material with the carbon nano tube growing on the surface, wherein the diameter of the carbon nano tube is 3-20nm, and the length of the carbon nano tube is 1-5 mu m;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and polyvinylidene fluoride into slurry according to the mass ratio of 6:1, coating the slurry on the graphene foam iron material prepared in the step seven, drying the slurry at the constant temperature of 80 ℃ for 8 hours, and compacting the slurry under the mechanical pressure of 10MPa to prepare the silicon-carbon composite material, wherein the silicon-carbon composite material comprises the following components in percentage by mass: 50% of graphene foam and 50% of silicon-based active material.
Example 4
The preparation method of the silicon-carbon composite material comprises the following steps:
the method comprises the following steps: pretreatment of foamed aluminium
The thickness is 5mm, the volume density is 5g/cm3Soaking foamed aluminum with the purity of more than or equal to 90 percent in 3M hydrochloric acid, ultrasonically cleaning for 20min at 100W, and then cleaning residual hydrochloric acid by using deionized water;
step two: loading of carbon nano toughener
Dispersing carbon nanofibers with the diameter of 10-50nm, the length of 1-50 microns and the carbon content of more than or equal to 95% in sodium dodecyl benzene sulfonate aqueous solution with the concentration of 3g/L to form solution A with the concentration of 3g/L of the carbon nanofibers, then uniformly coating the solution A on the foamed aluminum treated in the step one, drying the solution A at-0.1 MPa for 6 hours, wherein the loading capacity of the carbon nanofibers on the foamed aluminum is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing argon gas into the foamed aluminum obtained in the step two at-0.1-0.15 MPa in a tubular furnace, heating to 800-1200 ℃, keeping constant temperature, then introducing hydrogen gas to remove impurities on the surface of the foamed aluminum, then introducing a mixed gas of acetylene and hydrogen gas, wherein the flow rate of the mixed gas is 50sccm, the gas flow ratio of the mixed gas to the hydrogen gas is 1:1, continuously keeping constant temperature for growth for 25min, finally introducing argon gas, and cooling to room temperature at the speed of 100 ℃/min to obtain carbon nanofiber in-situ toughened foamed aluminum;
step four: foamed aluminum etching
And (3) soaking the foamed aluminum in-situ toughened by the carbon nano fibers obtained in the step three in hydrochloric acid: aluminum trichloride: deionized water according to a molar volume ratio of 3 mol: 1 mol: keeping the temperature at 60 ℃ in 10L of etching solution prepared according to the proportion, continuously etching for 30h, then cleaning with deionized water until the pH is neutral, and finally drying at 100 ℃ for 3h to obtain the carbon nanofiber in-situ toughened graphene foamed aluminum;
step five: preparing a catalyst;
mixing cobalt acetylacetonate: adding a mixture of nickel acetylacetonate and dibenzyl ether in a mass-volume ratio of 1g to 1000mL into ethylene glycol monomethyl ether, uniformly stirring, adding oleylamine, and refluxing at 200 ℃ for 25min to obtain a catalyst solution, wherein the volume ratio of the oleylamine to the dibenzyl ether is 0.5 to 1000;
step six: catalyst loading
Coating 5ml of catalyst solution on the surface of the graphene foamed aluminum prepared in the step four, drying for 15min at 60 ℃, repeating the coating and drying operations for 4 times, then placing the product in an atmosphere furnace at 350 ℃, calcining for 2h under the air condition, and finally naturally cooling to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foamed aluminum loaded in the sixth step into a constant-temperature area of a CVD atmosphere furnace, firstly introducing argon, then heating to 850 ℃ at the speed of 10 ℃/min, then introducing ethylene at the speed of 20mL/min to perform CVD growth of carbon nanotubes, continuing the growth for 50min, and naturally cooling to room temperature to obtain graphene foamed aluminum with the surface in-situ grown carbon nanotubes subjected to in-situ toughening by carbon nanofibers, wherein the number of graphene layers is 2-10; the diameter of the carbon nano tube growing on the surface in situ is 3-10nm, and the length is 1-10 mu m;
step eight: preparation of silicon-based active materials
Placing Si powder with the average grain diameter of 0.01-30 mu m in a constant temperature area of a vacuum atmosphere furnace, introducing argon for 0.5h, heating to 1000 ℃, and then continuously introducing a mixed gas of acetylene and hydrogen for 1h, wherein the volume flow ratio of the acetylene to the hydrogen is 1:15, switching to argon gas, and naturally cooling to room temperature to obtain the silicon-based active material with the carbon nano tube growing on the surface, wherein the diameter of the carbon nano tube is 3-20nm, and the length of the carbon nano tube is 1-5 mu m;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and styrene-butadiene latex into slurry according to the mass ratio of 6:1, coating the slurry on the graphene foamed aluminum material prepared in the step seven, drying the graphene foamed aluminum material at the constant temperature of 80 ℃ for 8 hours, and then compacting the graphene foamed aluminum material under the mechanical pressure of 10MPa to prepare a silicon-carbon composite material, wherein the silicon-carbon composite material comprises the following components in percentage by mass: 10% of graphene foam and 90% of silicon-based active material.
Example 5
The preparation method of the silicon-carbon composite material comprises the following steps:
the method comprises the following steps: foam nickel pretreatment
The thickness is 2mm, and the volume density is 5g/cm3Soaking foamed nickel with the purity of more than or equal to 90 percent in 2M hydrochloric acid, ultrasonically cleaning for 20min at 100W, and then cleaning residual hydrochloric acid by using deionized water;
step two: loading of carbon nano toughener
Dispersing carbon nano tubes with the diameter of 10-50nm, the length of 1-50 mu m and the carbon content of more than or equal to 95 percent in cetyl trimethyl ammonium bromide aqueous solution with the concentration of 3g/L to form solution A with the concentration of 3g/L of the carbon nano tubes, then evenly coating the solution A on the foamed nickel treated in the step one, drying the solution A for 6 hours under the pressure of-0.1 MPa, wherein the loading capacity of the carbon nano tubes on the foamed nickel is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing argon gas into the foamed nickel obtained in the step two at-0.1-0.15 MPa in a tubular furnace, heating to 800-1200 ℃, keeping constant temperature, then introducing hydrogen gas to remove impurities on the surface of the foamed nickel, then introducing a mixed gas of natural gas and hydrogen gas, wherein the flow rate of the mixed gas is 25sccm, the gas flow ratio of the natural gas to the hydrogen gas is 1:15, continuously keeping constant temperature for growth for 25min, finally introducing argon gas, and cooling to room temperature at the speed of 100 ℃/min to obtain the foamed nickel with the in-situ toughened carbon nano tube;
step four: foamed nickel etching
And (3) soaking the foamed nickel subjected to in-situ toughening by the carbon nano tube obtained in the step three in hydrochloric acid: ferric chloride: deionized water according to a molar volume ratio of 1 mol: 1 mol: 1L of etching solution prepared according to the proportion, keeping the temperature at 60 ℃ for continuously etching for 30h, then cleaning with deionized water until the pH is neutral, and finally drying at 100 ℃ for 3h to obtain the graphene foamed nickel with the in-situ toughened carbon nano tube;
step five: preparing a catalyst;
adding ferric acetylacetonate and benzyl ether into glycol dimethyl ether according to the mass-volume ratio of 1g:1000mL, uniformly stirring, adding oleylamine, and refluxing for 30min at 150 ℃ to obtain a catalyst solution, wherein the volume ratio of oleylamine to benzyl ether is 1: 2000;
step six: catalyst loading
Coating 5ml of catalyst solution on the surface of the graphene foam nickel prepared in the step four, drying for 15min at 60 ℃, repeating the coating and drying operations for 4 times, then placing the obtained product in an atmosphere furnace at 350 ℃ and calcining for 2h under the air condition, and finally naturally cooling to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the nickel foam loaded in the sixth step into a constant-temperature area of a CVD atmosphere furnace, firstly introducing argon, then heating to 900 ℃ at the speed of 15 ℃/min, then introducing natural gas at the speed of 20mL/min for CVD growth of the carbon nano tube, continuing the growth for 60min, and naturally cooling to room temperature to obtain the graphene nickel foam subjected to in-situ toughening by the carbon nano tube and having the surface in-situ grown carbon nano tube, wherein the number of graphene layers is 2-10; the diameter of the carbon nano tube growing on the surface in situ is 3-10nm, and the length is 1-10 mu m;
step eight: preparation of silicon-based active materials
Placing Si powder with the average grain diameter of 0.01-30 mu m in a constant temperature area of a vacuum atmosphere furnace, introducing argon for 0.5h, heating to 1000 ℃, and then continuously introducing a mixed gas of natural gas and hydrogen for 1h, wherein the volume flow ratio of the natural gas to the hydrogen is 1:15, switching to argon gas, and naturally cooling to room temperature to obtain the silicon-based active material with the carbon nano tube growing on the surface, wherein the diameter of the carbon nano tube is 3-20nm, and the length of the carbon nano tube is 1-5 mu m;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and sodium carboxymethylcellulose into slurry according to the mass ratio of 6:1, coating the slurry on the graphene foamed nickel material prepared in the step seven, drying at the constant temperature of 80 ℃ for 8 hours, and then compacting under the mechanical pressure of 10MPa to prepare the silicon-carbon composite material, wherein the silicon-carbon composite material comprises the following components in percentage by mass: 95% of graphene foam and 5% of silicon-based active material.
Example 6
The preparation method of the silicon-carbon composite material comprises the following steps:
the method comprises the following steps: foam iron pretreatment
The thickness is 5mm, the volume density is 5g/cm3Soaking the foamed iron with the purity of more than or equal to 90% in 2M hydrochloric acid, ultrasonically cleaning for 20min at 100W, and then cleaning the residual hydrochloric acid by using deionized water;
step two: loading of carbon nano toughener
Dispersing carbon nanofibers with the diameter of 10-50nm, the length of 1-50 microns and the carbon content of more than or equal to 95% in a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer aqueous solution with the concentration of 3g/L to form a solution A with the concentration of 3g/L of the carbon nanofibers, then uniformly coating the solution A on the foamed iron treated in the step one, and drying the foamed iron at-0.1 MPa for 6 hours, wherein the loading capacity of the carbon nanofibers on the foamed iron is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing argon gas into the foamed iron obtained in the step two at-0.1-0.15 MPa in a tubular furnace, heating to 800-1200 ℃, keeping constant temperature, then introducing hydrogen gas to remove impurities on the surface of the foamed iron, then introducing a mixed gas of water gas and hydrogen gas, wherein the flow rate of the mixed gas is 25sccm, the gas flow ratio of the water gas and the hydrogen gas is 1:15, continuously keeping constant temperature for growth for 25min, finally introducing argon gas, and cooling to room temperature at the speed of 100 ℃/min to obtain carbon nanofiber in-situ toughened foamed iron;
step four: foamed iron etching
And C, soaking the foamed iron subjected to the in-situ toughening by the carbon nano fibers obtained in the step three in hydrochloric acid: ferric chloride: deionized water according to a molar volume ratio of 3 mol: 1 mol: keeping the temperature at 60 ℃ in 10L of etching solution prepared according to the proportion, continuously etching for 30h, then cleaning with deionized water until the pH is neutral, and finally drying at 100 ℃ for 3h to obtain the carbon nanofiber in-situ toughened graphene foam iron;
step five: preparing a catalyst;
adding cobalt acetylacetonate and dibenzyl ether into triethylene glycol dimethyl ether according to the mass volume ratio of 1g:1000mL, uniformly stirring, adding oleylamine, and refluxing for 22min at 200 ℃ to obtain a catalyst solution, wherein the volume ratio of oleylamine to dibenzyl ether is 0.1: 100, respectively;
step six: catalyst loading
Coating 5ml of catalyst solution on the surface of the graphene foam iron prepared in the fourth step, drying the graphene foam iron at 60 ℃ for 15min, repeating the coating and drying operations for 4 times, then calcining the graphene foam iron in an atmosphere furnace at 350 ℃ for 2h under the air condition, and finally naturally cooling the graphene foam iron to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foam iron loaded in the sixth step into a constant-temperature area of a CVD atmosphere furnace, firstly introducing argon, then heating to 650 ℃ at the speed of 15 ℃/min, then introducing water gas at the speed of 20mL/min for CVD growth of carbon nanotubes, continuing the growth for 20min, and naturally cooling to room temperature to obtain graphene foam iron with the surface in-situ grown carbon nanotubes and the number of graphene layers being 2-10, wherein the graphene foam iron is subjected to in-situ toughening by carbon nanofibers; the diameter of the carbon nano tube growing on the surface in situ is 3-10nm, and the length is 1-10 mu m;
step eight: preparation of silicon-based active materials
Putting Si powder with the average grain diameter of 0.01-30 mu m in a constant temperature area of a vacuum atmosphere furnace, introducing argon for 0.5h, heating to 1000 ℃, and continuously introducing a mixed gas of water gas and hydrogen for 1h, wherein the volume flow ratio of the water gas to the hydrogen is 1:30, then switching to argon gas, and naturally cooling to room temperature to obtain the silicon-based active material with the carbon nano tube growing on the surface, wherein the diameter of the carbon nano tube is 3-20nm, and the length of the carbon nano tube is 1-5 mu m;
step nine: preparation of silicon-carbon composite material
And (3) preparing the silicon-based active material prepared in the step eight and polyvinylidene fluoride into slurry according to the mass ratio of 6:1, coating the slurry on the graphene foam iron material prepared in the step seven, drying the slurry at the constant temperature of 80 ℃ for 8 hours, and compacting the slurry under the mechanical pressure of 10MPa to prepare the silicon-carbon composite material, wherein the silicon-carbon composite material comprises the following components in percentage by mass: 50% of graphene foam and 50% of silicon-based active material.
The material obtained in example 1 above was characterized and the results are shown in FIGS. 1-3. FIG. 1 shows that the method successfully grows the carbon nano tube on the surface of the graphene foam in situ; FIG. 2 shows that carbon nanotubes can grow in situ on the surface of silicon powder during the preparation of the silicon-based active material; figure 3 shows that the carbon nano flexibilizer has good toughening effect on the foam metal.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. 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 invention. Thus, the present invention 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. A preparation method of a silicon-carbon composite material for a lithium ion battery is characterized by comprising the following steps:
the method comprises the following steps: metal foam pretreatment
Soaking the metal foam body in 0.1-3M hydrochloric acid, cleaning for 10-30min under 50-100W ultrasonic condition, and then cleaning with deionized water to remove residual hydrochloric acid;
step two: loading of carbon nano toughener
Dispersing the carbon nano toughener in a surfactant aqueous solution with the concentration of 0.1-5g/L to form a solution A with the concentration of 0.1-0.5g/L, then uniformly coating the solution A on the metal foam body treated in the step one, and then drying for 4-8h under the condition of-0.1 MPa, wherein the loading capacity of the carbon nano toughener on the metal foam body is 0.1-5mg/cm2；
Step three: CVD grown graphene foam
Introducing inert gas into the foam obtained in the step two in a tubular furnace under the condition of-0.1-0.15 MPa, heating to 800-;
step four: foam etch
Soaking the foam in situ toughened by the carbon nano toughener obtained in the step three in an etching solution, keeping the temperature at 40-80 ℃ for continuously etching for 12-48h, then cleaning with deionized water until the pH is neutral, and finally drying at 80-120 ℃ for 2-4h to obtain the graphene foam in situ toughened by the carbon nano toughener;
step five: preparing a catalyst;
adding metal organic salt and benzyl ether into polyhydric alcohol according to the mass volume ratio of 1g (200-2000) mL, adding a surfactant after uniformly stirring, and refluxing for 20-30min at the temperature of 150-250 ℃ to obtain a catalyst solution;
step six: catalyst loading
Coating 1-10ml of catalyst solution on the surface of the graphene foam in-situ toughened by the carbon nano flexibilizer prepared in the fourth step, drying for 5-20min at 40-80 ℃, repeating the coating and drying operations for 3-5 times, then calcining for 1-3h in an atmosphere furnace at 250-400 ℃ under the air condition, and finally naturally cooling to room temperature;
step seven: CVD growth of carbon nanotubes
Placing the foam loaded in the sixth step into a constant temperature area of a CVD atmosphere furnace, firstly introducing inert gas, then heating to 600-900 ℃ at the speed of 10-20 ℃/min, then introducing carbon source gas to carry out CVD growth of the carbon nano tube, continuing the growth for 10-60min, and naturally cooling to room temperature to obtain the graphene foam with the surface in-situ grown carbon nano tube and subjected to in-situ toughening by the carbon nano toughening agent;
step eight: preparation of silicon-based active materials
Mixing Si powder or SiOxPlacing the powder in a constant temperature area of a vacuum atmosphere furnace, introducing inert gas for 0.5h, heating to 800-1300 ℃, continuously introducing a mixed gas of carbon source gas and hydrogen for 0.3-2h, and switching to inert gas to naturally cool to room temperature to obtain the silicon-based active material with the carbon nano tube or the carbon nano sheet growing on the surface;
step nine: preparation of silicon-carbon composite material
Preparing the silicon-based active material prepared in the step eight and the binder into slurry according to the mass ratio of (1-9) to 1, coating the slurry on the graphene foam material prepared in the step seven, drying the slurry at the constant temperature of 80 ℃ for 4-12h, and then compacting the slurry under the mechanical pressure of 1-15MPa to prepare the silicon-carbon composite material;
wherein the carbon nano flexibilizer is one of a carbon nano tube, a graphene nano belt or a carbon nano fiber.
2. The method according to claim 1, wherein the metal foam body in the first step is one of nickel foam, copper foam, aluminum foam and iron foam, and has a thickness of 0.1-5.0mm and a bulk density of 0.1-10.0g/cm3The purity is more than or equal to 90 percent.
3. The preparation method of claim 1, wherein the carbon nano-toughener has a diameter of 10-50nm, a length of 1-50 μm and a carbon content of more than or equal to 95%;
the surfactant is one of cetyl trimethyl ammonium bromide, lauryl sodium sulfate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and sodium dodecyl benzene sulfonate.
4. The method according to claim 1, wherein the inert gas in the third, seventh and eighth steps is one or two of argon, high purity nitrogen, helium or radon;
in the third step, the carbon source gas is one or two of methane, ethylene, acetylene, natural gas or water gas.
5. The preparation method according to claim 1, wherein the etching solution in step four is hydrochloric acid: ferric chloride: deionized water according to a molar volume ratio (0.1-3) mol: 1 mol: (0.1-10) L.
6. The preparation method according to claim 1, wherein the metal organic salt in the fifth step is one or a mixture of two of ferric acetylacetonate, nickel acetylacetonate and cobalt acetylacetonate, and the mixing mass ratio of the two is 1: (1-5);
the polyalcohol is one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and ethylene glycol monomethyl ether;
the surfactant is one or a mixture of two of oleylamine and oleic acid, and the volume ratio of the surfactant to the dibenzyl ether is (0.2-1.0): (200-2000).
7. The preparation method according to claim 1, wherein the carbon source gas in the seventh step is a mixed gas of one or two or more of methane, acetylene, ethylene, natural gas or water gas, and the flow rate is 2-30 mL/min;
the obtained graphene foam is few-layer graphene, and the number of graphene layers is 2-10; the diameter of the carbon nano tube grown on the surface in situ is 3-10nm, and the length is 1-10 μm.
8. The method according to claim 1, wherein the carbon source gas in the eighth step is a mixed gas of one or two or more of methane, ethane, acetylene, ethylene, natural gas and water gas, and the volume flow ratio of the carbon source gas to the hydrogen gas is (1:1) - (1: 30);
the Si powder or SiOxThe average particle size of the powder is 0.01-30 μm;
the diameter of the carbon nano tube on the surface of the obtained silicon-based active material is 3-20nm, and the length of the carbon nano tube is 1-5 mu m; the plane size of the carbon nano-sheet is 5-50nm, and the thickness is 1-10 nm.
9. The method according to claim 1, wherein the binder in the ninth step is one of sodium carboxymethylcellulose, polytetrafluoroethylene, polyvinylidene fluoride, or styrene-butadiene latex;
the silicon-carbon composite material comprises the following components in percentage by mass: 10-95% of graphene foam and 5-90% of silicon-based active material.
10. Use of a silicon carbon composite material according to any one of claims 1 to 9 in a solid state battery.
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