CN107425180B - Three-dimensional graphene/silicon composite system, preparation method and application thereof - Google Patents
Three-dimensional graphene/silicon composite system, preparation method and application thereof Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The invention discloses a three-dimensional graphene/silicon composite system, and a preparation method and application thereof. The preparation method can comprise the following steps: compounding a transition metal simple substance and/or a compound containing a transition metal element with silicon nano particles, then reducing the compound at a high temperature in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template/silicon composite system, growing three-dimensional graphene on the composite system by using a chemical vapor deposition method to obtain the three-dimensional graphene/silicon composite system with a catalyst framework, and then carrying out etching treatment to obtain the three-dimensional graphene/silicon composite powder. The three-dimensional graphene/silicon composite system disclosed by the invention is small in volume effect, high in electronic conductivity, strong in flexibility, excellent in heat conduction and mechanical properties, wide in application prospect, simple in preparation process, high in efficiency and suitable for large-scale implementation, and particularly when being applied to a lithium ion battery cathode material, the cycle life and the stability of a battery can be improved under the condition of ensuring the electrode capacity.
Description
Technical Field
The invention particularly relates to a three-dimensional graphene/silicon composite system, a preparation method and application thereof, and belongs to the field of nanotechnology and the field of new energy application.
Background
The silicon material has the highest theoretical specific capacity (4200 mAhg)-1) Moderate lithium-removing/inserting potential (0.02-0.6 Vvs. Li/Li)+) High safety, low cost and environmental protection, and the likeHowever, the silicon cathode still has some problems, such as large volume effect (-320%), low electronic conductivity (-2.5 × 10)-4S·m-1) Etc., thereby limiting its application.
Disclosure of Invention
The invention mainly aims to provide a three-dimensional graphene/silicon composite system, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a three-dimensional graphene/silicon composite system, which comprises the following steps:
compounding a transition metal simple substance and/or a compound containing a transition metal element with silicon nanoparticles, and then carrying out high-temperature reduction at 400-1000 ℃ in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template/silicon composite system;
growing three-dimensional graphene on the three-dimensional porous metal catalyst template/silicon composite system by using a chemical vapor deposition method to obtain a three-dimensional graphene/silicon composite system with a catalyst framework;
and etching the three-dimensional graphene/silicon composite system with the catalyst framework to obtain the three-dimensional graphene/silicon composite powder.
The embodiment of the invention provides a preparation method of a three-dimensional graphene/silicon composite system, which comprises the following steps:
taking a transition metal simple substance and/or a compound containing a transition metal element as a raw material, and carrying out high-temperature reduction at 400-1000 ℃ in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template;
growing three-dimensional graphene on the three-dimensional porous metal catalyst template by using a chemical vapor deposition method to obtain three-dimensional graphene with a catalyst framework;
etching the three-dimensional graphene with the catalyst framework to obtain three-dimensional graphene powder;
and compounding the three-dimensional graphene powder with the silicon nanoparticles to obtain the three-dimensional graphite/silicon composite powder.
The embodiment of the invention also provides a three-dimensional graphene/silicon composite system prepared by any one of the methods.
The embodiment of the invention also provides application of the three-dimensional graphene/silicon composite system, such as application in preparation of lithium ion batteries.
Compared with the prior art, the invention has the advantages that:
(1) the three-dimensional graphene/silicon composite system provided by the invention has the advantages of small volume effect, high electronic conductivity, strong flexibility, excellent heat conduction and mechanical properties, wide application prospect, and capability of prolonging the cycle life and improving the stability of a battery under the condition of ensuring the electrode capacity when being particularly applied to a lithium ion battery cathode material.
(2) The preparation method of the three-dimensional graphene/silicon composite system provided by the invention is simple to operate, high in efficiency and suitable for large-scale implementation.
Drawings
Fig. 1 is a scanning electron microscope image of a three-dimensional graphene/silicon composite system in example 2 of the present invention.
Fig. 2 is a cycle curve diagram of a typical graphene/silicon composite system prepared in examples 1 to 4 of the present invention as a negative electrode of a lithium ion battery.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows. It is to be understood, however, that within the scope of the present invention, various features of the present invention and those specifically described below (e.g., examples) may be combined with one another to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
One aspect of the embodiments of the present invention provides a method for preparing a three-dimensional graphene/silicon composite system, including:
compounding a transition metal simple substance and/or a compound containing a transition metal element with silicon nanoparticles, and then carrying out high-temperature reduction at 400-1000 ℃ in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template/silicon composite system;
growing three-dimensional graphene on the three-dimensional porous metal catalyst template/silicon composite system by using a chemical vapor deposition method to obtain a three-dimensional graphene/silicon composite system with a catalyst framework;
and etching the three-dimensional graphene/silicon composite system with the catalyst framework to obtain the three-dimensional graphene/silicon composite powder.
Further, in the three-dimensional porous metal catalyst template/silicon composite system, the content of silicon nanoparticles is 1wt% -10 wt%, the particle size is 10 nm-200 nm, and the content of metal catalyst is 90wt% -99 wt%.
Another aspect of the embodiments of the present invention provides a method for preparing a three-dimensional graphene/silicon composite system, including:
taking a transition metal simple substance and/or a compound containing a transition metal element as a raw material, and carrying out high-temperature reduction at 400-1000 ℃ in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template;
growing three-dimensional graphene on the three-dimensional porous metal catalyst template by using a chemical vapor deposition method to obtain three-dimensional graphene with a catalyst framework;
etching the three-dimensional graphene with the catalyst framework to obtain three-dimensional graphene powder;
and compounding the three-dimensional graphene powder with the silicon nanoparticles to obtain the three-dimensional graphite/silicon composite powder.
Preferably, the preparation method comprises the following steps: compounding the three-dimensional graphene powder and the silicon nanoparticles in a liquid phase environment, and drying to obtain the three-dimensional graphite/silicon composite powder.
In some embodiments, the transition metal includes a combination of any one or more of Fe, Cu, Co, Ni, Pt, or Ru, but is not limited thereto.
In some embodiments, the transition metal element-containing compound includes any one or a combination of two or more of a transition metal oxide, a transition metal salt, or a transition metal hydrate, but is not limited thereto.
In some preferred embodiments, the chemical vapor deposition method uses a growth temperature of 400 to 1200 ℃, a growth time of 30s to 2h, a growth pressure of 1 torr to 800torr, and a growth atmosphere including hydrogen and/or argon, etc., but is not limited thereto.
Preferably, the growth atmosphere used in the chemical vapor deposition method includes, but is not limited to, hydrogen and/or argon.
Further, the carbon source used in the chemical vapor deposition method includes any one or a combination of solid phase, liquid phase or gas phase carbon source.
Wherein the solid carbon source includes any one or more of polymethyl methacrylate, polyvinylidene fluoride, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polydimethylsiloxane, glucose, sucrose, fructose, or cellulose, and is not limited thereto.
Wherein the liquid-phase carbon source includes any one or a combination of more of methanol, ethanol, propanol or aromatic hydrocarbon, and is not limited thereto.
Wherein the gas phase carbon source includes any one or a combination of more of methane, acetylene, ethylene, ethane, propane, carbon monoxide, or carbon dioxide, and is not limited thereto.
Furthermore, the number of graphene layers grown by the chemical vapor deposition method is 1-20.
In some embodiments, the preparation method may further comprise: under the condition of external assistance, growing and forming the three-dimensional graphene by using a chemical vapor deposition method; the external auxiliary condition includes any one of microwave and plasma conditions, but is not limited thereto.
In some preferred embodiments, the reducing atmosphere comprises hydrogen or hydrogen and an inert gas.
Preferably, the reducing atmosphere is prepared by mixing the following components in a flow ratio of 0-500: 10-1000 of argon and hydrogen.
In some embodiments, the preparation method may further comprise: and compounding the three-dimensional graphene powder, the silicon nano particles, the dispersing agent and the coupling agent in a liquid phase, and drying to obtain the three-dimensional graphite/silicon composite powder.
Further, the preparation method may include: uniformly dispersing silicon nanoparticles in an organic solvent containing a dispersing agent, adding a coupling agent, and fully mixing to form the silicon nanoparticle dispersion liquid. The process can be carried out at room temperature, but can be carried out at other suitable temperatures.
The dispersant can be selected from but not limited to any one or a combination of more than two of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, styrene-butadiene rubber, sodium carboxymethylcellulose, hexadecyl ammonium bromide, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyvinylidene fluoride, polytetrafluoroethylene, Triton-100, Tween and Tego disperss 610 s.
Wherein, the organic solvent can be selected from one or more of isopropyl alcohol, DBE (dibasic ester), ethyl carbitol acetate, butyl carbitol acetate, butyl cellosolve acetate, absolute ethyl alcohol, terpineol, dimethyl succinate, propylene glycol methyl ether acetate, dimethyl glutarate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate, butanol, toluene, xylene and dibutyl phthalate.
Wherein, the coupling agent can be selected from any one or combination of more of but not limited to titanate coupling agent, silane coupling agent or aluminate coupling agent.
In some embodiments, the preparation method may further comprise: and (3) etching the three-dimensional graphene with the catalyst framework by using a wet etching process, such as an etching solution, so as to obtain three-dimensional graphene powder.
The etching solution comprises any one or the combination of more than two of hydrochloric acid, nitric acid, ferric chloride, ferric nitrate, ammonium persulfate, Marble reagent and sulfuric acid. For example, the concentration of the etching solution may be 0.05 to 6M.
Another aspect of an embodiment of the present invention provides a three-dimensional graphene/silicon composite system prepared by any one of the methods described above.
Further, the sheet diameter of the three-dimensional graphene in the composite system is 0.5-50 μm, the thickness is 0.34-10 nm, the porosity is 60-90%, the particle size of the silicon nanoparticles is 10-200 nm, the content of the silicon nanoparticles in the composite system is 10-95 wt%, and the content of the three-dimensional graphene is 1-90 wt%.
Another aspect of the embodiments of the present invention provides a use of the three-dimensional graphene/silicon composite system, for example, a use in preparing a lithium ion battery or a lithium ion battery negative electrode material.
According to another aspect of the embodiment of the invention, a lithium ion battery negative electrode material is provided, which comprises the three-dimensional graphene/silicon composite system.
According to the invention, the two-dimensional graphene sheets are used for forming a three-dimensional network structure (namely three-dimensional graphene) through spatial cross-linking, so that the three-dimensional network structure has excellent electric conductivity, heat conductivity and mechanical properties, and after the two-dimensional graphene sheets are compounded with silicon, the electric conductivity of the silicon can be increased, and the volume effect of the silicon material in the lithium battery cathode circulation process can be effectively limited. When the three-dimensional graphene/silicon composite system is used as an active material and applied to a lithium ion battery cathode, the cycle life and the stability of the battery can be greatly improved under the condition of ensuring the capacity of an electrode.
The technical solution of the present invention will be described in detail below with reference to the specific embodiments and the accompanying drawings.
Example 1: putting 20g of nickel chloride into a tube furnace, keeping the temperature at 600 ℃ for 10 min, and keeping the atmosphere environment as follows: hydrogen gas: 300 sccm, argon: 100 sccm. The tube furnace was then raised to 1000 ℃ and held at 1000 ℃ for 10 min, at which time the atmosphere was: methane: 30 sccm, hydrogen: 200 sccm, argon: 200 sccm. The quartz tube was taken out and cooled to room temperature. With 1MFeCl3and/0.1M HCl is etched to finally obtain the three-dimensional graphene powder. 0.5g of nano silicon powder and 0.05g of polyvinylpyrrolidoneAnd adding ketone and 0.01g of silane coupling agent KH550 into 10g of N-methyl pyrrolidone, carrying out ultrasonic treatment for 1h, immersing the three-dimensional graphene into the solution for 30min, taking out and drying to obtain the three-dimensional graphene/silicon composite system.
Example 2: grinding and mixing 20g of nickel chloride and 0.5g of silicon nanoparticles for 0.5h, then placing the mixture into a tube furnace, keeping the temperature at 600 ℃ for 10 min, and keeping the atmosphere environment as follows: hydrogen gas: 300 sccm, argon: 100 sccm. The tube furnace was then raised to 1000 ℃ and held at 1000 ℃ for 10 min, at which time the atmosphere was: methane: 30 sccm, hydrogen: 200 sccm, argon: 200 sccm. The quartz tube was taken out and cooled to room temperature. And (3) etching by using 3M HCl, washing by using water, and drying to obtain a three-dimensional graphene/silicon composite system (as shown in figure 1).
Example 3: putting 20g of nickel chloride into a tube furnace, keeping the temperature at 600 ℃ for 10 min, and keeping the atmosphere environment as follows: hydrogen gas: 300 sccm, argon: 100 sccm. Then the tube furnace is raised to 800 ℃ and kept for 10 min, and the atmosphere environment is as follows: methane: 30 sccm, hydrogen: 200 sccm, argon: 200 sccm, and a gas pressure of 100 Torr. The quartz tube was taken out and cooled to room temperature. With 1M FeCl3and/0.1M HCl is etched to finally obtain the three-dimensional graphene powder. Adding 0.5g of nano silicon powder, 0.02g of SDS (sodium dodecyl sulfate) and 0.01g of silane coupling agent KH570 into ethanol at room temperature, carrying out ultrasonic treatment for 1h, immersing the three-dimensional graphene into the solution for 30min, taking out, and drying to obtain the three-dimensional graphene/silicon composite system.
Example 4: putting 20g of nickel chloride into a tube furnace, keeping the temperature at 600 ℃ for 10 min, and keeping the atmosphere environment as follows: hydrogen gas: 300 sccm, argon: 100 sccm. Then the tube furnace is raised to 900 ℃ and kept at 900 ℃ for 10 min, and the atmosphere environment is as follows: methane: 30 sccm, hydrogen: 200 sccm, argon: 200 sccm. The quartz tube was taken out and cooled to room temperature. And etching by using 3M HCl, and washing by using water to finally obtain the three-dimensional graphene powder. Adding 1g of nano silicon powder and 0.01g of titanate coupling agent into N, N-dimethylacetamide at room temperature, carrying out ultrasonic treatment for 1h, immersing the three-dimensional graphene into the solution for 30min, taking out and drying to obtain a three-dimensional graphene/silicon composite system.
Using the typical three-dimensional graphene prepared in examples 1-4 aboveThe silicon/lithium composite system product is used as a lithium ion battery cathode material, a cathode plate is prepared by taking foamed nickel as a current collector, the anode adopts a lithium plate, and 1mol/L LiPF is used6The three-component mixed solvent of (1) EC: DMC: EMC 1: 1: the CR2016 simulated battery is assembled by taking the 1, v/v solution as electrolyte and the polypropylene microporous membrane as a diaphragm. The cycle performance test uses a current of 0.1A/g to carry out a constant current charge and discharge experiment, the charge and discharge voltage is limited to 0-2.5V, and the test result is shown in figure 2 under the normal temperature condition.
It should be understood that the technical content and technical features of the present invention have been disclosed as above, however, those skilled in the art may still make various substitutions and modifications based on the teaching and disclosure of the present invention without departing from the spirit of the present invention, therefore, the scope of the present invention should not be limited to the disclosure of the embodiments, but should include various substitutions and modifications without departing from the present invention, and are covered by the claims of the present patent application.
Claims (16)
1. A preparation method of a three-dimensional graphene/silicon composite system is characterized by comprising the following steps:
compounding a transition metal simple substance and/or a compound containing a transition metal element with silicon nanoparticles, and then carrying out high-temperature reduction at 400-1000 ℃ in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template/silicon composite system, wherein the content of the silicon nanoparticles in the three-dimensional porous metal catalyst template/silicon composite system is 1-10 wt%, the content of a metal catalyst is 90-99 wt%, the particle size of the silicon nanoparticles is 10-200 nm, the transition metal is selected from Fe, Cu, Co, Ni, Pt or Ru, and the compound containing the transition metal element is selected from any one or combination of more than two of transition metal oxides, transition metal salts or transition metal hydrates;
growing three-dimensional graphene on the three-dimensional porous metal catalyst template/silicon composite system by using a chemical vapor deposition method under an external auxiliary condition to obtain the three-dimensional graphene/silicon composite system with the catalyst framework, wherein the chemical vapor deposition method adopts a growth temperature of 400-1200 ℃, a growth time of 30 s-2 h, a growth pressure of 1-800 torr and a growth atmosphere comprising hydrogen and/or argon, and the external auxiliary condition is selected from any one of microwave and plasma conditions;
and etching the three-dimensional graphene/silicon composite system with the catalyst framework to obtain the three-dimensional graphene/silicon composite system, wherein the sheet diameter of the three-dimensional graphene in the composite system is 0.5-50 mu m, the thickness is 0.34-10 nm, the porosity is 60-90%, the particle size of the silicon nanoparticles is 10-200 nm, the content of the silicon nanoparticles in the composite system is 10-95 wt%, and the content of the three-dimensional graphene is 1-90 wt%.
2. A preparation method of a three-dimensional graphene/silicon composite system is characterized by comprising the following steps:
taking a transition metal simple substance and/or a transition metal element-containing compound as a raw material, and carrying out high-temperature reduction at 400-1000 ℃ in a reducing atmosphere to prepare a three-dimensional porous metal catalyst template, wherein the transition metal is selected from Fe, Cu, Co, Ni, Pt or Ru, and the transition metal element-containing compound is selected from any one or a combination of more than two of transition metal oxides, transition metal salts or transition metal hydrates;
growing three-dimensional graphene on the three-dimensional porous metal catalyst template by using a chemical vapor deposition method under an external auxiliary condition to obtain the three-dimensional graphene with a catalyst framework, wherein the chemical vapor deposition method adopts a growth temperature of 400-1200 ℃, a growth time of 30 s-2 h, a growth pressure of 1-800 torr and a growth atmosphere comprising hydrogen and/or argon, and the external auxiliary condition is selected from any one of microwave and plasma conditions;
etching the three-dimensional graphene with the catalyst framework to obtain three-dimensional graphene powder;
uniformly mixing silicon nanoparticles and a coupling agent in an organic solvent to form a silicon nanoparticle dispersion liquid, uniformly mixing the three-dimensional graphene powder with the silicon nanoparticle dispersion liquid, and drying to obtain a three-dimensional graphene/silicon composite system, wherein the coupling agent is any one or the combination of more than two of titanate coupling agent, silane coupling agent or aluminate coupling agent;
the sheet diameter of the three-dimensional graphene in the composite system is 0.5-50 mu m, the thickness is 0.34-10 nm, the porosity is 60-90%, the particle size of the silicon nanoparticles is 10-200 nm, the content of the silicon nanoparticles in the composite system is 10-95 wt%, and the content of the three-dimensional graphene is 1-90 wt%.
3. The method of claim 2, wherein: the carbon source adopted in the chemical vapor deposition method is selected from a solid phase carbon source, a liquid phase carbon source or a gas phase carbon source.
4. The production method according to claim 3, characterized in that: the solid-phase carbon source is selected from one or more of polymethyl methacrylate, polyvinylidene fluoride, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polydimethylsiloxane, glucose, sucrose, fructose and cellulose.
5. The production method according to claim 3, characterized in that: the liquid-phase carbon source is selected from any one or a combination of more than two of methanol, ethanol, propanol or aromatic hydrocarbon.
6. The production method according to claim 3, characterized in that: the gas phase carbon source is selected from any one or the combination of more than two of methane, acetylene, ethylene, ethane, propane, carbon monoxide or carbon dioxide.
7. The production method according to claim 3, characterized in that: the number of graphene layers grown by the chemical vapor deposition method is 1-20.
8. The production method according to claim 1 or 2, characterized in that: the reducing atmosphere is selected from hydrogen or hydrogen and inert gases.
9. The method according to claim 8, wherein the reducing atmosphere is prepared by mixing a mixture of a reducing gas and a reducing gas at a flow ratio of 0to 500: 10-1000 of argon and hydrogen.
10. The method of claim 2, further comprising: uniformly dispersing silicon nanoparticles in an organic solvent containing a dispersing agent, adding a coupling agent, and fully mixing to form the silicon nanoparticle dispersion liquid.
11. The method of manufacturing according to claim 10, wherein: the dispersing agent is selected from one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, styrene butadiene rubber, sodium carboxymethylcellulose, hexadecyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylidene fluoride, polytetrafluoroethylene, Triton-100, Tween and Tego Dispers610 s.
12. The method of manufacturing according to claim 10, wherein: the organic solvent is selected from one or a combination of more than two of isopropanol, DBE, ethyl carbitol acetate, butyl carbitol acetate, butyl cellosolve acetate, absolute ethyl alcohol, terpineol, dimethyl succinate, propylene glycol methyl ether acetate, dimethyl glutarate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate, butanol, toluene, xylene and dibutyl phthalate.
13. The production method according to claim 1, characterized by comprising: and etching the three-dimensional graphene with the catalyst framework by using an etching solution to obtain three-dimensional graphene powder.
14. The method according to claim 13, wherein the etching solution is selected from any one or a combination of two or more of hydrochloric acid, nitric acid, ferric chloride, ferric nitrate, ammonium persulfate, Marble's reagent, and sulfuric acid.
15. Use of the three-dimensional graphene/silicon composite system prepared by the method of any one of claims 1 to 14 for preparing a lithium ion battery or a lithium ion battery negative electrode material.
16. A lithium ion battery negative electrode material, characterized by comprising the three-dimensional graphene/silicon composite system prepared by the method of any one of claims 1 to 14.
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| GB201818232D0 (en) | 2018-11-08 | 2018-12-26 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| GB201818235D0 (en) | 2018-11-08 | 2018-12-26 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| GB2580033B (en) | 2018-12-19 | 2021-03-10 | Nexeon Ltd | Electroactive materials for metal-Ion batteries |
| US11905593B2 (en) | 2018-12-21 | 2024-02-20 | Nexeon Limited | Process for preparing electroactive materials for metal-ion batteries |
| US10508335B1 (en) | 2019-02-13 | 2019-12-17 | Nexeon Limited | Process for preparing electroactive materials for metal-ion batteries |
| CN110518196A (en) * | 2019-07-11 | 2019-11-29 | 高芳 | A kind of negative electrode material of lithium battery |
| CN110474037B (en) * | 2019-08-30 | 2021-08-31 | 石家庄尚太科技股份有限公司 | Preparation method of porous silicon-carbon composite negative electrode material |
| US10964940B1 (en) | 2020-09-17 | 2021-03-30 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| CN111554928A (en) * | 2020-04-03 | 2020-08-18 | 新奥石墨烯技术有限公司 | Graphene-based composite material and preparation method and application thereof |
| CN113497223A (en) * | 2020-04-08 | 2021-10-12 | 广州维思新能源有限公司 | Preparation method of porous carbon layer structure coated with graphene nano-silicon composite material |
| CN117059790B (en) * | 2023-10-12 | 2024-03-26 | 中国科学院宁波材料技术与工程研究所 | Integrated battery assembly and preparation method and application thereof |
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