CN115799459A - Production process of graphene modified metal electrode - Google Patents
Production process of graphene modified metal electrode Download PDFInfo
- Publication number
- CN115799459A CN115799459A CN202310065368.5A CN202310065368A CN115799459A CN 115799459 A CN115799459 A CN 115799459A CN 202310065368 A CN202310065368 A CN 202310065368A CN 115799459 A CN115799459 A CN 115799459A
- Authority
- CN
- China
- Prior art keywords
- substrate layer
- metal electrode
- hydrogen
- heating
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 94
- 239000000758 substrate Substances 0.000 claims abstract description 80
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 66
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- 239000002346 layers by function Substances 0.000 claims abstract description 41
- 239000010453 quartz Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052786 argon Inorganic materials 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000004381 surface treatment Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 19
- 241000252506 Characiformes Species 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000000861 blow drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- AHBDJJPEQJQYMC-UHFFFAOYSA-N ethanol nickel(2+) dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] AHBDJJPEQJQYMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 34
- 238000000151 deposition Methods 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a production process of a graphene modified metal electrode, which comprises the following steps: s1, preparing a base layer; step S2, preparing a functional layer: s3, surface treatment; s4, placing molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube for molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and preserving heat for 40min to obtain a graphene modified metal electrode; the molybdenum trioxide nanosheets are deposited, and the large gaps among lattice layers of the molybdenum trioxide nanosheets enable the molybdenum trioxide nanosheets to be capable of rapidly inserting lithium ions and have high lithium storage capacity.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a production process of a graphene modified metal electrode.
Background
In the prior art, the conductive performance of the lithium battery electrode is generally enhanced by coating graphene on the surface of the substrate electrode. Firstly coating a graphene material on the surface of a substrate electrode, then coating a layer of adhesive on the surface of the substrate electrode, and solidifying the adhesive to fix the graphene material on the surface of the substrate electrode, thereby preparing the graphene modified substrate electrode. However, in the process of coating the adhesive, part of graphene coated on the surface of the substrate electrode is separated from the substrate electrode and directly suspended in the adhesive, and the graphene suspended in the adhesive is not in contact with the substrate electrode, i.e., cannot store charges, so that the utilization rate of the graphene is low, and the conductivity of the substrate electrode cannot be obviously improved.
Layered MoO 3 The application of the nano material as an electrode on a lithium ion battery is also receiving wide attention. Apparently, moO 3 The large gaps between the crystal lattice layers of the nano-sheets enable the lithium ion insertion to be rapidly carried out and have high lithium storage capacity.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide a production process of a graphene modified metal electrode.
The purpose of the invention can be realized by the following technical scheme:
a production process of a graphene modified metal electrode comprises the following steps:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, controlling the flow rate of the argon to be 200sccm and the flow rate of the hydrogen to be 20sccm, heating to 900 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, and preparing a substrate layer, wherein the use amount of the absolute ethyl alcohol is 8 percent of the weight of the foamed nickel;
in the step S1, taking foamed nickel as a substrate and absolute ethyl alcohol as a carbon source, and depositing a graphene layer on the surface of the foamed nickel to form a substrate layer which is foamed nickel composite graphene;
step S2, preparing a functional layer: immersing the prepared substrate layer into the solution a, taking out after soaking for 5min, airing, putting into a quartz tube, transferring into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen, controlling the flow rate of the argon to be 60sccm and the flow rate of the hydrogen to be 20sccm, heating to 750 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 40min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, forming a functional layer on the surface of the substrate layer, and controlling the dosage ratio of the substrate layer, the solution a and the absolute ethyl alcohol to be 1-2 g: 10 mL: 2mL;
in the step S2, a carbon nano tube layer is deposited again through a chemical vapor deposition method, and the conductivity is improved through the synergistic effect of the graphene and the carbon nano tube layer;
step S3, surface treatment: washing the substrate layer compounded with the functional layer by using deionized water, then placing the substrate layer in absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, then carrying out blow-drying by using nitrogen, placing the substrate layer in piranha etching solution, heating to 95 ℃, carrying out heat preservation treatment for 1h, taking out the substrate layer after the treatment is finished, carrying out blow-drying by using nitrogen after cleaning for later use, and controlling the weight ratio of the substrate layer compounded with the functional layer to the piranha etching solution to be 1: 50-70;
in the step S3, the surface treatment is carried out on the substrate layer compounded with the functional layer through piranha etching liquid, and the carboxylation is carried out on the surface of the formed functional layer, so that the subsequent reaction nucleation and deposition are facilitated;
s4, putting molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube for molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and preserving heat for 40min to prepare a graphene modified metal electrode, wherein the dosage ratio of the molybdenum trioxide powder to the substrate layer compounded with the functional layer is controlled to be 0.05-0.06 g: 1g;
step S4, taking molybdenum trioxide as a precursor, taking a substrate layer compounded with a functional layer as a deposition matrix, and depositing a nano molybdenum trioxide sheet on the surface of the functional layer by a chemical vapor deposition method to form a graphene modified metal electrode which is a multilayer structure electrode material;
further, the solution a is formed by mixing polyethylene glycol and 15% by mass of ethanol solution of nickel nitrate according to the weight ratio of 5-8: 100.
The invention has the beneficial effects that:
the invention discloses a graphene modified metal electrode, which is prepared by taking foamed nickel as a substrate, taking absolute ethyl alcohol as a carbon source, depositing a graphene layer on the surface of the foamed nickel to form a substrate layer which is foamed nickel composite graphene, then depositing a carbon nanotube layer by a chemical vapor deposition method again, improving the conductivity by the synergistic effect of the graphene and the carbon nanotube layer, then taking molybdenum trioxide as a precursor, using the substrate layer compounded with a functional layer as a deposition substrate, depositing a nano molybdenum trioxide sheet on the surface of the functional layer by the chemical vapor deposition method to form the graphene modified metal electrode which is a multilayer structure electrode material, firstly taking the foamed metal nickel as the substrate, depositing the graphene layer, depositing a large amount of graphene by a special structure of the foamed nickel to form a three-dimensional structure, then depositing the carbon nanotube, reducing the stacking of the graphene by using CNTs, increasing the specific surface area of the material, fully utilizing the excellent performances of the graphene and the carbon nanotube by compounding, providing an electronic transmission channel, improving the conductivity of the material, inhibiting the stacking of the graphene, increasing the specific surface area of the material, enabling the composite material to have better mechanical performance and finally the molybdenum trioxide performance, enabling the nanosheet to be inserted into a large electric lattice space for lithium storage.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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
A production process of a graphene modified metal electrode comprises the following steps:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, controlling the flow rate of the argon to be 200sccm and the flow rate of the hydrogen to be 20sccm, heating to 900 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, and preparing a substrate layer, wherein the use amount of the absolute ethyl alcohol is 8 percent of the weight of the foamed nickel;
step S2, preparing a functional layer: immersing the prepared substrate layer into the solution a, taking out after soaking for 5min, airing, putting into a quartz tube, transferring into a tubular furnace in a CVD system, vacuumizing, introducing argon and hydrogen, controlling the flow rate of the argon to be 60sccm and the flow rate of the hydrogen to be 20sccm, heating to 750 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 40min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, forming a functional layer on the surface of the substrate layer, and controlling the dosage ratio of the substrate layer, the solution a and the absolute ethyl alcohol to be 1 g: 10 mL: 2mL;
the solution a is formed by mixing polyethylene glycol and 15% by mass of nickel nitrate ethanol solution according to the weight ratio of 5: 100.
Step S3, surface treatment: washing the substrate layer compounded with the functional layer by deionized water, placing the substrate layer in absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, then carrying out blow-drying by nitrogen, placing the substrate layer in piranha etching solution, heating to 95 ℃, carrying out heat preservation treatment for 1h, taking out the substrate layer after the treatment is finished, carrying out blow-drying by nitrogen after cleaning for later use, and controlling the weight ratio of the substrate layer compounded with the functional layer to the piranha etching solution to be 1: 50;
and S4, putting the molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube for the molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and preserving the temperature for 40min to prepare the graphene modified metal electrode, wherein the using amount ratio of the molybdenum trioxide powder to the substrate layer compounded with the functional layer is controlled to be 0.056 g: 1g.
Example 2
A production process of a graphene modified metal electrode comprises the following steps:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, controlling the flow rate of the argon to be 200sccm and the flow rate of the hydrogen to be 20sccm, heating to 900 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, and preparing a substrate layer, wherein the use amount of the absolute ethyl alcohol is 8 percent of the weight of the foamed nickel;
step S2, preparing a functional layer: immersing the prepared substrate layer into the solution a, taking out after soaking for 5min, airing, putting into a quartz tube, transferring into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen, controlling the flow rate of the argon to be 60sccm and the flow rate of the hydrogen to be 20sccm, heating to 750 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 40min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, forming a functional layer on the surface of the substrate layer, and controlling the dosage ratio of the substrate layer, the solution a and the absolute ethyl alcohol to be 1.5 g: 10 mL: 2mL;
the solution a is formed by mixing polyethylene glycol and 15% by mass of nickel nitrate ethanol solution according to the weight ratio of 6: 100.
Step S3, surface treatment: washing the substrate layer compounded with the functional layer by deionized water, placing the substrate layer in absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, then carrying out blow-drying by nitrogen, placing the substrate layer in piranha etching solution, heating to 95 ℃, carrying out heat preservation treatment for 1h, taking out the substrate layer after the treatment is finished, carrying out blow-drying by nitrogen after cleaning for later use, and controlling the weight ratio of the substrate layer compounded with the functional layer to the piranha etching solution to be 1: 60;
and S4, putting the molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube of the molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and preserving the temperature for 40min to prepare the graphene modified metal electrode, wherein the using amount ratio of the molybdenum trioxide powder to the substrate layer compounded with the functional layer is controlled to be 0.06 g: 1g.
Example 3
A production process of a graphene modified metal electrode comprises the following steps:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, controlling the flow rate of the argon to be 200sccm and the flow rate of the hydrogen to be 20sccm, heating to 900 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, and preparing a substrate layer, wherein the use amount of the absolute ethyl alcohol is 8 percent of the weight of the foamed nickel;
step S2, preparing a functional layer: immersing the prepared substrate layer into the solution a, taking out after soaking for 5min, airing, putting into a quartz tube, transferring into a tubular furnace in a CVD system, vacuumizing, introducing argon and hydrogen, controlling the flow rate of the argon to be 60sccm and the flow rate of the hydrogen to be 20sccm, heating to 750 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 40min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, forming a functional layer on the surface of the substrate layer, and controlling the dosage ratio of the substrate layer, the solution a and the absolute ethyl alcohol to be 2 g: 10 mL: 2mL;
the solution a is formed by mixing polyethylene glycol and 15% by mass of nickel nitrate ethanol solution according to the weight ratio of 8: 100.
Step S3, surface treatment: washing the substrate layer compounded with the functional layer by using deionized water, then placing the substrate layer in absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, then carrying out blow-drying by using nitrogen, placing the substrate layer in piranha etching solution, heating to 95 ℃, carrying out heat preservation treatment for 1h, taking out the substrate layer after the treatment is finished, carrying out blow-drying by using nitrogen after cleaning for later use, and controlling the weight ratio of the substrate layer compounded with the functional layer to the piranha etching solution to be 1: 70;
and S4, putting the molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube for molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and keeping the temperature for 40min to obtain the graphene modified metal electrode, wherein the using amount ratio of the molybdenum trioxide powder to the substrate layer compounded with the functional layer is controlled to be 0.06 g: 1g.
Comparative example 1
In comparison with example 1, in comparative example 1, carbon nanotubes were not deposited, and the preparation method was as follows:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, controlling the flow rate of the argon to be 200sccm and the flow rate of the hydrogen to be 20sccm, heating to 900 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, and taking out to obtain a substrate layer;
step S2, surface treatment: washing the basal layer with deionized water, placing the washed basal layer in absolute ethyl alcohol, ultrasonically oscillating for 10min, then drying the basal layer with nitrogen, placing the basal layer in piranha etching solution, heating to 95 ℃, carrying out heat preservation treatment for 1h, taking out the basal layer after the treatment is finished, cleaning the basal layer, and drying the basal layer with nitrogen for later use, wherein the weight ratio of the basal layer to the piranha etching solution is controlled to be 1: 50;
and S3, putting the molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube for the molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and preserving the temperature for 40min to prepare the graphene modified metal electrode, wherein the using amount ratio of the molybdenum trioxide powder to the substrate layer compounded with the functional layer is controlled to be 0.056 g: 1g.
Comparative example 2
Compared with example 1, in the comparative example 1, molybdenum trioxide nanosheets are not deposited, and the preparation method is as follows:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, controlling the flow rate of the argon to be 200sccm and the flow rate of the hydrogen to be 20sccm, heating to 900 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, and taking out to obtain a substrate layer;
step S2, preparing a functional layer: immersing the prepared substrate layer into the solution a, taking out after 5min of immersion, airing, placing into a quartz tube, transferring into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen, controlling the flow rate of the argon to be 60sccm and the flow rate of the hydrogen to be 20sccm, heating to 750 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 40min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, and preparing the graphene modified metal electrode, wherein the dosage ratio of the substrate layer, the solution a and the absolute ethyl alcohol is controlled to be 1 g: 10 mL: 2mL;
the solution a is formed by mixing polyethylene glycol and 15% by mass of nickel nitrate ethanol solution according to the weight ratio of 5: 100.
Comparative example 3
The comparative example is a conventional method for preparing a graphene modified metal electrode, and the method comprises the following steps:
dissolving graphene powder in ethanol to prepare a graphene solution;
carrying out magnetization treatment on the iron oxide electrode to obtain the iron oxide electrode with magnetic adsorption capacity;
immersing the iron oxide electrode with the magnetic adsorption capacity in the graphene solution, and obtaining the iron oxide electrode with the surface adsorbed with graphene after 12 min;
and wrapping the iron oxide electrode with the graphene adsorbed on the surface by adopting a polypropylene membrane to obtain the graphene modified iron oxide electrode.
And (3) performance testing:
mixing LiPF 6 With Ethylene Carbonate (EC) and diethyl carbonate (DEC) to form LiPF 6 A1.0 mol/L solution (wherein the volume ratio of EC to DEC is 1: 1) was used to obtain a nonaqueous electrolytic solution. The obtained positive electrode, separator layer Polyethylene (PE), negative electrodes prepared in examples 1 to 3 and comparative examples 1 to 3 were stacked in this order by a winder to form an electrode group wound in a spiral shape, and the electrode group was placed in a battery can having an opening at one end and injected in an amount of 3.8g/AhAdding the non-aqueous electrolyte, and sealing to obtain the lithium battery.
The battery capacity testing method comprises the following steps: charging in a constant voltage charging mode, limiting the current to 0.1C (65 mA), and stopping the voltage to 4.4V; the discharge was performed by a constant current discharge method, the discharge current was 1C (650 mA), and the cut-off voltage of the discharge was 3.0 v, and the results are shown in table 1 below:
TABLE 1
It can be seen from table 1 above that the batteries prepared in examples 1-3 of the present invention have greater capacity and cycling performance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A production process of a graphene modified metal electrode is characterized by comprising the following steps:
step S1, preparing a basal layer: cleaning the surface of the foamed nickel, putting the cleaned foamed nickel into a quartz tube, pushing the quartz tube into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen into the tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 30min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, and taking out the mixture to obtain a substrate layer;
step S2, preparing a functional layer: immersing the prepared substrate layer into the solution a, taking out after soaking for 5min, airing, putting into a quartz tube, transferring into a tube furnace in a CVD system, vacuumizing, introducing argon and hydrogen, heating to 750 ℃ at the heating rate of 10 ℃/min, injecting absolute ethyl alcohol, carrying out heat preservation reaction for 40min, stopping introducing the hydrogen after the reaction is finished, cooling to room temperature, taking out, and forming a functional layer on the surface of the substrate layer;
step S3, surface treatment: washing the substrate layer compounded with the functional layer by using deionized water, then placing the substrate layer in absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, then carrying out blow-drying by using nitrogen, placing the substrate layer in piranha etching solution, heating to 95 ℃, carrying out heat preservation treatment for 1h, taking out the substrate layer after the treatment is finished, cleaning, and carrying out blow-drying by using nitrogen for later use;
and S4, putting the molybdenum trioxide powder into a quartz tube under the pressure of 100Pa and the argon flow of 100sccm, transferring the quartz tube into a tubular furnace in a CVD system, placing the surface-treated substrate layer compounded with the functional layer at the position 15cm away from the outlet of the furnace tube for molybdenum trioxide powder, heating to 850 ℃ at the heating rate of 20 ℃/min, and preserving the heat for 40min to obtain the graphene modified metal electrode.
2. The process of claim 1, wherein in step S1, the flow rate of argon is controlled to be 200 seem, and the flow rate of hydrogen is controlled to be 20 seem.
3. The process of claim 1, wherein in step S2, the flow rate of argon is controlled to be 60 seem, and the flow rate of hydrogen is controlled to be 20 seem.
4. The process for producing a graphene-modified metal electrode according to claim 1, wherein the ratio of the amount of the substrate layer, the solution a and the absolute ethyl alcohol in step S2 is controlled to be 1-2 g: 10 mL: 2mL.
5. The production process of the graphene modified metal electrode according to claim 4, wherein the solution a is prepared by mixing polyethylene glycol and 15% by mass of nickel nitrate ethanol solution according to a weight ratio of 5-8: 100.
6. The production process of the graphene modified metal electrode according to claim 1, wherein the weight ratio of the substrate layer compounded with the functional layer and the piranha etching solution is controlled to be 1: 50-70 in the step S3.
7. The process for producing a graphene-modified metal electrode according to claim 1, wherein in step S4, the amount ratio of the molybdenum trioxide powder to the substrate layer having the composite functional layer is controlled to be 0.05-0.06 g: 1g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310065368.5A CN115799459A (en) | 2023-02-06 | 2023-02-06 | Production process of graphene modified metal electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310065368.5A CN115799459A (en) | 2023-02-06 | 2023-02-06 | Production process of graphene modified metal electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115799459A true CN115799459A (en) | 2023-03-14 |
Family
ID=85429911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310065368.5A Pending CN115799459A (en) | 2023-02-06 | 2023-02-06 | Production process of graphene modified metal electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115799459A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| CN104726936A (en) * | 2015-03-27 | 2015-06-24 | 扬州大学 | Method for preparing orthogonal-phase MoO3 monocrystal nanosheet through chemical vapor deposition |
| CN105621487A (en) * | 2016-03-03 | 2016-06-01 | 广东工业大学 | Preparation method of molybdenum trioxide thin film and prepared photoelectric device |
| CN109065874A (en) * | 2018-08-22 | 2018-12-21 | 深圳市创世达实业有限公司 | A kind of MoO3/ rGO-N nanocomposite and its preparation method and application |
| CN112510187A (en) * | 2020-11-30 | 2021-03-16 | 中南大学 | Electrostatic self-assembly spherical molybdenum trioxide/MXene composite material and preparation method and application thereof |
| CN113299924A (en) * | 2021-06-03 | 2021-08-24 | 哈尔滨理工大学 | Preparation method and application of carbon nanotube/molybdenum oxide integrated array electrode material |
| CN115058699A (en) * | 2022-05-16 | 2022-09-16 | 西安电子科技大学 | Monolayer molybdenum disulfide based on chemical vapor deposition and preparation method thereof |
-
2023
- 2023-02-06 CN CN202310065368.5A patent/CN115799459A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| CN104726936A (en) * | 2015-03-27 | 2015-06-24 | 扬州大学 | Method for preparing orthogonal-phase MoO3 monocrystal nanosheet through chemical vapor deposition |
| CN105621487A (en) * | 2016-03-03 | 2016-06-01 | 广东工业大学 | Preparation method of molybdenum trioxide thin film and prepared photoelectric device |
| CN109065874A (en) * | 2018-08-22 | 2018-12-21 | 深圳市创世达实业有限公司 | A kind of MoO3/ rGO-N nanocomposite and its preparation method and application |
| CN112510187A (en) * | 2020-11-30 | 2021-03-16 | 中南大学 | Electrostatic self-assembly spherical molybdenum trioxide/MXene composite material and preparation method and application thereof |
| CN113299924A (en) * | 2021-06-03 | 2021-08-24 | 哈尔滨理工大学 | Preparation method and application of carbon nanotube/molybdenum oxide integrated array electrode material |
| CN115058699A (en) * | 2022-05-16 | 2022-09-16 | 西安电子科技大学 | Monolayer molybdenum disulfide based on chemical vapor deposition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| GHUZANFAR SAEED ET AL.: "Fabrication of 3D graphene-CNTs/α-MoO3 hybrid film as an advance electrode material for asymmetric supercapacitor with excellent energy density and cycling life" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7311169B2 (en) | Structurally controlled deposition of silicon on nanowires | |
| KR102533003B1 (en) | Silicon carbon composite material and manufacturing method thereof | |
| TW535313B (en) | Anode for secondary battery and secondary battery therewith | |
| JP5594656B2 (en) | Method for producing positive electrode material of lithium ion secondary battery | |
| JP6034621B2 (en) | Electrode of power storage device and power storage device | |
| CN108417798B (en) | ZnO nanosheet/carbon sponge flexible composite negative electrode material and preparation method thereof | |
| Guan et al. | A novel hollowed CoO-in-CoSnO 3 nanostructure with enhanced lithium storage capabilities | |
| CN104393233B (en) | Graphene array-based carbon-sulfur composite electrode and secondary cell | |
| CN114420938B (en) | Metal oxide amorphous carbon coated hard carbon composite material and preparation method and application thereof | |
| CN108735969A (en) | Negative electrode of lithium ion battery and flexible lithium ion battery | |
| CN108172781A (en) | A kind of Si-C composite material of Argent grain doping and its preparation method and application | |
| CN110416537B (en) | Lithium titanate composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN110767891B (en) | Preparation method of porous spherical silicon-based composite anode material | |
| CN112875680B (en) | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array | |
| Karimzadeh et al. | Emerging atomic layer deposition for the development of high-performance lithium-ion batteries | |
| CN112366299A (en) | Preparation method of graphite-silicon-based lithium ion battery negative electrode material and product thereof | |
| KR101274829B1 (en) | Secondary battery having lifetime improved | |
| KR101317812B1 (en) | Core-shell nano-structure, method of fabricating the same and lithium ion battery | |
| WO2015029128A1 (en) | Negative electrode active material, negative electrode mixture using same, negative electrode and lithium ion secondary battery | |
| KR101284025B1 (en) | Anode Materials for Secondary Batteries and Method Producing the Same | |
| CN112670501A (en) | Negative electrode material, preparation method of negative electrode material and lithium battery | |
| CN111883761A (en) | Silicon graphene composite lithium battery negative electrode material and preparation method thereof | |
| CN115799459A (en) | Production process of graphene modified metal electrode | |
| Shen et al. | Li⁃ storage of Li2ZnTi3O8@ C⁃ N anode materials with high specific capacities | |
| Lin et al. | Synthesis of carbon nanotube/graphene composites on Ni foam without additional catalysts by CVD and their nitrogen-plasma treatment for anode materials in lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230314 |
|
| RJ01 | Rejection of invention patent application after publication |