CN111341997A - Novel graphene membrane electrode preparation method - Google Patents
Novel graphene membrane electrode preparation method Download PDFInfo
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- CN111341997A CN111341997A CN202010134666.1A CN202010134666A CN111341997A CN 111341997 A CN111341997 A CN 111341997A CN 202010134666 A CN202010134666 A CN 202010134666A CN 111341997 A CN111341997 A CN 111341997A
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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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Abstract
The invention discloses a preparation method of a novel graphene membrane electrode, which comprises the following steps of respectively mixing and stirring 8-18 parts by weight of powdered graphite oxide, 1-3 parts by weight of chelating agent, 2-4 parts by weight of titanium source and 2-4 parts by weight of manganese source with 20-30 parts by weight of water with weakly acidic pH value for 10-20 min, and standing for 20-30 min, wherein the preparation method comprises the following beneficial effects: according to the novel graphene membrane electrode preparation method, a large amount of impurities in graphite are oxidized and removed, the graphite oxide dispersion liquid is concentrated, the concentration of the graphite is improved, the attachment degree of graphene on the suction filtration membrane is increased, the loss of the graphene on the suction filtration membrane is reduced, the graphene membrane and the suction filtration membrane are lubricated by high-temperature grease and then separated, and the graphene membrane is not easily damaged.
Description
This patent is the divisional application, and the information of former application is as follows, the name: novel graphene membrane electrode preparation method, application number: 2017109529423, filing date: 2017/10/13.
Technical Field
The invention relates to a preparation method of a graphene membrane electrode, in particular to a preparation method of a novel graphene membrane electrode.
Background
Graphene (a cellular planar thin film formed by carbon atoms in an sp2 hybridization manner, which is a quasi-two-dimensional material with a thickness of only one atomic layer, and is also called monoatomic layer graphite. physicists of manchester university, england, andem, and costing, norwalk, etc., graphene is successfully separated from graphite by using a micro-mechanical stripping method, so that the 2010 norbel prize is obtained together.
In the aspect of energy storage, graphene is also vigorously researched and developed by researchers in recent years. Two-dimensional film materials have also been studied in the industry as one form in which graphene can be functionalized, and nowadays, high conductivity, high strength and excellent toughness exhibited by graphene films that are self-assembled and closely packed layer by layer are also of great interest in the industry.
The graphene film prepared by the existing preparation method of the graphene film has low purity, and when the graphene film is used for manufacturing an electrode in a battery, the power generation efficiency is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a novel graphene membrane electrode and a manufacturing method thereof, so as to solve the problems in the background technology.
The purpose of the invention is realized by the following technical scheme: a preparation method of a novel graphene membrane electrode comprises the following process steps:
1) preparation of stock solution I: respectively taking 8-18 parts by weight of graphite oxide, 1-3 parts by weight of chelating agent, 2-4 parts by weight of titanium source and 2-4 parts by weight of manganese source in powder form, mixing and stirring the powder with 20-30 parts by weight of water with weakly acidic pH value for 10-20 min, standing for 20-30 min, then adding 0.5-1 part by weight of chelating agent, 0.8-1 part by weight of titanium source and 0.8-1 part by weight of manganese source, mixing and stirring the mixture with 10-15 parts by weight of water with weakly acidic pH value for 10-20 min, and standing for 20-30 min to obtain a stock solution I;
2) preparation of stock solution II: mixing the stock solution II with a strong oxidant solution according to a ratio of 4:1, repeatedly stirring for 3 times at 65-70 ℃ to obtain stock solution II, wherein the stirring time is 5-8 min each time, and the interval between the stirring times is 6-10 min;
3) preparation of stock solution III: adding a dispersing agent into the stock solution II obtained in the step 2), stirring for 5-10 min, and then performing ultrasonic dispersion treatment on the stock solution I to obtain a graphite oxide dispersion solution with the mass fraction of 30-50%, namely stock solution III;
4) concentration of stock solution III: drying the stock solution III obtained in the step 3) in a drying chamber at 70-85 ℃ until the mass fraction of water in the stock solution III is below 12%;
5) preparing a graphene film: pouring the stock solution III obtained in the step 4) onto a pumping membrane of a vacuum filtration device, and carrying out suction filtration on the stock solution III under the condition of ultrahigh vacuum so as to form a graphene membrane on the pumping membrane;
6) separation of graphene membrane: taking the suction filtration membrane with the graphene membrane in the vacuum device in the step 5), soaking in 70-80 ℃ silicone oil or fatty acid amide for 1-2 h, and then separating the graphene membrane from the suction filtration membrane by a special scraper;
7) cleaning and drying of graphene films: washing the graphene film obtained in the step 6) with flowing weak alkaline water with a pH value for 30-40 min, and drying in a drying chamber at 70-85 ℃ for 1-2 h.
The cutting edge of the film scraping knife used in the step 6) is conical, and the width of the cutting edge is 1 mm-1.4 mm.
The dispersing agent in the step 3) is one or two of polyvinylpyrrolidone and polyvinyl alcohol.
The pH value of the weak alkaline water in the step 7) is between 7.35 and 7.45.
The suction filtration membrane with the graphene membrane in the step 6) is completely immersed in the silicone oil or the fatty acid amide.
The titanium source is one or more of titanium tetrachloride or n-butyl titanate.
The manganese source is one or more of dicyclopentadienyl manganese or tris-bradymethyl cyclopentadienyl manganese.
The invention has the beneficial effects that: according to the novel graphene membrane electrode preparation method, a large amount of impurities in graphite are oxidized and removed, the graphite oxide dispersion liquid is concentrated, the concentration of the graphite is improved, the attachment degree of graphene on the suction filtration membrane is increased, the loss of the graphene on the suction filtration membrane is reduced, the graphene membrane and the suction filtration membrane are lubricated by high-temperature grease and then separated, and the graphene membrane is not easily damaged.
Detailed Description
The following further description is provided in conjunction with the detailed description, but the detailed description below should not be construed as limiting the invention. Various modifications and variations obvious to those skilled in the art, which can be made on the basis of the present invention, should be within the scope of the present invention.
A preparation method of a novel graphene membrane electrode comprises the following process steps:
1) preparation of stock solution I: respectively taking 8-18 parts by weight of graphite oxide, 1-3 parts by weight of chelating agent, 2-4 parts by weight of titanium source and 2-4 parts by weight of manganese source in powder form, mixing and stirring the powder with 20-30 parts by weight of water with weakly acidic pH value for 10-20 min, standing for 20-30 min, then adding 0.5-1 part by weight of chelating agent, 0.8-1 part by weight of titanium source and 0.8-1 part by weight of manganese source, mixing and stirring the mixture with 10-15 parts by weight of water with weakly acidic pH value for 10-20 min, and standing for 20-30 min to obtain a stock solution I;
2) preparation of stock solution II: mixing the stock solution II with a strong oxidant solution according to a ratio of 4:1, repeatedly stirring for 3 times at 65-70 ℃ to obtain stock solution II, stirring for 5-8 min each time with an interval of 6-10 min, and oxidizing a large amount of impurities in the graphite into ions by using the strong oxidant to remove;
3) preparation of stock solution III: adding a dispersing agent into the stock solution II obtained in the step 2), stirring for 5-10 min, and then performing ultrasonic dispersion treatment on the stock solution I to obtain a graphite oxide dispersion solution with the mass fraction of 30-50%, namely stock solution III;
4) concentration of stock solution III: placing the stock solution III obtained in the step 3) in a drying chamber at 70-85 ℃ for drying until the mass fraction of water in the stock solution III is below 12%, concentrating the stock solution III to improve the concentration of graphite in the stock solution III, so that the purity of graphene is improved, the adhesion of graphite on a suction filtration membrane is improved, and the loss of graphite materials is reduced;
5) preparing a graphene film: pouring the stock solution III obtained in the step 4) onto a pumping membrane of a vacuum filtration device, and carrying out suction filtration on the stock solution III under the condition of ultrahigh vacuum so as to form a graphene membrane on the pumping membrane;
6) separation of graphene membrane: taking the suction filtration membrane with the graphene membrane in the vacuum device in the step 5), soaking in 70-80 ℃ silicone oil or fatty acid amide for 1-2 h to ensure that the graphene membrane is sufficiently lubricated, and then separating the graphene membrane from the suction filtration membrane by a special scraper, so that the integrity of the separated graphene membrane is ensured;
7) cleaning and drying of graphene films: washing the graphene film obtained in the step 6) with flowing weak alkaline water with a pH value for 30-40 min, and drying in a drying chamber at 70-85 ℃ for 1-2 h.
The cutting edge of the film scraping knife used in the step 6) is conical, and the width of the cutting edge is 1 mm-1.4 mm.
The dispersing agent in the step 3) is one or two of polyvinylpyrrolidone and polyvinyl alcohol.
The pH value of the weak alkaline water in the step 7) is between 7.35 and 7.45.
The suction filtration membrane with the graphene membrane in the step 6) is completely immersed in the silicone oil or the fatty acid amide.
The titanium source is one or more of titanium tetrachloride or n-butyl titanate.
The manganese source is one or more of dicyclopentadienyl manganese or tris-bradymethyl cyclopentadienyl manganese.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (5)
1. A novel graphene membrane electrode preparation method is characterized by comprising the following steps: the method comprises the following process steps:
1) preparation of stock solution I: respectively taking 8-18 parts by weight of graphite oxide, 1-3 parts by weight of chelating agent, 2-4 parts by weight of titanium source and 2-4 parts by weight of manganese source in powder form, mixing and stirring the powder with 20-30 parts by weight of water with weakly acidic pH value for 10-20 min, standing for 20-30 min, then adding 0.5-1 part by weight of chelating agent, 0.8-1 part by weight of titanium source and 0.8-1 part by weight of manganese source, mixing and stirring the mixture with 10-15 parts by weight of water with weakly acidic pH value for 10-20 min, and standing for 20-30 min to obtain a stock solution I;
2) preparation of stock solution II: mixing the stock solution II with a strong oxidant solution according to a ratio of 4:1, repeatedly stirring for 3 times at 65-70 ℃ to obtain stock solution II, wherein the stirring time is 5-8 min each time, and the interval between the stirring times is 6-10 min;
3) preparation of stock solution III: adding a dispersing agent into the stock solution II obtained in the step 2), stirring for 5-10 min, and then performing ultrasonic dispersion treatment on the stock solution I to obtain a graphite oxide dispersion solution with the mass fraction of 30-50%, namely stock solution III;
4) concentration of stock solution III: drying the stock solution III obtained in the step 3) in a drying chamber at 70-85 ℃ until the mass fraction of water in the stock solution III is below 12%;
5) preparing a graphene film: pouring the stock solution III obtained in the step 4) onto a pumping membrane of a vacuum filtration device, and carrying out suction filtration on the stock solution III under the condition of ultrahigh vacuum so as to form a graphene membrane on the pumping membrane;
6) separation of graphene membrane: taking the suction filtration membrane with the graphene membrane in the vacuum device in the step 5), soaking in 70-80 ℃ silicone oil or fatty acid amide for 1-2 h, and then separating the graphene membrane from the suction filtration membrane by a special scraper;
7) cleaning and drying of graphene films: washing the graphene film obtained in the step 6) with flowing weak alkaline water with a pH value for 30-40 min, and then drying in a drying chamber at 70-85 ℃ for 1-2 h;
the cutting edge of the film scraping knife used in the step 6) is conical, and the width of the cutting edge is 1 mm-1.4 mm;
the dispersing agent in the step 3) is one or two of polyvinylpyrrolidone and polyvinyl alcohol.
2. The novel graphene membrane electrode according to claim 1, wherein: the pH value of the weak alkaline water in the step 7) is between 7.35 and 7.45.
3. The novel graphene membrane electrode according to claim 1, wherein: the suction filtration membrane with the graphene membrane in the step 6) is completely immersed in the silicone oil or the fatty acid amide.
4. The novel graphene membrane electrode according to claim 1, wherein: the titanium source is one or more of titanium tetrachloride or n-butyl titanate.
5. The novel graphene membrane electrode according to claim 1, wherein: the manganese source is one or more of dicyclopentadienyl manganese or tris-bradymethyl cyclopentadienyl manganese.
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| CN202010134666.1A CN111341997B (en) | 2017-10-13 | 2017-10-13 | Preparation method of graphene membrane electrode |
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| CN202010134666.1A CN111341997B (en) | 2017-10-13 | 2017-10-13 | Preparation method of graphene membrane electrode |
| CN201710952942.3A CN107768601B (en) | 2017-10-13 | 2017-10-13 | Novel graphene membrane electrode preparation method |
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| CN110911651A (en) * | 2018-09-17 | 2020-03-24 | 湖北虹润高科新材料有限公司 | Silicon/graphene composite negative electrode material for lithium ion battery, self-supporting negative electrode plate and preparation method thereof, and lithium ion battery |
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| CN107768601A (en) | 2018-03-06 |
| CN107768601B (en) | 2020-02-21 |
| CN111341997B (en) | 2021-05-28 |
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