CN116789118A - Method for preparing graphene - Google Patents

Method for preparing graphene Download PDF

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CN116789118A
CN116789118A CN202210242588.6A CN202210242588A CN116789118A CN 116789118 A CN116789118 A CN 116789118A CN 202210242588 A CN202210242588 A CN 202210242588A CN 116789118 A CN116789118 A CN 116789118A
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graphene
solution
liquid
organic solvent
liquids
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杨盛贤
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Qujing Huajin Rainforest Technology Co ltd
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Qujing Huajin Rainforest Technology Co ltd
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Abstract

The invention discloses a method for preparing graphene, and belongs to the technical field of nano materials. According to the invention, the chemical reagent is used for reducing the graphene oxide, then the dispersing agent is added to react with the graphene solution, and the graphene is kept uniformly dispersed in the solution through the reaction product, so that the aggregation of the graphene is avoided. Then filtering by different solvents (liquids), removing various impurities and enabling the graphene to be uniformly dispersed in the various solvents (liquids). Finally, removing residual moisture in the graphene solution (organic system) by using an electrodialysis electrolysis method to obtain the graphene solution which is uniformly dispersed in the organic solvent (liquid) after removing the moisture. The invention has simple process, high repeatability, application value and popularization possibility.

Description

Method for preparing graphene
Technical Field
The invention belongs to the technical field of new material preparation, and particularly provides a method for preparing graphene.
Background
Graphene is a single-layer two-dimensional material composed of closely packed carbon atoms. The carbon atom having 4 valence electrons, 3 of which are sp 2 The hybridization forms sigma bond, the sigma bond is connected with other three carbon atoms to form a hexagonal structure, and the 4 th non-bonded electron forms pi bond perpendicular to the plane. Based on the unique crystal structure, the graphene has particularly excellent optical, thermal, electrical, magnetic and mechanical properties, such as super-strong mechanical properties, super-high carrier mobility, super-high heat conduction performance, good electromagnetic shielding performance, good optical properties and the like.
Although graphene has many excellent characteristics, three major difficulties have hindered the large-scale application of graphene. Firstly, how to uniformly disperse graphene in various solutions; secondly, how to quickly and efficiently remove impurities in the graphene; three difficulties are that some downstream applications require tight control of moisture content, how to remove moisture introduced during graphene preparation.
The reason why graphene is difficult to disperse in a solvent (liquid) is that pi-pi interactions between carbon atoms and van der waals forces between sheets make graphene easy to agglomerate and difficult to disperse, which is an inherent property of graphene. Pure graphene is prone to agglomeration, resulting in many properties that are excellent on the nanoscale that decrease significantly or even disappear with the agglomeration of graphene sheets. The hydrophobic and oleophobic properties of graphene prevent graphene from being dispersed in water and widely dispersed in various organic solvents (liquids), and graphene can only be dispersed in a small amount and unstably in part of the organic solvents (liquids), so that the application is greatly limited. Therefore, developing a solution in which graphene is uniformly dispersed in different solvents (liquids) is of great importance, and is an important condition for promoting application and development of graphene.
A large amount of impurities can be introduced in the preparation process of the graphene, the quality of the graphene can be reduced by residual impurities, the application of the graphene is seriously influenced, and the purification difficulty is always a great difficulty for preventing the application of the graphene. When preparing graphene, graphene oxide is usually produced by using reagents such as graphite powder, sulfuric acid, nitrate, chlorate, potassium permanganate, hydrochloric acid, phosphoric acid and the like, and is reduced to obtain graphene, and impurity elements such as sodium, potassium, manganese, sulfur, nitrogen, chlorine, phosphorus and the like and a large amount of residual reducing agent are inevitably introduced into the graphene. Many downstream applications have high purity requirements for graphene, and the impurity content in graphene needs to be strictly controlled, so purification is of great importance.
The existing purification modes are mainly purification through dialysis, centrifugation, suction filtration, precipitation and other modes in the production stage of graphene oxide. However, these processes all suffer from various drawbacks, including: high cost, long time, poor effect, complex equipment, high content of residual impurities and the like. The removal of impurities in graphene is very difficult in industry, and no effective method exists at present, which is an important difficulty for restricting the preparation and application of graphene.
Some downstream applications have high requirements for moisture content in graphene, and strict control of moisture content is required, for example, ternary cathode materials in lithium ion batteries require less than 500 ppm moisture, lithium iron phosphate requires less than 1000 ppm moisture, and hard carbon requires less than 1000 ppm moisture. Using a graphene solution (organic system) as a lithium ion battery conductive agent, it is necessary to remove residual moisture in the graphene solution (organic system) so that the moisture content satisfies the standard of the lithium ion battery. In addition to lithium ion batteries, many downstream applications also require tight control of the moisture content in graphene solutions (organic systems).
Therefore, based on the prior art, a person skilled in the art needs to research a graphene preparation method with high efficiency, excellent performance, convenience and low cost, and simultaneously achieves the following three points: (1) So that the graphene is uniformly dispersed in various organic solvents (liquids); (2) efficiently removing various impurities in the graphene; (3) Residual moisture in the graphene solution (organic system) is removed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing graphene with high efficiency and excellent performance, which has the following three advantages: (1) So that the graphene is uniformly dispersed in various organic solvents (liquids); (2) efficiently removing various impurities in the graphene; (3) Residual moisture in the graphene solution (organic system) is removed.
The specific principle of action of the invention is as follows.
The principle of uniformly dispersing graphene in a solution is as follows: (1) After chemical reduction, unreacted reducing agent and small molecules of a reduction product are adsorbed on the surface of graphene through interactions of hydrogen bonds, van der Waals forces, intermolecular forces and the like, so that aggregation of the graphene is avoided, and the graphene is uniformly dispersed in a solution; (2) After chemical reduction, adding a dispersing agent into the graphene solution, wherein the dispersing agent has a dispersing effect in the presence of one or more of the following independent existence or simultaneous existence: the first case is that the dispersing agent reacts with various chemical substances in the graphene solution after chemical reduction to generate gas, the second case is that the dispersing agent is decomposed to generate gas, and the third case is that a plurality of dispersing agents react with each other to generate gas. The generated common gas is one or a mixture of several gases: oxygen, carbon dioxide, nitrogen, ammonia, hydrogen, ozone, fluorine, chlorine, bromine, nitrogen monoxide, nitrogen dioxide, chlorine dioxide. The generated gas is adsorbed on the surface of the graphene, so that agglomeration is avoided, and the graphene is kept uniformly dispersed in the solution; (3) After various small molecules adsorbed on the surface of graphene react with a dispersing agent, desorbing from the surface of graphene, dissolving in a solution, and substituting the adsorption with gas. After the dispersing agent is added, substances which keep the graphene uniformly dispersed are changed into gas from various small molecules.
The principle of removing impurities in the graphene solution is as follows: the gas adsorbed on the surface keeps the dispersion of the graphene, and the solvent (liquid) can smoothly flow through the graphene sheet layers, so that various impurities in the solution are taken away during filtration, and the pure graphene uniformly dispersed in the solution is obtained. The impurities removed include: (1) impurities contained in graphite powder; (2) The preparation method comprises the steps of introducing sodium, potassium, manganese, sulfur, nitrogen, chlorine, phosphorus and other impurity elements into reagents such as sulfuric acid, nitrate, chlorate, potassium permanganate, hydrochloric acid, phosphoric acid and the like used in the preparation of graphene oxide; (3) unreacted reducing agent and reduced product. The method is simple, quick and efficient, and is beneficial to reducing the production cost of graphene.
The invention can lead the graphene to be evenly dispersed in different solvents (liquid) according to the following principle: the solution in which graphene is uniformly dispersed in the first solvent (liquid) is replaced with the second solvent (liquid), and a solution in which graphene is uniformly dispersed in the second solvent (liquid) is obtained.
The principle of the invention for removing residual moisture in graphene solution (organic system) is as follows: using electrodialysis electrolyzed water, under the action of externally applied direct current electric field, a small amount of water contained in the organic solvent (liquid) is hydrolyzed into H + And OH (OH) - . By utilizing the selective permeability of anion and cation exchange membranes, OH - And H + Is removed from the organic solvent (liquid) under the action of external electric field, and respectively enters into positive and negative electrode chambers through anion and cation exchange membranes, and is arranged at the electrodeWhere it becomes oxygen and hydrogen escapes. Therefore, the residual moisture content in the graphene solution is continuously reduced until the requirement of downstream application on the moisture content is met. The electric potential of electrodialysis electrolysis reaction is controlled, only water electrolysis reaction occurs, the organic solvent (liquid) does not generate electrolysis reaction, and the system is kept stable, so that high-purity solution in which the graphene with residual water removed is uniformly dispersed in the organic solvent (liquid) is obtained.
The reason why the graphene can be continuously and uniformly dispersed in the organic solvent (liquid) is as follows: (1) After electrodialysis electrolysis is carried out to remove water, part of gas is adsorbed on the surface of the graphene, and the dispersion is kept continuously; (2) In the preparation process, a small amount of gas is desorbed and inevitably escapes from the surface of the graphene, and organic solvent (liquid) molecules rapidly replace the original gas positions and still remain dispersed.
The principle of the invention for adjusting the concentration of the graphene solution is as follows: for the uniformly dispersed graphene solution, a certain amount of solvent (liquid) is newly added, or the excessive solvent (liquid) is removed by filtration, so that the concentration of the graphene solution can be conveniently adjusted. Wherein the concentration of the single-layer graphene solution is generally 0.1 mg/mL to 10 mg/mL, the concentration of the few-layer graphene solution is generally 1 mg/mL to 20 mg/mL, and the concentration of the multi-layer graphene solution is generally 5 mg/mL to 200 mg/mL. By measuring the concentration of the solution, the graphene is well dispersed in the solvent (liquid).
The invention is realized by the following technical scheme, which comprises the following steps:
firstly, mixing a graphene oxide solution with a reducing agent, and reacting to obtain a chemically reduced graphene solution;
secondly, adding the solution obtained in the first step into a dispersing agent, mixing and reacting to obtain a solution containing impurities, wherein the solution contains graphene uniformly dispersed;
thirdly, adding the solution obtained in the second step into a solvent (liquid), filtering and replacing to remove impurities in the graphene solution, and obtaining a solution with uniformly dispersed graphene after removing the impurities;
fourthly, adding the solution obtained in the third step into an organic solvent (liquid), filtering and replacing to obtain a solution in which the graphene is uniformly dispersed in the organic solvent (liquid);
and fifthly, placing the solution obtained in the fourth step into an electrodialysis electrolytic tank, and removing residual moisture by electrodialysis electrolysis to obtain a solution in which the graphene after the removal of the moisture is uniformly dispersed in an organic solvent (liquid).
Preferably, the meaning of the solvent (liquid) in the present invention is as follows: according to the general rule, a liquid containing one component is called a solvent, and a liquid containing two or more components is called a solution.
Preferably, the graphene solution (organic system) in the present invention has the following meaning: a solution of graphene uniformly dispersed in an organic solvent (liquid).
Preferably, the graphene oxide in the first step is used as a mixture of one or more of the following: single-layer graphene oxide, few-layer graphene oxide, and multi-layer graphene oxide.
Preferably, the solvent (liquid) for preparing the graphene oxide solution in the first step is a common public solvent (liquid), and one or more of the following are commonly used for mixing: water, methanol, ethanol, propanol, acetone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone.
Preferably, in the first step, the concentration of the graphene oxide solution is 0.05-100 mg/mL according to different types of actually used graphene oxide, and the common concentration is as follows: 0.05 mg/mL, 0.1 mg/mL, 0.2 mg/mL, 0.3 mg/mL, 0.4 mg/mL, 0.5 mg/mL, 0.6 mg/mL, 0.7 mg/mL, 0.8 mg/mL, 0.9 mg/mL, 1 mg/mL, 1.5 mg/mL, 2 mg/mL, 2.5 mg/mL, 3 mg/mL, 4 mg/mL, 5 mg/mL, 6 mg/mL, 7 mg/mL, 8 mg/mL, 9 mg/mL, 10 mg/mL, 11 mg/mL, 12 mg/mL, 13 mg/mL, 14 mg/mL, 15 mg/mL, 20 mg/mL, 30 mg/mL, 40 mg/mL, 50 mg/mL, 60 mg/mL, 70 mg/mL, 80 mg/mL, 90 mg/mL, and 100/mL.
Preferably, in the first step, according to the specific graphene oxide used, a surfactant may be added when preparing the solution, where the surfactant is one or more of the following: polyvinylpyrrolidone, polyethylenimine, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium dodecylsulfonate, alkylphenol ethoxylates, triton x-100, polyethylene glycol, aqueous ammonia, N-diethylpropiolate, octadecylamine, gum arabic, cyclodextrin, DNA. Wherein the mass ratio of the graphene oxide to the surfactant is 1 (0-50). The mass ratio is as follows: 1:0, 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20.
Preferably, the reducing agent in the first step is one or more of the following mixtures: organic acids, borohydride, citrate, ascorbate, alcohols, saccharides, amino acids, sulfur-containing reducing agents, nitrogen-containing reducing agents, reducing plant extracts, metals, inorganic acids, bases. The reducing agents commonly used are one or more of the following: ascorbic acid, oxalic acid, gallic acid, citric acid, tannic acid, tartaric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, fatty acids, acrylic acid, trifluoroacetic acid, dehydroascorbic acid, gul Le Tangsuan, threonic acid, lithium borohydride, sodium borohydride, potassium borohydride, rubidium borohydride, aluminum borohydride, beryllium borohydride, calcium borohydride, zinc borohydride, magnesium borohydride, cesium borohydride, strontium borohydride, barium borohydride, cuprous borohydride, titanium borohydride, zirconium borohydride, yttrium borohydride, manganese borohydride, iron borohydride, nickel borohydride, borane, lithium citrate, magnesium citrate, aluminum citrate, potassium citrate, calcium citrate ammonium citrate, ferric citrate, ferrous citrate, nickel citrate, cobalt citrate, manganese citrate, chromium citrate, cupric citrate, zinc citrate, barium citrate, lithium ascorbate, sodium ascorbate, magnesium ascorbate, aluminum ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, ferrous ascorbate, nickel ascorbate, cobalt ascorbate, manganese ascorbate, chromium ascorbate, copper ascorbate, zinc ascorbate, barium ascorbate, stannous ascorbate, methanol, benzyl alcohol, ethanol, ethylene glycol, propanol, isopropanol, butanol, sorbitol, monosaccharides (glucose, fructose, galactose), disaccharides (sucrose, lactose, maltose), oligosaccharides (cyclodextrin), polysaccharides (chitosan), L-cysteine, L-glutathione, thiourea dioxide, ethanethiol, thiophene, lawsen reagent, lithium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonia water, hydrazine (hydrazine), hydrazine hydrate (hydrazine hydrate), ammonia borane, phenylhydrazine, urea, hydroxylamine hydrochloride, pyrrole, pyridine, benzylamine, p-phenylenediamine, ethylenediamine, dimethylketoxime, lithium nitrite, sodium nitrite, magnesium nitrite, aluminum nitrite, potassium nitrite, calcium nitrite, ammonium nitrite, iron nitrite, ferrous nitrite, nickel nitrite, cobalt nitrite, manganese nitrite, chromium nitrite, copper nitrite, barium nitrite, zinc nitrite, silver nitrite, tea extract, rose extract, iron tree leaf extract, orange peel extract, ginkgo leaf extract, lithium, sodium, magnesium, aluminum, potassium, calcium, beryllium, iron, zinc, tin, lithium aluminum hydride, sulfuric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, phosphoric acid, nitric acid, carbonic acid, lithium hydroxide, sodium hydroxide, potassium hydroxide.
Preferably, in the first step, the mass ratio of the graphene oxide to the reducing agent is 1 (1-200), and the mass ratio is as follows: 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:25, 1:30, 1:35, 1:40.
Preferably, the time of the chemical reduction reaction in the first step is 0 to 120 hours. The common usage is: 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 52, 54, 56, 58, 60, 64, 68, 72, 76, 80, 84, 88, 92, 96, 100, 104, 108, 112, 116, 120.
Preferably, the chemical reduction reaction temperature in the first step is-10 ℃ to 100 ℃, and is usually: -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃.
Preferably, the stirring speed of the chemical reduction reaction in the first step is 0-3000 r/min. The usual rotational speeds are: 0 r/min (i.e. standing), 10 r/min, 20 r/min, 30 r/min, 40 r/min, 50 r/min, 60 r/min, 70 r/min, 80 r/min, 90 r/min, 100 r/min, 110 r/min, 120 r/min, 130 r/min, 140 r/min, 150 r/min, 180 r/min, 200 r/min, 240 r/min, 300 r/min, 500 r/min, 600 r/min, 700 r/min, 800 r/min, 900 r/min, 1000 r/min.
Preferably, the chemical reduction reaction in the first step can adjust relevant parameters of the type of the reducing agent, the quality of the reducing agent, the reaction time, the reaction temperature and the stirring rotation speed during the experiment.
Preferably, the dispersant in the second step is one or more of the following: peroxides, superoxides, percarbonates, persulfates, permanganates and permanganates, manganates, ferrates and ferrates, chlorates and chlorates, carbonates, bicarbonates, bisulphates, ammonium salts, dichromates and bichromates, iodic acids and iodates, bromic and bromates, nitrous acids and nitrites, metals, metal hydrides, acids, bases, perborates, halogen intermetallics. Commonly used dispersants are one or more of the following mixtures: hydrogen peroxide, lithium peroxide, sodium peroxide, potassium peroxide, calcium peroxide, magnesium peroxide, zinc peroxide, strontium peroxide, barium peroxide, lead peroxide, urea hydrogen peroxide complex, 2-dihydro propane, 2, 5-dimethyl-2, 5-dihydro hexane, 2-bis- (t-butyl peroxide) propane, 2-bis- (t-butyl peroxide) butane, 2, 5-dimethyl-2, 5-bis- (t-butyl peroxide) hexane, 2-bis- (4, 4-di-t-butyl cyclohexyl peroxide) propane, 2, 5-dimethyl-2, 5-bis- (2-ethylhexanoyl peroxide) hexane 2, 5-dimethyl-2, 5-bis- (3, 5-trimethylhexanoyl) hexane, 2, 5-dimethyl-2, 5-bis- (benzoyl peroxide) hexane, 1-bis- (t-butyl peroxide) cyclohexane, 1-bis- (t-butyl peroxide) -3, 5-trimethylcyclohexane, acetyl sulfonyl peroxide cyclohexane bis- (1-hydroxycyclohexane) peroxide, 3,3,6,6,9,9-hexamethyl-1, 2,4, 5-tetraoxycyclononane, 2, 5-dimethyl-2, 5-bis- (tert-butyl peroxide) -3-hexyne, isopropyl hydroperoxide, 1, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, diisopropyl (yl) benzene hydroperoxide, di-tert-butylisopropyl (yl) benzene hydroperoxide pinane, menthane hydroperoxide, tetralin hydroperoxide, di-tert-butyl peroxide, tert-butylbenzene peroxide, tert-butylisopropyl (yl) benzene peroxide, 1, 3-bis- (2-tert-butylisopropyl) benzene peroxide, 1, 4-bis- (2-tert-butylisopropyl) benzene peroxide, diisopropylbenzene peroxide, isobutylmethylketone peroxide, methylethylketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, diacetone peroxide, acetyl peroxide, propionyl peroxide, isobutyryl peroxide, n-octanoyl peroxide n-nonanoyl peroxide, isononyl peroxide, decanoyl peroxide, dodecanoyl peroxide, benzoyl peroxide, di- (2-methylbenzoyl) peroxide, di- (2-chlorobenzoyl) peroxide, di- (2, 4-dichlorobenzoyl) peroxide, acetyl benzoyl peroxide, peroxyformic acid, peroxyacetic acid, succinic acid peroxide, azelaic acid diperoxide, dodecanedioic acid diperoxide, benzoyl peroxide, 3-chlorobenzoic acid peroxide, terephthalic acid, t-butylterephthalic acid, t-butyl peroxyacetate, t-butyl peroxydiethyl acetate, ethyl 3, 3-bis- (t-butyl peroxybutyrate, tert-butyl peroxyisobutyrate, n-butyl 4, 4-bis- (tert-butyl peroxypivalate), tert-butyl peroxypivalate, isopropyl peroxypivalate, tert-butyl peroxy2-ethylhexanoate 1, 3-tetramethylbutyl peroxy3, 5-trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, isopropyl peroxyneodecanoate, tert-butyl peroxybutenoate, tert-butyl peroxymaleic acid, tert-butyl peroxybenzoate, tert-butyl peroxyphthalate, bis- (tert-butyl peroxyphthalate), tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyoctadecanoyl carbonate 2, 4-trimethylpentyl-2-peroxy phenoxyacetate, 3-tert-butyl-3-o-hydroxymethylbenzoate, diethyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di- (2-ethylhexyl) peroxydicarbonate, di (isotridecyl) peroxydicarbonate, ditetradecyl peroxydicarbonate, dioctadecyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di- (4-tert-butylcyclohexyl) peroxydicarbonate, diphenyl peroxydicarbonate, bis- (2-phenoxyethyl) peroxydicarbonate, bis- (3, 5-trimethyl-1, 2-dioxolane), pinene peroxide, chenopodium oil, sodium superoxide, potassium superoxide, lithium percarbonate sodium percarbonate, potassium percarbonate, ammonium percarbonate, calcium percarbonate, aluminum percarbonate, magnesium percarbonate, lithium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate, permanganate, lithium permanganate sodium permanganate, potassium permanganate, ammonium permanganate, calcium permanganate, zinc permanganate, magnesium permanganate, silver permanganate, barium permanganate, lithium manganate, sodium manganate, potassium manganate, ferrate, lithium ferrate, sodium ferrate, potassium ferrate, perchloric acid, lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, ammonium perchlorate, calcium perchlorate, barium perchlorate, strontium perchlorate, lead perchlorate ferrous perchlorate, silver perchlorate, chloric acid, lithium chlorate, sodium chlorate, potassium chlorate, magnesium chlorate, ammonium chlorate, cesium chlorate, strontium chlorate, barium chlorate, calcium chlorate, copper chlorate, zinc chlorate, silver chlorate, chlorous acid, lithium chlorite, sodium chlorite, potassium chlorite, magnesium chlorite, ammonium chlorite, calcium chlorite, hypochlorous acid, lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, magnesium hypochlorite, calcium hypochlorite, ammonium hypochlorite, barium hypochlorite, chlorine dioxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, calcium carbonate, magnesium carbonate, aluminum carbonate, iron carbonate, copper carbonate, silver carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate, lithium bisulfate, sodium bisulfate, potassium bisulfate, magnesium bisulfate, calcium bisulfate, ammonium bicarbonate, ammonium nitrate, ammonium hypochlorite, ammonium nitrite, ammonium sulfate, ammonium bisulfate, ammonium fluoride, ammonium chloride, ammonium iodide, ammonium bromide, dichromic acid, lithium dichromate, sodium dichromate, potassium dichromate, ammonium dichromate, magnesium dichromate, silver dichromate, cesium dichromate, barium dichromate, aluminum dichromate, copper dichromate, zinc dichromate, chromium trioxide, periodic acid, ammonium periodate, barium periodate, sodium paraperiodate, sodium metaperiodate, potassium periodate, potassium paraperiodate, potassium metaperiodate, iodic acid, diiodide, ammonium iodate, sodium iodate, potassium iodate-in-iodic acid, potassium iodate-diiodidate, lithium iodate, calcium iodate, strontium iodate, barium iodate, manganese iodate, iron iodate, zinc iodate, silver iodate, cadmium iodate, lead iodate, sodium bromate, potassium bromate, magnesium bromate, strontium bromate, barium bromate, zinc bromate, silver, cadmium bromate lead bromate, hydrobromic acid, sodium bromate, potassium bromate, nitrous acid, lithium nitrite, sodium nitrite, magnesium nitrite, aluminum nitrite, potassium nitrite, calcium nitrite, ammonium nitrite, ferric nitrite, ferrous nitrite, nickel nitrite, cobalt nitrite, manganese nitrite, chromium nitrite, copper nitrite, barium nitrite, zinc nitrite, silver nitrite, lithium, sodium, magnesium, aluminum, potassium, calcium, beryllium, iron, zinc lithium hydride, sodium hydride, aluminum hydride, magnesium hydride, potassium hydride, calcium hydride, barium hydride, nickel hydride, copper hydride, zinc hydride, ascorbic acid, oxalic acid, gallic acid, citric acid, tannic acid, tartaric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, 2-methylbutyric acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, myristic acid, oleic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, fatty acid, acrylic acid, trifluoroacetic acid, dehydroascorbic acid, palo Le Tangsuan, threonic acid, sulfuric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, phosphoric acid, nitric acid, carbonic acid, aqueous ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium perborate, sodium perborate, potassium perborate, rubidium perborate, cesium perborate, calcium perborate, barium perborate, iodine fluoride, bromine monofluoride, chlorine monofluoride, iodine chloride, bromine chloride, iodine bromide, iodine trifluoride, bromine trifluoride, chlorine trifluoride, iodine pentafluoride, bromine pentafluoride, chlorine pentafluoride, iodine heptafluoride.
Preferably, the mass ratio of the dispersant to the initial graphene oxide in the second step is (1-1000): 1, which is usually: 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, 200:1, 210:1, 220:1, 230:1, 240:1, 250:1, 260:1, 270:1, 280:1, 290:1, 300:1, 350:1, 400:1, 450:1, 500:1.
Preferably, the reaction time in the second step is 1 minute to 120 hours, and is usually: 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 52, 54, 56, 58, 60, 64, 68, 72, 76, 80, 84, 88, 92, 96, 100, 104, 108, 112, 116, 120.
Preferably, the reaction temperature in the second step is-10 ℃ to 100 ℃, and is usually: -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃.
Preferably, the stirring speed of the reaction in the second step is 0-3000 r/min, and is usually: 0 r/min (i.e. standing), 10 r/min, 20 r/min, 30 r/min, 40 r/min, 50 r/min, 60 r/min, 70 r/min, 80 r/min, 90 r/min, 100 r/min, 110 r/min, 120 r/min, 130 r/min, 140 r/min, 150 r/min, 180 r/min, 200 r/min, 240 r/min, 300 r/min, 500 r/min, 600 r/min, 700 r/min, 800 r/min, 900 r/min, 1000 r/min.
Preferably, the dispersing agent in the second step is present singly or in combination of two or more of the following: the first case is that the dispersing agent reacts with various chemical substances in the graphene solution after chemical reduction to generate gas, the second case is that the dispersing agent is decomposed to generate gas, and the third case is that a plurality of dispersing agents react with each other to generate gas. The generated common gas is one or a mixture of the following components: oxygen, carbon dioxide, nitrogen, ammonia, hydrogen, ozone, fluorine, chlorine, bromine, nitrogen monoxide, nitrogen dioxide, chlorine dioxide. The reaction also produces soluble products. Typical examples of the dispersing action of the dispersant are as follows: (1) The reducing agent is ascorbic acid, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (2) The reducing agent is ascorbic acid, the dispersing agent is sodium percarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (3) The reducing agent is ascorbic acid, the dispersing agent is sodium carbonate, and the generated gas is as follows: carbon dioxide. (4) The reducing agent is ascorbic acid, the dispersing agent is hydrogen peroxide and sodium carbonate, and the generated gas is as follows: oxygen, carbon dioxide. (5) The reducing agent is ascorbic acid, the dispersing agent is sodium bicarbonate, and the generated gas is as follows: carbon dioxide. (6) The reducing agent is ascorbic acid, the dispersing agent is hydrogen peroxide and sodium bicarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (7) The reducing agent is oxalic acid, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (8) The reducing agent is oxalic acid, the dispersing agent is sodium percarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (9) The reducing agent is oxalic acid, the dispersing agent is sodium carbonate, and the generated gas is as follows: carbon dioxide. (10) The reducing agent is oxalic acid, the dispersing agent is hydrogen peroxide and sodium carbonate, and the generated gas is as follows: oxygen, carbon dioxide. (11) The reducing agent is oxalic acid, the dispersing agent is sodium bicarbonate, and the generated gas is as follows: carbon dioxide. (12) The reducing agent is oxalic acid, the dispersing agent is hydrogen peroxide and sodium bicarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (13) The reducing agent is citric acid, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (14) The reducing agent is citric acid, the dispersing agent is sodium percarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (15) The reducing agent is citric acid, the dispersing agent is sodium carbonate, and the generated gas is as follows: carbon dioxide. (16) The reducing agent is citric acid, the dispersing agent is hydrogen peroxide and sodium carbonate, and the generated gas is as follows: oxygen, carbon dioxide. (17) The reducing agent is citric acid, the dispersing agent is sodium bicarbonate, and the generated gas is as follows: carbon dioxide. (18) The reducing agent is citric acid, the dispersing agent is hydrogen peroxide and sodium bicarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (19) The reducing agent is sodium ascorbate, sodium oxalate and sodium citrate, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (20) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (21) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium percarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (22) The reducing agent is ascorbic acid and citric acid, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (23) The reducing agent is ascorbic acid and citric acid, the dispersing agent is sodium percarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (24) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is hydrogen peroxide and sodium carbonate, and the generated gas is as follows: oxygen, carbon dioxide. (25) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is hydrogen peroxide and sodium bicarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (26) The reducing agent is ascorbic acid, the dispersing agent is potassium dichromate and ammonium sulfate, and the generated gas is as follows: oxygen, nitrogen. (27) The reducing agent is ascorbic acid, the dispersing agent is potassium permanganate, and the generated gas is as follows: oxygen. (28) The reducing agent is ascorbic acid, the dispersing agent is potassium ferrate, and the generated gas is as follows: oxygen. (29) The reducing agent is ascorbic acid, the dispersing agent is sodium persulfate, and the generated gas comprises: oxygen. (30) The reducing agent is ascorbic acid, the dispersing agent is potassium chlorate, and the generated gas is as follows: oxygen. (31) The reducing agent is ascorbic acid, the dispersing agent is potassium perchlorate, and the generated gas is as follows: oxygen. (32) The reducing agent is ascorbic acid, the dispersing agent is calcium hydride, and the generated gas is as follows: hydrogen gas. (33) The reducing agent is ascorbic acid, the dispersing agent is potassium dichromate, and the generated gas is as follows: oxygen. (34) The reducing agent is ascorbic acid and hydrazine hydrate, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen, nitrogen. (35) The reducing agent is ammonia water, sodium borohydride and ascorbic acid, the dispersing agent is hydrogen peroxide, and the generated gas is: oxygen, nitrogen. (36) The reducing agent is ascorbic acid, the dispersing agent is hydrogen peroxide and potassium permanganate, and the generated gas is as follows: oxygen. (37) The reducing agent is ascorbic acid, the dispersing agent is ammonium persulfate, and the generated gas comprises: oxygen, ammonia. (38) The reducing agent is ascorbic acid, the dispersing agent is potassium manganate and hydrogen peroxide, and the generated gas is as follows: oxygen. (39) The reducing agent is ascorbic acid, the dispersing agent is sodium perborate and sodium bicarbonate, and the generated gas is as follows: oxygen, carbon dioxide. (40) The reducing agent is ammonia water, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen, nitrogen. (41) The reducing agent is ammonia water and glucose, the dispersing agent is ascorbic acid and hydrogen peroxide, and the generated gas is as follows: oxygen, nitrogen. (42) The reducing agent is ammonia water and glucose, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen, nitrogen. (43) The reducing agent is ammonia water and glucose, the dispersing agent is ammonium chloride and sodium nitrite, and the generated gas is as follows: nitrogen gas. (44) The reducing agent is ammonia water and glucose, the dispersing agent is ammonium bicarbonate, and the generated gas is as follows: carbon dioxide, ammonia. (45) The reducing agent is ammonia water and glucose, the dispersing agent is ammonium nitrite, and the generated gas is as follows: nitrogen gas. (46) The reducing agent is ammonia water and hydrazine hydrate, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen, nitrogen. (47) The reducing agent is ammonia water and sodium borohydride, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen, nitrogen. (48) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is aluminum, and the generated gas is as follows: hydrogen gas. (49) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is hydrogen chloride and aluminum, and the generated gas is as follows: hydrogen gas. (50) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium bicarbonate and aluminum, and the generated gas is as follows: carbon dioxide, hydrogen. (51) The reducing agent is ammonia water and glucose, the dispersing agent is sodium hydroxide and aluminum, and the generated gas is as follows: hydrogen gas. (52) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium percarbonate, hydrogen chloride and aluminum, and the generated gas is as follows: oxygen, carbon dioxide, hydrogen. (53) The reducing agent is ascorbic acid and citric acid, the dispersing agent is zinc, and the generated gas is as follows: hydrogen gas. (54) The reducing agent is ascorbic acid and citric acid, the dispersing agent is hydrogen peroxide and zinc, and the generated gas is as follows: the reducing agent of oxygen and hydrogen (55) is ascorbic acid, the dispersing agent is hydrogen peroxide, hydrogen chloride and zinc, and the generated gases are as follows: oxygen, hydrogen. (56) The reducing agent is ammonia water and glucose, the dispersing agent is hydrogen peroxide and zinc, and the generated gas is as follows: oxygen, nitrogen, hydrogen. (57) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium carbonate and zinc, and the generated gas is as follows: carbon dioxide, hydrogen. (58) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium carbonate, hydrogen peroxide and zinc, and the generated gas is as follows: oxygen, carbon dioxide, hydrogen. (59) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium carbonate, hydrogen chloride and zinc, and the generated gas is as follows: carbon dioxide, hydrogen. (60) The reducing agent is ascorbic acid, oxalic acid and zinc, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: hydrogen and oxygen. (61) The reducing agent is hydroiodic acid, the dispersing agent is hydrogen peroxide, and the generated gas is as follows: oxygen. (62) The reducing agent is ascorbic acid, the dispersing agent is hydrogen chloride and sodium chlorite, and the generated gas is as follows: chlorine dioxide. (63) The reducing agent is ascorbic acid, the dispersing agent is sodium bicarbonate, sodium bisulfate, hydrogen chloride and sodium chlorite, and the generated gases are as follows: carbon dioxide, chlorine dioxide. (64) The reducing agent is ascorbic acid and oxalic acid, the dispersing agent is sodium bicarbonate, hydrogen chloride and sodium chlorite, and the generated gas is as follows: carbon dioxide, chlorine dioxide. The general examples set forth above are merely illustrative of the principles of the present invention, and the experimental protocols that are actually used are not limited to those set forth above. All experiments performed in accordance with the principles of the present invention and with the various reagents exemplified herein are included within the scope of the present invention.
Preferably, the reaction in the second step can adjust relevant parameters of the type of the dispersant, the quality of the dispersant, the reaction time, the reaction temperature and the stirring rotation speed in the experimental process.
Preferably, the filtration and displacement in the third step is performed in one or more of the following combinations: normal pressure filtration, reduced pressure filtration, gravity filtration, vacuum filtration, centrifugal filtration, dialysis, and soaking replacement.
Preferably, in the third step, the filtering and replacing are performed according to the different sheet diameter and the number of layers of the graphene, and the used equipment is one or more of the following combinations: a filter screen, a filter membrane, a filter bag and a filter paper with the mesh number of 10-5000 meshes. The usual mesh numbers are: 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 550 mesh, 600 mesh, 650 mesh, 700 mesh, 750 mesh, 800 mesh, 1000 mesh.
Preferably, the filtering and replacing in the third step remove impurities in the graphene solution, wherein the impurity removal standard is that the impurity content in the graphene solution meets the requirement standard of the downstream application on the impurity content in the graphene material. Removed impurities include, but are not limited to: impurities in the graphite powder, impurities introduced during preparation of graphene, impurities introduced during reduction of graphene, and impurities introduced during preparation of a graphene solution.
Preferably, the filtration and displacement in the third step may be performed by using only one solvent (liquid), or may be performed by using a plurality of solvents (liquids) in sequence. By utilizing the mutual solubility of solvents (liquids), graphene uniformly dispersed in one solvent (liquid) is fully replaced by different solvents (liquids) in sequence, and uniformly dispersed in other solvents (liquids), so that a solution in which graphene is uniformly dispersed in different solvents (liquids) is sequentially obtained.
Preferably, the solvent (liquid) used for the filtration and displacement in the third step is one of the following three: water, an organic solvent (liquid), and a mixed solution of water and the organic solvent (liquid).
Preferably, the organic solvent (liquid) used in the filtration and displacement in the third step is one or more of the following: hydrocarbon solvents (liquids), halogenated hydrocarbon solvents (liquids), alcohol solvents (liquids), phenol solvents (liquids), ether solvents (liquids), aldehyde solvents (liquids), ketone solvents (liquids), ester solvents (liquids), acid and acid anhydride solvents (liquids), amine solvents (liquids), amide solvents (liquids), nitrile solvents (liquids), nitrogen-containing compound solvents (liquids), sulfur-containing compound solvents (liquids). The common organic solvents (liquids) are one or more of the following mixtures: CBrF 3 、CClF 3 、CCl 2 F 2 、CCl 3 F、CCl 4 、CCl 4 S、CF 4 、CS 2 、CHBrCl 2 、CHBr 2 Cl、CHBr 3 、CHCl 2 F、CHCl 3 、CHF 3 、CHF 3 O 3 S、CH 2 ClBr、CH 2 Br 2 、CH 2 Cl 2 、CH 2 O、CH 2 O 2 、CH 3 Br、CH 3 Cl、CH 3 I、CH 3 NCO、CH 3 ON、CH 3 NO 2 、CH 4 O、CH 5 N、CH 6 ClN 3 O、CH 6 N 2 、C 2 Cl 2 F 4 、C 2 Cl 3 F 3 、C 2 Cl 4 、C 2 Cl 4 F 2 、C 2 Cl 6 、C 2 HCl 2 F 3 、C 2 HCl 2 N、C 2 HCl 3 、C 2 HO 2 Cl 3 、C 2 HCl 5 、C 2 HF 3 O 2 、C 2 H 2 Br 4 、C 2 H 2 ClF 3 、C 2 H 2 ClN、C 2 H 2 Cl 2 、C 2 H 2 Cl 2 O、C 2 H 2 O 2 Cl 2 、C 2 H 2 Cl 4 、C 2 H 2 F 2 、C 2 H 2 O 4 、C 2 H 3 Cl、C 2 H 3 ClF 2 、C 2 H 3 ClO、C 2 H 3 ClO 2 、C 2 H 3 O 2 Cl、C 2 H 3 Cl 3 、C 2 H 3 F 3 O、C 2 H 3 N、C 2 H 4 、C 2 H 4 BrCl、C 2 H 4 Br 2 、C 2 H 4 Cl 2 、C 2 H 4 Cl 2 O、C 2 H 4 F 2 、C 2 H 4 O、C 2 H 4 O 2 、C 2 H 4 O 2 S、C 2 H 4 O 3 、C 2 H 5 Br、C 2 H 5 BrO、C 2 H 5 Cl、C 2 H 5 ClO、C 2 H 5 N、C 2 H 5 ON、C 2 H 5 NO 2 、C 2 H 6 、C 2 H 6 N 2 O、C 2 H 6 O、C 2 H 6 O 2 、C 2 H 6 OS、C 2 H 6 O 2 S、C 2 H 6 O 4 S、C 2 H 6 S、C 2 H 7 N、C 2 H 7 NO、C 2 H 7 O 4 P、C 2 H 8 N 2 、C 3 Cl 2 F 4 O、C 3 F 6 O、C 3 H 3 F 3 O、C 3 H 3 N、C 3 H 4 Cl 2 、C 3 H 4 O、C 3 H 4 O 2 、C 3 H 4 O 3 、C 3 H 4 N 2 、C 3 H 5 BrO、C 3 H 5 BrO 2 、C 3 H 5 Br 2 Cl、C 3 H 5 Br 3 、C 3 H 5 Cl、C 3 H 5 OCl、C 3 H 5 ClO 2 、C 3 H 5 Cl 3 、C 3 H 5 N、C 3 H 5 NO、C 3 H 6 、C 3 H 6 Br 2 、C 3 H 6 Br 2 O、C 3 H 6 ClNO、C 3 H 6 Cl 2 、C 3 H 6 Cl 2 O、C 3 H 6 O、C 3 H 6 O 2 、C 3 H 6 O 3 、C 3 H 6 O 3 S、C 3 H 7 Br、C 3 H 7 Cl、C 3 H 7 ClO、C 3 H 7 ClO 2 、C 3 H 7 I、C 3 H 7 N、C 3 H 7 ON、C 3 H 7 NO 2 、C 3 H 7 NO 3 、C 3 H 8 、C 3 H 8 O、C 3 H 8 O 2 、C 3 H 8 O 3 、C 3 H 8 S、C 3 H 9 BO 3 、C 3 H 9 N、C 3 H 9 NO、C 3 H 9 O 4 P、C 3 H 10 N 2 、C 4 Cl 6 、C 4 F 6 O 3 、C 4 H 4 N 2 、C 4 H 4 O、C 4 H 4 S、C 4 H 5 Cl、C 4 H 5 N、C 4 H 5 NO 2 、C 4 H 6 、C 4 H 6 Cl 2 O 2 、C 4 H 6 O、C 4 H 6 O 2 、C 4 H 6 O 3 、C 4 H 6 O 4 、C 4 H 6 O 4 Pb·3H 2 O、C 4 H 7 N、C 4 H 7 NO、C 4 H 7 ClO 2 、C 4 H 8 、C 4 H 8 Cl 2 、C 4 H 8 O、C 4 H 8 OCl 2 、C 4 H 8 O 2 、C 4 H 8 O 2 S、C 4 H 8 O 3 、C 4 H 8 S、C 4 H 9 Br、C 4 H 9 Cl、C 4 H 9 ClO、C 4 H 9 I、C 4 H 9 N、C 4 H 9 NO、C 4 H 9 NO 2 、C 4 H 10 、C 4 H 10 N 2 O、C 4 H 10 O、C 4 H 10 O 2 、C 4 H 10 O 2 S、C 4 H 10 O 3 、C 4 H 10 O 4 S、C 4 H 10 S、C 4 H 11 N、C 4 H 11 NO、C 4 H 11 NO 2 、C 4 H 11 O 4 P、C 4 H 12 Si、C 4 H 13 N 3 、C 4 H 19 NO 2 、C 5 Cl 6 、C 5 H 4 O 2 、C 5 H 5 N、C 5 H 6 、C 5 H 6 O、C 5 H 6 O 2 、C 5 H 7 NO 2 、C 5 H 8 、C 5 H 8 O、C 5 H 8 O 2 、C 5 H 8 O 3 、C 5 H 9 BrO 2 、C 5 H 9 ClO 2 、C 5 H 9 N、C 5 H 9 ON、C 5 H 9 O、C 5 H 10 、C 5 H 10 Cl 2 、C 5 H 10 N 2 、C 5 H 10 O、C 5 H 10 O 2 、C 5 H 10 O 3 、C 5 H 10 O 4 、C 5 H 11 Br、C 5 H 11 Cl、C 5 H 11 I、C 5 H 11 N、C 5 H 11 NO、C 5 H 11 NO 2 、C 5 H 11 NO 3 、C 5 H 12 、C 5 H 12 N 2 、C 5 H 12 ON 2 、C 5 H 12 O、C 5 H 12 O 2 、C 5 H 12 O 3 、C 5 H 12 O 4 、C 5 H 12 S、C 5 H 13 N、C 5 H 13 NO、C 5 H 13 NO 2 、C 6 F 6 、C 6 H 2 Cl 4 、C 6 H 3 ClN 2 O 4 、C 6 H 3 Cl 3 、C 6 H 3 Cl 3 O、C 6 H 4 BrCl、C 6 H 4 Br 2 、C 6 H 4 ClNO 2 、C 6 H 4 Cl 2 、C 6 H 4 Cl 2 O、C 6 H 4 N 2 O 4 、C 6 H 5 Br、C 6 H 5 BrO、C 6 H 5 Cl、C 6 H 5 ClO、C 6 H 5 F、C 6 H 5 I、C 6 H 5 NO 2 、C 6 H 6 、C 6 H 6 ClN、C 6 H 6 O、C 6 H 6 O 2 、C 6 H 6 OS、C 6 H 6 O 3 、C 6 H 7 N、C 6 H 8 N 2 、C 6 H 8 O、C 6 H 8 O 2 、C 6 H 8 O 4 、C 6 H 10 、C 6 H 10 O、C 6 H 10 O 2 、C 6 H 10 O 3 、C 6 H 10 O 4 、C 6 H 11 N、C 6 H 11 ON、C 6 H 12 、C 6 H 12 ClO、C 6 H 12 Cl 2 O 2 、C 6 H 12 Cl 3 O 4 P、C 6 H 12 O、C 6 H 12 O 2 、C 6 H 12 O 2 S、C 6 H 12 O 3 、C 6 H 12 O 4 、C 6 H 13 Br、C 6 H 13 Cl、C 6 H 13 N、C 6 H 13 NO、C 6 H 14 、C 6 H 14 O、C 6 H 14 O 2 、C 6 H 14 O 3 、C 6 H 14 O 4 、C 6 H 14 O 6 、C 6 H 15 O 3 B、C 6 H 15 N、C 6 H 15 NO、C 6 H 15 NO 2 、C 6 H 15 NO 3 、C 6 H 15 O 4 P、C 6 H 18 NOP、C 6 H 18 N 4 、C 6 H 18 OSi 2 、C 7 H 4 Cl 3 F、C 7 H 5 Cl 3 、C 7 H 5 F 3 、C 7 H 5 N、C 7 H 5 N 3 O 6 、C 7 H 6 Cl 2 、C 7 H 6 O、C 7 H 6 O 2 、C 7 H 7 Br、C 7 H 7 BrO、C 7 H 7 Cl、C 7 H 7 NO、C 7 H 7 NO 2 、C 7 H 7 NO 3 、C 7 H 8 、C 7 H 8 O、C 7 H 8 O 2 、C 7 H 8 O 3 、C 7 H 9 N、C 7 H 10 O 3 、C 7 H 12 、C 7 H 12 O、C 7 H 12 O 2 、C 7 H 12 O 4 、C 7 H 12 O 5 、C 7 H 13 N、C 7 H 14 、C 7 H 14 O、C 7 H 14 O 2 、C 7 H 14 O 3 、C 7 H 14 O 4 、C 7 H 15 Br、C 7 H 16 、C 7 H 16 O、C 7 H 16 O 2 、C 7 H 16 O 3 、C 7 H 16 O 4 、C 7 H 17 N、C 7 H 18 N 2 、C 8 H 4 F 6 、C 8 H 6 、C 8 H 7 N、C 8 H 8 、C 8 H 8 O、C 8 H 8 O 2 、C 8 H 8 O 3 、C 8 H 9 NO、C 8 H 9 NO 3 、C 8 H 9 O、C 8 H 10 、C 8 H 10 O、C 8 H 10 O 2 、C 8 H 11 N、C 8 H 12 、C 8 H 12 O 4 、C 8 H 14 O、C 8 H 14 O 2 、C 8 H 14 O 2 N 2 、C 8 H 14 O 3 、C 8 H 14 O 4 、C 8 H 14 O 5 、C 8 H 14 O 6 、C 8 H 15 N、C 8 H 16 、C 8 H 16 O、C 8 H 16 O 2 、C 8 H 16 O 3 、C 8 H 16 O 4 、C 8 H 17 Cl、C 8 H 18 、C 8 H 18 O、C 8 H 18 O 2 、C 8 H 18 O 3 、C 8 H 18 O 4 、C 8 H 18 O 5 、C 8 H 19 N、C 8 H 19 O 3 P、C 8 H 19 O 4 P、C 8 H 20 O 4 Si、C 8 H 23 N 5 、C 8 H 24 O 4 Si 4 、C 9 H 6 N 2 O 2 、C 9 H 6 O 2 、C 9 H 7 N、C 9 H 7 NO、C 9 H 8 、C 9 H 8 O、C 9 H 9 N、C 9 H 10 、C 9 H 10 O、C 9 H 10 O 2 、C 9 H 10 O 3 、C 9 H 12 、C 9 H 12 O、C 9 H 12 O 2 、C 9 H 13 N、C 9 H 14 O、C 9 H 14 O 6 、C 9 H 16 、C 9 H 16 O、C 9 H 16 O 2 、C 9 H 16 O 4 、C 9 H 17 N、C 9 H 18 、C 9 H 18 O、C 9 H 18 O 2 、C 9 H 18 O 4 、C 9 H 20 、C 9 H 20 O、C 9 H 20 O 2 、C 9 H 20 O 3 、C 9 H 21 N、C 9 H 21 NO 3 、C 10 H 7 Br、C 10 H 7 Cl、C 10 H 8 、C 10 H 10 O、C 10 H 10 O 2 、C 10 H 10 O 4 、C 10 H 11 N、C 10 H 12 、C 10 H 12 O、C 10 H 12 O 2 、C 10 H 12 O 3 、C 10 H 13 NO、C 10 H 14 、C 10 H 14 O、C 10 H 14 NO 5 PS、C 10 H 15 N、C 10 H 16 、C 10 H 16 ClN、C 10 H 16 O、C 10 H 16 O 8 N 2 、C 10 H 18 、C 10 H 18 O、C 10 H 18 O 4 、C 10 H 19 N、C 10 H 20 、C 10 H 20 O、C 10 H 20 O 2 、C 10 H 20 O 4 、C 10 H 21 N、C 10 H 22 、C 10 H 22 O、C 10 H 22 O 2 、C 10 H 22 O 3 、C 10 H 22 O 4 、C 10 H 22 O 5 、C 10 H 22 S、C 10 H 23 N、C 10 H 23 NO、C 11 H 10 、C 11 H 12 O 2 、C 11 H 14 O、C 11 H 14 O 2 、C 11 H 14 O 3 、C 11 H 16 、C 11 H 16 O、C 11 H 17 N、C 11 H 20 、C 11 H 20 O、C 11 H 20 O 2 、C 11 H 20 O 4 、C 11 H 21 N、C 11 H 22 、C 11 H 22 O、C 11 H 22 O 2 、C 11 H 24 、C 11 H 24 O、C 12 H 10 、C 12 H 10 O、C 12 H 12 、C 12 H 14 O 4 、C 12 H 16 、C 12 H 16 O、C 12 H 16 O 2 、C 12 H 16 O 3 、C 12 H 18 、C 12 H 20 O 4 、C 12 H 20 O 7 、C 12 H 22 、C 12 H 22 O、C 12 H 22 O 4 、C 12 H 22 O 6 、C 12 H 23 N、C 12 H 24 、C 12 H 24 O、C 12 H 24 O 2 、C 12 H 25 Br、C 12 H 25 Cl、C 12 H 26 、C 12 H 26 O、C 12 H 26 O 3 、C 12 H 26 S、C 12 H 27 O 3 B、C 12 H 27 N、C 12 H 27 O 4 P、C 13 H 10 O、C 13 H 10 O 3 、C 13 H 12 、C 13 H 18 O、C 13 H 20 、C 13 H 20 O、C 13 H 22 O 2 、C 13 H 24 、C 13 H 24 O、C 13 H 25 N、C 13 H 26 、C 13 H 26 O、C 13 H 26 O 2 、C 13 H 28 、C 14 H 10 、C 14 H 12 O 2 、C 14 H 12 O 3 、C 14 H 14 、C 14 H 14 O、C 14 H 20 O、C 14 H 22 、C 14 H 23 N、C 14 H 26 、C 14 H 26 O、C 14 H 26 O 4 、C 14 H 27 N、C 14 H 28 、C 14 H 28 O、C 14 H 28 O 2 、C 14 H 30 、C 14 H 30 O、C 15 H 22 O、C 15 H 24 、C 15 H 24 O、C 15 H 27 N 3 O、C 15 H 28 、C 15 H 28 O、C 15 H 28 O 2 、C 15 H 29 N、C 15 H 30 、C 15 H 30 O、C 15 H 30 O 2 、C 15 H 32 、C 15 H 32 O、C 15 H 33 O 3 B、C 15 H 33 N、C 16 H 10 、C 16 H 22 O 4 、C 16 H 24 O、C 16 H 26 、C 16 H 27 N、C 16 H 30 、C 16 H 30 O、C 16 H 31 N、C 16 H 32 、C 16 H 32 O、C 16 H 32 O 2 、C 16 H 34 、C 16 H 34 O、C 16 H 35 N、C 16 H 35 O 4 P、C 17 H 28 、C 17 H 32 、C 17 H 33 N、C 17 H 34 、C 17 H 34 O、C 17 H 34 O 2 、C 17 H 36 、C 17 H 36 O、C 18 H 12 、C 18 H 15 O 4 P、C 18 H 18 O 5 、C 18 H 30 、C 18 H 32 O 7 、C 18 H 34 、C 18 H 34 O 2 、C 18 H 34 O 4 、C 18 H 35 N、C 18 H 36 、C 18 H 36 O、C 18 H 36 O 2 、C 18 H 37 N、C 18 H 37 NO、C 18 H 38 、C 18 H 38 O、C 18 H 39 N、C 19 H 16 、C 19 H 20 O 4 、C 19 H 32 、C 19 H 36 、C 19 H 36 O 2 、C 19 H 38 、C 19 H 38 O、C 19 H 38 O 2 、C 19 H 40 、C 20 H 32 O、C 20 H 34 、C 20 H 36 O 4 、C 20 H 38 、C 20 H 38 O 2 、C 20 H 40 、C 20 H 40 O、C 20 H 42 、C 20 H 43 N、C 21 H 21 O 4 P、C 21 H 36 、C 21 H 42 O 4 、C 21 H 44 、C 22 H 34 O 2 、C 21 H 40 、C 21 H 42 、C 22 H 42 O 2 、C 22 H 42 O 4 、C 22 H 42 、C 22 H 44 、C 22 H 44 O 2 、C 22 H 46 、C 23 H 44 、C 23 H 46 、C 23 H 46 O 2 、C 23 H 48 、C 24 H 38 O 4 、C 24 H 46 、C 24 H 48 、C 24 H 50 、C 24 H 51 O 4 P、C 25 H 48 、C 25 H 48 O 4 、C 25 H 50 、C 25 H 52 、C 26 H 42 O 4 、C 26 H 46 、C 26 H 50 、C 26 H 50 O 4 、C 26 H 52 、C 26 H 54 、C 27 H 36 O 2 、C 27 H 52 、C 27 H 54 、C 27 H 56 、C 28 H 54 、C 28 H 56 、C 28 H 58 、C 29 H 56 、C 29 H 58 、C 29 H 60 、C 30 H 54 、C 30 H 58 、C 30 H 60 、C 30 H 62 、C 57 H 104 O 9 Polyethylene glycol (commonly used molecular weight is 100-6000, commonly used is: PEG-100, PEG-200, PEG-300, PEG-400, PEG-500, PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000), pine oil, turpentine, camphor oil, petroleum ether, gasoline, kerosene, solvent naphtha, liquid paraffin, diesel oil, heavy oil, aviation kerosene, lubricating oil, silicone oil, no. 6 solvent oil, no. 70 solvent oil, no. 120 solvent oil, no. 170 solvent oil, no. 200 solvent oil, no. 260 solvent oil, fusel oil, corn oil, rapeseed oil, olive oil, palm oil, cottonseed oil, peanut oil, soybean oil, coconut oil, tea seed oil, sesame oil, rice bran oil, castor oil, linseed oil, safflower oil, cotton seed oil, walnut oil, grape seed oil, pumpkin seed oil, sunflower seed oil, orange oil, perilla oil, almond oil, lemon oil, sea buckthorn oil, evening primrose oil, glass oil, sesame oil, linseed oil, camellia oil, peony seed oil, lard, tallow, shea butter, chicken oil, fish oil, whale oil, deep sea oil, deep-drum oil. The chemical compounds expressed by the above formula are according to the general rules of disclosureThere are two cases: (1) A formula represents a single structure chemical; (2) Isomers of the same formula but different structures, each formula comprising all isomers of the same formula, are shown in the present specification as representing all isomers associated therewith. The mixing of the organic solvents (liquids) includes the following two cases: (1) Mixing organic solvents (liquids) of different molecular formulas with each other; (2) Organic solvent (liquid) formed by mixing isomers with the same molecular formula.
Preferably, the third case of the solution used for filtration and replacement in the third step is a mixed solution of water and an organic solvent (liquid) as described in [0042 ].
Preferably, the organic solvent (liquid) used for the filtration and displacement in the fourth step is one or more of the following: hydrocarbon solvents (liquids), halogenated hydrocarbon solvents (liquids), alcohol solvents (liquids), phenol solvents (liquids), ether solvents (liquids), aldehyde solvents (liquids), ketone solvents (liquids), ester solvents (liquids), acid and acid anhydride solvents (liquids), amine solvents (liquids), amide solvents (liquids), nitrile solvents (liquids), nitrogen-containing compound solvents (liquids), sulfur-containing compound solvents (liquids). The common organic solvent (liquid) is the same as that used for the filtration and replacement described in the third step, that is, the common organic solvent (liquid) exemplified in [0042 ].
Preferably, the graphene solution uniformly dispersed in the first organic solvent (liquid) in the fourth step may be filtered and replaced by using the second organic solvent (liquid) to obtain the graphene solution uniformly dispersed in the second organic solvent (liquid). The organic solvent (liquid) used for filtration and replacement is as described in [0042 ].
Preferably, the filtration and displacement in the fourth step is performed in the same manner as the filtration and displacement in the third step.
Preferably, in the fifth step, the electrodialysis electrolysis reaction uses a constant voltage power supply, and a constant voltage interval applied to each electrodialysis membrane pair is 1.0-10.0 v, which is usually: 1.2V, 1.23V, 1.25V, 1.28V, 1.3V, 1.35V, 1.4V, 1.45V, 1.5V, 1.55V, 1.6V, 1.65V, 1.7V, 1.75V, 1.8V, 1.85V, 1.9V, 1.95V, 2.0V, 2.1V, 2.2V, 2.3V, 2.4V, 2.5V, 2.6V, 2.7V, 2.8V, 2.9V, 3.0V, 3.1V, 3.2V, 3.3V, 3.4V, 2.5V, 3.6V, 3.7V, 3.8V, 3.9V, 4.0V, 4.1V, 4.2V, 4.3V, 4.5V, 4.6V, 4.7V, 4.8V, 4.9V, 5.0V.
Preferably, the electrodialysis electrolysis in the fifth step may be performed using different voltages sequentially in the reaction.
Preferably, the electrodialysis electrolysis in the fifth step is carried out for a duration of 10 seconds to 120 hours, usually: 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 52, 54, 56, 58, 60, 64, 68, 72, 76, 80, 84, 88, 92, 96, 100, 104, 108, 112, 116, 120.
Preferably, in the fifth step, the temperature of the electrodialysis electrolysis reaction is-40 ℃ to 200 ℃, the proper reaction temperature is selected according to the freezing point and the boiling point of a water/organic solvent (liquid) system, and the volatilization loss of the organic solvent (liquid) is reduced as much as possible while the residual moisture is removed by rapid electrolysis. The temperatures commonly used are: -25 ℃, -20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃.
Preferably, in the fifth step, the stirring rotation speed of the electrodialysis electrolysis reaction is 0-3000 r/min, and is usually: 0 r/min (i.e. standing), 10 r/min, 20 r/min, 30 r/min, 40 r/min, 50 r/min, 60 r/min, 70 r/min, 80 r/min, 90 r/min, 100 r/min, 110 r/min, 120 r/min, 130 r/min, 140 r/min, 150 r/min, 180 r/min, 200 r/min, 240 r/min, 300 r/min, 500 r/min, 600 r/min, 700 r/min, 800 r/min, 900 r/min, 1000 r/min.
Preferably, in the fifth step, the same organic solvent (liquid) as the solvent (liquid) in the graphene solution is used as the polar water in the positive and negative electrode chambers of the electrodialysis cell.
Preferably, the electrodialysis cell in the fifth step is one or more of the following: a single-tank type electrolytic tank for placing one membrane pair, a double-tank type electrolytic tank for placing two membrane pairs and a multi-tank type electrolytic tank for placing a plurality of membrane pairs. Placing multiple pairs of membranes in the tank can improve process efficiency.
Preferably, the anion exchange membrane and the cation exchange membrane used in the electrodialysis electrolytic cell in the fifth step need to be homogeneous membranes with high exchange capacity, small porosity, low resistance, difficult leakage, good mechanical property, good thermal stability and good chemical stability. The exchange membrane is one or more of the following: cation exchange membranes, anion exchange membranes and proton exchange membranes, and the specifically used exchange membranes are public and commonly used exchange membranes.
Preferably, the graphene solution in the electrodialysis electrolytic cell in the fifth step is added in one of the following three ways: disposable, batch-wise, continuous.
Preferably, the electrodialysis cell in the fifth step is used in combination of one or two of the following: a fixed closed type electrolytic tank and an electrolytic tank with two open ends. The fixed closed electrolytic tank has no inlet end and outlet end, and the electrolyte in the tank has no fluidity. The electrolyte in the electrolytic tank with the two open ends has fluidity, the graphene solution flows in from the inlet end, flows out from the outlet end after electrodialysis electrolytic reaction, and the graphene solution in the tank is kept to have fluidity by a micropump, so that the electrodialysis electrolytic reaction can be continuously carried out.
Preferably, in the electrodialysis electrolysis in the fifth step, a plurality of open-ended cells may be used in combination. The graphene solution flows out from the outlet end after undergoing electrodialysis electrolysis reaction in the upper-stage electrolytic tank, enters the inlet end of the lower-stage electrolytic tank, and continues to undergo electrodialysis electrolysis reaction in the lower-stage electrolytic tank, so that the reaction efficiency is improved.
Preferably, in the electrodialysis electrolysis reaction in the fifth step, the relevant parameters of reaction voltage, reaction time, reaction temperature, stirring rotation speed, graphene solution adding rate and graphene solution flowing into and out of the electrolytic tank can be adjusted in the experimental process.
Preferably, the electrodialysis in the fifth step is used for removing residual moisture by electrolysis, wherein the moisture removal standard is that the moisture content in the graphene solution meets the requirement standard of downstream application on the moisture content.
Preferably, the graphene is uniformly dispersed in the organic solvent (liquid) in the fifth step, and the method further comprises uniformly dispersing the graphene after removing the moisture in a solution formed in the first organic solvent (liquid), and filtering and replacing the graphene with the second organic solvent (liquid) to obtain a solution formed by uniformly dispersing the graphene after removing the moisture in the second organic solvent (liquid). The organic solvent (liquid) used for filtration and replacement is one or more of the following: the hydrocarbon solvent (liquid), the halogenated hydrocarbon solvent (liquid), the alcohol solvent (liquid), the phenol solvent (liquid), the ether solvent (liquid), the aldehyde solvent (liquid), the ketone solvent (liquid), the ester solvent (liquid), the acid and acid anhydride solvent (liquid), the amine solvent (liquid), the amide solvent (liquid), the nitrile solvent (liquid), the nitrogen compound solvent (liquid), and the sulfur compound solvent (liquid), and the common organic solvent (liquid) are the same as those used for the filtration and the replacement in the third step, that is, the common organic solvent (liquid) exemplified in [0042 ].
Preferably, the filtration and displacement in the fifth step is performed in the same manner as the filtration and displacement in the third step.
Preferably, in order to meet the requirement of the concentration of the graphene solution in the application, the method for preparing the graphene can add more solvent (liquid) into the graphene solution or filter and remove the redundant solvent (liquid).
Preferably, in order to meet the requirement of drying graphene in application, the method for preparing graphene can be used for drying in a common manner to obtain dried graphene. Common drying modes include: air drying, natural air drying, freeze drying, vacuum drying, spray drying, microwave drying, and supercritical drying.
Preferably, the graphene prepared by the method can be used in the following fields: lithium ion battery, sodium ion battery, potassium ion battery, magnesium ion battery, lithium air battery, aluminum air battery, solid state battery, conductive agent, graphene paper, super capacitor, solar battery, light-transmitting coating, flexible display device, transparent conductive film, photodetector, heat dissipation coating, heat sink, heat generating sheet, conductive coating, conductive ink, conductive adhesive, antistatic coating, antistatic plastic, conductive rubber, conductive film, anticorrosive coating, metal composite, cable material, hydrogel, aerogel, 3D printing material, electromagnetic shielding material, chemical sensor, biosensor, blood sensor, gas sensor, drug carrier, medical imaging, building material, wear resistant coating, reinforced plastic, graphene tire, foaming material, water-impermeable plastic, reinforced material, graphene fiber, graphene brake sheet, carbon composite material, oil absorption sponge, seawater, sewage purification, seawater uranium extraction, seawater extraction lithium, analysis membrane, ion sieve, mask, catalyst carrier, hydrogen evolution catalyst, oxygen evolution catalyst.
The beneficial effects of the invention are as follows: the invention aims to provide a high-efficiency and excellent graphene preparation method, which has the following three advantages: (1) So that the graphene is uniformly dispersed in various organic solvents (liquids); (2) efficiently removing various impurities in the graphene; (3) Residual moisture in the graphene solution (organic system) is removed. By measuring the concentration of the graphene solution, the dispersion uniformity of graphene in the solvent (liquid) is good. By testing the moisture content in the graphene solution (organic system), it is known that the residual moisture in the graphene solution (organic system) is very small, meeting the criteria for moisture content for downstream applications.
The accompanying drawings of the specification.
Fig. 1 is a scanning electron microscope image of graphene oxide.
Fig. 2 is a scanning electron microscope image of graphene prepared according to the present invention.
Fig. 3 is an X-ray diffraction pattern of graphene oxide.
Fig. 4 is an X-ray diffraction pattern of graphene prepared in example 1.
Fig. 5 is a measured value, average value and standard deviation of the concentration of graphene solution (chemical reduction+dispersant).
Fig. 6 is a measurement, average and standard deviation of graphene solution (chemical reduction + dispersant + filter displacement) concentration.
Fig. 7 is a measurement, average and standard deviation of graphene solution (chemical reduction + dispersant + filtration displacement + electrodialysis electrolysis water removal) concentration.
Fig. 8 is a graph of the moisture content (organic system) of a graphene solution.
Fig. 9 is graphene solution conductivity.
Fig. 10 is a schematic diagram of electrodialysis electrolytic water removal.
FIG. 11 is a schematic diagram of the steps of the present invention.
Detailed Description
Example 1.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
And adding 20-g ascorbic acid into the solution, uniformly mixing, and standing at 15 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
500 mL of 30% hydrogen peroxide solution was added to the above solution, and the mixture was stirred at a rotation speed of 100 r/min at 15℃for 5 minutes, followed by standing for 24 hours, to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 350 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 1.6V for reaction for 24 hours under the standing condition of 5 ℃, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in ethanol.
Example 2.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding 10 g ascorbic acid into the solution, uniformly mixing, and standing at 0 ℃ for reaction for 2 hours to obtain a chemically reduced graphene solution.
60 g sodium percarbonate is added into the solution, the mixture is stirred and reacted for 5 minutes at the temperature of 20 ℃ at the rotating speed of 100 r/min, and then stirred and reacted for 24 hours at the rotating speed of 10 r/min, so that the uniformly dispersed graphene solution is obtained.
The above solution was filtered using a 400 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 2.0V for reaction for 4 hours under the standing condition of 10 ℃, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in ethanol.
Example 3.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
And adding 20-g ascorbic acid into the solution, uniformly mixing, and standing at 0 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
200 ml of 30% hydrogen peroxide solution and 30 g sodium carbonate are added into the solution, and after stirring and reacting for 5 minutes at a rotating speed of 100 r/min at 20 ℃, the mixture is left to stand for reacting for 20 hours, so as to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 300 mesh screen to give a black viscous sample.
And adding ethanol into the sample for multiple times, and repeatedly filtering to remove impurities to obtain a solution in which the graphene is uniformly dispersed in the ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, standing at 0 ℃, applying a constant voltage of 1.6V for reaction for 96 hours, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in ethanol.
And adding N-methyl pyrrolidone into the solution for multiple times, repeatedly filtering, and replacing ethanol with the N-methyl pyrrolidone to obtain a solution in which the graphene with water removed is uniformly dispersed in the N-methyl pyrrolidone.
Example 4.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding 5 g ascorbic acid and 15 g oxalic acid into the solution, uniformly mixing, and standing at 5 ℃ for reaction for 12 hours to obtain a chemically reduced graphene solution.
Adding 40 g sodium bicarbonate into the solution, stirring at a rotating speed of 100 r/min for reaction for 5 minutes at 20 ℃, and standing for reaction for 16 hours to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 350 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, and under the standing condition of 10 ℃, applying a constant voltage of 1.5V for electrolytic reaction for 6 hours in the step 1, applying a constant voltage of 1.6V for electrolytic reaction for 6 hours in the step 2, applying a constant voltage of 1.7V for electrolytic reaction for 6 hours in the step 3, applying a constant voltage of 1.8V for electrolytic reaction for 6 hours in the step 4, and removing residual moisture through electrodialysis electrolysis to obtain the solution of graphene uniformly dispersed in ethanol after moisture removal.
And adding dimethylbenzene into the solution for multiple times, repeatedly filtering, and replacing ethanol with dimethylbenzene to obtain a solution in which the graphene with water removed is uniformly dispersed in the dimethylbenzene.
Example 5.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
And adding 20-g ascorbic acid into the solution, uniformly mixing, and standing at 5 ℃ for reaction for 18 hours to obtain a chemically reduced graphene solution.
60 g potassium dichromate and 20 g ammonium sulfate are added into the solution, and after stirring and reacting for 5 minutes at 20 ℃ and a rotating speed of 100 r/min, the solution is kept stand for 24 hours, so that a uniformly dispersed graphene solution is obtained.
The above solution was filtered using a 400 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
Placing the solution into an electrodialysis electrolytic tank, standing at 10 ℃, applying a constant voltage of 1.4V for 12 hours, applying a constant voltage of 1.6V for 12 hours, applying a constant voltage of 1.8V for 12 hours, applying a constant voltage of 2.0V for 12 hours, applying a constant voltage of 1.4V for 24 hours, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after moisture removal is uniformly dispersed in ethanol.
And adding gasoline into the solution for multiple times, repeatedly filtering, and replacing ethanol with gasoline to obtain graphene solution which is uniformly dispersed in the gasoline after water is removed.
Example 6.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
And adding 35 g ascorbic acid into the solution, uniformly mixing, and standing at 10 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
50 g potassium permanganate is added into the solution, stirred at the rotating speed of 100 r/min for reaction for 5 minutes at the temperature of 20 ℃, and then the mixture is stood for 8 hours, so that a uniformly dispersed graphene solution is obtained.
The above solution was filtered using a 300 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
The solution was put into an electrodialysis cell, a multi-cell containing 3 membrane pairs was used, the constant voltage applied to each membrane pair was 2.0V, the electrodialysis was carried out for 6 hours at 5 ℃ under stationary conditions, and the residual moisture was removed by electrodialysis electrolysis, to obtain a solution in which the graphene after the removal of moisture was uniformly dispersed in ethanol.
And adding N, N-dimethylformamide into the solution for multiple times, repeatedly filtering, and replacing ethanol with the N, N-dimethylformamide to obtain a solution in which the graphene after the water removal is uniformly dispersed in the N, N-dimethylformamide.
Example 7.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
And adding 15 g ascorbic acid and 5 g hydrazine hydrate into the solution, uniformly mixing, and standing at 10 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
500 ml of 30% hydrogen peroxide solution was added to the above solution, and the mixture was stirred at 20℃and a rotation speed of 100 r/min for 5 minutes, followed by standing for 16 hours, to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 350 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 1.6V for reaction for 24 hours at the temperature of 5 ℃, stirring the solution in the tank at the rotating speed of 60 r/min in the reaction process, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in ethanol.
And adding N-methyl pyrrolidone into the solution for multiple times, repeatedly filtering, and replacing ethanol with the N-methyl pyrrolidone to obtain a solution in which the graphene with water removed is uniformly dispersed in the N-methyl pyrrolidone.
Example 8.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
And adding 25 g sodium ascorbate into the solution, uniformly mixing, and standing at 10 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
500 mL of 30% hydrogen peroxide solution was added to the above solution, and the mixture was stirred at a rotation speed of 100 r/min at 15℃for 5 minutes, followed by standing for 12 hours, to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 400 mesh screen to give a black viscous sample.
And adding ethanol into the sample for multiple times, repeatedly filtering, and removing impurities to obtain a solution in which the graphene is uniformly dispersed in the ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 1.8V for reaction for 24 hours at the temperature of 5 ℃, continuously adding the graphene solution which is prepared in one step and uniformly dispersed in ethanol in the reaction process by using a peristaltic pump, stirring the solution in the tank at the rotating speed of 60 r/min, and removing residual moisture through electrodialysis electrolysis to obtain the solution with the graphene uniformly dispersed in ethanol after the moisture removal.
Adding methanol into the solution for multiple times, repeatedly filtering, and replacing ethanol with methanol to obtain solution with graphene uniformly dispersed in methanol after removing water.
And adding acetone into the solution for multiple times, repeatedly filtering, and replacing methanol with acetone to obtain a solution in which the graphene with water removed is uniformly dispersed in the acetone.
Example 9.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding 40 g ascorbic acid into the solution, uniformly mixing, and standing at 0 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
1000 mL of 30% hydrogen peroxide solution was added to the above solution, and after stirring at a rotation speed of 100 r/min at 5℃for 5 minutes, the mixture was allowed to stand for 36 hours to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 300 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
Placing the solution into an electrodialysis electrolytic cell with two open ends, using a micropump to keep the graphene solution continuously entering and exiting the electrolytic cell at a certain flow rate, applying constant voltage of 2.1V for reaction for 4 hours at 5 ℃, and stirring the solution in the cell at a rotating speed of 60 r/min. And graphene solution flows in from the inlet end, is dehydrated through electrodialysis electrolytic reaction, and flows out from the outlet end to obtain a solution in which the graphene after the moisture is removed is uniformly dispersed in ethanol.
And adding rapeseed oil into the solution for multiple times, repeatedly filtering, and replacing ethanol by using the rapeseed oil to obtain a solution in which the graphene with water removed is uniformly dispersed in the rapeseed oil.
Example 10.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
20 mL of 25% ammonia water solution and 15 g glucose were added to the above solution, and the mixture was stirred at a stirring speed of 100 r/min at 90℃for 2 hours to obtain a chemically reduced graphene solution.
400 mL of 30% hydrogen peroxide solution was added to the above solution, and after stirring and reacting at a rotation speed of 100 r/min at 5℃for 5 minutes, the solution was allowed to stand for 20 hours to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 350 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And adding N-methyl pyrrolidone into the solution for multiple times, repeatedly filtering, and replacing ethanol with the N-methyl pyrrolidone to obtain a solution in which the graphene is uniformly dispersed in the N-methyl pyrrolidone.
And (3) placing the solution into an electrodialysis electrolytic tank, standing at 5 ℃, applying a constant voltage of 1.6V for reaction for 12 hours, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in the N-methylpyrrolidone.
Example 11.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding a proper amount of ammonia water into the solution, adjusting the pH to be 11, adding 20 g glucose, and stirring at the rotation speed of 600 r/min at the temperature of 90 ℃ for reaction for 2 hours to obtain a chemically reduced graphene solution.
5 g oxalic acid is added into the solution, and the graphene solution is obtained after glucose and oxalic acid are reduced together by stirring and reacting for 2 hours at 20 ℃ and a rotating speed of 200 r/min.
13.5 g ammonium chloride and 17.25 g sodium nitrite are added into the solution, and the mixture is stirred and reacted for 4 hours at the temperature of 85 ℃ and the rotating speed of 100 r/min, so as to obtain the uniformly dispersed graphene solution.
The above solution was filtered using a 400 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding N, N-dimethylformamide into the solution for multiple times, repeatedly filtering, and replacing water by using the N, N-dimethylformamide to obtain a solution in which the graphene is uniformly dispersed in the N, N-dimethylformamide.
And (3) placing the solution into an electrodialysis electrolytic cell, applying a constant voltage of 1.8V for reaction for 24 hours at the temperature of 25 ℃, stirring the solution in the cell at the rotating speed of 100 r/min, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in N, N-dimethylformamide.
Example 12.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding a proper amount of ammonia water into the solution, adjusting the pH to be 11, adding 15 g glucose, and stirring at the rotation speed of 120 r/min for reaction for 2 hours at the temperature of 90 ℃ to obtain a chemically reduced graphene solution.
And adding 20 g ammonium bicarbonate and 20 g ammonium nitrite into the solution, and stirring at a rotating speed of 30 r/min at 90 ℃ for reacting for 12 hours to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 300 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
Adding methanol into the solution for multiple times, repeatedly filtering, and replacing water with methanol to obtain a solution with graphene uniformly dispersed in methanol.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing methanol with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And (3) placing the graphene solution uniformly dispersed in ethanol into an electrodialysis electrolytic tank, applying a constant voltage of 1.9V for reaction for 6 hours at a standing condition of 5 ℃, and removing residual moisture through electrodialysis electrolysis to obtain a solution with the graphene uniformly dispersed in ethanol after the moisture is removed.
And adding N-methyl pyrrolidone into the solution for multiple times, repeatedly filtering, and replacing ethanol with the N-methyl pyrrolidone to obtain a solution in which the graphene with water removed is uniformly dispersed in the N-methyl pyrrolidone.
Example 13.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding a proper amount of ammonia water into the solution, adjusting the pH to be 11, adding 20 g hydrazine hydrate, and stirring at the rotating speed of 120 r/min at the temperature of 90 ℃ for reaction for 2 hours to obtain a chemically reduced graphene solution.
500 mL of 30% hydrogen peroxide solution was added to the above solution, and the mixture was stirred at a rotation speed of 100 r/min at 20℃for 5 minutes, followed by standing for 24 hours, to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 350 mesh screen to give a black viscous sample.
And adding ethanol into the sample for multiple times, repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the ethanol, and obtaining a solution in which graphene is uniformly dispersed in the ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 2.0V for reaction for 6 hours under the standing condition of 5 ℃, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in ethanol.
And adding ethyl acetate into the solution for multiple times, repeatedly filtering, and replacing ethanol with ethyl acetate to obtain a solution in which the graphene with water removed is uniformly dispersed in the ethyl acetate.
Example 14.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding 2 g ascorbic acid, 13g oxalic acid and 5 g citric acid into the solution, uniformly mixing, and standing at 10 ℃ for reaction for 32 hours to obtain a chemically reduced graphene solution.
20 g sodium carbonate, 20 mL of 37% hydrogen chloride solution and 15 g aluminum powder are added into the solution, and after stirring and reacting for 15 minutes at the rotating speed of 100 r/min at the temperature of 20 ℃, standing and reacting for 24 hours, the uniformly dispersed graphene solution is obtained.
The above solution was filtered using a 350 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 1.8V for reaction for 24 hours under the standing condition of 5 ℃, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in ethanol.
And adding chloroform into the solution for multiple times, repeatedly filtering, and replacing ethanol with chloroform to obtain a solution in which the graphene after the water is removed is uniformly dispersed in the chloroform.
Example 15.
1 g graphene oxide is taken and dissolved in 5L pure water, and the mixture is stirred for 2 hours by ultrasonic waves.
Adding 10 g sodium ascorbate, 10 g citric acid and 10 g oxalic acid into the solution, uniformly mixing, and standing at 15 ℃ for reaction for 24 hours to obtain a chemically reduced graphene solution.
10 mL of 37% hydrogen chloride solution and 20 g zinc powder are added into the solution, and after stirring and reacting for 5 minutes at the speed of 100 r/min at the temperature of 20 ℃, the solution is stood for reacting for 24 hours, so as to obtain the uniformly dispersed graphene solution.
The above solution was filtered using a 300 mesh screen to give a black viscous sample.
And adding pure water into the sample for multiple times, and repeatedly filtering to remove impurities until the conductivity of the filtrate is equal to that of the pure water, so as to obtain a solution in which graphene is uniformly dispersed in the pure water.
And adding ethanol into the solution for multiple times, repeatedly filtering, and replacing water with ethanol to obtain a solution in which graphene is uniformly dispersed in ethanol.
And adding N, N-dimethylformamide into the solution for multiple times, repeatedly filtering, and replacing ethanol with the N, N-dimethylformamide to obtain a solution in which the graphene is uniformly dispersed in the N, N-dimethylformamide.
And (3) placing the solution into an electrodialysis electrolytic tank, firstly applying a constant voltage of 1.5V for reaction for 12 hours at 25 ℃, then applying a constant voltage of 1.8V for reaction for 12 hours, stirring the solution in the tank at the rotating speed of 120 r/min, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the removal of the moisture is uniformly dispersed in N, N-dimethylformamide.
And (3) carrying out spray drying on the solution to obtain the dried graphene.
Example 16.
1 g graphene oxide was dissolved in 250 mL of N, N-dimethylformamide and stirred ultrasonically for 2 hours to form a graphene oxide solution of 4 mg/mL.
Adding 1 g ascorbic acid and 4 g sodium borohydride into the solution, and stirring at the rotation speed of 200 r/min at 15 ℃ for reaction for 6 hours to obtain a chemically reduced graphene solution.
50 mL of 30% hydrogen peroxide solution was added to the above solution, and the mixture was stirred at 20℃and a rotation speed of 200 r/min for 5 minutes, followed by standing for 18 hours, to obtain a uniformly dispersed graphene solution.
The above solution was filtered using a 400 mesh screen to give a black viscous sample.
And adding N, N-dimethylformamide into the sample for multiple times, and repeatedly filtering to remove impurities to obtain a solution in which the graphene is uniformly dispersed in the N, N-dimethylformamide.
And (3) placing the solution into an electrodialysis electrolytic tank, applying a constant voltage of 2.0V for reaction for 6 hours at a standing condition of 5 ℃, and removing residual moisture through electrodialysis electrolysis to obtain a solution in which the graphene after the moisture removal is uniformly dispersed in N, N-dimethylformamide.
Summary of the effects of the invention.
The reduction effect of graphene can be characterized by an X-ray diffraction pattern. The graphene oxide surface contains a large number of oxygen-containing functional groups, and the oxygen-containing functional groups increase the interplanar spacing of the graphene sheets. After reduction to remove the oxygen-containing functional group, the interplanar spacing becomes smaller. Bragg's law by crystalline X-ray diffraction: 2dsin theta=nλ, and according to the 2θ angle of the characteristic peak in the spectrum, the interplanar distance d can be calculated, so that the reduction effect of the graphene is judged. The X-ray wavelength used in the detection was 0.15406 nm, and the diffraction order n was 1. Fig. 3 is an X-ray diffraction pattern of graphene oxide, 2θ=12.93°, interplanar spacing d= 0.717858 nm. Fig. 4 is an X-ray diffraction pattern of graphene prepared in example 1, 2θ=25.37°, d= 0.350789nm, and d is reduced after chemical reduction, and the graphene is reduced.
The uniformity of the dispersion of graphene in a solution can be judged by measuring the mean and standard deviation of the concentration. A total of 12 samples were measured, 7 samples were taken from each group, and the mean and standard deviation of the concentrations were calculated from the measured values. FIG. 5 shows the measurement result of the concentration of graphene solution (chemical reduction+dispersing agent), wherein the average value of the concentration of a sample is distributed between 4.69 and 4.80 mg/mL, and the standard deviation is between 0.059 and 0.119 mg/mL. FIG. 6 shows the measurement result of graphene solution (chemical reduction+dispersant+filtration displacement) concentration, wherein the average sample concentration is distributed between 5.43 and 5.58 mg/mL, and the standard deviation is between 0.051 and 0.095 mg/mL. FIG. 7 shows the measurement result of the concentration of graphene solution (chemical reduction+dispersant+filtration replacement+electrodialysis electrolysis water removal), wherein the average value of the sample concentration is distributed between 5.89 and 6.01 mg/mL, and the standard deviation is between 0.053 and 0.104 mg/mL. And in consideration of experimental errors, the standard deviation of each sample is small, the concentration is uniform, and the uniformity of the dispersion of graphene in a solvent (liquid) is good. After the dispersing agent is added, the surface of the graphene adsorbs gas, so that the concentration of the solution is lower, the graphene is dispersed in the solvent (liquid), the dispersion is more loose, the space between the sheets is more, and other materials can enter the sheets more easily, so that a composite material is formed with the graphene. A small amount of gas escapes after the replacement of the solvent (liquid), the concentration is slightly improved, and the uniformity of the dispersion is unchanged. After electrodialysis electrolytic dehydration, the average value of the solution concentration is almost unchanged, and the standard deviation is very small, which indicates that the electrodialysis electrolytic dehydration does not influence the dispersion uniformity of graphene in an organic solvent (liquid). In conclusion, the graphene prepared by the method has good uniformity in dispersion in the organic solvent (liquid), the sheets are more dispersed, more space is reserved between the sheets, and the graphene is more beneficial to being compounded with other materials, so that the graphene has more application possibility in the downstream industry.
After electrodialysis electrolysis for water removal, the residual moisture content was measured by a karl fischer coulomb method using a trace moisture meter, and the measurement results are shown in fig. 8. As can be seen from fig. 8, the graphene solutions dispersed in different organic solvents (solutions) can all use the electrodialysis electrolysis method to remove residual moisture, and the residual moisture content in the finally obtained solution is very low, so that the requirement standard of many downstream applications on moisture can be met. The higher the voltage, the longer the electrolysis time and the lower the residual moisture content.
The effect of removing impurities in graphene can be illustrated by the conductivity of a solution, and the lower the conductivity of the solution is, the lower the impurity content is. Fig. 9 is a conductivity measurement result of graphene solution, and the lower the solution conductivity, the lower the impurity content. The solution before filtration contains a large amount of impurities, and the conductivity is high. Impurities are effectively removed after multiple times of filtration, and the conductivity of the solution is equal to that of the solvent (liquid), so that the invention is an efficient and feasible purification mode.
In summary, the invention provides a high-efficiency and excellent graphene preparation method, which has the following three effects: (1) So that the graphene is uniformly dispersed in various organic solvents (liquids); (2) efficiently removing various impurities in the graphene; (3) Residual moisture in the graphene solution (organic system) is removed.
The invention is not a matter of the known technology.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (10)

1. A method for preparing graphene, comprising the steps of:
firstly, mixing a graphene oxide solution with a reducing agent, and reacting to obtain a chemically reduced graphene solution;
secondly, adding the solution obtained in the first step into a dispersing agent, mixing and reacting to obtain a solution containing impurities, wherein the solution contains graphene uniformly dispersed;
thirdly, adding the solution obtained in the second step into a solvent (liquid), filtering and replacing to remove impurities in the graphene solution, and obtaining a solution with uniformly dispersed graphene after removing the impurities;
fourthly, adding the solution obtained in the third step into an organic solvent (liquid), filtering and replacing to obtain a solution in which the graphene is uniformly dispersed in the organic solvent (liquid);
and fifthly, placing the solution obtained in the fourth step into an electrodialysis electrolytic tank, and removing residual moisture by electrodialysis electrolysis to obtain a solution in which the graphene after the removal of the moisture is uniformly dispersed in an organic solvent (liquid).
2. The method for preparing graphene according to claim 1, wherein the reducing agent in the first step is one or more of the following: organic acids, borohydrides, citrates, ascorbates, alcohols, sugars, amino acids, sulfur-containing reducing agents, nitrogen-containing reducing agents, reducing plant extracts, metals, inorganic acids, bases; the mass ratio of the graphene oxide to the reducing agent is 1 (1-200), the reaction time of chemical reduction is 0-120 hours, the reaction temperature is-10-100 ℃, and the stirring speed of the reaction is 0-3000 r/min.
3. The method for preparing graphene according to claim 1, wherein the dispersant in the second step is one or more of the following: peroxides, superoxides, percarbonates, persulfates, permanganates and permanganates, manganates, ferrates and ferrates, chlorates and chlorates, carbonates, bicarbonates, bisulphates, ammonium salts, bichromates and bichromates, iodic acids and iodates, bromic and bromates, nitrous acids and nitrites, metals, metal hydrides, acids, bases, perborates, halogen intermetallics; the mass ratio of the dispersing agent to the initial graphene oxide is (1-1000) 1, the reaction time is 1 minute-120 hours after the dispersing agent is added, the reaction temperature is-10-100 ℃, and the reaction stirring speed is 0-3000 r/min.
4. The method for preparing graphene according to claim 1, wherein the solvent (liquid) is added for filtration and displacement in the third step, in one or more of the following combinations: normal pressure filtration, reduced pressure filtration, gravity filtration, vacuum filtration, centrifugal filtration, dialysis and soaking replacement; the equipment used is one or more of the following combinations: a filter screen, a filter membrane, a filter bag and a filter paper with the mesh number of 10-5000 meshes; the solvent (liquid) used is one of the following three: water, an organic solvent (liquid), and a mixed solution of water and the organic solvent (liquid), wherein the organic solvent (liquid) is one or more of the following mixed materials: hydrocarbon solvents (liquids), halogenated hydrocarbon solvents (liquids), alcohol solvents (liquids), phenol solvents (liquids), ether solvents (liquids), aldehyde solvents (liquids), ketone solvents (liquids), ester solvents (liquids), acid and acid anhydride solvents (liquids), amine solvents (liquids), amide solvents (liquids), nitrile solvents (liquids), nitrogen-containing compound solvents (liquids), sulfur-containing compound solvents (liquids).
5. The method for preparing graphene according to claim 1, wherein the removing of impurities in the graphene solution in the third step means adding a solvent (liquid) into the solution in which graphene is uniformly dispersed, filtering and replacing until the content of impurities in the graphene solution reaches the required standard for the content of impurities in the graphene solution in the downstream application, so as to obtain the solution in which graphene is uniformly dispersed after removing the impurities.
6. The method for preparing graphene according to claim 1, wherein the fourth step of adding an organic solvent (liquid) for filtration and displacement means a solution formed by uniformly dispersing graphene in a first solvent (liquid), and adding an organic solvent (liquid) as a second solvent (liquid) for displacement to obtain a solution formed by uniformly dispersing graphene in a second organic solvent (liquid); the organic solvent (liquid) used for filtration and replacement is the same as the organic solvent (liquid) used for filtration and replacement in the third step.
7. The method for preparing graphene according to claim 1, wherein the electrolytic cell used in the electrodialysis electrolysis in the fifth step contains one or more electrodialysis membrane pairs; the same organic solvent (liquid) as the graphene solution is used as the polar water in the anode chamber and the cathode chamber of the electrolytic cell; the mode of adding the graphene solution into the electrolytic tank is one of the following three modes: adding at one time, adding in batches and continuously adding; the electrolytic tank is used by one or two of the following components: a fixed closed type electrolytic tank and an electrolytic tank with two open ends.
8. The method for preparing graphene according to claim 1, wherein in the fifth step, a constant voltage power supply is used for electrodialysis electrolysis, the constant voltage applied to each electrodialysis membrane pair is 1.0-10.0V, the reaction time is 10 seconds to 120 hours, the reaction temperature is-40-200 ℃, and the reaction stirring speed is 0-3000 r/min.
9. The method for preparing graphene according to claim 1, wherein the electrodialysis is performed to remove residual moisture in the fifth step, and the moisture removal criterion is that the moisture content in the graphene solution meets the requirement criterion of downstream application for moisture content.
10. The method for preparing graphene according to claim 1, wherein the graphene is uniformly dispersed in an organic solvent (liquid) in the fifth step, and further comprising uniformly dispersing the graphene after the removal of the moisture in a solution formed in the first organic solvent (liquid), and filtering and replacing the solution with a second organic solvent (liquid) to obtain a solution formed by uniformly dispersing the graphene after the removal of the moisture in the second organic solvent (liquid); the organic solvent (liquid) used for filtration and replacement is the same as the organic solvent (liquid) used for filtration and replacement in the third step.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118067702A (en) * 2024-04-24 2024-05-24 北京理工大学 Ultraviolet/visible spectrophotometry for sensitively and rapidly detecting total triterpene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118067702A (en) * 2024-04-24 2024-05-24 北京理工大学 Ultraviolet/visible spectrophotometry for sensitively and rapidly detecting total triterpene
CN118067702B (en) * 2024-04-24 2024-08-09 北京理工大学 Ultraviolet/visible spectrophotometry for sensitively and rapidly detecting total triterpene

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