An electrolyte slurry for continuously electrochemically reducing graphene oxide to prepare reduced graphene in a liquid flow

Abstract

The present invention provides an electrolyte slurry for preparing reduced graphene by continuous electrochemical reduction of graphene oxide in a liquid flow, belonging to the technical field of graphene material preparation. The electrolyte slurry is composed of graphene oxide and an electrolyte, wherein the electrolyte is composed of an electrolyte, a solvent, and an additive; the additive is a surfactant and / or a reducing agent; the graphene oxide is pure graphene oxide, or a graphene oxide mixture containing a certain concentration of graphite or graphite oxide. In the electrolyte slurry, the mass concentration of graphene oxide is 0.01-100g / L, and the concentration of the electrolyte in the electrolyte is 0.01 to 30mol / L. The electrolyte slurry of the present invention can be used for continuous electrochemical reduction of graphene oxide in a liquid flow, and can produce reduced graphene continuously, stably, at low cost, and in a green large-scale manner.

Description

Technical Field

[0001] The invention relates to the technical field of graphene material preparation, and in particular to an electrolyte slurry for preparing reduced graphene by continuous electrochemical reduction of graphene oxide through liquid flow. Background Art

[0002] Graphene is composed of a single layer of sp 2 The honeycomb hexagonal planar two-dimensional crystal formed by the arrangement of hybrid carbon atoms, on the two-dimensional plane, sp 2 The hybridized carbon atoms are connected to three adjacent carbon atoms through σ bonds. The remaining p electron orbitals are perpendicular to the graphene plane and form large π bonds with the surrounding atoms, which gives graphene good electrical and thermal conductivity and mechanical properties. The electron mobility is as high as 200,000 cm 2 / (V·s), conductivity reaches 10 6 Graphene boasts a high 1000 W / (m·K) / s, a thermal conductivity of 5000 W / (m·K), and a strength of 130 GPa. These exceptional properties offer enormous potential for applications in optoelectronic devices, chemical power sources (such as solar cells and lithium-ion batteries), gas sensors, antistatic and heat dissipation materials, and other fields. However, this requires high-quality graphene that can be produced on a large scale. However, current preparation methods present significant challenges for industrial application.

[0003] Among existing graphene production technologies, redox processing is the mainstream method for industrial graphene production, offering high yields and ease of scalable production. However, the graphene oxide obtained through chemical oxidation contains numerous oxygen-containing functional groups, creating numerous structural defects that significantly reduce the electrical and thermal conductivity of graphene. Reduction treatment is required to obtain higher-quality graphene products.

[0004] Existing reduction methods mainly include chemical reduction and thermal reduction. The chemical reduction method requires the use of strong reducing agents (such as hydrazine, hydrazine hydrate, dimethylhydrazine, sodium borohydride, potassium borohydride, etc.). The reduction process will cause serious environmental pollution, which is not conducive to environmental protection and green production. The thermal reduction method requires the use of a high-temperature environment above 1000°C, which has problems such as high energy consumption, making the production cost of graphene high. As a result, the existing mainstream reduction methods are not conducive to the large-scale industrial production and large-scale industrial application of high-quality graphene.

[0005] The Chinese invention patent with publication number CN104593802B discloses an electrochemical preparation method for graphene, which includes providing an electrode with electrocatalytic activity, dripping a graphene oxide solution onto the surface of the pre-treated electrocatalytic electrode, and drying to obtain a graphene oxide-modified electrode; immersing the graphene oxide-modified electrode in a salt solution with a concentration of 10 mmol / L to 500 mmol / L and a pH of 7, adjusting the electrode potential to -1.2V to -2V, and reacting for 1s to 1h to obtain the desired graphene. The disadvantage of this method is that due to the small amount of graphene oxide modified with the electrode, the preparation efficiency and yield of the reduced graphene are low, and it can only be operated intermittently, not continuously. The drop casting method reduces graphene oxide on the electrode. In addition to the disadvantages of low yield and complex operation, the reduced graphene oxide obtained on the electrode is mostly a graphene film, which cannot be dispersed and reused separately. It has a narrow application scenario and is mostly used for sensor electrodes.

[0006] Chinese invention patent publication number CN106676562B discloses a method for preparing graphene through electrochemical reduction, comprising the following steps: first, adding graphite oxide to deionized water and ultrasonically exfoliating to obtain a graphene oxide solution; adding sulfuric acid to the graphene oxide solution, then electroreducing it at a voltage of 1.5V for 10 minutes to 2 hours, filtering it, and then washing it with water to obtain the graphene. This invention uses concentrated sulfuric acid as the electrolyte to dehydrate the graphene, and then further combines this with electrochemical reduction of the graphene. The method has the advantages of simple process, high reproducibility, high yield, and easy control. However, graphene has strong adsorption properties and has a high adsorption capacity for viscous sulfuric acid, which makes subsequent cleaning and separation particularly difficult. This is also one of the important factors that generally lead to significant cost increases in the current oxidation method for preparing graphene. In addition, in a pure acidic electrolyte system, graphene is prone to agglomeration and sedimentation. The patent emphasizes the use of sulfuric acid with a mass concentration of 98% (wt) precisely because it takes advantage of the viscous nature of concentrated sulfuric acid, allowing graphene to exist stably in the electrolyte. Graphene cannot be stably dispersed in ordinary sulfuric acid solutions, and the small amount of sulfuric acid remaining in the graphene after cleaning will also have a great impact on downstream application scenarios. At the same time, this method is a laboratory preparation method. When it is scaled up industrially, the gas generated during the reaction forms foam and a surface film on the surface of the graphene oxide solution, forming a micro-short circuit, which makes it impossible to smoothly carry out electrochemical reduction. After reduction, the π electrons on the graphene surface return to a free state. Due to its large specific surface area, the π-π interaction between carbon atoms, and the van der Waals force between the sheets, the graphene sheets are adsorbed together and easily agglomerated, which is not conducive to subsequent applications.

[0007] Based on the above statements, although there are patents or literature reports on electrochemical reduction of graphene oxide, there are still significant technical challenges in applying the electrochemical method to scale up or mass-produce reduced graphene oxide.

[0008] Liquid flow continuous electrochemical reduction of graphene oxide is a new preparation technology for reducing graphene that was first developed by the applicant. This method realizes the electrochemical reduction of electrolyte slurry during the circulation process to obtain high-quality graphene, breaking the limitation that existing electrochemical reduction can only prepare small amounts of graphene through electrode modification or intermittent operation in the laboratory using simple beakers and other components. The system is stable and suitable for industrial amplification and large-scale continuous production. It can improve the utilization rate of raw materials, enhance the reduction effect of graphene oxide, and significantly improve the reduction capacity. It is environmentally friendly, energy-saving and low-cost. It is a method for continuous, stable, green, low-cost, and industrial-scale production of reduced graphene. The electrolyte slurry protected by this application is also one of the key factors in achieving this goal. Summary of the Invention

[0009] The object of the present invention is to provide an electrolyte slurry for preparing reduced graphene by liquid flow continuous electrochemical reduction of graphene oxide in order to solve the above-mentioned problems. The electrolyte slurry can be used for liquid flow continuous electrochemical reduction of graphene oxide, and can prepare reduced graphene continuously, stably, greenly, at low cost and on a large scale.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0011] Disclosed is an electrolyte slurry for preparing reduced graphene by continuous electrochemical reduction of graphene oxide in a liquid flow. The electrolyte slurry consists of graphene oxide and an electrolyte, wherein the electrolyte consists of an electrolyte, a solvent, and an additive; the additive is a surfactant and / or a reducing agent; and the graphene oxide is pure graphene oxide or a graphene oxide mixture containing a certain concentration of graphite or graphite oxide.

[0012] In the present invention, preferably, the mass concentration of graphene oxide in the electrolyte slurry is 0.01-100 g / L.

[0013] In the present invention, preferably, the electrolyte is an acidic electrolyte, a neutral electrolyte or an alkaline electrolyte, and the concentration of the electrolyte in the electrolyte is 0.01 to 30 mol / L.

[0014] In the present invention, preferably, the solvent can be one or more combinations of pure water, methanol, ethanol, ethylene glycol, glycerol, isopropyl alcohol, propanol, propylene glycol, butanol, butylene glycol, isobutyl alcohol, pentanol, isopentanol, octanol, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, nitrogen methyl pyrrolidone, and ethyl acetate.

[0015] In the present invention, preferably, the mass ratio of the graphene oxide to the additive is 1:0.001 to 1:0.4.

[0016] In the present invention, preferably, the surfactant is sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium octadecyl sulfate, tetrabutylammonium acetate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetramethylammonium fluoride, tetraethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, choline chloride, tetrabutylammonium fluoride, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium perchlorate, tetramethylammonium perchlorate, tetra-n-hexylammonium perchlorate, tetrapropylammonium perchlorate, tridecylmethylammonium chloride, dodecyl ammonium chloride, tetraethylammonium bromide, tetramethylammonium chloride, tetraethylammonium perchlorate, tetramethylammonium perchlorate, tetra-n-hexylammonium perchlorate, tetrapropylammonium perchlorate, tridecylmethylammonium chloride, dodecyl ammonium chloride, tetraethylammonium bromide, tetraethyl ...ethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium perchlorate, tetraethylammonium per Alkyltrimethylammonium bromide, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, decanyltrimethylammonium bromide, N,N,N-trimethyl-1-tetradecylammonium bromide, tetramethylammonium iodide, tetrabutylammonium trifluoromethanesulfonate, octadecyltrimethylammonium bromide, polyvinylpyrrolidone, sodium cholate, polyoxyethylene lauryl ether, Tween 20-80, Span 20-80, polyvinyl alcohol or one or more combinations thereof. In the present invention, the purpose of adding a surfactant is to enable the slurry to be uniformly dispersed. For slurries with high graphite content, graphite is easy to settle. On the original basis, some surfactant needs to be added to make it more stable. In actual production, the amount of the surfactant can be appropriately selected and adjusted according to the content and composition of the slurry. For raw materials with a relatively high graphene oxide content, a small amount of surfactant can achieve a stable effect.

[0017] In the present invention, preferably, the reducing agent is one or more combinations of zinc-acetic acid, diisobutylaluminum hydride, triethylsilane, dicarbonyldicyclopentadienyltitanium, and glucose. In the present invention, the reducing agent is used as a reducing agent, and its amount can be adjusted according to the oxygen content of the graphene oxide in the electrolyte slurry. For electrolyte slurries with high oxygen content, the amount of the reducing agent can be increased. For electrolyte slurries with low oxygen content, the reduction effect can be achieved by adding less or no reducing agent.

[0018] In the present invention, preferably, the electrolyte is an acidic electrolyte, which can be one or more combinations of formic acid, acetic acid, phytic acid, oxalic acid, nitrous acid, sulfurous acid, phosphoric acid, ascorbic acid, citric acid, and malic acid.

[0019] In the present invention, preferably, the electrolyte is a neutral electrolyte, which can be one or more combinations of sulfate, sulfite, nitrate, and perchlorate. The sulfate is one or more combinations of sodium sulfate, potassium sulfate, lithium sulfate, or ammonium sulfate. The sulfite is one or more combinations of sodium sulfite, lithium sulfite, potassium sulfite, and ammonium sulfite. The perchlorate is one or more combinations of ammonium perchlorate, sodium perchlorate, lithium perchlorate, and potassium perchlorate.

[0020] In the present invention, preferably, the electrolyte is an alkaline electrolyte, which can be one or more combinations of inorganic bases or organic base compounds, and can also be an inorganic base, a quaternary ammonium base, a thiosulfate, a quaternary ammonium perchlorate, a halogen quaternary ammonium salt, and an acid root quaternary ammonium salt. The inorganic base is one or more combinations of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, and lithium hydroxide; the thiosulfate is one or more combinations of sodium thiosulfate, lithium thiosulfate, ammonium thiosulfate, and potassium thiosulfate; the halogen quaternary ammonium salt is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; and the quaternary ammonium base is one or more of choline and hexamethylammonium hydroxide.

[0021] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0022] 1. The main oxygen-containing groups in the graphene oxide structure are hydroxyl, epoxy and carboxyl groups. Whether they can be effectively removed is the key to preparing reduced graphene. The present invention uses a neutral, acidic or alkaline electrolyte solution as the background conductive electrolyte. The electrolyte provides conductive ions in the electrochemical reduction process. The additive contains a portion of a reducing agent for reducing graphene oxide, which can promote the cathode to produce more hydrogen radicals and react with the graphene oxide flowing through the cathode surface. Hydrogen radicals have strong reducing properties and react efficiently and quickly. They capture the oxygen functional groups in the graphene oxide structure to generate water molecules or gases to achieve the purpose of removing the graphene oxygen-containing groups. The additive also contains a portion of a surfactant to prevent the graphite and graphene in the slurry from settling and agglomerating. Therefore, the electrolyte slurry of the present invention can be used for liquid flow continuous electrochemical reduction of graphene oxide, and can prepare reduced graphene continuously, stably, greenly, at low cost and on a large scale.

[0023] 2. When graphene is prepared by electrochemical reduction of graphene oxide in the prior art, since the amount of graphene oxide used for the modified electrode is relatively small, it is usually necessary to use purer graphene oxide to avoid the impurity graphite contained therein making the current effect weak and reducing the reduction effect. The graphene oxide used in the slurry of the present invention is not limited to a source. The graphene oxide material obtained by chemical oxidation or the slightly oxidized graphene material obtained by electrochemical stripping can be used as raw materials, and the characteristic that the raw materials also contain a portion of graphite impurities can be used to serve the production of the present invention. Using such a graphene oxide mixture can, on the one hand, reduce the process of separating and purifying graphene from graphite and graphene mixture materials, has a low technical threshold, and is easier to source raw materials. On the other hand, the graphite edge opened after chemical intercalation or electrochemical intercalation can be directly used as a stabilizer for graphene in the electrolyte. In addition, after homogenization, the graphite, graphene oxide and electrolyte become a slurry, which flows creepingly in the electrolytic cell. When passing through the electrode surface, it has a longer contact time with the electrode. At the same time, the graphite particles in the slurry can act as a conductor, forming a "cathode-graphite-graphene" conductive path when flowing through the cathode surface, so that the current of the electrode is not only distributed on its own surface, but also diffused in the slurry. The entire creeping graphene oxide slurry acts as an extension of the cathode, improving the reduction efficiency. Therefore, electrochemical reduction occurs not only near the surface of the cathode conductor, but also in the creeping slurry. At the same time, graphite as a conductor disperses the surface current of the cathode conductor, increasing the reaction area and reaction sites of the electrode. In addition, the slow circulation of the electrolyte in the electrolytic cell gives graphene oxide more opportunities and longer time to participate in the reduction reaction, so that the electrical energy is more fully utilized, the degree of reduction is more sufficient, and the reduction efficiency is higher. In addition, after the current is dispersed, the bubbles precipitated on the surface of the cathode conductor are reduced, further strengthening the contact between the cathode conductor and the slurry, and reducing the interface resistance, so that the expansion of the slurry as the cathode is further enhanced. Therefore, the slurry of the present invention can improve the utilization rate of raw materials, enhance the reduction effect of graphene oxide, and at the same time can significantly increase the reduction capacity, is environmentally friendly, energy-saving and low-cost.

[0024] 3. The reduced graphene produced by continuous electrochemical reduction of graphene oxide using the electrolyte slurry of the present invention is less likely to agglomerate. A highly dispersed graphene solution or slurry can be obtained through simple washing and separation. Existing graphene oxide reduction technologies have difficulty achieving good dispersion in solvents after reduction of graphene oxide.

[0025] 4. The electrolyte slurry of the present invention does not involve strong reducing agents such as hydrazine, hydrazine hydrate, dimethylhydrazine, sodium borohydride, potassium borohydride, etc., which can avoid serious environmental pollution caused by the reduction process. At the same time, it does not involve the high temperature conditions used in the thermal reduction method, which can comprehensively reduce the production cost of reduced graphene and is conducive to the industrial mass production of graphene. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a scanning electron microscope image of the reduced graphene obtained in the present invention.

[0027] Figure 2 This is a state diagram of the reduced graphene slurry obtained in the present invention after being stored for 6 months. DETAILED DESCRIPTION

[0028] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] The present invention provides an electrolyte slurry for preparing reduced graphene by continuous electrochemical reduction of graphene oxide in a liquid flow manner. The electrolyte slurry is composed of graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive; the additive is a surfactant and / or a reducing agent; and the graphene oxide is pure graphene oxide or a graphene oxide mixture containing a certain concentration of graphite or graphite oxide. The electrolyte and additive function in the electrochemical reduction process to provide conductive ions, act as stabilizers for uniformly dispersing the graphene oxide, and act as reducing agents for reducing the graphene oxide.

[0030] In some embodiments of the present invention, the mass concentration of the graphene oxide is 0.01-100 g / L.

[0031] In some embodiments of the present invention, the electrolyte is preferably an acidic electrolyte, a neutral electrolyte or an alkaline electrolyte, and the concentration of the electrolyte in the electrolyte is 0.01 to 30 mol / L.

[0032] In some embodiments of the present invention, the solvent may be one or more of pure water, methanol, ethanol, ethylene glycol, glycerol, isopropyl alcohol, propanol, propylene glycol, butanol, butanediol, isobutyl alcohol, pentanol, isopentanol, octanol, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, nitrogen-methyl pyrrolidone, and ethyl acetate.

[0033] In some embodiments of the present invention, the mass ratio of the graphene oxide to the additive is preferably 1:0.001 to 1:0.4.

[0034] In some embodiments of the present invention, the surfactant is preferably sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium octadecyl sulfate, tetrabutylammonium acetate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetramethylammonium fluoride, tetraethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, choline chloride, tetrabutylammonium fluoride, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium perchlorate, tetramethylammonium perchlorate, tetrahexylammonium perchlorate, tetrapropylammonium perchlorate, tridecylmethylammonium chloride , dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, decantrimethylammonium bromide, N,N,N-trimethyl-1-tetradecylammonium bromide, tetramethylammonium iodide, tetrabutylammonium trifluoromethanesulfonate, octadecyltrimethylammonium bromide, polyvinyl pyrrolidone, sodium cholate, polyoxyethylene lauryl ether, Tween 20-80, Span 20-80, and polyvinyl alcohol. One or more combinations thereof.

[0035] In some embodiments of the present invention, the reducing agent is preferably one or more combinations of zinc-acetic acid, diisobutylaluminum hydride, triethylsilane, dicyclopentadienyltitanium dicarbonyl, and glucose.

[0036] In some embodiments of the present invention, the electrolyte is preferably an acidic electrolyte, which can be one or more combinations of formic acid, carboxylic acid, acetic acid, phytic acid, carbonic acid, oxalic acid, nitrous acid, sulfurous acid, phosphoric acid, ascorbic acid, citric acid, and malic acid.

[0037] In some embodiments of the present invention, the electrolyte is preferably a neutral electrolyte, which can be one or more combinations of sulfate, sulfite, chloride, nitrate, and perchlorate. The sulfate is one or more combinations of sodium sulfate, potassium sulfate, lithium sulfate, or ammonium sulfate. The sulfite is one or more combinations of sodium sulfite, lithium sulfite, potassium sulfite, and ammonium sulfite. The perchlorate is one or more combinations of ammonium perchlorate, sodium perchlorate, lithium perchlorate, and potassium perchlorate.

[0038] In some embodiments of the present invention, the electrolyte is an alkaline electrolyte, which can be one or more combinations of inorganic bases or organic base compounds, and can also be quaternary ammonium bases, thiosulfates, quaternary ammonium perchlorates, halogen quaternary ammonium salts, and acid root quaternary ammonium salts; the inorganic base is one or more combinations of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, and lithium hydroxide; the thiosulfate is one or more combinations of sodium thiosulfate, lithium thiosulfate, ammonium thiosulfate, and potassium thiosulfate; the halogen quaternary ammonium salt is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; the quaternary ammonium base is one or more of choline and hexamethylammonium hydroxide; the organic base is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and hexamethylammonium hydroxide.

[0039] The electrochemical reduction device used in the following examples is an electrochemical reduction device assembled using a cathode electrode, an anode electrode, an electrolytic cell, a power supply, and a circulation pump. The cathode electrode and the anode electrode are both plate-shaped and arranged in the electrolytic cell and are respectively connected to a power supply. The electrolyte slurry is slowly circulated in the electrolytic cell by the action of the circulation pump.

[0040] Example 1

[0041] An electrolyte slurry for preparing reduced graphene by continuous electrochemical reduction of graphene oxide in a liquid flow is provided. The electrolyte slurry comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first dissolving and uniformly mixing an electrolyte carboxylic acid, a solvent pure water, a surfactant sodium dodecylbenzenesulfonate, and a reducing agent zinc-acetic acid to form an electrolyte. The graphene oxide material and the electrolyte are then thoroughly mixed to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 0.01 g / L, the concentration of the electrolyte in the electrolyte is 0.01 mol / L, the mass ratio of the graphene oxide to the sodium dodecylbenzenesulfonate is 1:0.001, and the mass ratio of the graphene oxide to the reducing agent zinc-acetic acid is 1:0.001.

[0042] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 12 m / min. The electrochemical reduction voltage was 7 V and the reduction temperature was 28°C.

[0043] Example 2

[0044] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry of reduced graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte acetic acid, a solvent (the solvent is a mixed solution of water and methanol, with a volume ratio of 9.5:0.5), the surfactant sodium octadecyl sulfate, and the reducing agent diisobutylaluminum hydride to form an electrolyte. The graphene oxide material and the electrolyte are then fully mixed to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 0.05 g / L, the concentration of the electrolyte in the electrolyte is 0.1 mol / L, the mass ratio of the graphene oxide to the sodium octadecyl sulfate is 1:0.003, and the mass ratio of the graphene oxide to the reducing agent diisobutylaluminum hydride is 1:0.002.

[0045] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 10 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 30°C.

[0046] Example 3

[0047] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, consisting of graphene oxide and an electrolyte, wherein the electrolyte consists of an electrolyte, a solvent and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte phytic acid, a solvent (the solvent is a mixed solution of water and ethanol, with a volume ratio of 9:1), a surfactant tetrabutylammonium acetate and a reducing agent triethyl silicon, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material with the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 0.1 g / L, the concentration of the electrolyte in the electrolyte is 1 mol / L, the mass ratio of the graphene oxide to the tetrabutylammonium acetate is 1:0.007, and the mass ratio of the graphene oxide to the triethyl silicon is 1:0.003.

[0048] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 8 m / min. The electrochemical reduction voltage was 3 V and the reduction temperature was 40°C.

[0049] Example 4

[0050] A kind of liquid flow continuous electrochemical reduction graphene oxide prepares the electrolyte slurry of reduced graphene, is composed of graphene oxide and electrolyte, wherein electrolyte is composed of electrolyte, solvent and additive.Additive is surfactant and reducing agent.Prepare electrolyte slurry, first take electrolyte carbonic acid, solvent (solvent is water and ethylene glycol mixed solution, volume ratio 9: 1), surfactant choline chloride and reducing agent dicarbonyl dicyclopentadienyl titanium, dissolve and mix uniformly, be configured to electrolyte, then graphene oxide material and electrolyte are fully mixed uniformly, obtain described electrolyte slurry.Wherein the mass concentration of graphene oxide is 0.3g / L, the concentration of electrolyte in electrolyte is 0.5mol / L, the mass ratio of graphene oxide to choline chloride is 1: 0.008, and the mass ratio of graphene oxide to dicarbonyl dicyclopentadienyl titanium is 1: 0.004.

[0051] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 7 m / min. The electrochemical reduction voltage was 10 V and the reduction temperature was 35°C.

[0052] Example 5

[0053] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reduced graphene, comprising graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte oxalic acid, a solvent (a mixed solution of water and glycerol, in a volume ratio of 9:1), and the additive tetrapropylammonium perchlorate to form an electrolyte, and then thoroughly mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 0.8 g / L, the concentration of the electrolyte in the electrolyte is 0.8 mol / L, and the mass ratio of the graphene oxide to the tetrapropylammonium perchlorate is 1:0.001.

[0054] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 6 m / min. The electrochemical reduction voltage was 2 V and the reduction temperature was 36°C.

[0055] Example 6

[0056] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry of reduced graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first dissolving and uniformly mixing an electrolyte silicic acid, a solvent (a mixed solution of water and isopropyl alcohol, with a volume ratio of 9:1), a surfactant tridecylmethylammonium chloride, and a reducing agent zinc-acetic acid to form an electrolyte. The graphene oxide material and the electrolyte are then fully mixed to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 1 g / L, the concentration of the electrolyte in the electrolyte is 1 mol / L, the mass ratio of the graphene oxide to the tridecylmethylammonium chloride is 1:0.009, and the mass ratio of the graphene oxide to the reducing agent zinc-acetic acid is 0.01.

[0057] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 5 m / min. The electrochemical reduction voltage was 10 V and the reduction temperature was 32°C.

[0058] Example 7

[0059] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reduced graphene, comprising graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte nitrous acid, a solvent (the solvent is a mixed solution of water and propanol, with a volume ratio of 9:1), the surfactant hexadecyltrimethylammonium bromide, and the reducing agent diisobutylaluminum hydride to form an electrolyte, and then thoroughly mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 2 g / L, the concentration of the electrolyte in the electrolyte is 3 mol / L, the mass ratio of the graphene oxide to the hexadecyltrimethylammonium bromide is 1:0.01, and the mass ratio of the graphene oxide to the diisobutylaluminum hydride is 1:0.01.

[0060] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 4 m / min. The electrochemical reduction voltage was 10 V and the reduction temperature was 35°C.

[0061] Example 8

[0062] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking an electrolyte, citric acid, a solvent (the solvent is a mixed solution of water and propylene glycol, with a volume ratio of 9:1), a surfactant, decanyltrimethylammonium bromide, and a reducing agent, diisobutylaluminum hydride, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 3 g / L, the concentration of the electrolyte in the electrolyte is 5 mol / L, the mass ratio of the graphene oxide to the decanyltrimethylammonium bromide is 1:0.03, and the mass ratio of the graphene oxide to the diisobutylaluminum hydride is 1:0.007.

[0063] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 3 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0064] Example 9

[0065] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry of reduced graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additive is a surfactant reducing agent. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte sodium sulfate, a solvent (the solvent is a mixed solution of water and butanol, with a volume ratio of 8:2), the surfactant N,N,N-trimethyl-1-tetradecylammonium bromide, and the reducing agent triethylsilane to form an electrolyte. The graphene oxide material and the electrolyte are then thoroughly mixed to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 8 g / L, the concentration of the electrolyte in the electrolyte is 8 mol / L, the mass ratio of the graphene oxide to the N,N,N-trimethyl-1-tetradecylammonium bromide is 1:0.02, and the mass ratio of the graphene oxide to the triethylsilane is 1:0.01.

[0066] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 2 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0067] Example 10

[0068] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte lithium sulfite, a solvent (the solvent is a mixed solution of water and butanediol, with a volume ratio of 9:1), a surfactant tetramethylammonium iodide, and a reducing agent triethylsilane, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 10 g / L, the concentration of the electrolyte in the electrolyte is 10 mol / L, the mass ratio of the graphene oxide to the tetramethylammonium iodide is 1:0.05, and the mass ratio of the graphene oxide to the triethylsilane is 1:0.008.

[0069] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 2 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0070] Example 11

[0071] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, comprising graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte carbonic acid, a solvent (the solvent is a mixed solution of water and isobutanol, with a volume ratio of 9:1), and a surfactant tetrabutylammonium trifluoromethanesulfonate to form an electrolyte, and then fully mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 15 g / L, the concentration of the electrolyte in the electrolyte is 12 mol / L, and the mass ratio of the graphene oxide to the tetrabutylammonium trifluoromethanesulfonate is 1:0.08.

[0072] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 1 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0073] Example 12

[0074] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, consisting of graphene oxide and an electrolyte, wherein the electrolyte consists of an electrolyte, a solvent, and an additive. The electrolyte slurry is prepared by first taking the electrolyte ammonium perchlorate, a solvent (the solvent is a mixed solution of water and amyl alcohol, with a volume ratio of 9:1), and the additives polyvinyl pyrrolidone and glucose, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material with the electrolyte to obtain the electrolyte slurry. The mass concentration of graphene oxide is 20 g / L, the concentration of the electrolyte in the electrolyte is 14 mol / L, the mass ratio of graphene oxide to polyvinyl pyrrolidone is 1:0.01, and the mass ratio of graphene oxide to glucose is 1:0.01.

[0075] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 0.9 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35° C.

[0076] Example 13

[0077] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, comprising graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte ammonium sulfite, a solvent (the solvent is a mixed solution of water and isoamyl alcohol, with a volume ratio of 9:1), polyvinyl alcohol, and zinc-acetic acid as additives to form an electrolyte, and then fully mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 30 g / L, the concentration of the electrolyte in the electrolyte is 15 mol / L, the mass ratio of the graphene oxide to the polyvinyl alcohol is 1:0.2, and the mass ratio of the graphene oxide to the zinc-acetic acid is 1:0.2.

[0078] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 6 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0079] Example 14

[0080] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, comprising graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte sodium hydroxide, a solvent (the solvent is a mixed solution of water and butyl octanol, with a volume ratio of 9:1), a surfactant polyoxyethylene lauryl ether, and a reducing agent diisobutylaluminum hydride, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material with the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 40 g / L, the concentration of the electrolyte in the electrolyte is 18 mol / L, the mass ratio of the graphene oxide to the polyoxyethylene lauryl ether is 1:0.08, and the mass ratio of the graphene oxide to the diisobutylaluminum hydride is 1:0.05.

[0081] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 5 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0082] Example 15

[0083] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte sodium carbonate, a solvent (the solvent is a mixed solution of water and ethanol, with a volume ratio of 9:1), the surfactant Tween 20, and the reducing agent tetrabutylammonium chloride, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 50 g / L, the concentration of the electrolyte in the electrolyte is 20 mol / L, the mass ratio of the graphene oxide to the Tween 20 is 1:0.12, and the mass ratio of the graphene oxide to the tetrabutylammonium chloride is 1:0.02.

[0084] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 4 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0085] Example 16

[0086] An electrolyte slurry for preparing reduced graphene by continuous electrochemical reduction of graphene oxide in a liquid flow is provided. The electrolyte slurry comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first dissolving and uniformly mixing the electrolyte sodium bicarbonate, a solvent (a mixed solution of water and N,N-dimethylformamide in a volume ratio of 9:1), the surfactant Tween 80, and the reducing agent zinc-acetic acid to form an electrolyte. The graphene oxide material and the electrolyte are then thoroughly mixed to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 60 g / L, the concentration of the electrolyte in the electrolyte is 30 mol / L, the mass ratio of the graphene oxide to the Tween 80 is 1:0.15, and the mass ratio of the graphene oxide to the zinc-acetic acid is 1:0.10.

[0087] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 3 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0088] Example 17

[0089] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, consisting of graphene oxide and an electrolyte, wherein the electrolyte consists of an electrolyte, a solvent and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte sodium thiosulfate, a solvent (the solvent is water), Span 80 and reduced diisobutylaluminum hydride, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material with the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 70g / L, the concentration of the electrolyte in the electrolyte is 12mol / L, the mass ratio of the graphene oxide to Span 80 is 1:0.08, and the mass ratio of the graphene oxide to the diisobutylaluminum hydride is 1:0.02.

[0090] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 0.1 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35° C.

[0091] Example 18

[0092] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene comprises graphene oxide and an electrolyte, wherein the electrolyte comprises an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte tetramethylammonium hydroxide, a solvent (the solvent is a mixed solution of water and tetrahydrofuran, with a volume ratio of 9:1), a surfactant Span 20, and an additive triethyl silicon, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material and the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 80 g / L, the concentration of the electrolyte in the electrolyte is 12 mol / L, the mass ratio of the graphene oxide to the Span 20 is 1:0.04, and the mass ratio of the graphene oxide to the triethyl silicon is 1:0.05.

[0093] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 2 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35°C.

[0094] Example 19

[0095] A kind of liquid flow continuous electrochemical reduction graphene oxide prepares the electrolyte slurry of reduced graphene, is composed of graphene oxide and electrolyte, wherein electrolyte is composed of electrolyte, solvent and additive.Additive is surfactant and reducing agent.Prepare electrolyte slurry, first take electrolyte tetrabutylammonium hydroxide, solvent (solvent is water and dimethyl sulfoxide mixed solution, volume ratio 9: 1), surfactant tetraethylammonium perchlorate and reducing agent dicarbonyl dicyclopentadienyl titanium, dissolve and mix uniformly, be configured to electrolyte, then graphene oxide material and electrolyte are fully mixed uniformly, obtain described electrolyte slurry.Wherein the mass concentration of graphene oxide is 90g / L, the concentration of electrolyte in electrolyte is 12mol / L, the mass ratio of graphene oxide to tetraethylammonium perchlorate is 1: 0.06, and the mass ratio of graphene oxide to dicarbonyl dicyclopentadienyl titanium is 1: 0.03.

[0096] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into the electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 1 m / min. The electrochemical reduction voltage was 5 V, the reduction temperature was 35° C., and the reduction time was 25 h.

[0097] Example 20

[0098] A liquid flow continuous electrochemical reduction of graphene oxide to prepare an electrolyte slurry for reducing graphene, consisting of graphene oxide and an electrolyte, wherein the electrolyte consists of an electrolyte, a solvent, and an additive. The additives are a surfactant and a reducing agent. The electrolyte slurry is prepared by first taking the electrolyte hexamethylammonium hydroxide, a solvent (the solvent is a mixed solution of water and nitrogen methyl pyrrolidone, with a volume ratio of 9:1), a surfactant sodium lauryl sulfate, and a reducing agent diisobutylaluminum hydride, dissolving and mixing them uniformly to form an electrolyte, and then fully mixing the graphene oxide material with the electrolyte to obtain the electrolyte slurry. The mass concentration of the graphene oxide is 100 g / L, the concentration of the electrolyte in the electrolyte is 12 mol / L, the mass ratio of the graphene oxide to the sodium lauryl sulfate is 1:0.01, and the mass ratio of the graphene oxide to the diisobutylaluminum hydride is 1:0.04.

[0099] Graphene was prepared using the electrolyte slurry of this embodiment. The electrolyte slurry was injected into an electrolytic cell and allowed to circulate slowly in the electrolytic cell at a flow rate of 0.1 m / min. The electrochemical reduction voltage was 5 V and the reduction temperature was 35° C.

[0100] Using the method of the embodiment of the present invention, the oxygen content of the graphene oxide before reduction is 53.6%-56.7% (the present invention is not limited to this range), and the oxygen content after reduction can be controlled within 20% according to different working conditions, and can be as low as 3%. The obtained reduced graphene is not easy to agglomerate, and a highly dispersed graphene solution or slurry can be obtained after simple cleaning and separation. The results of scanning electron microscopy show that the prepared graphene / carbon composite material has good uniformity. Figure 1 The graphene solution slurry was stored for 10 days, 2 months, and 6 months. The slurry uniformity was still good and no agglomeration occurred. Figure 2 .

[0101] In addition, it is worth pointing out that the graphene obtained by conventional reduction inevitably produces irreversible agglomeration during the reduction process. Even through subsequent crushing and ultrasound, it is difficult to achieve good dispersion, which also limits the application field of reduced graphene oxide. Among the current mainstream graphene application fields, the fields of energy storage and composite materials are the most representative, and both fields require highly dispersed graphene slurries or solutions to prepare uniform and stable materials. Other fields, such as graphene heat dissipation materials, optoelectronic devices and other fields also require highly dispersed graphene products. The slurry of the present invention is used to produce reduced graphene oxide, and the reduction is carried out in a stably dispersed slurry system. The process does not cause the agglomeration of graphene, and another significant feature of electrochemistry is that by controlling the electrochemical reduction parameters, the reduction degree of graphene oxide can be directly adjusted, and a certain type of group on the face or edge of graphene oxide can be removed, achieving the purpose of repairing the structure without losing its good dispersibility in the solvent. Reduced graphene oxide with different reduction degrees has a wider range of applicable working conditions.

[0102] The above description is a detailed description of the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the patent application of the present invention. Any equivalent changes or modifications completed under the technical spirit suggested by the present invention should fall within the patent scope covered by the present invention.

Claims

1. An application of an electrolyte slurry in the preparation of reduced graphene by continuous electrochemical reduction of graphene oxide, characterized in that: The electrolyte slurry is composed of graphene oxide and an electrolyte, wherein the electrolyte is composed of an electrolyte, a solvent and an additive; the additive is a surfactant and / or a reducing agent; the graphene oxide is pure graphene oxide, or a graphene oxide mixture containing a certain concentration of graphite or graphite oxide; the application method is: using an electrochemical reduction device assembled with a cathode electrode, an anode electrode, an electrolytic cell, a power supply and a circulation pump, wherein the cathode electrode and the anode electrode are both plate-shaped and arranged in the electrolytic cell, and are respectively connected to a power supply, and the electrolyte slurry is slowly circulated in the electrolytic cell by the action of the circulation pump.

2. The use according to claim 1, characterized in that: In the electrolyte slurry, the mass concentration of graphene oxide is 0.01-100 g / L.

3. The use according to claim 1, characterized in that: The electrolyte is an acidic electrolyte, a neutral electrolyte or an alkaline electrolyte, and the concentration of the electrolyte in the electrolyte is 0.01-30 mol / L.

4. The use according to claim 1, characterized in that: The solvent is one or a combination of pure water, methanol, ethanol, ethylene glycol, glycerol, isopropyl alcohol, propanol, propylene glycol, butanol, butanediol, isobutyl alcohol, amyl alcohol, isopentanol, and octanol.

5. The use according to claim 1, characterized in that: The mass ratio of the graphene oxide to the additive is 1:0.001 to 1:0.

4.

6. The use according to claim 1, characterized in that: The surfactant is sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium octadecyl sulfate, tetrabutylammonium acetate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetramethylammonium fluoride, tetraethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, choline chloride, tetrabutylammonium fluoride, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium perchlorate, tetramethylammonium perchlorate, tetra-n-hexylammonium perchlorate, tetrapropylammonium perchlorate, tridecylmethyl ammonium One or more combinations of ammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetramethylammonium iodide, tetrabutylammonium trifluoromethanesulfonate, octadecyltrimethylammonium bromide, polyvinyl pyrrolidone, sodium cholate, polyoxyethylene lauryl ether, Tween 20-80, Span 20-80, and polyvinyl alcohol.

7. The use according to claim 1, characterized in that: The reducing agent is one or more combinations of zinc-acetic acid, diisobutylaluminum hydride, triethylsilane, dicarbonyldicyclopentadienyltitanium, and glucose.

8. The use according to claim 1, characterized in that: The electrolyte is an acidic electrolyte, which is one or more combinations of formic acid, acetic acid, phytic acid, carbonic acid, oxalic acid, nitrous acid, sulfurous acid, phosphoric acid, ascorbic acid, citric acid, and malic acid.

9. The use according to claim 1, characterized in that: The electrolyte is a neutral electrolyte, which is one or more combinations of sulfate, sulfite, nitrate, and perchlorate; the sulfate is one or more combinations of sodium sulfate, potassium sulfate, lithium sulfate, or ammonium sulfate; the sulfite is one or more combinations of sodium sulfite, lithium sulfite, potassium sulfite, and ammonium sulfite; and the perchlorate is one or more combinations of ammonium perchlorate, sodium perchlorate, lithium perchlorate, and potassium perchlorate.

10. The use according to claim 1, characterized in that: The electrolyte is an alkaline electrolyte, which is one or more combinations of inorganic base or organic base compounds.

11. The use according to claim 10, characterized in that: The alkaline electrolyte is a quaternary ammonium base, a thiosulfate or an acid radical quaternary ammonium salt.

12. The use according to claim 11, characterized in that: The inorganic base is one or more combinations of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, and lithium hydroxide; the thiosulfate is one or more combinations of sodium thiosulfate, lithium thiosulfate, ammonium thiosulfate, and potassium thiosulfate; the organic base is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, hexamethylammonium hydroxide, and choline.

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