CN113830760B - Method for preparing graphene oxide by stable electrolysis - Google Patents
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Abstract
The invention relates to the field of graphene oxide preparation, in particular to a method for preparing graphene oxide by stable electrolysis. In the two-phase liquid which is incompatible with the isolation protection liquid and the electrolyte, the intercalated graphite electrode is soaked in the isolation protection liquid and then gradually enters the electrolyte, the counter electrode is placed in the electrolyte, voltage is applied between the intercalated graphite electrode and the counter electrode, and the intercalated graphite electrode is electrified, oxidized and peeled off. Then separating the material from incompatible two-phase liquid, and then carrying out shearing stripping, cleaning, acid removal and other procedures to obtain the graphene oxide product. The method has the characteristics of no metal impurities in the product, controllable oxidation degree of graphene, stable electrolysis process, no wetting of electrolyte, long-time continuous production and the like.
Description
Technical Field
The invention relates to the field of graphene oxide preparation, in particular to a method for preparing graphene oxide by stable electrolysis.
Background
Graphene oxide is the most important derivative of graphene because graphene oxide is grafted with a large number of oxygen-containing functional groups on the two-dimensional carbon planes of graphite, such as: hydroxyl, epoxy, carbonyl, carboxyl, and the like. The surface of the inert graphene is converted into a hydrophilic active surface, and the graphene oxide is more convenient to compound and apply with various materials due to the characteristics of easy dispersion, easy film formation and easy functionalization during application. Currently, graphene oxide is widely applied to a plurality of application fields such as polymer composite materials, filtering membrane materials, high heat conduction materials, medicines, catalyst carriers, super capacitor materials and the like.
Currently, the more established graphene oxide preparation method is generally the Hummers method or its modified method. The basic idea is that in the concentrated sulfuric acid environment, the composite strong oxidant is utilized to carry out strong oxidation treatment on graphite flake or powder material to obtain graphite oxide, and then the graphite oxide is peeled off to obtain graphene oxide, and the method has the defects of unsafety, environmental protection, low quality and the like. The invention in China (publication No. CN107215867A, patent No. 201610167450.9) proposes a method for continuously preparing graphene oxide microplates based on electrochemical treatment, namely, continuous graphite products such as flexible graphite coiled materials, strips or carbon fiber wires are used as raw materials, and the graphene oxide microplates are peeled into the graphene oxide microplates through electrochemical intercalation and electrolytic oxidation peeling in sequence under the driving of a feeding device. The patent method sequentially passes through a two-step electrolysis process of concentrated sulfuric acid electrolysis intercalation and dilute sulfuric acid electrolysis oxidation stripping, and is more scientific than the previous one-step acid or salt electrolysis graphene stripping method of a plurality of patents or documents, the oxidation degree is controllable, and the oxidation reaction is more fully and uniformly. However, the greatest disadvantage of this method is that the intercalated graphite compound after electrolysis intercalation is unstable, and when water in the electrolyte or water vapor in the air is encountered, intercalation is easily removed, so that the intercalation electrode is failed, and thus cannot enter the next oxidation stripping stage, so that there is a need for a method capable of stabilizing the intercalated graphite compound without affecting the second step of electrolysis oxidation stripping.
Disclosure of Invention
The invention aims to provide a method for preparing graphene oxide by stable electrolysis, which solves the problems that when the graphene oxide is prepared by the existing two-step electrolysis method, intercalation graphite absorbs water and is separated out due to moisture absorption, the quality of an electrolyzed product is reduced, and even intercalation oxidation is impossible.
In order to solve the problems, the technical scheme of the invention is as follows:
in the method, in two-phase liquid incompatible with an isolation protection liquid and an electrolyte, a graphite electrode after intercalation is soaked in the isolation protection liquid, then gradually enters the electrolyte, a counter electrode is placed in the electrolyte, voltage is applied between the intercalated graphite electrode and the counter electrode, and the intercalation graphite electrode is electrified, oxidized and peeled off; then separating the solid phase material from the incompatible two-phase liquid, and then carrying out shearing stripping, cleaning and acid removal procedures to obtain the graphene oxide product.
According to the method for preparing graphene oxide by stable electrolysis, the isolation protection liquid is used for maintaining the intercalation state of the graphite electrode, does not react with the intercalation agent and the electrolyte, and is incompatible with the electrolyte; the isolation protective liquid comprises one or more than two of saturated alkane, cycloalkane, isoparaffin, aromatic hydrocarbon and unsaturated hydrocarbon.
In the method for preparing graphene oxide by stable electrolysis, preferably, the isolation protection liquid is 26 # liquid paraffin oil, 32 # paraffin oil or D65 # white oil mixed by a plurality of alkanes.
In the method for preparing graphene oxide by stable electrolysis, the intercalated graphite electrode is placed in electrolyte for electrolytic oxidation stripping, wherein the electrolyte in the electrolyte comprises one or more than two mixtures of sulfuric acid, nitric acid, perchloric acid, ammonium sulfate, sodium sulfate and potassium perchlorate, and the solvent in the electrolyte comprises one or more than two mixtures of water, formyl, ethanol and acetone.
In the method for preparing graphene oxide by stable electrolysis, the intercalation graphite electrode is a first-order or low-order graphite interlayer compound, and the graphite material comprises, but is not limited to, graphite paper, graphite fiber, graphite powder or graphite plate.
The intercalation agent includes but is not limited to sulfuric acid, nitric acid, perchloric acid, sulfur trioxide, ferric trichloride or aluminum chloride.
According to the method for preparing graphene oxide by stable electrolysis, the intercalation graphite electrode gradually enters the electrolyte from the isolation protection liquid, wherein the entering mode comprises one mode or a mixture of more than two modes of intermittent or continuous intercalation of the intercalation graphite electrode into the electrolyte, intermittent or continuous increase of the electrolyte and intermittent or continuous decrease of the isolation protection liquid; the speed range of the intercalation graphite electrode gradually entering the electrolyte from the isolation protection liquid is 0.01 mm-100 mm/min.
In the method for preparing graphene oxide by stable electrolysis, the voltage applied between the intercalation graphite electrode and the counter electrode comprises direct current voltage, pulse voltage or alternating current voltage, and the voltage range is 1V-10 kV.
According to the method for preparing graphene oxide by stable electrolysis, solid phase materials are separated from incompatible two-phase liquid, and the separation method comprises one or more than two mixing methods of a static settlement method, a centrifugal settlement method, a screen filtering method and a squeezing method.
The design principle of the invention is as follows:
the two-step electrolysis is used as an efficient, safe and green process method for preparing graphene oxide, so that the graphene oxide is more and more widely applied to gradually replacing the traditional oxidation method. In order to make the intercalation agent absorb moisture or water and release when the intercalation graphite electrode contacts with air or electrolyte, the phenomenon of absorbing moisture or water is eliminated by adopting an isolating protective liquid layer.
Saturated liquid saturated alkanes, cycloalkanes, isoparaffins, aromatic hydrocarbons, unsaturated hydrocarbons and mixtures thereof in the range of 0 ℃ to 80 ℃ can be rendered immiscible with the intercalating agent or electrolyte and also non-reactive after mixing with the electrolyte and the intercalating agent. This can act as an inert, water-barrier layer to prevent water vapor in the air or water in the electrolyte from contacting the intercalation agent in the intercalation electrode, causing the intercalation agent to absorb moisture or water and to de-intercalate the graphite electrode. Meanwhile, the method can also keep the concentration of the electrolyte for a long time, and the electrolyte of the electrolytic tank can be continuously used.
The invention has the advantages that:
1. as the components of the electrolyte for isolating and protecting the liquid layer, the electrolyte meets the requirements of the liquid which is not reacted and is not mutually dissolved after being mixed with the intercalation agent and the electrolyte, and can protect the intercalation agent in the intercalation electrode from being separated out due to water absorption for a long period.
2. Can keep liquid state within the temperature range of 0-80 ℃, can be mutually insoluble with the electrolyte layer and split phases when standing, and is convenient for reuse after separation.
3. In the long-time second-step oxidation stripping, the anode intercalation graphite electrode immersed in the paraffin oil can not absorb water from the air or the electrolyte for a long time to fail.
Drawings
FIG. 1 is a schematic diagram of a dedicated apparatus for a method of preparing graphene oxide by stable electrolysis;
in the figure, a separating agent liquid layer 1, a separating agent overflow port 2, a negative electrode graphite electrode plate 3, a positive electrode intercalation graphite electrode 4, an electrolyte inlet and outlet 5, an electrolyte liquid layer 6 and an electrolytic cell 7.
Detailed Description
As shown in fig. 1, the special device for preparing graphene oxide by stable electrolysis of the invention mainly comprises: the separator liquid layer 1, the separator overflow port 2, the negative electrode graphite electrode plate 3, the positive electrode intercalation graphite electrode 4, the electrolyte inlet and outlet 5, the electrolyte liquid layer 6 and the electrolytic cell 7 have the following specific structures:
the inner cavity of the electrolytic cell 7 is provided with a separating agent liquid layer 1 and an electrolyte liquid layer 6 in a layered manner. The upper part of the side surface of the electrolytic cell 7 is communicated with a horizontal isolating agent overflow port 2, the lower part of the side surface of the electrolytic cell 7 is communicated with a horizontal electrolyte inlet and outlet 5, and two negative graphite electrode plates 3 (counter electrodes) and one positive intercalated graphite electrode 4 are inserted into the isolating agent liquid layer 1 and the electrolyte liquid layer 6.
The present invention will be described below with reference to a few specific examples for better understanding of the present invention, but the embodiments of the present invention are not limited to the following examples.
Example 1
In the embodiment, no. 26 liquid paraffin oil is used as an isolation protection liquid and 70wt% sulfuric acid aqueous solution is used as an electrolyte, two incompatible two-phase liquids are used, the paraffin oil has small density, and the paraffin oil is positioned above the sulfuric acid liquid level. And (3) immersing the graphite paper subjected to concentrated sulfuric acid intercalation as an anode intercalation graphite electrode in a paraffin oil isolation protection liquid. Then gradually downwards extending into sulfuric acid electrolyte, placing negative graphite electrode plate counter electrode in the electrolyte, applying direct current voltage between intercalation graphite electrode and counter electrode, electrifying, oxidizing and stripping. The speed of the positive electrode intercalation graphite electrode entering the electrolyte is 1mm/min, and a direct current voltage of 4V is applied. And separating the graphene oxide material from the incompatible two-phase liquid after the electrolytic oxidation stripping is finished, and then performing the procedures of shearing stripping, cleaning, acid removal and the like to obtain a graphene oxide product.
The method has the characteristics of no metal impurities in the product, controllable oxidation degree of graphene, stable electrolysis process, no wetting of electrolyte, long-time continuous production and the like. The single-layer rate of the obtained graphene oxide solution is 95%, wherein the distribution range of the graphene oxide sheet diameter is 1-10 mu m, the thickness range of the graphene oxide sheet layer is 1-3 nanometers, and the carbon-oxygen mole ratio is 1.6. The yield from the graphite raw material to the graphene oxide solution was 160wt%.
Example 2
In the embodiment, 32 # liquid paraffin oil is used as an isolation protection liquid and 65wt% sulfuric acid aqueous solution is used as an electrolyte, two incompatible two-phase liquids are used, the paraffin oil has small density, and the paraffin oil is positioned above the sulfuric acid liquid level. And (3) immersing the graphite fiber which is intercalated by the concentrated sulfuric acid into the isolating protection liquid of paraffin oil as an anode intercalated graphite electrode. Then injecting sulfuric acid electrolyte through the electrolyte inlet and outlet step by step, placing a negative graphite electrode plate counter electrode in the electrolyte, applying alternating voltage between the intercalation graphite electrode and the counter electrode, and electrifying, oxidizing and stripping. The liquid level of the sulfuric acid electrolyte was raised at a rate of 1.5mm/min, and an alternating voltage of 5V was applied. When the liquid level rises, excessive isolation protection liquid can flow out from the overflow port to the corresponding special container, and the special container can be reused. After the reaction is finished, separating an upper isolation protection liquid layer and a lower dilute sulfuric acid aqueous solution layer containing materials through standing and phase separation, shearing and stripping the aqueous phase material layer by a high-speed shearing machine, and then cleaning, deacidifying and concentrating by a cross-flow machine to obtain the graphene oxide aqueous slurry solution. The separated protective liquid layer can be reused after being accumulated. The single-layer rate of the obtained graphene oxide solution is 75%, wherein the distribution range of the graphene oxide sheet diameter is 1-15 mu m, the thickness range of the graphene oxide sheet layer is 1-5 nanometers, and the carbon-oxygen mole ratio is 2.1. The yield from the graphite raw material to the graphene oxide solution was 120wt%.
Example 3
In the embodiment, D65 white oil is used as an isolation protection liquid and an ammonium sulfate aqueous solution with the concentration of 20wt% is used as an electrolyte, two incompatible two-phase liquids are used, the paraffin oil has small density, and the paraffin oil is positioned above the sulfuric acid liquid level. And (3) immersing the graphite paper subjected to concentrated sulfuric acid intercalation as an anode intercalation graphite electrode in a paraffin oil isolation protection liquid. Then gradually downwards extending into ammonium sulfate electrolyte, placing a negative graphite electrode plate counter electrode in the electrolyte, applying alternating voltage between the intercalation graphite electrode and the counter electrode, and electrifying, oxidizing and stripping. The speed of the positive electrode intercalation graphite electrode entering the electrolyte is 2mm/min, and an alternating voltage of 5V is applied. After the reaction is finished, separating an upper isolation protection liquid layer and a lower ammonium sulfate aqueous solution layer containing materials through standing and phase separation, shearing and stripping the aqueous material layer by a high-speed shearing machine, and then cleaning and concentrating by a cross-flow machine to obtain the graphene oxide aqueous slurry solution. The separated protective liquid layer can be reused after being accumulated. The single-layer rate of the obtained graphene oxide solution is 40%, wherein the distribution range of the graphene oxide sheet diameter is 1-30 mu m, the thickness range of the graphene oxide sheet layer is 0.5-5 nanometers, and the carbon-oxygen molar ratio is 3.2. The yield from the graphite raw material to the graphene oxide solution was 90wt%.
The result shows that the method can realize green, efficient and low-cost preparation of the graphene oxide, has controllable graphene oxidation degree and stable electrolysis process, can realize continuous production without wetting electrolyte, and has great application value. The above three examples are further illustrative of the present invention in which the isolation protective solution, electrolyte and electrolytic oxidative stripping process can be modified and improved in several ways, and are also considered to be within the scope of the present invention without departing from the principles of the present technology.
Claims (9)
1. A method for preparing graphene oxide by stable electrolysis is characterized in that in two-phase liquid incompatible with an isolation protection liquid and an electrolyte, a graphite electrode after intercalation is soaked in the isolation protection liquid, then gradually enters the electrolyte, a counter electrode is placed in the electrolyte, voltage is applied between the intercalation graphite electrode and the counter electrode, and electrification oxidation stripping is performed; then separating the solid phase material from incompatible two-phase liquid, and performing shearing stripping, cleaning and acid removal procedures to obtain a graphene oxide product;
the isolating protective liquid is used for maintaining the intercalation state of the graphite electrode, does not react with the intercalation agent and the electrolyte, and is incompatible with the electrolyte; the isolating protective liquid is used as an inert water-resisting layer to prevent water vapor in air or water in the electrolyte from contacting with the intercalation agent in the intercalation electrode, so that the intercalation agent absorbs moisture or water to separate from the graphite electrode, and the concentration of the electrolyte is maintained.
2. The method for preparing graphene oxide by stable electrolysis according to claim 1, wherein the isolation and protection liquid comprises one or a mixture of more than two of saturated alkane, cycloalkane, isoparaffin, aromatic hydrocarbon and unsaturated hydrocarbon.
3. The method for preparing graphene oxide by stable electrolysis according to claim 2, wherein the isolating protection liquid is preferably a liquid paraffin oil No. 26, a paraffin oil No. 32 or a white oil No. D65, which are mixed by a plurality of alkanes.
4. The method for preparing graphene oxide by stable electrolysis according to claim 1 or 2, wherein the intercalated graphite electrode is placed in an electrolyte for electrolytic oxidation stripping, the electrolyte in the electrolyte comprises one or more than two mixtures of sulfuric acid, nitric acid, perchloric acid, ammonium sulfate, sodium sulfate and potassium perchlorate, and the solvent in the electrolyte comprises one or more than two mixtures of water, formyl, ethanol and acetone.
5. The method of preparing graphene oxide by stable electrolysis according to claim 1, wherein the intercalated graphite electrode is a first or lower order graphite intercalation compound, and the graphite material includes, but is not limited to, graphite paper, graphite fiber, graphite powder or graphite sheet.
6. The method of preparing graphene oxide by stable electrolysis according to claim 1, wherein the intercalating agent includes, but is not limited to, sulfuric acid, nitric acid, perchloric acid, sulfur trioxide, ferric trichloride or aluminum chloride.
7. The method for preparing graphene oxide by stable electrolysis according to claim 1, wherein the intercalation graphite electrode gradually enters the electrolyte from the isolation protection liquid, the entering mode comprises one mode or a mixture effect of two or more modes of intermittent or continuous intercalation of the intercalation graphite electrode into the electrolyte, intermittent or continuous increase of the electrolyte, and intermittent or continuous decrease of the isolation protection liquid; the speed range of the intercalation graphite electrode gradually entering the electrolyte from the isolation protection liquid is 0.01 mm-100 mm/min.
8. The method for preparing graphene oxide by stable electrolysis according to claim 1, wherein the voltage applied between the intercalation graphite electrode and the counter electrode comprises a direct current voltage, a pulse voltage or an alternating current voltage, and the voltage is in the range of 1V to 10kV.
9. The method for preparing graphene oxide by stable electrolysis according to claim 1, wherein the solid phase material is separated from incompatible two-phase liquid, and the separation method comprises one or more of a static sedimentation method, a centrifugal sedimentation method, a screen filtration method and a pressing method.
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