CN108117065B - Method for preparing graphene by adopting alternate current stripping - Google Patents
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Abstract
A method for preparing graphene by adopting alternate current stripping belongs to the field of graphene preparation. The method comprises the following specific steps: 1. preparing electrolyte solution with certain concentration; 2. high-purity graphite plates are used as a positive electrode and a negative electrode, the distance between the polar plates is fixed, and the high-purity graphite plates are circularly stripped in electrolyte in a mode of regularly exchanging the electrodes; 3. stripping is completed after a certain time, the electrode is taken out, and the electrolyte is filtered and washed; 4. and (4) taking the solid, performing ultrasonic dispersion uniformly, and centrifuging to obtain a supernatant, namely the graphene. The method is simple and convenient in operation process, and is easy for preparing the graphene with low oxidation degree in a large scale. By adopting the alternative electrode stripping method, the graphene can be stripped at the anode and then immediately reduced by adopting cathode current, so that the prepared graphene is low in oxidation degree and small in defect. Graphene with specific sheet diameter size (100 nanometers to several micrometers) can be prepared by adjusting proper alternating frequency, the single-layer and double-layer rate is up to more than 80%, and the graphene has wider application in biological pharmacy and composite materials.
Description
Technical Field
The invention belongs to the field of graphene preparation, and particularly relates to a preparation method for stripping graphene by adopting alternating current.
Background
The graphene is formed by passing sp through carbon atoms2Six-membered ring lattice structure materials formed by hybridization were first produced in 2004 by Andre geom and konstatin Novoselov, british scientists, using tape to exfoliate graphite. The graphene layer is very thin, has a thickness of only one atomic layer, is about 0.335nm, and is the most strong material known in the world, and the strength of the graphene layer is as high as 130 GP. The theoretical value of the specific surface area of the graphene is about 2600m2The thermal conductivity at room temperature reaches (5.3 +/-0.48) multiplied by 103W·m-1·K-1The breaking strength and Young modulus are respectively as high as 40N/m and 1.0TPa, and the composite material has good electric conductivity, heat conductivity and mechanical properties. The excellent performance determines that the graphene has wide application prospects in many fields, such as super capacitors, electrochemical sensors, field effect transistors, microbial fuel cells, dye-sensitized solar cells and the like, so that the research heat of the scientific community on the graphene is brought.
In view of the bright application prospect of graphene, how to prepare high-quality and applicable graphene at low cost is an important research content faced by scientists at the present stage. The main methods used at present are chemical and electrochemical methods, and various peeling methods and their advantages and disadvantages are described in detail below.
The chemical methods mainly include a mechanical exfoliation method, a graphite oxide reduction method, a Chemical Vapor Deposition (CVD) method, an epitaxial growth method, and the like. The mechanical stripping method is a method of stripping graphene from a graphite material by applying a certain mechanical force to the graphite material. The method has the defects of large preparation contingency, inconsistent product graphene size, low yield, incapability of realizing large-area and large-scale preparation of the graphene, simple process and high sample quality, and is suitable for basic research in laboratories. The graphite oxide reduction method is to adopt strong acid and strong oxide action or heat treatment of natural graphite to obtain graphene oxide, and remove related oxygen-containing groups by using a reducing agent after ultrasonic dispersion to obtain reduced graphene oxide. The method has the advantages of low cost and capability of realizing the mass production of the graphene. However, part of oxygen-containing functional groups in graphene prepared by a redox method cannot be completely removed, the crystal structure is damaged to a certain extent, and a complete graphene lamellar structure is difficult to obtain, so that some physical and chemical properties are lost. CVD is to deposit carbon atoms on the surface of a substrate to form single-layer graphene in decomposable high-temperature hydrocarbon gas through high-temperature annealing, and the method has the characteristics of controllability, simple process, capability of producing large-area (up to several square meters) graphene and the like. However, the prepared graphene has crystal boundary defects, pinholes, wrinkles and cracks, generates impurities, has strong dependence on equipment environment, and is high in cost and large in pollution. The epitaxial growth method is essentially a chemical reaction for reconstructing carbon atoms, and can be divided into a SiC epitaxial growth method and a metal substrate epitaxial growth method. The process conditions are high temperature (typically >1300 ℃), ultra-vacuum (typically <10-6Pa), at which point the Si atoms in the SiC are removed and the remaining C atoms grow into graphene. The method is suitable for preparing large-area and high-quality graphene, can realize preparation of wafer-level large-scale graphene materials, but is difficult to transfer due to the influence of a substrate when the graphene is transferred from a preparation substrate to a target substrate, and is not beneficial to large-scale application due to the high cost of the substrate corrosion method.
The electrochemical method is that electric field force is applied to graphite to generate voltage, electrolyte molecules are driven to be inserted between graphite layers, and electrodes are simultaneously usedElectrolysis of nearby water produces O2And opening a graphite boundary layer at the edge position of graphite to further promote the intercalation of molecules, so that the distance between graphite layers is increased, and the van der Waals force between the layers is weakened, thereby stripping and preparing the graphene. The electrochemical method can achieve the preparation purpose without using an oxidant or a reducing agent, has the advantages of simple production process, low cost, cleanness, environmental protection and the like, and in the electrolytic process, the current and the voltage are easy to accurately control, so that the controllable preparation and the performance regulation of the graphene are easy to realize. There have been some researches on the process for preparing graphene by electrochemical stripping, such as selecting (NH) in a system of inorganic salt aqueous solution, anode being graphite sheet electrode and cathode being platinum electrode4)2SO4、Na2SO4And K2SO4And the like as an electrolyte. In the process, firstly, water is reduced at the cathode by using the bias voltage generated on the electrode to generate a strong nucleophilic reagent OH-Tapping the graphite at the edge position; thereby causing depolarization and expansion of the graphite edges, water molecules and
inserting the layer; the electrolysis of which will generate SO2、O2And the like, which further expand the inter-laminar spacing of the graphite flakes, resulting in oxidation and exfoliation of the graphite. Therefore, the oxygen generated in the electrochemical preparation process can oxidize the prepared graphene, and the oxygen content of the product is higher.
Disclosure of Invention
In order to overcome the defects of the prior art, a preparation method for stripping graphene by adopting alternating current is provided.
The technical scheme adopted by the invention comprises the following steps:
(1) preparing electrolyte solution with certain concentration;
(2) taking a high-purity graphite plate as a positive electrode and a negative electrode, fixing the distance between the polar plates, and carrying out positive-negative alternate cyclic stripping in the electrolyte by a direct current in a timing alternate electrolysis mode;
(3) stripping for a period of time, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) taking the filtered solid, ultrasonically dispersing the solid in deionized water uniformly, and centrifuging to obtain a supernatant which is a graphene aqueous solution;
(5) and drying the supernatant to obtain the graphene.
The preparation method for stripping graphene by adopting alternating current is characterized in that the concentration of the electrolyte in the preparation process is 0.05-2 mol/l; the electrolyte can adopt one or a mixture of more of sodium nitrate, sodium sulfate, ammonium sulfate, sodium chloride and ammonium chloride.
According to the preparation method for stripping graphene by adopting alternating current, the carbon content of the high-purity graphite plate is more than 99% in the preparation process; the electrolytic stripping temperature is 10-90 ℃.
According to the preparation method for stripping graphene by adopting alternating current, the distance between the polar plates in the preparation process is preferably 3-10 cm.
The preparation method for stripping graphene by adopting alternating current is characterized in that the frequency of the timing exchange electrode in the preparation process is 1-30 min/time. The direct current voltage adopted by electrolysis is 5-20V.
The preparation method for stripping graphene by adopting alternating current is characterized in that the electrolysis time in the preparation process is 1-10 h.
The preparation method of the graphene by adopting the alternating current stripping mode can be used for selecting spray drying and freeze drying in the drying mode in the preparation process.
The invention has the beneficial effects that: the stripping method of the exchange electrode can be used for stripping graphene at the anode and then instantly adopting cathode current reduction, so that the prepared graphene is low in oxidation degree and small in defect, the graphene with a specific sheet diameter size (100 nanometers to several micrometers) can be prepared after the proper alternating frequency is adjusted, the single-layer and double-layer rates are up to more than 80%, and the graphene has wider application in biological pharmacy and composite materials.
Drawings
FIG. 1 is a schematic diagram of an experimental apparatus for preparing graphene;
fig. 2 TEM images of graphene;
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the present invention is not limited to the following examples. The length, width and thickness ratio of the graphite plate is 4:2: 1.
Example 1
(1) Preparing 0.5mol/l NaNO3250ml of electrolyte solution;
(2) taking high-purity graphite plates as a positive electrode and a negative electrode, setting the distance between fixed polar plates to be 3.5cm, and circularly stripping in electrolyte at a constant voltage of 10V in a timing alternating electrode mode, wherein the exchange frequency is selected to be 1 min/time;
(3) stripping for 5h, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) and taking the solid after suction filtration, adding 200ml of deionized water, carrying out ultrasonic treatment for 15min, dispersing uniformly, and centrifuging to obtain a supernatant, namely the graphene aqueous solution.
(5) And (4) freeze-drying the supernatant to obtain the graphene.
The concentration of the graphene solution in example 1 is 1.66mg/ml, the carbon content of the graphene is 90.58%, ID/IG0.85, average size 128nm, single and double layer rate 88%.
Example 2
(1) Preparation of 2mol/l (NH)4)2SO41000ml of electrolyte solution;
(2) taking high-purity graphite plates as a positive electrode and a negative electrode, setting the distance between fixed polar plates to be 10cm, and carrying out cyclic stripping in electrolyte at a constant voltage of 10V by a timing alternating electrode mode, wherein the exchange frequency is selected for 30 min/time;
(3) stripping for 10h, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) and taking the solid after suction filtration, adding 200ml of deionized water, carrying out ultrasonic treatment for 15min, dispersing uniformly, and centrifuging to obtain a supernatant, namely the graphene aqueous solution.
(5) And (4) freeze-drying the supernatant to obtain the graphene.
The concentration of the graphene solution in example 2 is 10.08mg/ml, the carbon content of the graphene is 72.4%, ID/IG1.44, pingThe average size is 320nm, and the single-layer and double-layer rates are 70%.
Example 3
(1) Preparing 500ml of NaCl electrolyte solution with the concentration of 1 mol/l;
(2) taking high-purity graphite plates as a positive electrode and a negative electrode, setting the distance between fixed polar plates to be 5cm, and circularly stripping in electrolyte at a constant voltage of 10V by a timing alternating electrode mode, wherein the exchange frequency is selected to be 20 min/time;
(3) stripping for 1h, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) and taking the solid after suction filtration, adding 200ml of deionized water, carrying out ultrasonic treatment for 15min, dispersing uniformly, and centrifuging to obtain a supernatant, namely the graphene aqueous solution.
(5) And (4) freeze-drying the supernatant to obtain the graphene.
The concentration of the graphene solution in example 3 is 0.55mg/ml, the carbon content of the graphene is 97.07%, ID/IG0.92, average size 380nm, and 76% monolayer and bilayer rate.
Example 4
(1) 2mol/l of NH is prepared4250ml of Cl electrolyte solution;
(2) taking high-purity graphite plates as a positive electrode and a negative electrode, setting the distance between fixed polar plates to be 7cm, and circularly stripping in electrolyte at a constant voltage of 10V in a timing alternating electrode mode, wherein the exchange frequency is selected for 15 min/time;
(3) after stripping for 8h, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) and taking the solid after suction filtration, adding 200ml of deionized water, carrying out ultrasonic treatment for 15min, dispersing uniformly, and centrifuging to obtain a supernatant, namely the graphene aqueous solution.
(5) And (4) freeze-drying the supernatant to obtain the graphene.
The concentration of the graphene solution in example 4 was 2.73mg/ml, the carbon content of graphene was 83.2%, ID/IGThe average size was 370nm, and the monolayer and bilayer rates were 77.4% for 1.32.
Example 5
(1) Preparing 250ml of 1mol/l NaCl electrolyte solution;
(2) taking high-purity graphite plates as a positive electrode and a negative electrode, setting the distance between fixed polar plates to be 5cm, and circularly stripping in electrolyte at a constant voltage of 10V by a timing alternating electrode mode, wherein the exchange frequency is selected to be 20 min/time;
(3) stripping for 1h, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) and taking the solid after suction filtration, adding 200ml of deionized water, carrying out ultrasonic treatment for 15min, dispersing uniformly, and centrifuging to obtain a supernatant, namely the graphene aqueous solution.
(5) And (4) freeze-drying the supernatant to obtain the graphene.
The concentration of the graphene solution in example 5 is 0.55mg/ml, the carbon content of the graphene is 97.07%, ID/IG0.92, average size 120nm, single and double layer ratio 81.6%.
Example 6
(1) 1mol/l NaCl and 1mol/l NaNO are prepared3The total volume of the electrolyte solution is 500 ml;
(2) taking high-purity graphite plates as a positive electrode and a negative electrode, setting the distance between fixed polar plates to be 5cm, and circularly stripping in electrolyte at a constant voltage of 10V by a timing alternating electrode mode, wherein the exchange frequency is selected for 10 min/time;
(3) stripping for 5h, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) and taking the solid after suction filtration, adding 200ml of deionized water, carrying out ultrasonic treatment for 15min, dispersing uniformly, and centrifuging to obtain a supernatant, namely the graphene aqueous solution.
(5) And (4) freeze-drying the supernatant to obtain the graphene.
The concentration of the graphene solution in example 6 is 3.74mg/ml, the carbon content of the graphene is 82.17%, ID/IGThe average size was 460nm, and the monolayer and bilayer rates were 82.8%, 1.11.
Claims (6)
1. A method for preparing graphene by adopting alternate current stripping is characterized by comprising the following steps:
(1) preparing electrolyte solution with certain concentration;
(2) taking a high-purity graphite plate as a positive electrode and a negative electrode, fixing the distance between the polar plates, and carrying out positive-negative alternate cyclic stripping in an electrolyte by using direct current in a timing alternate electrolysis mode;
(3) stripping for a period of time, taking out the electrode, and carrying out suction filtration and washing on the electrolyte;
(4) taking the filtered solid, ultrasonically dispersing the solid in deionized water uniformly, and centrifuging to obtain a supernatant which is a graphene aqueous solution;
(5) drying the supernatant to obtain graphene;
the concentration of the electrolyte is 0.05-2 mol/l; the electrolyte adopts one or a mixture of more of sodium nitrate, sodium sulfate, ammonium sulfate, sodium chloride and ammonium chloride; stripping graphene at the anode by a stripping method of an exchange electrode, immediately adopting cathode current reduction, adopting a timing exchange electrode, and carrying out exchange for 1-30 min/time; the direct current voltage adopted by electrolysis is 5-20V.
2. The method for preparing graphene by adopting alternating current exfoliation according to claim 1, wherein the carbon content of the high-purity graphite plate in the preparation process is more than 99%.
3. The method for preparing graphene by adopting alternating current exfoliation according to claim 1, wherein the electrolytic exfoliation temperature is 10-90 ℃.
4. The method for preparing graphene by adopting alternating current exfoliation according to claim 1, wherein the inter-plate distance is 3-10 cm.
5. The method for preparing graphene by adopting alternating current exfoliation according to claim 1, wherein the electrolysis time is 1-10 h.
6. The method for preparing graphene by adopting alternating current exfoliation according to claim 1, wherein the drying manner is spray drying and freeze drying.
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| CN114540656B (en) * | 2022-02-25 | 2022-11-25 | 南京工程学院 | Preparation method of high-quality electronic aluminum foil |
| CN114604864B (en) * | 2022-04-11 | 2023-08-22 | 东北大学 | Method for preparing graphene by stripping graphite material through limited-area electrochemical method |
| CN115536014B (en) * | 2022-09-21 | 2023-11-21 | 石家庄铁道大学 | Method for electrochemically preparing graphene |
| CN115784216B (en) * | 2023-01-05 | 2024-03-19 | 沈阳理工大学 | Preparation method of graphene applied to lead-carbon battery anode material |
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| JP2015038017A (en) * | 2013-07-18 | 2015-02-26 | 積水化学工業株式会社 | Method for producing secondary graphite, method for producing flaked graphite, secondary graphite, and flaked graphite |
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