CN110371961A - A kind of method of electrolytic preparation high intrinsic degree graphene - Google Patents
A kind of method of electrolytic preparation high intrinsic degree graphene Download PDFInfo
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Abstract
The invention belongs to technical field of preparation for inorganic material more particularly to a kind of preparation methods of high intrinsic degree graphene, method includes the following steps: graphite material is prepared into anode；Sulfate is prepared into electrolyte, first pre-processes electrode under the conditions of alive outside, then the pH value of addition ammonium hydroxide regulation solution to alkalinity, and carries out the electrolysis stripping of graphite anode at a certain temperature；Electrolysate is carried out again to be separated by solid-liquid separation the graphene with drying to obtain high intrinsic degree；The pH value of control electrolyte can guarantee that solvent to the lower oxidation activity of graphite material, advantageously reduces product graphene oxidizability, be more advantageous to the quality for improving graphene；The present invention prepares graphene using conventional industrial chemicals, and low raw-material cost is easy to get, and is convenient for industrialization.
Description
Technical field
The invention belongs to technical field of preparation for inorganic material more particularly to a kind of sides of electrolytic preparation high intrinsic degree graphene
Method.
Background technique
It is to play the excellent conductive and thermal conduction characteristic of graphene, push graphite that low-coat scale, which prepares high intrinsic degree graphene,
Alkene is applied to the key technical problem that the fields such as electric heating, sensing and energy storage must solve.Pass through graphite using cheap graphite as raw material
Interlayer intercalation and removing are the most important technology paths for preparing high intrinsic degree graphene.For the technology path, high intrinsic
Degree is the premise for realizing its application of aspects, while should also take into account the feature of environmental protection and safety of preparation system and process.However, opening
Hair is provided simultaneously with high intrinsic degree, high yield, environmental-friendly preparation strategy and still suffers from challenge, passes through principle innovation and technique skill
Art improves the important subject for realizing that the low-coat scaleization preparation of high intrinsic degree graphene is still grapheme material field.
Electrolysis method prepares graphene and has received widespread attention because of the features such as it is quick, and versus environmental is friendly.
There is lot of documents to report the method by electrolytic preparation graphene, such as: mentioning in CN108675287A, in liquid
Anodic removing is carried out in fused salt can obtain graphene, and temperature is needed to reach certain condition；It is adopted in CN107628609A
It uses expanded graphite as cathode and anode, using acidic electrolysis bath, applies two-way alternating impulse voltage between cathode and anode,
Electrolysis obtains reunion shape graphene oxide mixed solution；CN206108905U refers to a kind of using graphite paper as anode, acid
Property the ammonium sulfate method that continuously prepares graphene as one kind of electrolyte, but oxidizability is unknown.Parvez(ACS Nano
2013,7,3598) etc. using acid dilute sulfuric acid as electrolyte, obtained that oxidizability is higher, the thicker oxidation state graphene of the number of plies；
Muratlu (Carbon, 2012,50,142) et al. uses lauryl sodium sulfate as electrolyte, and having prepared thickness is about
The oxidation state graphene of 1.2nm；Song et al. (Journal of Power Sources 2014,249,48-58) is in neutral item
Part has used potassium nitrate solution to be electrolyte and control the number of plies for reducing removing graphene compared with low potential.But lower
Consistent with the stripping process in sulfate under pH, nitrate can also generate the higher Nano graphite layer of thicker and oxidizability；And
Zeng etc. (ChemSusChem 2011,4,1587), by electrochemical stripping, has equally prepared higher oxygen in phosphate
The graphene oxide of degree.It can be seen that electrochemical process removing graphene extremely relies on electrolyte, actually in acidity
Under the conditions of obtained graphene due to the effect of acid condition, cause the graphene oxidizability separated also higher, such as in this base
The intrinsic graphene of high intrinsic degree is obtained on plinth, it is also necessary to subsequent further reducing process.
It has not yet to see and has been reported that in electrolysis method technique, regulate and control sulfate liquor pH value to alkaline condition using ammonium hydroxide
The method of the lower graphene for preparing high intrinsic degree.
Summary of the invention
The purpose of the present invention is to provide a kind of method of electrolytic preparation high intrinsic degree graphene, this method includes following step
It is rapid:
(1) preparation of reactant:
By graphite material, by sheeting equipment, be pressed into graphite flake, the graphite material be crystalline flake graphite, graphite powder,
One of graphite foil is a variety of, and sheeting thickness is 2~5mm, anode reactant A when as electrolysis；
Choose cathode of the platinum electrode as electrolysis；
Sulfate is chosen as electrolyte, 0.1-3mol/L is made into, as sulfate liquor B；It is characterized by:
The sulfate is selected from one of ammonium sulfate, hydrogen sulfate ammonia, sodium sulphate, sodium bisulfate, potassium sulfate, potassium acid sulfate
Or it is a variety of；
Ammonium hydroxide is further added in the solution B, and conciliation B solution pH value is 8-14, and mixed solution is uniformly mixed, and obtains
Alkaline electrolyte solution C；
(2) reaction removing:
Electrolytic solution device is placed in 0~5 DEG C of isoperibol, using reactant A as anode, platinum electrode is as cathode, solution B
As electrolyte, under the DC voltage of 2.5-3.5V, stablizes and keep 1~3h；
Then electrode is transferred in alkaline electrolyte solution C, voltage stabilization continues 0.5~1.5h of energization in 5~15V,
It is precipitated in solution C bottom.
Preferably, the step (1) is preferably below one or more:
The graphite foil sheeting thickness is preferably 2~3mm；
The sulfate concentration is 0.5-2mol/L；
Ammonium hydroxide is further added in the solution B, and conciliation B solution pH value is 9-10, and mixed solution is uniformly mixed, and obtains
Alkaline electrolyte solution C；
The step (2) is preferably below one or more:
Electrolytic solution device is placed in 0~5 DEG C of isoperibol, using reactant A as anode, platinum electrode is as cathode, solution B
As electrolyte, under the DC voltage of 2.5-3.5V, stablizes and keep 1~2h；
Electrode is transferred in alkaline electrolyte solution C, voltage stabilization is in 5~10V；
Electrode is transferred in alkaline electrolyte solution C, after burning voltage, continues 1~1.5h of energization, in solution C bottom
It is precipitated.
Preferably, step (1) the alkaline electrolyte solution C is preferably in B solution according to 1~5% volume ratio, i.e., often
The ammonium hydroxide of 30% mass fraction of 1~5mL, preferably 2-3% volume ratio is added in 100mL B solution, and the pH value for regulating and controlling B solution is 8-
14, and mixed liquor average rate is stirred 15-20 minutes；And ultrasound 1-10 minutes under the power of room temperature (15-30 DEG C) 30-60W, it is excellent
30-50W power ultrasound is selected to obtain for 1-5 minutes.
Further, this method is further comprising the steps of:
(3) cleaning is extracted:
The precipitating that step (2) stripping reaction obtains be dissolved in organic solvent, in room temperature (15-30 DEG C) 180-
Ultrasound 20-40 minutes, obtain solution D under the power of 240W；
Solution D is centrifuged 20-40 minutes with the rate of 2000-4000rpm；
Lower sediment clean and reuse after centrifugation, can anode reactant A of the secondary use in preparation step (1)；
Upper liquid after centrifugation filters cleaning 5~10 times with deionized water, the solid after being separated.
It is preferred that step (3) organic solvent is N-N dimethylformamide, N first class pyrrolidones, one in isopropanol
Kind is a variety of；The amount of the organic solvent is 1~2ml/mg of the precipitating that step (2) stripping reaction obtains.
Further, this method is further comprising the steps of:
(4) dry: the solid after step (3) separation is dry, obtain high intrinsic degree graphene.
Preferably, the drying means in the step (4) is one of forced air drying, oven drying or freeze-drying.
The invention further relates to the high intrinsic degree graphene that any of the above-described method is prepared, gained graphene is not oxidation
Graphene but the intrinsic graphene of low degree of oxidation, oxygen content is lower, ratio of the oxygen element relative to graphene gross mass
No more than 20%；The graphene size being prepared is larger, is not less than 2 μm；The number of plies is less, and the number of plies is less than 10 layers.
Compared to the prior art, the beneficial effects of the present invention are:
(1) by the way that ammonium hydroxide is added in the electrolytic solution, the graphene-structured after making preparation more tends to consolidate, survivable, oxygen
Change degree reduce, relatively before technique being capable of the intrinsic higher intrinsic graphene of degree.Simultaneously because the addition of ammonium hydroxide, so that solution
More hydroxide ions can be ionized to assemble in anode, be more advantageous to the intercalation stripping effect for improving the graphite material of anode,
So that graphite removing is more complete.And the graphene after removing has the less number of plies and biggish size, sees Fig. 1 and Fig. 2；By
Example 1 and the comparison of the x-ray photoelectron spectroscopy in example 2 can be seen that graphite after regulation electrolyte ph to acidity is added in ammonium hydroxide
The oxygen content of alkene declines obvious (Fig. 3 and Fig. 4)；Embodiment 3-6 is identical as 1 effect of embodiment；
(2) more existing volume production graphene high oxidation degree, small size, the status more than the number of plies, technique graphite obtained
Alkene maximum oxygen content is no more than 20%, and size is more than 2 μm, and the number of plies advantageously improves less than 10 layers and realizes high intrinsic degree graphite
It is prepared by the low-coat scaleization of alkene；
(3) present invention prepares graphene using conventional industrial chemicals, and raw material is easy to get low in cost, is convenient for industrialization.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 and Fig. 2 is the transmission electron microscope and atomic force microscopy diagram of graphene prepared by embodiment 1.
Fig. 3 is the x-ray photoelectron spectroscopy figure of graphene prepared by embodiment 1.
Fig. 4 is the x-ray photoelectron spectroscopy figure of graphene prepared by embodiment 2.
Specific embodiment
The present invention will be further described with reference to the examples below.Described embodiment and its result are merely to illustrate
The present invention, without the present invention described in detail in claims should will not be limited.
Embodiment 1
A kind of preparation method of high intrinsic degree graphene, which is characterized in that method includes the following steps:
(1) preparation of reactant: by graphite foil, it is pressed into graphite flake, sheeting thickness is 3mm thickness, when as electrolysis
Anode reactant A；Choose cathode of the platinum electrode as electrolysis；Choose the ammonium sulfate B that ammonium sulfate is made into 1mol/L；In B
According to 2% volume ratio in solution, i.e., the pH value of the ammonium hydroxide regulation B solution of 30% mass fraction of 2mL is added in every 100mL B solution
It is 9, and mixed liquor average rate is stirred 15 minutes, and ultrasound 5 minutes under the power of room temperature (25 DEG C) 50W, obtains alkaline electrolysis
Liquor C；
(2) electrolytic solution device reaction removing: is placed in 0 DEG C of isoperibol；Using reactant A as anode, platinum electrode conduct
Cathode, solution B is as electrolyte, under the DC voltage of 3V, stablizes and keeps 2h；It is molten that electrode is then transferred to alkaline electrolyte
In liquid C, voltage stabilization continues energization 1h in 10V, is precipitated in solution C bottom；
(3) cleaning is extracted: carrying out the precipitating that step (2) reaction obtains to be dissolved in organic solvent N-N dimethylformamide
In, N-N dimethylformamide additional amount is the 1ml/mg of precipitating；30 points of the ultrasound under room temperature (25 DEG C) and the power of 240W
Clock obtains solution D, and solution D is centrifuged 30 minutes with the rate of 3000rpm；Upper liquid after centrifugation is filtered clear with deionized water
It washes 10 times, the solid after being separated；
(4) dry: the solid after step (3) separation being freeze-dried, high intrinsic degree graphene is obtained；It transmits electricity
Mirror figure and atomic force microscopy diagram are shown in that Fig. 1 and Fig. 2, x-ray photoelectron spectroscopy figure are shown in Fig. 3 respectively.
(5) the graphene oxygen content obtained is about 16%, and size is more than 2.5 μm, and the number of plies is less than 8 layers.
Embodiment 2
The preparation method of high oxidation graphene is primarily characterized in that the step (2) being different from embodiment 1, the implementation
Example in step (2) be not added ammonium hydroxide adjust pH value of solution, specific method the following steps are included:
(1) preparation of reactant: by graphite foil, it is pressed into graphite flake, sheeting thickness is 3mm thickness, when as electrolysis
Anode reactant A；Choose cathode of the platinum electrode as electrolysis；Choose the ammonium sulfate B that ammonium sulfate is made into 1mol/L；
(2) electrolytic solution device reaction removing: is placed in 0 DEG C of isoperibol；Using reactant A as anode, platinum electrode conduct
Cathode, solution B is as electrolyte, under the DC voltage of 3V, stablizes and keeps 2h；It then improves voltage and is kept stable at 10V,
Continue energization 1h, is precipitated in solution B bottom.
(3) cleaning is extracted: carrying out the precipitating that step (2) reaction obtains to be dissolved in organic solvent N-N dimethylformamide
In, N-N dimethylformamide additional amount is the 1ml/mg of precipitating；30 points of the ultrasound under room temperature (25 DEG C) and the power of 240W
Clock obtains solution D, and solution D is centrifuged 30 minutes with the rate of 3000rpm；Upper liquid after centrifugation is filtered clear with deionized water
It washes 10 times, the solid after being separated.
It is dry: the solid after step (3) separation being freeze-dried, the graphene of high oxidation is obtained；Its X-ray photoelectricity
Sub- power spectrum is shown in Fig. 4, and the high oxidation degree graphene oxygen content of acquisition is about 62%, and the oxygen of the remote super graphene that ammonium hydroxide acquisition is not added contains
Amount.
Embodiment 3
A kind of preparation method of high intrinsic degree graphene, which is characterized in that method includes the following steps:
(1) by flaky graphite, graphite flake, sheeting thickness 4mm, when as electrolysis the preparation of reactant: are pressed into
Anode reactant A；Choose cathode of the platinum electrode as electrolysis；Ammonium hydrogen sulfate is chosen as electrolyte, is made into 0.6mol/L sulphur
Sour hydrogen ammonium salt solution B；According to 3% volume ratio in B solution, i.e., the ammonia of 30% mass fraction of 3mL is added in every 100mL B solution
Water, the pH value for regulating and controlling B solution is 10, and mixed liquor average rate is stirred 15 minutes, and ultrasonic under the power of room temperature (25 DEG C) 40W
5 minutes, obtain alkaline electrolyte solution C；
(2) electrolytic solution device reaction removing: is placed in 2 DEG C of isoperibols；Using reactant A as anode, platinum electrode conduct
Cathode, solution B is as electrolyte, under the DC voltage of 3V, stablizes and keeps 1.5h；Electrode is then transferred to alkaline electrolyte
In solution C, voltage stabilization is precipitated in 10V energization 1h in solution C bottom；
(3) cleaning is extracted: carrying out the precipitating that step (2) reaction obtains to be dissolved in organic solvent N-N dimethylformamide
In, N-N dimethylformamide additional amount is the 1ml/mg of precipitating；Ultrasound 30 minutes, obtain under the power of room temperature (25 DEG C) 240W
To solution D, solution D is centrifuged 30 minutes with the rate of 3000rpm.Upper liquid after centrifugation filters cleaning 8 with deionized water
Time, the solid after being separated；
(4) dry: the solid after step (3) separation being subjected to oven drying, obtains high intrinsic degree graphene.
(5) the graphene oxygen content obtained is about 12%, and size is more than 2.5 μm, and the number of plies is less than 10 layers.
Embodiment 4
A kind of preparation method of high intrinsic degree graphene, which is characterized in that method includes the following steps:
(1) graphite foil the preparation of reactant: is pressed into graphite flake by sheeting equipment；Sheeting thickness is 2mm, is made
Anode reactant A when to be electrolysed；Choose cathode of the platinum electrode as electrolysis.Sodium sulphate is chosen as electrolyte, is made into
The metabisulfite solution B of 0.6mol/L；According to 4% volume ratio in B solution, i.e., 30% mass of 4mL is added in every 100mL B solution
The ammonium hydroxide of score, the pH value for regulating and controlling B solution is 11, and mixed liquor average rate is stirred 20 minutes, and in the function of room temperature (25 DEG C) 50W
Ultrasound 7 minutes, obtain alkaline electrolyte solution C under rate；
(2) electrolytic solution device reaction removing: is placed in 3 DEG C of isoperibols；Using reactant A as anode, platinum electrode conduct
Cathode, solution B is as electrolyte, under the DC voltage of 3V, stablizes and keeps 1h；It is molten that electrode is then transferred to alkaline electrolyte
In liquid C, voltage stabilization continues energization 0.5h in 6V, is precipitated in solution C bottom；
(3) cleaning is extracted: it carries out the precipitating that step (2) reaction obtains to be dissolved in organic solvent N-Methyl pyrrolidone,
N-Methyl pyrrolidone additional amount is the 1ml/mg of precipitating；Ultrasound 30 minutes, obtain molten under the power of room temperature (25 DEG C) 240W
Solution D is centrifuged 30 minutes by liquid D with the rate of 3000rpm.Upper liquid after centrifugation filters cleaning 10 times with deionized water, obtains
Solid after to separation；
(4) dry: the solid after step (3) separation being freeze-dried, high intrinsic degree graphene is obtained.
(5) the graphene oxygen content obtained is about 16%, and size is more than 2 μm, and the number of plies is less than 9 layers.
Embodiment 5
A kind of preparation method of high intrinsic degree graphene, which is characterized in that method includes the following steps:
(1) crystalline flake graphite the preparation of reactant: is pressed into graphite flake, the preferred stone of graphite material by sheeting equipment
Black foil, sheeting thickness 3mm, anode reactant A when as electrolysis；Choose cathode of the platinum electrode as electrolysis；Choose sulfuric acid
Hydrogen sodium is made into the sodium bisulfate B of 1mol/L as electrolyte；According to 3% volume ratio in B solution, i.e., every 100mL B is molten
The ammonium hydroxide of 30% mass fraction of 3mL is added in liquid, and the pH value for regulating and controlling B solution is 10, and mixed liquor average rate is stirred 20 minutes, and
Ultrasound 10 minutes, obtain alkaline electrolyte solution C under the power of room temperature (25 DEG C) 60W；
(2) electrolytic solution device reaction removing: is placed in 0 DEG C of isoperibol；Using reactant A as anode, platinum electrode conduct
Cathode, solution B is as electrolyte, under the DC voltage of 3V, stablizes and keeps 1.5h；Electrode is then transferred to alkaline electrolyte
In solution C, voltage stabilization continues energization 1h in 12V, is precipitated in solution C bottom；
(3) cleaning is extracted: the precipitating that step (2) reaction obtains be dissolved in organic solvent isopropanol, isopropanol
Additional amount is the 1ml/mg of precipitating；Under the power of room temperature (25 DEG C) 180W ultrasound 40 minutes, obtain solution D, by solution D with
The rate of 2000rpm is centrifuged 40 minutes；Upper liquid after centrifugation filters cleaning 7 times, consolidating after being separated with deionized water
Body；
It is dry: the solid after step (3) separation being subjected to forced air drying, obtains high intrinsic degree graphene.
The graphene oxygen content of acquisition is about 18%, and size is more than 2 μm, and the number of plies is less than 10 layers.
Embodiment 6
A kind of preparation method of high intrinsic degree graphene, which is characterized in that method includes the following steps:
(1) preparation of reactant: graphite powder is pressed into graphite flake by sheeting equipment, sheeting thickness 5mm makees
Anode reactant A when to be electrolysed；Choose cathode of the platinum electrode as electrolysis.Potassium sulfate is chosen as electrolyte, is configured to
The sulfate liquor B of 2mol/L；According to 2% volume ratio in B solution, i.e., 30% mass point of 2mL is added in every 100mL B solution
Several ammonium hydroxide, the pH value for regulating and controlling B solution is 10, and mixed liquor average rate is stirred 15 minutes, and in the power of room temperature (25 DEG C) 30W
Lower ultrasonic 5 minutes, obtain alkaline electrolyte solution C；
(2) electrolytic solution device reaction removing: is placed in 3 DEG C of isoperibols；Using reactant A as anode, platinum electrode conduct
Cathode, solution B is as electrolyte, under the DC voltage of 3V, stablizes and keeps 2h；It is molten that electrode is then transferred to alkaline electrolyte
In liquid C, voltage stabilization continues energization 0.5h in 10V, is precipitated in solution C bottom；
(3) cleaning is extracted: carrying out the precipitating that step (2) reaction obtains to be dissolved in organic solvent N-Methyl pyrrolidone
In, N-Methyl pyrrolidone additional amount is the 2ml/mg of precipitating；Ultrasound 20 minutes, obtain under the power of room temperature (25 DEG C) 240W
Solution D is centrifuged 20 minutes by solution D with the rate of 4000rpm；Upper liquid after centrifugation filters cleaning 10 times with deionized water,
Solid after being separated；
(4) dry: the solid after step (3) separation being freeze-dried, high intrinsic degree graphene is obtained.
(5) the graphene oxygen content obtained is about 20%, and size is more than 2.5 μm, and the number of plies is less than 10 layers.
Claims (8)
1. a kind of method of electrolytic preparation high intrinsic degree graphene, method includes the following steps:
(1) preparation of reactant:
Graphite material is pressed into graphite flake by sheeting equipment, the graphite material is crystalline flake graphite, graphite powder, graphite
One of foil is a variety of, and sheeting thickness is 2~5mm, anode reactant A when as electrolysis；
Choose cathode of the platinum electrode as electrolysis；
Sulfate is chosen as electrolyte, 0.1-3mol/L is made into, as sulfate liquor B；It is characterized by:
The sulfate is selected from one of ammonium sulfate, hydrogen sulfate ammonia, sodium sulphate, sodium bisulfate, potassium sulfate, potassium acid sulfate or more
Kind；
Ammonium hydroxide is further added in the solution B, and conciliation B solution pH value is 8-14, and mixed solution is uniformly mixed, and obtains alkalinity
Electrolyte solution C；
(2) reaction removing:
Electrolytic solution device is placed in 0~5 DEG C of isoperibol, using reactant A as anode, platinum electrode is as cathode, solution B conduct
Electrolyte is stablized under the DC voltage of 2.5-3.5V and keeps 1~3h；
Then electrode is transferred in alkaline electrolyte solution C, voltage stabilization continues 0.5~1.5h of energization, molten in 5~15V
Liquid C is precipitated bottom.
2. the method according to claim 1, wherein the step (1) is preferably below one or more:
The graphite foil sheeting thickness is preferably 2~3mm；
The sulfate concentration is 0.5-2mol/L；
Ammonium hydroxide is further added in the solution B, and conciliation B solution pH value is 9-10, and mixed solution is uniformly mixed, and obtains alkalinity
Electrolyte solution C；
The step (2) is preferably below one or more:
Electrolytic solution device is placed in 0~5 DEG C of isoperibol, using reactant A as anode, platinum electrode is as cathode, solution B conduct
Electrolyte is stablized under the DC voltage of 2.5-3.5V and keeps 1~2h；
Electrode is transferred in alkaline electrolyte solution C, voltage stabilization is in 5~10V；
Electrode is transferred in alkaline electrolyte solution C, after burning voltage, continues 1~1.5h of energization, is obtained in solution C bottom
Precipitating.
3. the method according to claim 1, wherein the step (1) alkaline electrolyte solution C is preferably in B
According to 1~5% volume ratio in solution, i.e., the ammonium hydroxide of 30% mass fraction of 1~5mL, preferably 2- is added in every 100mL B solution
3% volume ratio, the pH value for regulating and controlling B solution is 8-14, and mixed liquor average rate is stirred 15-20 minutes；And room temperature 30-60W's
Ultrasound 1-10 minutes under power obtain for preferably 30-50W power ultrasound 1-5 minutes.
4. this method is further comprising the steps of the method according to claim 1, wherein further:
(3) cleaning is extracted:
The precipitating that step (2) stripping reaction obtains be dissolved in organic solvent, is surpassed under the power of room temperature 180-240W
Sound 20-40 minutes, obtain solution D；
Solution D is centrifuged 20-40 minutes with the rate of 2000-4000rpm；
Lower sediment clean and reuse after centrifugation, can anode reactant A of the secondary use in preparation step (1)；
Upper liquid after centrifugation filters cleaning 5~10 times with deionized water, the solid after being separated.
5. the method according to claim 1, wherein step (3) organic solvent is N-N dimethyl formyl
One of amine, N first class pyrrolidones, isopropanol are a variety of；The amount of the organic solvent is that step (2) stripping reaction obtains
1~2ml/mg of precipitating.
6. according to the method described in claim 4, this method is further comprising the steps of it is characterized in that, further:
(4) dry: the solid after step (3) separation is dry, obtain high intrinsic degree graphene.
7. according to the method described in claim 6, it is characterized in that, the drying means in the step (4) is forced air drying, dries
One of case drying or freeze-drying.
8. the high intrinsic degree graphene that any one of claim 1-7 method is prepared, gained graphene is not graphene oxide
But the intrinsic graphene of low degree of oxidation, oxygen content is lower, and oxygen element is no more than relative to the ratio of graphene gross mass
20%；The graphene size being prepared is larger, is not less than 2 μm；The number of plies is less, and the number of plies is less than 10 layers.
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| CN111224149A (en) * | 2019-12-13 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation method of battery anode of graphene nanosheet based on electrochemical cathode stripping and aluminum ion battery |
| CN111470499A (en) * | 2020-04-07 | 2020-07-31 | 中钢集团南京新材料研究院有限公司 | Method for electrochemically preparing graphene |
| CN114195139A (en) * | 2021-12-23 | 2022-03-18 | 中钢集团南京新材料研究院有限公司 | High-purity graphene, and preparation method and application thereof |
| CN114684814A (en) * | 2022-04-24 | 2022-07-01 | 江苏大学 | Preparation method of self-supporting flexible graphene film and application of self-supporting flexible graphene film to flexible supercapacitor |
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| CN111224149A (en) * | 2019-12-13 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation method of battery anode of graphene nanosheet based on electrochemical cathode stripping and aluminum ion battery |
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| CN111470499B (en) * | 2020-04-07 | 2022-03-04 | 中钢集团南京新材料研究院有限公司 | Method for electrochemically preparing graphene |
| CN114195139A (en) * | 2021-12-23 | 2022-03-18 | 中钢集团南京新材料研究院有限公司 | High-purity graphene, and preparation method and application thereof |
| CN114684814A (en) * | 2022-04-24 | 2022-07-01 | 江苏大学 | Preparation method of self-supporting flexible graphene film and application of self-supporting flexible graphene film to flexible supercapacitor |
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