CN114132922A - Method for preparing graphene in large scale - Google Patents
Method for preparing graphene in large scale Download PDFInfo
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- CN114132922A CN114132922A CN202010913637.5A CN202010913637A CN114132922A CN 114132922 A CN114132922 A CN 114132922A CN 202010913637 A CN202010913637 A CN 202010913637A CN 114132922 A CN114132922 A CN 114132922A
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/192—Preparation by exfoliation starting from graphitic oxides
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Abstract
The graphene is prepared by intercalation oxidation, hydrolysis reaction, filtration, acid pickling and expansion of graphite, wherein the hydrolysis reaction comprises two steps of high-temperature hydrolysis and heat preservation, the high-temperature hydrolysis reaction is to control the speed and time of adding deionized water, so that the temperature in the deionized water adding process is not more than 100 ℃, the overhigh temperature in the deionized water adding process can be avoided, the difficulty in cooling and the overhigh energy consumption in cooling are avoided, the cooling time after the deionized water is added in the large-scale graphene production process is shortened, and the heat preservation reaction is to keep the temperature for a period of time after the deionized water is added, so that the oxidation of the graphite is more uniform, the time is saved for the subsequent filtration and acid pickling steps, the cost is saved, a stable product is obtained, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a method for preparing graphene in a large scale.
Background
Since the rise of nano materials, graphene has been the hot spot of research of scientists. Graphene is a single-layer two-dimensional graphite crystal composed of hexagonal lattices and formed by passing sp between adjacent carbon atoms2Hybridization to form sigma-bonds forming continuously extended and rigid interconnectionsA planar structure with strong performance. The thickness of graphene is only 0.335nm, which is only twenty-ten-thousandth of hair, and is a basic unit for constructing hybrid carbon such as zero-dimensional fullerene, one-dimensional carbon nanotube, three-dimensional bulk phase graphite and the like. Graphene is currently the thinnest and strongest material known in the world, with tensile moduli and intrinsic strengths of 1000GPa and 130GPa, respectively. The graphene has excellent thermal conductivity, and the thermal conductivity reaches 5000W.m-1.K-1. Compared with other carbon materials, the graphene has larger specific surface area, and the theoretical specific surface area of the graphene is 2630m2.g-1And the theoretical specific surface area of the carbon nano tube is 1315m2.g-110-20m of fullerene (C60)2.g-1。
At present, the method for preparing graphene mainly comprises a (first) micromechanical stripping method, wherein the graphene is obtained by continuously stripping oriented pyrolytic graphite through an adhesive tape, and the prepared graphene is extremely limited and does not meet the requirement of large-scale production; (II) a Si substrate epitaxial growth method, which takes single crystal 6H-SiC as a raw material, thermally decomposes Si at high temperature and under the condition of ultrahigh vacuum, and rearranges the residual carbon atoms on the surface of the SiC through a structure to form a graphene layer, wherein the graphene prepared by the method is difficult to transfer, and the preparation conditions are harsh and are not suitable for large-scale production of the graphene; (III) preparing graphene by catalyzing and adsorbing hydrocarbon gas on the surface of smooth metal or nonmetal through chemical vapor deposition (CVD method), wherein the method has high process requirement and low yield; the (IV) redox method is a mainstream method for preparing graphene on a large scale at present, and is high in cost. Therefore, many patents for preparing graphene by an improved oxidation-reduction method have appeared, for example, patent (CN 104355308B) discloses a method for preparing graphene with a large specific surface area, which comprises performing low-medium temperature and high-temperature reaction on expanded graphite, performing ultrasonic treatment, acid washing and water washing on the product for 5 minutes to 2 hours to obtain a neutral graphene oxide hydrogel-like product, and then performing ultrasonic treatment and hydrazine hydrate reduction on the product to prepare graphene with a large specific surface area. Obviously, the method has the advantages of high price of the adopted raw materials, fluffy expanded graphite, difficulty in transportation and infiltration, complex steps, long time consumption, large energy consumption of multiple times of ultrasonic treatment, and unsuitability for large-scale production of graphene.
In order to save cost and energy consumption, shorten preparation time and obtain graphene with high yield and good quality, it is necessary to develop a method for preparing graphene on a large scale in order to meet the requirements of customers.
Disclosure of Invention
Based on the above, the invention provides a method for preparing graphene in a large scale so as to solve the above problems.
The technical scheme of the invention comprises the following steps:
a method for large-scale preparation of graphene, comprising: intercalation oxidation, hydrolysis reaction, filtration, acid washing and expansion,
intercalation oxidation: adding concentrated acid and an oxidant into the graphite, and stirring to react to obtain a mixed solution S1;
and (3) hydrolysis reaction: adding deionized water into the mixed solution S1 to obtain a mixed solution S2; then, after the mixed solution S2 is cooled, adding hydrogen peroxide without the unreacted oxidant to obtain an intercalated graphite solution SG, wherein the temperature of the reaction solution is kept not more than 100 ℃ in the deionized water adding process and the heat preservation process, and the whole hydrolysis reaction is carried out in stirring;
and (3) filtering: filtering the intercalated graphite solution SG to obtain a filter cake G,
acid washing and drying: carrying out acid washing on the filter cake G by using dilute hydrochloric acid to obtain an acid washing filter cake XG, and then drying the acid washing filter cake XG;
crushing: crushing the dried filter cake XG sample;
expansion: and (4) performing high-temperature expansion on the crushed product to obtain a product graphene AG.
In one embodiment, the sum of the time for adding the deionized water and the holding time after adding the deionized water is 0.5-3 h.
In one embodiment, the holding temperature is 91-97 ℃.
In one embodiment, the time for adding the deionized water is 0.5-1h, and the heat preservation time is 1-1.5 h.
In the hydrolysis reaction, the heat preservation time after the deionized water is added is optimized, the heat preservation time is respectively 0.5h, 1h, 1.5h and 2h, different heat preservation times are respectively adopted for preparing the graphene, the experiment results such as the filtering and acid washing time and the specific surface area of the prepared graphene are compared, so that the different heat preservation times have certain influence on the filtering and acid washing intercalated graphite solution and the specific surface area of the prepared graphene, and the preferable heat preservation time is 1-1.5 h.
In one embodiment, the filtration time is 20-40 min.
In one embodiment, the filtration mode is one or a combination of suction filtration, pressure filtration and tubular membrane separation.
In one embodiment, the acid washing comprises performing first acid washing and second acid washing on the filter cake G by using dilute hydrochloric acid to obtain a first acid washing filter cake XG1 and a second acid washing filter cake XG2 in sequence; wherein the first pickling time is 5-15min, and the second pickling time is 10-20 min.
In one embodiment, the concentrated acid in the oxidation reaction is one or a combination of concentrated sulfuric acid, concentrated nitric acid and perchloric acid; the oxidant is one or a combination of more of potassium permanganate, potassium dichromate, sodium hypochlorite, potassium chlorate, potassium hypochlorite, potassium persulfate, phosphorus pentoxide, potassium ferrite, sodium nitrate and potassium nitrate.
In one embodiment, the intercalation oxidation includes low-temperature reaction and medium-temperature reaction, wherein the low-temperature reaction temperature is 10-13 ℃; the medium-temperature reaction comprises a first-stage medium-temperature reaction and a second-stage medium-temperature reaction, wherein the first-stage medium-temperature reaction temperature is 35-38 ℃, and the second-stage medium-temperature reaction temperature is 60-63 ℃.
In one embodiment, the low-temperature reaction time is 0.5-1.2h, the medium-temperature reaction time in the first stage is 2-3h, and the medium-temperature reaction time in the second stage is 1-1.3 h.
In one embodiment, the drying time of the graphene is 12-16 h.
In one embodiment, the temperature of the mixed solution S2 is reduced to 40-60 ℃ during the hydrolysis reaction.
In one embodiment, the graphite is one or a combination of several of intercalated graphite, expanded graphite or flake graphite; further the graphite is preferably intercalated graphite.
In one embodiment, the number of graphene layers is 4 to 8.
The invention has the beneficial effects that:
(1) through intercalation oxidation and hydrolysis reaction to graphite, make the intercalation material get into between the graphite layer more easily, the intercalation and the oxidation of graphite are more even, have avoided graphite edge and the serious phenomenon that but the inlayer oxidation is not enough of surface oxidation, save time for subsequent filtration and pickling, have reduced manufacturing cost, practice thrift the energy consumption.
(2) By keeping the temperature in the hydrolysis reaction process not to exceed 100 ℃, the method is more suitable for industrial production, avoids the problem of overhigh temperature in the deionized water adding process, solves the problem of overlong cooling time after overhigh temperature rise of deionized water in large-scale preparation of graphene, simultaneously obtains intercalated graphite with more uniform oxidation, ensures more uniform subsequent expansion, and prepares graphene with little difference in layer number.
(3) The method of preserving heat for a period of time after adding the deionized water is adopted, so that the yield of the graphene is improved, the method is further suitable for industrial production, and the income is improved.
Drawings
FIG. 1 is a scanning electron micrograph of graphene of example 1 at different magnifications;
FIG. 2 is a scanning electron micrograph of graphene of example 4 at different magnifications.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. However, the present invention may be embodied in many different forms and is not limited to the embodiments described below. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
According to the method, the graphene is prepared by carrying out intercalation oxidation, hydrolysis reaction, filtration, acid pickling and expansion on graphite, wherein the optimized hydrolysis reaction process is a high-temperature hydrolysis heat preservation reaction, the deionized water adding process is controlled not to exceed 100 ℃ by controlling the deionized water adding speed and time, so that the subsequent cooling difficulty caused by overhigh temperature rise in the deionized water adding process, overlarge cooling energy consumption and overlong cooling time are avoided; the graphite is further added with deionized water and then is subjected to heat preservation for a period of time, so that the oxidation of the graphite is more uniform, the time is saved for the subsequent filtering and pickling steps, and the energy and the cooling time can be effectively saved by adopting the high-temperature hydrolysis heat preservation reaction, so that the efficiency is improved, and the cost is saved; in addition, the yield of the graphene is improved, the number of layers of the prepared graphene is small, the number of layers of the prepared graphene is less, and the specific surface area of the prepared graphene is larger.
The intercalation oxidation comprises low-temperature reaction and medium-temperature reaction, and the method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10-13 ℃, and mechanically stirring for 0.5-1.2 h;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature which is 35-38 ℃, keeping the first-stage medium-temperature reaction temperature at 35-38 ℃, mechanically stirring for 2-3h, then continuously raising the temperature to a second-stage medium-temperature reaction temperature which is 60-63 ℃, keeping the second-stage medium-temperature reaction temperature, and mechanically stirring for 1-1.3h to obtain a mixed solution S1;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent of deionized water into the mixed solution S1 obtained in the step 2), wherein the temperature in the deionized water adding process is not more than 100 ℃, the temperature is 91-97 ℃ after the deionized water is added, and the mechanical stirring is carried out for 0.5-3h to obtain a mixed solution S2; then, cooling to 40-60 ℃, adding 3 times of hydrogen peroxide by weight equivalent, and stirring for 0.5-1h to obtain an intercalated graphite solution SG;
wherein, the time for adding the deionized water is further preferably 0.5-1h, the heat preservation temperature is further preferably 91-93 ℃, and the heat preservation time is further preferably 1-1.5 h;
4) and (3) filtering: after the reaction is finished, filtering to obtain a filter cake G, wherein the filtering time is 20-40 min;
5) acid washing: washing the filter cake obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 5-15min, so as to obtain a first acid washing filter cake XG 1; then carrying out second acid washing, and washing the first acid washing filter cake XG2 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 10-20min, so as to obtain a second acid washing filter cake XG 2;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 12-16 h;
7) crushing: crushing the dried sample of the filter cake XG 2;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG.
In the method for preparing graphene in a large scale, in 3) a high-temperature hydrolysis heat-preservation reaction, the temperature of a deionized water adding process is controlled not to exceed 100 ℃, and the time for adding deionized water is 0.5-1.75h, preferably 0.5-1h, so that adverse effects caused by overhigh temperature of the deionized water adding process in the hydrolysis process are avoided, heat generated by a reaction liquid and deionized water is effectively utilized in the deionized water adding process, energy waste is avoided, and the problems of difficulty in cooling after overhigh temperature rise in the hydrolysis process, overlong cooling time and overhigh energy consumption in the large-scale preparation of graphene are solved; after the deionized water is added, the heat preservation temperature is still kept between 91 and 97 ℃, the further optimization is between 91 and 93 ℃, the heat preservation time is between 0.5 and 2 hours, the further optimization is between 1 and 1.5 hours, the intercalation reaction of the graphite is more uniform and efficient, oxygen-containing groups are better and uniformly distributed among material layers, the subsequent filtration and acid pickling treatment of the reaction product graphite solution are improved in efficiency, the filtration and acid pickling time is shortened, and the cost is saved.
Example 1
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1.2 hours;
2) and (3) medium-temperature reaction: after the low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature which is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, then continuously raising the temperature to a second-stage medium-temperature reaction temperature which is 60 ℃, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-1;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), wherein the temperature is not more than 100 ℃ in the deionized water adding process, keeping the temperature at 92 ℃ after the deionized water is added, and mechanically stirring for 0.5h to obtain a mixed solution S2-1; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide by weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution SG 1;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-1, wherein the suction filtration time is 40 min;
5) acid washing: washing the filter cake G-1 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 15min, so as to obtain a first acid washing filter cake XG 1-1; carrying out second acid washing, and washing the first acid washing filter cake XG1-1 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 20min, so as to obtain a second acid washing filter cake XG 2-1;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 12 h;
7) crushing: crushing the dried sample of the filter cake XG 2-1;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-1.
Example 2
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1.2 hours;
2) and (3) medium-temperature reaction: after the low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature which is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, then continuously raising the temperature to a second-stage medium-temperature reaction temperature which is 60 ℃, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-2;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2) for 0.5h, wherein the temperature is not more than 100 ℃ in the deionized water adding process, preserving the temperature at 97 ℃ after the deionized water is added, and mechanically stirring for 1h to obtain a mixed solution S2-2; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide by weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution SG 2;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-2, wherein the suction filtration time is 25 min;
5) acid washing: washing the filter cake G-2 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 8min, so as to obtain a first acid washing filter cake XG 1-2; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-2 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 15min, so as to obtain a second acid washing filter cake XG 2-2;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 12 h;
7) crushing: crushing the dried sample of the filter cake XG 2-2;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-2.
Example 3
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 hour;
2) and (3) medium-temperature reaction: after the low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, continuing raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, mechanically stirring for 1 hour, and obtaining a mixed solution S1-3;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), wherein the temperature is not more than 100 ℃ in the deionized water adding process, keeping the temperature at 92 ℃ after the deionized water is added, and mechanically stirring for 1h to obtain a mixed solution S2-3; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 1h to obtain an intercalated graphite solution SG 3;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-3, wherein the suction filtration time is 20 min;
5) acid washing: washing the filter cake G-3 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 5min, so as to obtain a first acid washing filter cake XG 1-3; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-3 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 10min, so as to obtain a second acid washing filter cake XG 2-3;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 16 h;
7) crushing: crushing the dried sample of the filter cake XG 2-3;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-3.
Example 4
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 hour;
2) and (3) medium-temperature reaction: after the low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature which is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, then continuously raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour at 60 ℃ to obtain a mixed solution S1-4;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), wherein the temperature is not more than 100 ℃ in the deionized water adding process, keeping the temperature at 93 ℃ after the deionized water is added, and mechanically stirring for 1.5 hours to obtain a mixed solution S2-4; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide by weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution SG 4;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-4, wherein the suction filtration time is 22 min;
5) acid washing: washing the filter cake G-4 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 6min, so as to obtain a first acid washing filter cake XG 1-4; carrying out second acid washing, and washing a first acid washing filter cake XG1-4 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 12min, so as to obtain a second acid washing filter cake XG 2-4;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 16 h;
7) crushing: crushing the dried sample of the filter cake XG 2-4;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-4.
Example 5
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 hour;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature which is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, then continuing raising the temperature to a second-stage medium-temperature reaction temperature which is 60 ℃, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-5;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), adding deionized water for 0.5h, wherein the temperature is not more than 100 ℃ in the deionized water adding process, preserving the temperature at 91 ℃ after adding deionized water, and mechanically stirring for 2h to obtain a mixed solution S2-5; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 1h to obtain an intercalated graphite solution SG 5;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-5, wherein the suction filtration time is 30 min;
5) acid washing: washing the filter cake G-5 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 9min, so as to obtain a first acid washing filter cake XG 1-5; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-5 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 15min, so as to obtain a second acid washing filter cake XG 2-5;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 16 h;
7) crushing: crushing the dried sample of the filter cake XG 2-5;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-5.
Example 6
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 hour;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, then continuously raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-6;
3) high-temperature hydrolysis heat preservation reaction: adding deionized water with the weight equivalent of 30 times into the reaction solution obtained in the step 2), adding deionized water for 1h, wherein the temperature is not more than 100 ℃ in the deionized water adding process, preserving the temperature at 92 ℃ after adding deionized water, and mechanically stirring for 3h to obtain a mixed solution S2-6; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 1h to obtain an intercalated graphite solution SG 6;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-6, wherein the suction filtration time is 32 min;
5) acid washing: washing the filter cake G-6 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 12min, so as to obtain a first acid washing filter cake XG 1-6; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-6 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 18min, so as to obtain a second acid washing filter cake XG 2-6;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 14 h;
7) crushing: crushing the dried sample of the filter cake XG 2-6;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-6.
Example 7
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 13 ℃, and mechanically stirring for 0.5 h;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 38 ℃, keeping the first-stage medium-temperature reaction temperature at 38 ℃, mechanically stirring for 3 hours, continuing raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 63 ℃, and mechanically stirring for 1.3 hours to obtain a mixed solution S1-7;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), wherein the temperature is not more than 100 ℃ in the deionized water adding process, keeping the temperature at 92 ℃ after the deionized water is added, and mechanically stirring for 0.5h to obtain a mixed solution S2-7; then, cooling to 40 ℃, adding 3 times of hydrogen peroxide by weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution SG 7;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-7, wherein the suction filtration time is 33 min;
5) acid washing: washing the filter cake G-7 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 11min, so as to obtain a first acid washing filter cake XG 1-7; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-7 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 17min, so as to obtain a second acid washing filter cake XG 2-7;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 14 h;
7) crushing: crushing the dried sample of the filter cake XG 2-7;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-7.
Example 8
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 13 ℃, and mechanically stirring for 0.5 h;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 38 ℃, keeping the first-stage medium-temperature reaction temperature at 38 ℃, mechanically stirring for 2 hours, continuing raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 63 ℃, and mechanically stirring for 1.3 hours to obtain a mixed solution S1-8;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), adding deionized water for 1.75h, wherein the temperature is not more than 100 ℃ in the deionized water adding process, preserving the temperature at 92 ℃ after adding deionized water, and mechanically stirring for 1h to obtain a mixed solution S2-8; then, cooling to 40 ℃, adding 3 times of hydrogen peroxide by weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution SG 8;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-8, wherein the suction filtration time is 32 min;
5) acid washing: washing the filter cake G-8 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 10min, so as to obtain a first acid washing filter cake XG 1-8; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-8 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 16min, so as to obtain a second acid washing filter cake XG 2-8;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 14 h;
7) crushing: crushing the dried sample of the filter cake XG 2-8;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-8.
Example 9
The method for preparing the graphene in a large scale comprises the following steps:
1) and (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the flake graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 h;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, then continuously raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-9;
3) high-temperature hydrolysis heat preservation reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), wherein the temperature is not more than 100 ℃ in the deionized water adding process, keeping the temperature at 92 ℃ after the deionized water is added, and mechanically stirring for 1h to obtain a mixed solution S2-9; then, cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 1h to obtain an intercalated graphite solution SG 9;
4) and (3) suction filtration: after the reaction is finished, carrying out suction filtration to obtain a filter cake G-9, wherein the suction filtration time is 40 min;
5) acid washing: washing the filter cake G-9 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 15min, so as to obtain a first acid washing filter cake XG 1-9; carrying out second acid washing, namely washing and washing a first acid washing filter cake XG1-9 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 20min, so as to obtain a second acid washing filter cake XG 2-9;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 14 h;
7) crushing: crushing the dried sample of the filter cake XG 2-9;
8) expansion: and expanding the crushed sample at 920 ℃ to obtain the product graphene AG-9.
Comparative example 1
1) And (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 hour;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, continuing raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-D1;
3) and (3) hydrolysis reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), adding the deionized water for 0.5h, and obtaining a mixed solution S2-D1 after the deionized water is added; cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution DSG 1;
4) tubular membrane separation: after the reaction is finished, performing tubular membrane separation to obtain a filter cake G-D1, wherein the separation time is 50 min;
5) acid washing: washing the filter cake G-D1 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 40min, so as to obtain a first acid washing filter cake XG 1-D1; carrying out second acid washing, and washing the first acid washing filter cake XG1-D1 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 90min, so as to obtain a second acid washing filter cake XG 2-D1;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 12 h;
7) crushing: crushing the dried sample of the filter cake XG 2;
8) expansion: and (3) expanding the crushed sample at 920 ℃ to obtain the product graphene AG-D1.
Comparative example 2
1) And (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the intercalated graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate and 0.5 times of weight equivalent of sodium nitrate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 hour;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, continuing raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-D2;
3) and (3) hydrolysis reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), adding the deionized water for 0.5h, and obtaining a mixed solution S2-D2 after the deionized water is added; cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution DSG 2;
4) and (3) filter pressing: after the reaction is finished, performing filter pressing to obtain a filter cake G-D2, wherein the filter pressing time is 45 min;
5) acid washing: washing the filter cake G-D2 obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 40min, so as to obtain a first acid washing filter cake XG 1-D2; carrying out second acid washing, and washing the first acid washing filter cake XG1-D2 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 70min, so as to obtain a second acid washing filter cake XG 2-D2;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 12 h;
7) crushing: crushing the dried sample of the filter cake XG 2-D2;
8) expansion: and (3) expanding the crushed sample at 920 ℃ to obtain the product graphene AG-D2.
Comparative example 3
1) And (3) low-temperature reaction: adding 35 times of weight equivalent of concentrated sulfuric acid into the flake graphite, mixing, adding 1.6 times of weight equivalent of potassium permanganate into the mixed solution, keeping the temperature at 10 ℃, and mechanically stirring for 1 h;
2) and (3) medium-temperature reaction: after low-temperature reaction, raising the temperature to a first-stage medium-temperature reaction temperature, wherein the first-stage medium-temperature reaction temperature is 35 ℃, keeping the first-stage medium-temperature reaction temperature at 35 ℃, mechanically stirring for 2 hours, continuing raising the temperature to a second-stage medium-temperature reaction temperature, keeping the second-stage medium-temperature reaction temperature at 60 ℃, and mechanically stirring for 1 hour to obtain a mixed solution S1-D3;
3) and (3) hydrolysis reaction: adding 30 times of weight equivalent deionized water into the reaction solution obtained in the step 2), adding the deionized water for 0.5h, and obtaining a mixed solution S2-D3 after the deionized water is added; cooling to 60 ℃, adding 3 times of hydrogen peroxide in weight equivalent, and stirring for 0.5h to obtain an intercalated graphite solution DSG 3;
4) and (3) suction filtration: after the reaction is finished, performing tubular membrane separation to obtain a filter cake G-D3, wherein the separation time is 60 min;
5) acid washing: washing the filter cake G obtained in the step 4) by using a dilute hydrochloric acid solution with the mass fraction of 1% for the first acid washing, wherein the first acid washing time is 50min, so as to obtain a first acid washing filter cake XG 1-D3; carrying out second acid washing, and washing the first acid washing filter cake XG1-D3 by using a dilute hydrochloric acid solution with the mass fraction of 0.5%, wherein the second acid washing time is 80min, so as to obtain a second acid washing filter cake XG 2-D3;
6) and (3) drying: drying in a forced air drying oven at 80 deg.C for 12 h;
7) crushing: crushing the dried sample of the filter cake XG 2-D3;
8) expansion: and (3) expanding the crushed sample at 920 ℃ to obtain the product graphene AG-D3.
The prepared graphenes of examples 1-9 and comparative examples 1-3 were subjected to resistivity and BET tests and the results are shown in table 1.
By comparing the embodiment 1, the embodiment 3, the embodiment 4 and the embodiment 5, the deionized water adding time is set to be 0.5h in the step 3) high-temperature hydrolysis heat preservation reaction, the heat preservation temperature range is 91-93 ℃, and the heat preservation time after adding the deionized water is changed, so that the different heat preservation times have influence on the subsequent suction filtration and acid washing time and the specific surface area of the graphene, and the heat preservation time is further preferably 1-1.5h for shortening the subsequent suction filtration and acid washing time and obtaining higher specific surface area.
Compared with the example 3, in the step 3) of the high-temperature hydrolysis heat preservation reaction, the deionized water adding time is set to be 0.5h, the heat preservation time is set to be 1h, the heat preservation temperature is changed to be 97 ℃ in the example 2, the heat preservation temperature is set to be 92 ℃ in the example 3, the subsequent suction filtration and acid washing time of the example 2 is obviously longer than that of the example 3, the specific surface area of the graphene prepared in the example 2 is lower than that of the graphene prepared in the example 3, and therefore, the heat preservation temperature is further preferably 91-93 ℃.
By comparing the example 7 with the example 1, the heat preservation time is kept at 0.5h, the deionized water adding time in the high-temperature hydrolysis heat preservation reaction in the step 3) is prolonged, the subsequent filtering and acid washing time is correspondingly improved, the specific surface area of the prepared graphene is correspondingly increased, and the effect of enabling the intercalated graphite to be oxidized more uniformly by prolonging the temperature and the time of adding the deionized water when the heat preservation time is 0-0.5h is further illustrated. The comparison between the example 5 and the example 6 shows that the setting of the heat preservation time to 2 hours and the extension of the deionized water adding time in the high-temperature hydrolysis heat preservation reaction in the step 3) do not greatly affect the time of the subsequent filtering and pickling steps, and do not greatly affect the specific surface area of the prepared graphene, which indicates that the meaning is not great when the heat preservation time is too long and the deionized water adding time is further extended. Compared with the example 8, when the deionized water adding time is set to be 1.75h, the heat preservation time in the high-temperature hydrolysis heat preservation reaction in the step 3) is obviously prolonged, the filtering and acid washing time and the specific surface area of the prepared graphene are not greatly influenced, and further the fact that the deionized water adding time and the heat preservation time are within a certain range, the filtering and acid washing time is shorter, the specific surface area of the prepared graphene is larger, and the total time of adding the deionized water and preserving heat is prolonged all the time, so that the intercalated graphite is not oxidized more uniformly. Example 8 compared with example 3, when the holding time is set to 1h, the deionized water adding time in the high-temperature hydrolysis holding reaction in step 3) is prolonged, and no increase is brought to the specific surface area of the graphene which is subsequently filtered, pickled and prepared. It is further demonstrated that there are preferred ranges for both the deionized water addition time and the incubation time, rather than the longer the time, the better. In conclusion, the total time of adding deionized water and the total heat preservation time is preferably 1.5-2.5h, the heat preservation time is preferably 1-1.5h, and the time of adding deionized water is preferably 0.5-1h, so that the time and the cost are effectively saved, and the method is suitable for large-scale production of graphene.
The embodiment 3 is compared with the comparative example 1 and the comparative example 2, the step 3) of high-temperature hydrolysis heat preservation reaction is added, the heat preservation temperature range is set to be 91-97 ℃, the time for adding deionized water is 0.5-1h, the time range for keeping the heat preservation temperature is 1-1.5h, the specific surface area of the prepared graphene can be obviously improved, the filtering and pickling time for processing the intercalated graphite solution is shortened, and the problems that adverse effects are caused by overhigh temperature rise during deionized water adding in the large-scale production process, the temperature is difficult to reduce after the overhigh temperature rise and the time is long for temperature reduction can be avoided by setting the heat preservation temperature to be 91-97 ℃.
Example 3 adopts intercalated graphite as a raw material, example 9 adopts flake graphite as a raw material, and a comparison between examples 3 and 9 shows that the specific surface area of graphene prepared from the flake graphite is lower than that of graphene prepared from the intercalated graphite, but in actual production, the cost of the flake graphite is lower than that of the intercalated graphite, so that the raw material can be adjusted correspondingly according to the requirements of customers.
The comparison difference between the comparative example 1 and the comparative example 2 is that the comparative example 2 adds another oxidant sodium nitrate except potassium permanganate in the low-temperature reaction, and the experimental result shows that the difference between the specific surface area of the graphene prepared by adding sodium nitrate in the comparative example 2 and the comparative example 1 is not large, so that the sodium nitrate can be saved, the cost is reduced, the hazardous waste treatment cost is reduced, and the large-scale production is adapted. It should be further noted that, in comparative example 1, intercalated graphite is used as a reaction raw material, and in comparative example 3, crystalline flake graphite is used as a reaction raw material, it is obvious that the specific surface area of comparative example 1 is higher than that of comparative example 3, but the cost of crystalline flake graphite in actual production is much lower than that of intercalated graphite, and crystalline flake graphite can also be used under the condition that the requirement on the specific surface area of a customer is not so high.
In summary, compared with the prior art, the invention has the following advantages: (1) the method is suitable for large-scale preparation of graphene, and avoids the problems of overhigh temperature in the process of adding deionized water in the large-scale preparation of graphene and difficulty in cooling after adding deionized water; (2) the filtering and pickling time is shortened, and the energy consumption is reduced; (3) the prepared graphene has fewer layers; (4) a small amount of potassium permanganate is adopted to reduce the oxidation degree of the graphene; (5) the yield of graphene is improved.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail. In the above description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Moreover, the technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for large-scale preparation of graphene, comprising: intercalation oxidation, hydrolysis reaction, filtration, acid washing and expansion, which is characterized in that,
intercalation oxidation: adding concentrated acid and an oxidant into the graphite, and stirring to react to obtain a mixed solution S1;
and (3) hydrolysis reaction: adding deionized water into the mixed solution S1 to obtain a mixed solution S2; then, after the mixed solution S2 is cooled, adding hydrogen peroxide without the unreacted oxidant to obtain an intercalated graphite solution SG, wherein the temperature of the reaction solution is kept not more than 100 ℃ in the deionized water adding process and the heat preservation process, and the whole hydrolysis reaction is carried out in stirring;
and (3) filtering: filtering the intercalated graphite solution SG to obtain a filter cake G,
acid washing and drying: carrying out acid washing on the filter cake G by using dilute hydrochloric acid to obtain an acid washing filter cake XG, and then drying the acid washing filter cake XG;
crushing: crushing the dried filter cake XG sample;
expansion: and (4) performing high-temperature expansion on the crushed product to obtain a product graphene AG.
2. The method for large-scale preparation of graphene according to claim 1, wherein the incubation temperature is 91-97 ℃.
3. The method for large-scale preparation of graphene according to claim 1 or 2, wherein the sum of the time for adding deionized water and the holding time after adding deionized water is 0.5-3 h.
4. The method for large-scale preparation of graphene according to claim 3, wherein the time for adding deionized water is 0.5-1h, and the holding time is 1-1.5 h.
5. The method for large-scale preparation of graphene according to claim 1, wherein the filtration time is 20-40 min.
6. The method for large-scale preparation of graphene according to claim 1, wherein the acid washing comprises performing first acid washing and second acid washing on the filter cake G by using dilute hydrochloric acid to obtain a first acid washing filter cake XG1 and a second acid washing filter cake XG2 in sequence; wherein the first pickling time is 5-15min, and the second pickling time is 10-20 min.
7. The method for large-scale preparation of graphene according to claim 1, wherein the intercalation oxidation comprises a low-temperature reaction and a medium-temperature reaction, wherein the low-temperature reaction temperature is 10-13 ℃; the medium-temperature reaction comprises a first-stage medium-temperature reaction and a second-stage medium-temperature reaction, wherein the first-stage medium-temperature reaction temperature is 35-38 ℃, and the second-stage medium-temperature reaction temperature is 60-63 ℃.
8. The method for large-scale preparation of graphene according to claim 7, wherein the low-temperature reaction time is 0.5-1.2h, the first-stage medium-temperature reaction time is 2-3h, and the second-stage medium-temperature reaction time is 1-1.3 h.
9. The method for large-scale preparation of graphene according to claim 1, wherein the temperature of the mixed solution S2 in the hydrolysis reaction is 40-60 ℃.
10. The method for large-scale preparation of graphene according to claim 1, wherein the graphite is one or a combination of intercalated graphite and flake graphite.
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