CN107416801B - Preparation method of three-dimensional porous graphene - Google Patents

Preparation method of three-dimensional porous graphene Download PDF

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CN107416801B
CN107416801B CN201710804793.6A CN201710804793A CN107416801B CN 107416801 B CN107416801 B CN 107416801B CN 201710804793 A CN201710804793 A CN 201710804793A CN 107416801 B CN107416801 B CN 107416801B
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CN107416801A (en
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王丽
李彦
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Anhui Xuantong Electromechanical Technology Co.,Ltd.
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention relates to the field of battery materials, and particularly discloses a preparation method of three-dimensional porous graphene, which comprises the following steps: s1: adding a cross-linking agent into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 8-10h at the temperature of 120-180 ℃ to obtain a mixed solution; s2: adding dodecyl dimethyl amine oxide into the mixed solution at the temperature of 10-25 ℃, fully stirring to be uniform, then adding ammonium bicarbonate and ammonium nitrate, slowly stirring for 0.5-1h, then freeze-drying for 1-2 days, and taking out; s3: and quickly pushing the taken dry matter into a reducing atmosphere at the temperature of 200-300 ℃ for pre-sintering for 12-24h, then heating to the temperature of 500-700 ℃ for calcining for 3-5h, and cooling to obtain the three-dimensional porous graphene. The three-dimensional graphene obtained by the invention has the advantages of full through between holes, large specific surface area, stable three-dimensional structure formed by overlapping and high conductivity, and can be effectively applied to battery materials to improve the energy density and the use safety of batteries.

Description

Preparation method of three-dimensional porous graphene
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method of three-dimensional porous graphene.
Background
Graphene, as a novel carbon nanomaterial, is tightly stacked by single-layer sp2 carbon atoms to form a two-dimensional honeycomb structure, has various advantages of high conductivity, good mechanical properties and the like, and is widely applied to the field of lithium battery materials at present. However, few graphene layers have high activity and large surface energy of the graphene layer, so that the peeled graphene layer is easy to fold and agglomerate, the specific surface area and the conductivity of the graphene layer are greatly reduced, and the energy density and the lithium storage performance of the battery are further influenced.
Researches show that the graphene with the two-dimensional honeycomb structure is three-dimensionally modified, so that the graphene can be better embedded into the material, the specific surface area of the graphene is fully utilized, the conductivity of the material can be improved, the internal resistance of the battery is reduced, and the energy density of the battery is improved. For example, a chinese patent entitled "method for preparing three-dimensional graphene or a composite system thereof" (application No. 201310175590.7) discloses the following preparation scheme: the method comprises the following steps of carrying out high-temperature reduction on a transition metal simple substance and/or a compound containing a transition metal element to prepare a three-dimensional porous metal catalyst template, and then growing three-dimensional graphene by using a chemical vapor deposition method to obtain the three-dimensional graphene with a catalyst framework. However, the method relies on the use of a guide template, which is difficult to remove, expensive, and difficult to implement on an industrial scale.
Disclosure of Invention
The invention aims to provide a preparation method of three-dimensional porous graphene with large specific surface area, good conductivity and stable structure.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of three-dimensional porous graphene comprises the following steps:
s1: adding a cross-linking agent into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 8-10h at the temperature of 120-180 ℃ to obtain a mixed solution;
s2: adding dodecyl dimethyl amine oxide into the mixed solution at the temperature of 10-25 ℃, fully stirring to be uniform, then adding ammonium bicarbonate and ammonium nitrate, slowly stirring for 0.5-1h, then freeze-drying for 1-2 days, and taking out;
s3: quickly pushing the taken dry matter into a reducing atmosphere at the temperature of 200-300 ℃ for pre-sintering for 12-24h, then heating to the temperature of 500-700 ℃ for calcining for 3-5h, and cooling to obtain the three-dimensional porous graphene;
the mass ratio of the graphene oxide to the cross-linking agent, the dodecyl dimethyl amine oxide, the ammonium bicarbonate and the ammonium nitrate in the dispersion liquid is 40-70:5-10:1-5:1-5: 1-5.
The beneficial effect that adopts above-mentioned technical scheme to produce lies in: according to the invention, the dispersed graphene oxide sheets are treated by the cross-linking agent and the dodecyl dimethyl amine oxide to promote the graphene oxide to be connected into a three-dimensional network structure, then the ammonium bicarbonate and the ammonium nitrate are slowly added into the graphene oxide sheets, then the freeze drying treatment is carried out, so that the interaction force among the graphene sheets can be reduced, the structure is stabilized, and then the calcination is carried out at a specific step temperature, so that the holes of the three-dimensional graphene obtained by reduction are fully communicated, the specific surface area is large, and the specific surface area can be as high as 2300m2The formed three-dimensional porous structure is stable, the conductivity is about 89s/cm, the conductivity is good, and the conductive material can be effectively applied to battery materials, so that the energy density and the use safety of the battery are improved. In particular, prepared by the inventionThe lithium titanate composite negative electrode material obtained by compounding the three-dimensional graphene has the specific capacity of 174.25mAh/g at the charging rate of 0.2C, and the capacity retention rate of 99.21% after the lithium titanate composite negative electrode material is cycled for 50 times at the rate of 3C.
As a further preferred embodiment: the cross-linking agent is one of acrylamide, polyurethane, ethylenediamine and propylenediamine; and the mass ratio of the graphene oxide to the cross-linking agent, the dodecyl dimethyl amine oxide, the ammonium bicarbonate and the ammonium nitrate in the dispersion liquid in the step S1 is 50:5-6:4-5:2-3: 2-3.
Further, step S3 is to quickly push the taken-out dried substance into a reducing atmosphere of 260-.
Specifically, the graphene oxide dispersion liquid in step S1 is prepared according to the following method: adding deionized water with the mass being 20-30 times that of a dispersing agent, mixing, then adding graphene oxide, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, wherein the dispersing agent is one of polyethylene glycol, polyvinyl alcohol and sodium methyl cellulose, and the mass ratio of the dispersing agent to the graphene oxide is 1: 5-10.
Preferably, the reducing atmosphere in step S3 is a hydrogen atmosphere; the conditions of ultrasonic dispersion are: performing ultrasonic dispersion for 1-2h under the power of 200-; the freeze drying in step S2 is carried out at-40 to-20 ℃ for 24 to 48 hours.
Detailed Description
To further illustrate the technical solution of the present invention, the following is further illustrated by examples 1 to 8 and comparative examples 1 to 3.
Example 1:
1) adding 160ml of deionized water into 8g of polyethylene glycol, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of acrylamide into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 24 hours, and taking the mixture out;
4) quickly pushing the taken dry substance into a 270 ℃ hydrogen atmosphere for presintering for 23h, then heating to 670 ℃ for calcining for 4h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 2300m2(ii)/g, conductivity 89 s/cm.
According to the following steps of 1: 10, respectively adding Li4Ti5O12 into the three-dimensional graphene, performing ball milling dispersion for 2 hours by using ethanol as a dispersing agent, then performing vacuum drying, calcining the dried material for 4 hours in an air atmosphere at 600 ℃, and cooling to obtain the battery composite negative electrode material, wherein the discharge specific capacity of the battery composite negative electrode material at 0.2C multiplying power is 174.12mAh/g, and the capacity retention rate of the battery composite negative electrode material after 3C multiplying power is cycled for 50 times is 99.21%.
Example 2:
1) adding 160ml of deionized water into 8g of sodium methylcellulose, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 400W of power and 30 ℃ to obtain a graphene oxide dispersion liquid;
2) adding 6g of propylene diamine into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 8h at the temperature of 170 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 30 hours, and taking the mixture out;
4) quickly pushing the taken dry substance into a 280 ℃ hydrogen atmosphere for presintering for 23h, then heating to 650 ℃ for calcining for 5h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 2280m2(ii)/g, conductivity 87 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 174.25mAh/g, and the capacity retention rate after cycling at 3C rate for 50 times is 99.03%.
Example 3:
1) adding 160ml of deionized water into 8g of polyethylene glycol, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of acrylamide into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 24 hours, and taking the mixture out;
4) rapidly pushing the taken dry substance into a hydrogen atmosphere at 240 ℃ for pre-sintering for 20h, then heating to 700 ℃ for calcining for 4h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 2190m2The specific conductivity is 85 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 173.11mAh/g, and the capacity retention rate after 50 times of 3C rate cycling is 89.99%.
Example 4:
1) adding 160ml of deionized water into 8g of polyethylene glycol, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of acrylamide into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 24 hours, and taking the mixture out;
4) quickly pushing the taken dry substance into a hydrogen atmosphere at 300 ℃ for presintering for 15h, then heating to 550 ℃ for calcining for 3h, cooling to obtain three-dimensional porous graphene, and detecting the specific surface area of the three-dimensional porous grapheneIs 2200m2The specific conductivity is 85 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 173.76mAh/g, and the capacity retention rate after 50 times of 3C rate cycling is 89.25%.
Example 5:
1) adding 160ml of deionized water into 8g of sodium methylcellulose, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain a graphene oxide dispersion liquid;
2) adding 6g of polyurethane into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 4g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 24 hours, and taking the mixture out;
4) rapidly pushing the taken dry substance into a hydrogen atmosphere at 240 ℃ for pre-sintering for 20h, then heating to 700 ℃ for calcining for 4h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 2180m2(ii)/g, conductivity 84 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 173.11mAh/g, and the capacity retention rate after 50 times of 3C rate cycling is 89.87%.
Example 6:
1) adding 200ml of deionized water into 8g of sodium methylcellulose, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 1.5h under the conditions of 400W of power and 30 ℃ to obtain a graphene oxide dispersion liquid;
2) adding 5g of polyurethane into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 8 hours at the temperature of 170 ℃ to obtain a mixed liquid;
3) adding 3g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 2.5g of ammonium bicarbonate and 2.5g of ammonium nitrate, slowly stirring the mixture for 0.5h, then freeze-drying the mixture for 40h, and taking the mixture out;
4) quickly pushing the taken dry substance into 280 ℃ hydrogen atmosphere for presintering for 24h, then heating to 660 ℃ for calcining for 5h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 2160m2The specific conductivity is 85 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 173.01mAh/g, and the capacity retention rate after cycling at 3C rate for 50 times is 90.08%.
Example 7:
1) adding 240ml of deionized water into 8g of polyvinyl alcohol, mixing, adding 70g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 200W power and 30 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of ethylenediamine into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 10 hours at the temperature of 150 ℃ to obtain a mixed solution;
3) adding 6g of dodecyl dimethyl amine oxide into the mixed solution at the low temperature of 10 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 48 hours, and taking the mixture out;
4) quickly pushing the taken dry substance into a hydrogen atmosphere at 260 ℃ for presintering for 23h, then heating to 680 ℃ for calcining for 5h, and cooling to obtain the three-dimensional porous graphene, wherein the specific surface area of the three-dimensional porous graphene is 2150m through detection2The specific conductivity is 85 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 173.14mAh/g, and the capacity retention rate after 50 times of 3C rate cycling is 99.05%.
Example 8:
1) adding 200ml of deionized water into 8g of polyvinyl alcohol, mixing, then adding 60g of graphene oxide, and performing ultrasonic dispersion for 1.5h under the conditions of 400W of power and 30 ℃ to obtain a graphene oxide dispersion liquid;
2) adding 6g of polyurethane into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 160 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 4g of ammonium bicarbonate and 4g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 42 hours, and taking the mixture out;
4) rapidly pushing the taken dry matter into 200 ℃ hydrogen atmosphere for presintering for 24h, then heating to 500 ℃ for calcining for 5h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 2160m2The specific conductivity is 85 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 173.97mAh/g, and the capacity retention rate after cycling at 3C rate for 50 times is 89.84%.
Comparative example 1:
1) adding 160ml of deionized water into 8g of polyethylene glycol, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of acrylamide into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 3g of ammonium bicarbonate and 3g of ammonium nitrate into the mixed solution at the temperature of 20 ℃, slowly stirring for 1h, then freeze-drying for 24h, and taking out;
4) quickly pushing the taken dry substance into a 270 ℃ hydrogen atmosphere for presintering for 23h, then heating to 670 ℃ for calcining for 4h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 1100m2(ii)/g, conductivity 46 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 169.54mAh/g, and the capacity retention rate after cycling at 3C rate for 50 times is 88.24%.
Comparative example 2:
1) adding 160ml of deionized water into 8g of polyethylene glycol, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of acrylamide into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 24 hours, and taking the mixture out;
4) quickly pushing the taken dry substance into a 270 ℃ hydrogen atmosphere for presintering for 23h, then heating to 670 ℃ for calcining for 4h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 1400m2(ii)/g, conductivity 51 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 168.21mAh/g, and the capacity retention rate after cycling at 3C rate for 50 times is 88.17%.
Comparative example 3:
1) adding 160ml of deionized water into 8g of polyethylene glycol, mixing, adding 50g of graphene oxide, and performing ultrasonic dispersion for 2 hours under the conditions of 300W of power and 25 ℃ to obtain graphene oxide dispersion liquid;
2) adding 6g of acrylamide into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 9 hours at the temperature of 150 ℃ to obtain a mixed liquid;
3) adding 5g of dodecyl dimethyl amine oxide into the mixed solution at the temperature of 20 ℃, fully stirring the mixture to be uniform, then adding 3g of ammonium bicarbonate and 3g of ammonium nitrate, slowly stirring the mixture for 1 hour, then freeze-drying the mixture for 24 hours, and taking the mixture out;
4) quickly pushing the taken dry substance into hydrogen atmosphere at 150 ℃ for presintering for 23h, then heating to 500 ℃ for calcining for 4h, cooling to obtain three-dimensional porous graphene, and detecting that the specific surface area of the three-dimensional porous graphene is 1300m2(ii)/g, conductivity 54 s/cm.
The three-dimensional graphene prepared in the step 4) is used as a raw material, the battery composite negative electrode material is prepared according to the method in the embodiment 1, the specific discharge capacity at 0.2C rate is 168.54mAh/g, and the capacity retention rate after 50 times of 3C rate cycling is 88.89%.
From the application effects of the three-dimensional graphene prepared in the above embodiments and comparative examples, the three-dimensional graphene prepared by the method disclosed by the invention can show higher electrochemical activity when applied to a battery electrode material.

Claims (7)

1. A preparation method of three-dimensional porous graphene comprises the following steps:
s1: adding a cross-linking agent into the graphene oxide dispersion liquid, and carrying out hydrothermal reaction for 8-10h at the temperature of 120-180 ℃ to obtain a mixed solution;
s2: adding dodecyl dimethyl amine oxide into the mixed solution at the temperature of 10-25 ℃, fully stirring to be uniform, then adding ammonium bicarbonate and ammonium nitrate, slowly stirring for 0.5-1h, then freeze-drying for 1-2 days, and taking out;
s3: quickly pushing the taken dry matter into a reducing atmosphere at the temperature of 200-300 ℃ for pre-sintering for 12-24h, then heating to the temperature of 500-700 ℃ for calcining for 3-5h, and cooling to obtain the three-dimensional porous graphene;
the mass ratio of the graphene oxide to the cross-linking agent, the dodecyl dimethyl amine oxide, the ammonium bicarbonate and the ammonium nitrate in the dispersion liquid is 40-70:5-10:1-5:1-5: 1-5;
the cross-linking agent is one of acrylamide, polyurethane, ethylenediamine and propylenediamine.
2. The method for producing three-dimensional porous graphene according to claim 1, wherein: and the mass ratio of the graphene oxide to the cross-linking agent, the dodecyl dimethyl amine oxide, the ammonium bicarbonate and the ammonium nitrate in the dispersion liquid in the step S1 is 50:5-6:4-5:2-3: 2-3.
3. The method for producing three-dimensional porous graphene according to claim 2, wherein: step S3 is to quickly push the taken-out dried substance into a reducing atmosphere of 260-280 ℃ for pre-burning for 23-24h, then raise the temperature to 650-680 ℃ for calcining for 4-5h, and cool.
4. The method for producing three-dimensional porous graphene according to claim 3, wherein: the graphene oxide dispersion liquid in the step S1 is prepared according to the following method: adding deionized water with the mass being 20-30 times that of a dispersing agent, mixing, then adding graphene oxide, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, wherein the dispersing agent is one of polyethylene glycol, polyvinyl alcohol and sodium methyl cellulose, and the mass ratio of the dispersing agent to the graphene oxide is 1: 5-10.
5. The method for producing three-dimensional porous graphene according to claim 4, wherein: the reducing atmosphere in step S3 is a hydrogen atmosphere.
6. The method for producing three-dimensional porous graphene according to claim 5, wherein: the conditions of ultrasonic dispersion are: ultrasonic dispersion is carried out for 1-2h under the power of 200-400W and the temperature condition of 20-30 ℃.
7. The method for producing three-dimensional porous graphene according to claim 6, wherein: the freeze drying in step S2 is carried out at-40 to-20 ℃ for 24 to 48 hours.
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