CN108793135B - Graphene porous membrane and preparation method thereof - Google Patents
Graphene porous membrane and preparation method thereof Download PDFInfo
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Abstract
The graphene porous membrane has a communicating pore structure with an adjustable pore diameter within the range of 20-200 nm, and the specific surface area of the graphene porous membrane is 1000-1750 m2The specific conductivity is 15-100S/cm; the preparation method of the graphene porous membrane comprises the following steps: preparing graphene oxide base water dispersion liquid; preparing the graphene oxide-based composite membrane; preparing the graphene porous membrane; according to the invention, the graphene which is easy to disperse is used as a microwave absorbent, so that the uniformity of microwave treatment is improved, and the preparation process of the graphene porous membrane is simplified; the water-soluble polymer is used as a structure regulation component, so that the regulation of the pore structure and the orientation degree of the graphene porous membrane is realized; the prepared graphene porous membrane has an adjustable interconnected pore structure, has good effective specific surface area and electrical conductivity, has excellent electronic conductive network and abundant ion transmission channels, can be further compounded with other materials, and is expected to be widely applied to the fields of energy storage and conversion, catalysis and the like.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to a graphene porous membrane with a communication hole structure and a high specific surface area and a preparation method thereof.
Background
The graphene is a flexible two-dimensional material with high conductivity and high specific surface area, and has wide application prospects in the fields of electrochemical energy storage, sensors, catalysis and the like. Graphene can support various electrochemical active materials to construct an electrode with a self-supporting structure, and is very suitable for an energy storage element of an electronic device which is gradually miniaturized, lightened, flexible and foldable in recent years.
At present, graphene self-supporting structures can be mainly classified into graphene aerogels and graphene films. The graphene aerogel is generally obtained by reducing and self-assembling graphene oxide through processes of sol-gel, hydrothermal or solvothermal and the like, a three-dimensional porous network structure of the graphene aerogel can contain a large amount of active substances and is beneficial to ion transmission, but the volume specific capacity is low due to the ultralow stacking density of the graphene aerogel, and the graphene aerogel does not have flexibility basically due to the disordered orientation of the graphene. The graphene film is generally prepared by preparing a film from a graphene oxide dispersion liquid by methods such as suction filtration, film scraping, spin coating, drop coating, spray coating, dip coating and the like, and then performing post-treatment such as chemical reduction, high-temperature calcination and the like. Although the graphene film has high electric and thermal conductivity, the graphene sheets are stacked more densely, so that the loading capacity of active substances is extremely low, electrolyte ions are difficult to migrate in the graphene film, particularly in the vertical direction, and the reachable specific surface area of the ions is low; this results in lower specific mass capacity and poor rate performance when used as an energy storage material.
Chinese patent CN107416814A discloses "a method for preparing graphene by solid phase assisted microwave", but it only discloses a reduction process by external heating, so that it is difficult to obtain a graphene self-supporting structure with pores, and the equipment is complicated. Chinese patent CN 107500271a discloses a "preparation method of flexible graphene membrane", although the obtained graphene membrane has certain pores inside, the pore size distribution is extremely irregular and does not have a communicating pore structure. In view of the above, there is a need in the art to find a graphene porous membrane with a high specific surface area and a self-supporting structure to meet the development requirement of a flexible energy storage device with miniaturization, light weight and high performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a graphene porous membrane, the orientation degree of which is between that of a graphene aerogel and a compact graphene membrane; the second object of the present invention is to provide a method for preparing the graphene porous membrane.
In order to achieve the purpose, the invention adopts the following technical scheme.
The graphene porous membrane is characterized in that a communicating pore structure with an adjustable pore diameter within a range of 20-200 nm is arranged inside the graphene porous membrane, the specific surface area of the graphene porous membrane is 1000-1750 m2/g, the conductivity of the graphene porous membrane is 15-100S/cm, and the graphene porous membrane has an electronic conductive network and an ion transmission channel.
The preparation method of the graphene porous membrane is characterized by comprising the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be 9-10 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 0.5-5 mg/mL;
then adding a water-soluble polymer and a microwave absorbent, mechanically stirring and mixing for 0.5-1 hour at room temperature (25 ℃), and controlling the mass ratio of the graphene oxide to the water-soluble polymer to the microwave absorbent to be 100: 5-50: 0.2-10 to obtain graphene oxide-based aqueous dispersion;
(2) preparation of graphene oxide-based composite film
Transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter by adopting a polymer filter membrane with the pore diameter of less than or equal to 0.45 micrometer, and performing vacuum filtration by using a vacuum pump to prepare a graphene oxide-based composite membrane;
(3) preparation of graphene porous membrane
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing argon or nitrogen for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and treating for 5-60 s by microwave medium fire or high fire to prepare a target product, namely the graphene porous membrane.
Further, the water-soluble polymer in the step (1) is one of poly (ethylene oxide-propylene oxide) block copolymer, polyvinyl alcohol, polyvinylpyrrolidone or hydroxymethyl cellulose.
Further, the microwave absorbent in the step (1) is easily dispersible graphene, and the easily dispersible graphene is obtained by reducing graphene oxide dispersion liquid through cobalt-60 gamma ray radiation or through hydrazine hydrate or through chemical reduction of sodium borohydride.
Further, the polymer filter membrane in the step (2) is one of a mixed cellulose ester filter membrane, a polyvinylidene fluoride filter membrane, a polytetrafluoroethylene filter membrane, a polycarbonate filter membrane or a polypropylene filter membrane.
Further, the solvent filter in the step (2) is composed of a funnel type filter cup, a middle sand core filter head and a stainless steel fixing clamp.
Further, the vacuum pump in the step (2) adopts a circulating water type vacuum pump, and the vacuum degree is kept to be less than 1 kPa.
The principle of the invention is as follows: in the process of filtering and film forming, the water-soluble polymer can be assembled on the surface of graphene oxide to serve as a structure regulation component, and the easily-dispersible graphene uniformly dispersed in the graphene oxide film serves as a microwave absorbent; in the microwave treatment process, the easily-dispersible graphene is beneficial to absorbing microwave energy, high-temperature reduction of graphene oxide and decomposition of a water-soluble polymer are induced, and the generated gas can cause the formation of a communication pore structure. Meanwhile, the addition of the water-soluble polymer inhibits the tight stacking of graphene lamellar layers, and is beneficial to the separation of the graphene lamellar layers in the microwave treatment process.
The invention has the positive effects that:
(1) the graphene which is easy to disperse is used as a microwave absorbent, so that the uniformity of microwave treatment is greatly improved, and the preparation process of the graphene porous membrane is simplified.
(2) The water-soluble polymer is used as a structure regulation component, so that the pore structure and the orientation degree of the graphene porous membrane can be regulated.
(3) The prepared graphene porous membrane has a communicating pore structure with the pore diameter adjustable within the range of 20-200 nm, the effective specific surface area can reach 1000-1650 m2/g, the conductivity can reach 15-100S/cm, the graphene porous membrane has an excellent electronic conductive network and rich ion transmission channels, can be further compounded with other materials, and is expected to be widely applied to the fields of energy storage and conversion, catalysis and the like.
Drawings
Fig. 1 is a flow chart of a method for preparing a graphene porous membrane according to the present invention.
Fig. 2 is a cross-sectional field emission scanning electron microscope photograph of the graphene porous membrane prepared in example 1.
FIG. 3 is a SEM photograph of a cross-section of comparative sample 1 prepared in comparative example 1.
FIG. 4 is a SEM photograph of a cross-sectional area of comparative sample 2 prepared in comparative example 2.
Detailed Description
The following provides a detailed description of the present invention with reference to the accompanying drawings, and 5 examples and 2 comparative examples are provided to further illustrate the present invention. The technical features of the respective embodiments may be combined with each other as long as they do not conflict with each other.
Example 1
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be =9 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 2 mg/mL;
then polyvinylpyrrolidone and the easily dispersible graphene prepared by the radiation reduction of cobalt-60 gamma rays are added, the mixture is mechanically stirred and mixed for 1 hour at the room temperature (25 ℃), and the mass ratio of the graphene oxide to the polyvinylpyrrolidone to the easily dispersible graphene prepared by the radiation reduction of cobalt-60 gamma rays is controlled to be 100: 30: 0.5, so that the graphene oxide base aqueous dispersion is obtained.
(2) Preparation of graphene oxide-based composite film
Transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a polyvinylidene fluoride filter membrane with the pore diameter of 0.45 micrometer, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to prepare the graphene oxide-based composite membrane.
(3) Preparation of graphene porous membrane
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave high-fire treatment for 5s to prepare a target product, namely the graphene porous membrane.
Comparative example 1 (comparison with example 1)
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be 9-10 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 2 mg/mL;
then adding polyvinylpyrrolidone, mechanically stirring and mixing for 1 hour at room temperature (25 ℃), and controlling the mass ratio of graphene oxide to polyvinylpyrrolidone to be 100: 30 to obtain the graphene oxide-based aqueous dispersion.
(2) Preparation of graphene oxide-based composite film
Transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a polyvinylidene fluoride filter membrane with the pore diameter of 0.45 micrometer, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to prepare the graphene oxide-based composite membrane.
(3) Preparation of comparative sample 1
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave high-fire treatment for 5s to prepare a comparative sample 1.
Comparative example 2 (comparison with example 1)
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be 9-10 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 2 mg/mL;
then adding the easily dispersible graphene prepared by the radiation reduction of cobalt-60 gamma rays, mechanically stirring and mixing for 1 hour at room temperature (25 ℃), and controlling the mass ratio of the graphene oxide to the easily dispersible graphene prepared by the radiation reduction of cobalt-60 gamma rays to be 100: 0.5 to obtain the graphene oxide-based aqueous dispersion.
(2) Preparation of graphene oxide-based composite film
Transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a polyvinylidene fluoride filter membrane with the pore diameter of 0.45 micrometer, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to prepare the graphene oxide-based composite membrane.
(3) Preparation of comparative sample 2
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave high-fire treatment for 5s to prepare a comparative sample 2.
As can be seen from the field emission scanning electron microscope image in fig. 2, the graphene porous membrane prepared in example 1 contains a large number of interconnected pores having an average pore diameter of about 100 nm. The specific surface area of the prepared graphene porous membrane is 1634m2/g, and the conductivity is 35.4S/cm.
As can be seen from the image of the field emission scanning electron microscope in FIG. 3, the cross section of the comparative sample 1 without the addition of the easily dispersible graphene as the microwave absorbent still has a dense morphology after the microwave treatment, and it can be seen that the added polymer is not decomposed at all. Thus, comparative sample 1 prepared in comparative example 1 was insulating and had a specific surface area of only 116m 2/g.
As can be seen from the image of the field emission scanning electron microscope in fig. 4, the graphene film of comparative example 2 without the water-soluble polymer added has pores, but the distribution is very uneven, and the average pore diameter is about 500nm, so that comparative sample 2 prepared by comparative example 2 becomes very loose, the specific surface area is 1280m2/g, and the conductivity is 10.8S/cm.
Example 2
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be =10 by using ammonia water, mechanically stirring for 72 hours to obtain graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 5 mg/mL;
then adding poly (ethylene oxide-propylene oxide) block copolymer and easily dispersible graphene obtained by chemical reduction of hydrazine hydrate, mechanically stirring and mixing for 0.5 hour at the room temperature of 25 ℃, and controlling the mass ratio of the graphene oxide to the poly (ethylene oxide-propylene oxide) block copolymer to the easily dispersible graphene obtained by chemical reduction of hydrazine hydrate to be 100: 10: 5 to obtain the graphene oxide-based aqueous dispersion.
(2) Preparation of graphene oxide-based composite film
And (2) transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a polycarbonate filter membrane with the pore diameter of 0.22 micron, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to obtain the graphene oxide-based composite membrane.
(3) Preparation of graphene porous membrane
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave high-fire treatment for 10s to prepare a target product, namely the graphene porous membrane.
Example 3
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be =9 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 0.5 mg/mL;
and then adding polyvinyl alcohol and the easily dispersible graphene obtained by chemical reduction of sodium borohydride, mechanically stirring and mixing for 1 hour at room temperature (25 ℃), and controlling the mass ratio of the graphene oxide to the polyvinyl alcohol to the easily dispersible graphene obtained by chemical reduction of sodium borohydride to be 100: 50: 2 to obtain the graphene oxide-based aqueous dispersion.
(2) Preparation of graphene oxide-based composite film
And (2) transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a polytetrafluoroethylene filter membrane with the pore diameter of 0.22 micron, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to prepare the graphene oxide-based composite membrane.
(3) Preparation of graphene porous membrane
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave medium fire treatment for 60s to obtain a target product, namely the graphene porous membrane.
Example 4
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be =9 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 1 mg/mL;
and then adding polyvinylpyrrolidone and the easily dispersible graphene obtained by chemical reduction of sodium borohydride, mechanically stirring and mixing for 0.75 hour at room temperature (25 ℃), and controlling the mass ratio of the graphene oxide to the polyvinylpyrrolidone to the easily dispersible graphene obtained by chemical reduction of sodium borohydride to be 100: 20: 10 to obtain the graphene oxide-based aqueous dispersion.
(2) Preparation of graphene oxide-based composite film
And (2) transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a polypropylene filter membrane with the pore diameter of 0.45 micrometer, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to obtain the graphene oxide-based composite membrane.
(3) Preparation of graphene porous membrane
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave high-fire treatment for 20s to prepare a target product, namely the graphene porous membrane.
Example 5
A preparation method of a graphene porous membrane comprises the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be =10 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 3 mg/mL;
then adding hydroxymethyl cellulose and the easily dispersible graphene prepared by cobalt-60 gamma ray radiation reduction, mechanically stirring and mixing for 1 hour at the room temperature (25 ℃), and controlling the mass ratio of the graphene oxide to the hydroxymethyl cellulose to the easily dispersible graphene obtained by sodium borohydride chemical reduction to be 100: 5: 0.2 to obtain the graphene oxide base aqueous dispersion.
(2) Preparation of graphene oxide-based composite film
And (2) transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter consisting of a funnel-type filter cup, a middle sand core filter head and a stainless steel fixing clamp by adopting a mixed cellulose ester filter membrane with the pore diameter of 0.22 micron, and performing vacuum filtration by using a circulating water type vacuum pump to keep the vacuum degree to be less than 1kPa to prepare the graphene oxide-based composite membrane.
(3) Preparation of graphene porous membrane
And (3) transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and performing microwave medium fire treatment for 30s to prepare a target product, namely the graphene porous membrane.
The test results of the graphene porous membranes prepared in examples 1 to 5 and comparative examples 1 and 2 prepared in comparative examples 1 to 2 are as follows (see table 1).
TABLE 1 test results of the graphene porous membranes prepared in examples 1 to 5 and comparative examples 1 and 2 prepared in comparative examples 1 to 2
Analysis of results of examples and comparative examples
As is evident from the test results of table 1:
(1) whether to add the easily dispersible graphene is a decisive factor for reducing the graphene oxide and forming a porous structure.
(2) With the increase of the content of the water-soluble polymer, the average pore diameter of the graphene porous membrane is reduced, the specific surface area is increased, and the conductivity is increased firstly and then reduced.
(3) The results of examples 1-5 and comparative examples 1-2 demonstrate that: the graphene porous membrane prepared by the invention has a communicating pore structure with adjustable pore diameter within the range of 20-200 nm, has better effective specific surface area and conductivity performance, and can be used for preparing a flexible electrochemical energy storage device with high energy density.
Claims (5)
1. The preparation method of the graphene porous membrane is characterized by comprising the following steps:
(1) preparation of graphene oxide-based aqueous Dispersion
Adding graphite oxide into deionized water, adjusting the pH to be 9-10 by using ammonia water, mechanically stirring for 72 hours to obtain a graphene oxide colloid dispersion liquid, and controlling the concentration of graphene oxide to be 0.5-5 mg/mL;
then adding a water-soluble polymer and a microwave absorbent, mechanically stirring and mixing for 0.5-1 hour at the room temperature of 25 ℃, and controlling the mass ratio of the graphene oxide to the water-soluble polymer to the microwave absorbent to be 100: 5-50: 0.2-10 to obtain graphene oxide-based aqueous dispersion;
the water-soluble polymer in the step (1) is one of poly (ethylene oxide-propylene oxide) block copolymer, polyvinyl alcohol, polyvinylpyrrolidone or hydroxymethyl cellulose;
the microwave absorbent in the step (1) is easily dispersible graphene, wherein the easily dispersible graphene is obtained by reducing graphene oxide dispersion liquid through cobalt-60 gamma ray radiation or through hydrazine hydrate or through chemical reduction of sodium borohydride;
(2) preparation of graphene oxide-based composite film
Transferring the graphene oxide-based aqueous dispersion obtained in the step (1) to a solvent filter by adopting a polymer filter membrane with the pore diameter of less than or equal to 0.45 micrometer, and performing vacuum filtration by using a vacuum pump to prepare a graphene oxide-based composite membrane;
(3) preparation of graphene porous membrane
Transferring the graphene oxide-based composite membrane prepared in the step (2) into a glass container with an air extractor, introducing inert gas for protection, keeping the vacuum degree to be less than 100Pa, placing the glass container in the center of a microwave oven tray, and treating the glass container with microwave medium fire or high fire for 5-60 s to prepare a target product, namely a graphene porous membrane;
the graphene porous membrane is internally provided with a communicating pore structure with an adjustable pore diameter within the range of 20-200 nm, and the specific surface area of the graphene porous membrane is 1000-1750 m2The specific surface area is 15-100S/cm, and the specific surface area has an electron conductive network and an ion transmission channel.
2. The method according to claim 1, wherein the polymeric filter membrane in step (2) is one of a mixed cellulose ester filter membrane, a polyvinylidene fluoride filter membrane, a polytetrafluoroethylene filter membrane, a polycarbonate filter membrane, or a polypropylene filter membrane.
3. The method according to claim 1, wherein the solvent filter of step (2) is composed of a funnel-type filter cup, an intermediate sand core filter head and a stainless steel fixing clip.
4. The method according to claim 1, wherein the vacuum pump in the step (2) is a circulating water type vacuum pump, and the vacuum degree is kept to be less than 1 kPa.
5. The graphene porous membrane prepared by the preparation method of the graphene porous membrane according to claim 1, wherein the graphene porous membrane is internally provided with a communication pore structure with adjustable pore diameter within the range of 20-200 nm, and the specific surface area of the graphene porous membrane is 1000-1750 m2The specific surface area is 15-100S/cm, and the specific surface area has an electron conductive network and an ion transmission channel.
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| CN102832050A (en) * | 2012-08-29 | 2012-12-19 | 华东理工大学 | Method for preparing graphene/carbon nanotube hybrid in hierarchical structure |
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Application publication date: 20181113 Assignee: JIANGSU XINGHE GROUP CO.,LTD. Assignor: EAST CHINA University OF SCIENCE AND TECHNOLOGY Contract record no.: X2022980002450 Denomination of invention: Graphene porous membrane and preparation method thereof Granted publication date: 20210914 License type: Exclusive License Record date: 20220314 |