CN108793135A - A kind of graphene perforated membrane and preparation method thereof - Google Patents
A kind of graphene perforated membrane and preparation method thereof Download PDFInfo
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Abstract
A kind of graphene perforated membrane of the present invention, internal with aperture adjustable intercommunicating pore structure within the scope of 20~200nm, specific surface area is 1000~1750m2/ g, conductivity are 15~100S/cm；The preparation method of the graphene perforated membrane contains following steps：(1) graphite oxide alkenyl aqueous dispersions are prepared；(2) graphene oxide group compound film is prepared；(3) graphene perforated membrane is prepared；The present invention uses easy dispersed graphite alkene as microwave absorption, improves the uniformity of microwave treatment, simplifies the preparation flow of graphene perforated membrane；Using water-soluble polymer as structure regulating component, the adjusting to the porous membrane pore structure of graphene and the degree of orientation is realized；The graphene perforated membrane of preparation has adjustable intercommunicating pore structure, effective ratio area and conductivity performance are good, excellent electronic conduction network and abundant ion transmission channel are had both, can also be further compound with other materials, it is expected to be widely applied to the fields such as energy storage and conversion, catalysis.
Description
Technical field
The present invention relates to grapheme material technical fields, specifically, being one kind having intercommunicating pore structure and high-ratio surface
Long-pending graphene perforated membrane and preparation method thereof.
Background technology
Graphene be it is a kind of have high conductivity, the flexible two-dimensional material of high-specific surface area, electrochemical energy storage, sensing
The fields such as device, catalysis have broad application prospects.Graphene can load various electroactive substance structure self-supporting knots
The electrode of structure is highly suitable for the electronic equipment constantly developed in recent years to miniaturization, lighting, flexible foldable direction
Energy-storage travelling wave tube.
Currently, graphene self supporting structure can be divided mainly into graphene aerogel and graphene film.The graphene airsetting
Glue is usually so that graphene oxide reduction self assembly is obtained by processes such as sol-gel, hydro-thermal or solvent heats, and three-dimensional is more
Pore network structure can accommodate a large amount of active materials and be transmitted conducive to ion, but its ultralow bulk density leads to volume and capacity ratio
Low and unordered graphene orientation makes graphene aerogel not have flexibility substantially.And the graphene film is usually first by oxygen
Graphite alkene dispersion liquid is prepared by the methods of suction filtration, knifing, spin coating, drop coating, spraying and dip-coating and is formed a film, then using chemistry
What the post-processings such as reduction, high-temperature calcination obtained.Although the graphene film has high electrical and thermal conductivity, graphene film heap
It is folded comparatively dense so that active material load capacity is extremely low and electrolyte ion is vertically oriented in graphene film, especially and moves
Difficulty is moved, it is low that ion reaches specific surface area；Times of this lower specific discharge capacity and difference when resulting in it as energy storage material
Rate performance.
Chinese patent CN107416814A is disclosed " a kind of method that solid phase assisted microwave synthesis prepares graphene ", but it is only public
A kind of external reduction process heated has been opened, has been difficult to obtain the graphene self supporting structure with hole accordingly, and equipment is more
It is complicated.Chinese patent CN 107500271A disclose " a kind of preparation method of Flexible graphene film ", though the graphene film of acquisition
It is so internal that there is certain hole, but its pore-size distribution is extremely irregular and does not have intercommunicating pore structure.In view of this, in the industry there is an urgent need for
A kind of graphene perforated membrane with high-specific surface area and self supporting structure is found, it is soft with satisfaction miniaturization, lighting, high-performance
Property energy-storage travelling wave tube development needs.
Invention content
It is an object of the invention to solve the deficiencies in the prior art, provide a kind of graphene perforated membrane, the degree of orientation between
Between graphene aerogel and solid graphite alkene film；It is a second object of the invention to provide the system of the graphene perforated membrane
Preparation Method.
In order to achieve the above object, present invention employs following technical schemes.
A kind of graphene perforated membrane, which is characterized in that the inside of the graphene perforated membrane has aperture in 20~200nm
Adjustable intercommunicating pore structure in range, specific surface area are 1000~1750m2/ g, conductivity are 15~100S/cm, have both electricity
Subconductivity network and ion transmission channel.
The preparation method of the graphene perforated membrane, which is characterized in that contain following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9~10 with ammonium hydroxide, mechanical agitation 72 hours is aoxidized
Graphene colloid dispersion solution controls a concentration of 0.5~5mg/mL of graphene oxide；
Water-soluble polymer and microwave absorption are added, at (25 DEG C), mechanical agitation mixes 0.5~1 hour at room temperature,
And control graphene oxide: water-soluble polymer: the mass ratio of microwave absorption is 100: 5~50: 0.2~10, is aoxidized
Graphene-based aqueous dispersions；
(2) graphene oxide group compound film is prepared
Using the polymeric filters of aperture≤0.45 micron, the graphite oxide alkenyl aqueous dispersions that step (1) is obtained turn
It moves on in a solvent filter, is filtered by vacuum using vacuum pump, graphene oxide group compound film is made；
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Argon gas or nitrogen keep vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, micro-
5~60s of wave moderate heat or high fire processing, is made target product --- graphene perforated membrane.
Further, the water-soluble polymer described in step (1) is poly- (ethylene oxide-propylene oxide) block copolymer, gathers
One kind of vinyl alcohol, polyvinylpyrrolidone or hydroxymethyl cellulose.
Further, the microwave absorption described in step (1) is easy dispersed graphite alkene, and the easy dispersed graphite alkene is by aoxidizing
What graphene dispersing solution was obtained by the reduction of -60 gamma ray radiation of cobalt or through hydrazine hydrate or through sodium borohydride electronation.
Further, the polymeric filters described in step (2) are mixed ester membranes, Kynoar filter membrane, poly- four
One kind of vinyl fluoride filter membrane, polycarbonate leaching film or polypropylene filter.
Further, the solvent filter described in step (2) is by funneling filter cup, intermediate sand core filtering head and stainless steel
Geometrical clamp composition processed.
Further, the vacuum pump described in step (2) uses circulating water type vacuum pump, and vacuum degree is kept to be less than 1kPa.
The principle of the present invention is：In filtering film forming procedure, water-soluble polymer can be pretended in surface of graphene oxide group
For structure regulating component, the easy dispersed graphite alkene in graphene oxide membrane is dispersed in as microwave absorption；At microwave
During reason, easy dispersed graphite alkene is conducive to absorb microwave energy, the high temperature reduction and water-soluble poly of meeting induced oxidation graphene
The decomposition of object is closed, the gas of generation can lead to the formation of intercommunicating pore structure.Meanwhile the addition of water-soluble polymer inhibits graphite
The Close stack of alkene piece interlayer, is conducive to the separation of graphene film interlayer in microwave processing process.
The positive effect of the present invention is：
(1) it uses easy dispersed graphite alkene as microwave absorption, substantially increases the uniformity of microwave treatment, simplify stone
The preparation flow of black alkene perforated membrane.
(2) it uses water-soluble polymer as structure regulating component, realizes to the porous membrane pore structure of graphene and take
Adjusting to degree.
(3) the graphene perforated membrane prepared has aperture adjustable intercommunicating pore structure, effective ratio within the scope of 20~200nm
Surface area is up to 1000~1650m2/ g, conductivity have both excellent electronic conduction network and abundant up to 15~100S/cm
Ion transmission channel, and can also be further compound with other materials, it is expected to be widely applied to energy storage and conversion, catalysis etc.
Field.
Description of the drawings
Fig. 1 is the flow diagram of the preparation method of graphene perforated membrane of the present invention.
Fig. 2 is the section field emission scanning electron microscope photo of graphene perforated membrane prepared by embodiment 1.
Fig. 3 is the section field emission scanning electron microscope photo of comparative sample 1 prepared by comparative example 1.
Fig. 4 is the section field emission scanning electron microscope photo of comparative sample 2 prepared by comparative example 2.
Specific implementation mode
The specific implementation mode that the present invention is provided below in conjunction with attached drawing, provides 5 embodiments and 2 comparing embodiments with right
The present invention is further detailed.Technical characteristic involved by each embodiment is as long as they do not conflict with each other
It is combined with each other.
Embodiment 1
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9 with ammonium hydroxide, mechanical agitation 72 hours obtains graphite oxide
Alkene colloidal dispersion controls a concentration of 2mg/mL of graphene oxide；
It adds polyvinylpyrrolidone and restores easily dispersed graphite alkene obtained through -60 gamma ray radiation of cobalt, (25
DEG C) mechanical agitation mixes 1 hour at room temperature, and controls graphene oxide: polyvinylpyrrolidone: through -60 gamma ray spoke of cobalt
The mass ratio for penetrating reduction easily dispersed graphite alkene obtained is 100: 30: 0.5, obtains graphite oxide alkenyl aqueous dispersions.
(2) graphene oxide group compound film is prepared
Use aperture for 0.45 micron of Kynoar filter membrane, the graphite oxide alkenyl that step (1) is obtained is water-dispersed
Liquid is transferred to a solvent filter being made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp
In, it keeps vacuum degree to be filtered by vacuum less than 1kPa using circulating water type vacuum pump, graphene oxide group compound film is made.
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
High fire processing 5s, is made target product --- graphene perforated membrane.
Comparative example 1 (is compared) with embodiment 1
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9~10 with ammonium hydroxide, mechanical agitation 72 hours is aoxidized
Graphene colloid dispersion solution controls a concentration of 2mg/mL of graphene oxide；
Polyvinylpyrrolidone is added, mechanical agitation mixes 1 hour at room temperature at (25 DEG C), and controls graphene oxide
: the mass ratio of polyvinylpyrrolidone is 100: 30, obtains graphite oxide alkenyl aqueous dispersions.
(2) graphene oxide group compound film is prepared
Use aperture for 0.45 micron of Kynoar filter membrane, the graphite oxide alkenyl that step (1) is obtained is water-dispersed
Liquid is transferred to a solvent filter being made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp
In, it keeps vacuum degree to be filtered by vacuum less than 1kPa using circulating water type vacuum pump, graphene oxide group compound film is made.
(3) comparative sample 1 is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
High fire processing 5s, is made comparative sample 1.
Comparative example 2 (is compared) with embodiment 1
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9~10 with ammonium hydroxide, mechanical agitation 72 hours is aoxidized
Graphene colloid dispersion solution controls a concentration of 2mg/mL of graphene oxide；
It adds through -60 gamma ray radiation of cobalt reduction easily dispersed graphite alkene obtained, at (25 DEG C), machinery stirs at room temperature
Mixing 1 hour is mixed, and controls graphene oxide: the quality through -60 gamma ray radiation of cobalt reduction easily dispersed graphite alkene obtained
Than being 100: 0.5, graphite oxide alkenyl aqueous dispersions are obtained.
(2) graphene oxide group compound film is prepared
Use aperture for 0.45 micron of Kynoar filter membrane, the graphite oxide alkenyl that step (1) is obtained is water-dispersed
Liquid is transferred to a solvent filter being made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp
In, it keeps vacuum degree to be filtered by vacuum less than 1kPa using circulating water type vacuum pump, graphene oxide group compound film is made.
(3) comparative sample 2 is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
High fire processing 5s, is made comparative sample 2.
In the graphene perforated membrane prepared by embodiment 1 it can be seen from the field emission scanning electron microscope image of Fig. 2
Containing a large amount of average pore sizes 100nm or so intercommunicating pore.Prepared graphene perforated membrane specific surface area is 1634m2/ g, electricity
Conductance is 35.4S/cm.
Comparative example 1 is not added with easy dispersed graphite alkene conduct it can be seen from the field emission scanning electron microscope image of Fig. 3
Fine and close pattern is still presented in the microwaved rear section of comparative sample 1 of microwave absorption, and can be clearly visible the poly- of addition
Object is closed not decompose completely.Therefore, the comparative sample 1 prepared by comparative example 1 is insulation, and specific surface area only has 116m2/g。
Comparative example 2 is not added with the stone of water-soluble polymer it can be seen from the field emission scanning electron microscope image of Fig. 4
Although hole occurs after microwave treatment in black alkene film, its distributed pole is uneven, and average pore size is about 500nm, this makes
Comparative sample 2 prepared by comparative example 2 becomes extremely loose, specific surface area 1280m2/ g, conductivity 10.8S/cm.
Embodiment 2
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=10 with ammonium hydroxide, mechanical agitation 72 hours obtains graphite oxide
Alkene colloidal dispersion controls a concentration of 5mg/mL of graphene oxide；
The easy dispersion stone for adding poly- (ethylene oxide-propylene oxide) block copolymer and being obtained through hydrazine hydrate electronation
Black alkene, at (25 DEG C), mechanical agitation mixes 0.5 hour at room temperature, and controls graphene oxide: poly- (ethylene oxide-propylene oxide)
Block copolymer: the mass ratio of the easy dispersed graphite alkene obtained through hydrazine hydrate electronation is 100: 10: 5, obtains graphite oxide
Alkenyl aqueous dispersions.
(2) graphene oxide group compound film is prepared
Use aperture for 0.22 micron of polycarbonate leaching film, the graphite oxide alkenyl aqueous dispersions that step (1) is obtained
It is transferred in the solvent filter that one is made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp,
It keeps vacuum degree to be filtered by vacuum less than 1kPa using circulating water type vacuum pump, graphene oxide group compound film is made.
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
High fire processing 10s, is made target product --- graphene perforated membrane.
Embodiment 3
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9 with ammonium hydroxide, mechanical agitation 72 hours obtains graphite oxide
Alkene colloidal dispersion controls a concentration of 0.5mg/mL of graphene oxide；
The easy dispersed graphite alkene for adding polyvinyl alcohol and being obtained through sodium borohydride electronation, in (25 DEG C) machine at room temperature
Tool is stirred 1 hour, and controls graphene oxide: polyvinyl alcohol: the easy dispersed graphite obtained through sodium borohydride electronation
The mass ratio of alkene is 100: 50: 2, obtains graphite oxide alkenyl aqueous dispersions.
(2) graphene oxide group compound film is prepared
Use aperture for 0.22 micron of teflon membrane filter, the graphite oxide alkenyl that step (1) is obtained is water-dispersed
Liquid is transferred to a solvent filter being made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp
In, it keeps vacuum degree to be filtered by vacuum less than 1kPa using circulating water type vacuum pump, graphene oxide group compound film is made.
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
Moderate heat handles 60s, and target product --- graphene perforated membrane is made.
Embodiment 4
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9 with ammonium hydroxide, mechanical agitation 72 hours obtains graphite oxide
Alkene colloidal dispersion controls a concentration of 1mg/mL of graphene oxide；
The easy dispersed graphite alkene for adding polyvinylpyrrolidone and being obtained through sodium borohydride electronation, in (25 DEG C) room
The lower mechanical agitation of temperature mixes 0.75 hour, and controls graphene oxide: polyvinylpyrrolidone: being obtained through sodium borohydride electronation
The mass ratio of the easy dispersed graphite alkene arrived is 100: 20: 10, obtains graphite oxide alkenyl aqueous dispersions.
(2) graphene oxide group compound film is prepared
Use aperture for 0.45 micron of polypropylene filter, the graphite oxide alkenyl aqueous dispersions that step (1) is obtained turn
It moves on in the solvent filter that one is made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp, makes
It keeps vacuum degree to be filtered by vacuum less than 1kPa with circulating water type vacuum pump, graphene oxide group compound film is made.
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
High fire processing 20s, is made target product --- graphene perforated membrane.
Embodiment 5
A kind of preparation method of graphene perforated membrane, contains following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=10 with ammonium hydroxide, mechanical agitation 72 hours obtains graphite oxide
Alkene colloidal dispersion controls a concentration of 3mg/mL of graphene oxide；
It adds hydroxymethyl cellulose and restores easily dispersed graphite alkene obtained through -60 gamma ray radiation of cobalt, (25
DEG C) mechanical agitation mixes 1 hour at room temperature, and controls graphene oxide: hydroxymethyl cellulose: obtained through sodium borohydride electronation
The mass ratio of the easy dispersed graphite alkene arrived is 100: 5: 0.2, obtains graphite oxide alkenyl aqueous dispersions.
(2) graphene oxide group compound film is prepared
Use aperture for 0.22 micron of mixed ester membranes, the graphite oxide alkenyl moisture that step (1) is obtained
Dispersion liquid is transferred to a solvent filter being made of funneling filter cup, intermediate sand core filtering head and stainless steel geometrical clamp
In, it keeps vacuum degree to be filtered by vacuum less than 1kPa using circulating water type vacuum pump, graphene oxide group compound film is made.
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, is passed through
Inert gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave
Moderate heat handles 30s, and target product --- graphene perforated membrane is made.
The test result of comparative sample 1 and 2 prepared by graphene perforated membrane and comparative example 1-2 prepared by embodiment 1-5 is such as
Under (be shown in Table 1).
The test knot of comparative sample 1 and 2 prepared by graphene perforated membrane and comparative example 1-2 prepared by 1. embodiment 1-5 of table
Fruit
Examples and Comparative Examples interpretation of result
It will be obvious that from the test result of table 1：
(1) easy dispersed graphite alkene, which whether is added, to be redox graphene and forms the deciding factor of porous structure.
(2) with the raising of water-soluble polymer content, the average pore size of graphene perforated membrane reduces, specific surface area increases
And conductivity first increases and then decreases.
(3) result of embodiment 1-5 and comparative example 1-2 prove：There is graphene perforated membrane prepared by the present invention aperture to exist
Adjustable intercommunicating pore structure within the scope of 20~200nm, effective ratio area and conductivity performance are more preferable, can be used for preparing high energy
The flexible electrochemical energy storage device of metric density.
Claims (7)
1. a kind of graphene perforated membrane, which is characterized in that the inside of the graphene perforated membrane has aperture in 20~200nm models
Interior adjustable intercommunicating pore structure is enclosed, specific surface area is 1000~1750m2/ g, conductivity are 15~100S/cm, have both electronics
Conductive network and ion transmission channel.
2. a kind of preparation method of graphene perforated membrane as described in claim 1, which is characterized in that contain following steps：
(1) graphite oxide alkenyl aqueous dispersions are prepared
Graphite oxide is added in deionized water, adjusts pH=9~10 with ammonium hydroxide, mechanical agitation 72 hours obtains graphite oxide
Alkene colloidal dispersion controls a concentration of 0.5~5mg/mL of graphene oxide；
Add water-soluble polymer and microwave absorption, 25 DEG C at room temperature mechanical agitation mix 0.5~1 hour, and control
Graphene oxide: water-soluble polymer: the mass ratio of microwave absorption is 100: 5~50: 0.2~10, obtains graphene oxide
Base aqueous dispersions；
(2) graphene oxide group compound film is prepared
Using the polymeric filters of aperture≤0.45 micron, the graphite oxide alkenyl aqueous dispersions that step (1) obtains are transferred to
It in one solvent filter, is filtered by vacuum using vacuum pump, graphene oxide group compound film is made；
(3) graphene perforated membrane is prepared
Graphene oxide group compound film made from step (2) is transferred in the glass container with air extractor, inertia is passed through
Gas keeps vacuum degree to be less than 100Pa to protect, and the glass container is placed in tray of microwave oven center, microwave moderate heat
Or 5~60s of high fire processing, target product --- graphene perforated membrane is made.
3. preparation method according to claim 2, which is characterized in that the water-soluble polymer described in step (1) is poly- (oxygen
Change ethylene oxide-propylene oxide) block copolymer, polyvinyl alcohol, polyvinylpyrrolidone or hydroxymethyl cellulose one kind.
4. preparation method according to claim 2, which is characterized in that the microwave absorption described in step (1) is easily dispersion
Graphene, the easy dispersed graphite alkene are restored by -60 gamma ray radiation of cobalt by graphene oxide dispersion or through hydration
Hydrazine is obtained through sodium borohydride electronation.
5. preparation method according to claim 2, which is characterized in that the polymeric filters described in step (2) are that mixing is fine
One kind of the plain ester filter membrane of dimension, Kynoar filter membrane, teflon membrane filter, polycarbonate leaching film or polypropylene filter.
6. preparation method according to claim 2, which is characterized in that the solvent filter described in step (2) is by funneling
Filter cup, intermediate sand core filtering head and stainless steel geometrical clamp composition.
7. preparation method according to claim 2, which is characterized in that the vacuum pump described in step (2) uses circulating water type
Vacuum pump keeps vacuum degree to be less than 1kPa.
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| CN111653436A (en) * | 2020-06-10 | 2020-09-11 | 贵州梅岭电源有限公司 | Application of carbon aerogel/graphene film in flexible supercapacitor |
| CN113924268A (en) * | 2019-06-13 | 2022-01-11 | 2599218 安大略公司 | Apparatus, method, and system for manufacturing graphene film |
| CN114180558A (en) * | 2021-12-27 | 2022-03-15 | 广东墨睿科技有限公司 | Preparation method of graphene micro-nano cavity superconducting film, related product and application |
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| CN113924268A (en) * | 2019-06-13 | 2022-01-11 | 2599218 安大略公司 | Apparatus, method, and system for manufacturing graphene film |
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| CN111653436A (en) * | 2020-06-10 | 2020-09-11 | 贵州梅岭电源有限公司 | Application of carbon aerogel/graphene film in flexible supercapacitor |
| CN114180558A (en) * | 2021-12-27 | 2022-03-15 | 广东墨睿科技有限公司 | Preparation method of graphene micro-nano cavity superconducting film, related product and application |
| CN114180558B (en) * | 2021-12-27 | 2023-09-08 | 广东墨睿科技有限公司 | Preparation method of graphene micro-nano cavity superconducting film, related product and application |
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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 |