CN104528707A - Preparation method of high-conductivity graphene membrane - Google Patents
Preparation method of high-conductivity graphene membrane Download PDFInfo
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- CN104528707A CN104528707A CN201510036318.XA CN201510036318A CN104528707A CN 104528707 A CN104528707 A CN 104528707A CN 201510036318 A CN201510036318 A CN 201510036318A CN 104528707 A CN104528707 A CN 104528707A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 16
- 229940071870 hydroiodic acid Drugs 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 229920004935 Trevira® Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000006396 nitration reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 230000007547 defect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 239000003223 protective agent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 6
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
The invention belongs to the technical field of preparation of graphene materials, and particularly relates to a preparation method of a high-conductivity graphene membrane. The preparation method comprises the following steps: preparing graphene oxide through an improved Hummer method in the presence of phosphoric acid protective agent, filtering through a polyester fiber filter membrane to obtain a graphene oxide membrane, and reducing the obtained graphene oxide membrane in a hydriodic acid-ethanol mixed solution to obtain the graphene membrane. The preparation method is simple and convenient to operate, has simple requirements for equipment and technology, and is cheap in raw materials and low in cost; and the prepared graphene membrane has few defects and high conductivity. The preparation method is easy to realize large-scale industrial production.
Description
Technical field:
The invention belongs to grapheme material preparing technical field, particularly a kind of preparation method of high-electroconductivity graphene film.
Background technology:
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.It has very excellent performance, and such as its specific surface area is up to 2630m
2.g
-1, sign mobility is up to 200000cm
2.v
-1.s
-1, Young's modulus is nearly to 1.0TPa, and thermal conduction constant is 5000W.m
-1.K
-1, optical transmittance is up to 97.7%, and a little characteristics of Graphene make this type material be subject to extensive concern.
At present, the preparation method of Graphene mainly contains mechanically peel method, chemical Vapor deposition process, epitaxial growth method and chemistry redox method etc., these have its relative merits: mechanically peel method is due to the limitation of stripping means, and it is not suitable for heavy industrialization and prepares Graphene; Chemical Vapor deposition process and epitaxial growth method method owing to having complex process, condition is harsh, productive rate is low, high in cost of production shortcoming, limits its large-scale industrial production at Graphene and application; Oxidation reduction process is current low cost, prepares the method that Graphene is comparatively general on a large scale.Grapheme conductive film, due to characteristics such as its outstanding mechanical property, electroconductibility and light transmissions, has huge application prospect in touch-screen, solar cell, ultracapacitor, lithium ion cell electrode and some flexible electrodes etc.But at present the specific conductivity of graphene film prepared of oxidation reduction process is lower, that oxidation leaves defect on Graphene on the one hand, thus affect the transmission of graphene sheet layer basal plane electronics, that reduction can not thoroughly the oxygen-containing functional group removing on graphene oxide on the other hand, and defect can be left on Graphene after oxygen-containing functional group removing, cause the transmission performance of electronics greatly to decline, thus the specific conductivity of prepared graphene film is reduced.Therefore a kind of simple efficient in the urgent need to developing, the preparation method of high connductivity graphene film.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high-electroconductivity graphene film is provided, graphene film defect prepared by the method is few, mechanical property is high, the Graphene that electric conductivity is obtained compared with conventional oxidation reduction method and graphene film are improved largely, and are with a wide range of applications.
To achieve these goals, specifically comprise the following steps when the present invention prepares high-electroconductivity graphene film:
(1) the Hummer legal system passing through to improve under the protectant existence of phosphoric acid is for graphene oxide:
A. first natural flake graphite and potassium permanganate are added in there-necked flask according to the ratio that weight ratio is 1:6, and slowly add the mixing acid of the vitriol oil and strong phosphoric acid, stir 30min; Wherein, the vitriol oil in nitration mixture: the volume ratio of strong phosphoric acid is 9:1; The ratio of natural flake graphite and nitration mixture is 1g:120ml;
B. the stirred in water bath reaction 12h again there-necked flask being moved to 50 degrees Celsius obtains graphite oxide solution;
C. then preparation distilled water and hydrogen peroxide volume ratio are be frozen into ice cube after the solution of 20:1, the graphite oxide solution be obtained by reacting is poured in the distilled water containing hydrogen peroxide and dissolve rear filtration completely to ice cube, be the dilute hydrochloric acid washing of 10% again by weight percent concentration, finally wash with water to pH value of solution=7, obtain graphene oxide at 40 degrees Celsius of lower vacuum-drying 12h; Wherein, the corresponding 100ml distilled water of every 1g natural flake graphite;
(2) graphene oxide membrane is obtained by trevira membrane filtration: first the graphene oxide that step (1) obtains is distributed in water the graphene oxide water solution being mixed with 0.5-3mg/ml; Graphene oxide water solution obtains graphene oxide membrane by trevira filter membrane vacuum filtration; Again by for subsequent use after 40 degrees Celsius of lower vacuum-drying 8-12h for the graphene oxide membrane obtained;
(3) graphene oxide membrane is reduced and is obtained graphene film under hydroiodic acid HI alcohol mixeding liquid: first prepare hydroiodic acid HI with ethanol contend than being 1:1-1:10, the mixed solution of preferred 1:2-1:4, mixed solution is put into air-tight bottle, again graphene oxide membrane is suspended in inside air-tight bottle, but do not contact the mixed solution of hydroiodic acid HI and ethanol, then under airtight condition, reaction 12-40h is carried out in 80 degrees Celsius of oil baths, preferred 18-24h; After reaction terminates, rinsed with in water and ethanol successively by the graphene film of reduction, room temperature is dried, and namely prepares high-electroconductivity graphene film.
The weight percent concentration of hydrogen peroxide of the present invention is 30%, and the weight percent concentration of hydroiodic acid HI is 55%.
The present invention passes through the thickness of the volume of controlled oxidization graphene aqueous solution and the size controlled oxidization graphene film of trevira filter membrane; The graphene oxide membrane prepared be 1 μm-10 μm, be preferably 3 μm-5 μm.
The present invention compared with prior art, have the following advantages: one is in oxidising process, use strong phosphoric acid as protective material, reduce heat release, the graphene oxide defect comparing traditional Hummer legal system standby is less, the two dimensional structure of better maintenance carbon atom, the graphene-structured obtained through reduction is complete, and electric conductivity is high; Two is adopt the oxide-reduction method improved, and does not use NO3-N and NO2-N, avoid NO, NO in oxidising process
2deng the generation of toxic gas, the graphene oxide extent of exfoliation that the more traditional Hummer method of the graphene oxide obtained obtains is high; Three is the mixed solution redox graphene films adopting hydroiodic acid HI and ethanol, and hydroiodic acid HI and graphene oxide membrane interaction, obtain graphene film, and under the repair of alcohol vapor, repair the vacancy defect of graphene membrane surface; Its preparation method is simple, easy to operate, and to equipment, processing requirement simply, cheaper starting materials, cost is low, and the graphene film defect of preparation is few, and electric conductivity is high, is easy to realize large-scale industrial production.
Accompanying drawing illustrates:
The graphene oxide membrane (the right) of Fig. 1 prepared by the embodiment of the present invention 1 and the photo of graphene film (left side).
The stress-strain curve of the tensile strength test of the graphene oxide membrane of Fig. 2 prepared by the embodiment of the present invention 1 and graphene film.
The graphene oxide of Fig. 3 prepared by the embodiment of the present invention 1 and the XRD figure of Graphene.
The TEM figure of the Graphene of Fig. 4 prepared by the embodiment of the present invention 1.
The AFM figure of the Graphene of Fig. 5 prepared by the embodiment of the present invention 1.
Embodiment:
Below by embodiment, also the invention will be further described by reference to the accompanying drawings.
Embodiment 1:
The detailed process that the present embodiment prepares high-electroconductivity graphene film is:
(1) get 1g graphite and 6g potassium permanganate joins in there-necked flask, slowly add the nitration mixture 120ml that the vitriol oil (98%) and strong phosphoric acid (85%) volume ratio are 9:1, stir 30min; Due to exothermic heat of reaction, the temperature of reaction is 30-35 degree;
(2) there-necked flask is moved to 50 degree of stirred in water bath 12h, obtain the graphite oxide solution of purple;
(3) 5ml hydrogen peroxide (30%) is joined in 100ml distilled water be frozen into ice cube, again graphite oxide solution is poured in ice cube, after dissolving completely to ice cube, (now solution is glassy yellow) filters, then wash with the dilute hydrochloric acid 100ml that massfraction is 10%, then be washed with distilled water to solution in neutral, obtain graphene oxide at 40 degrees Celsius of lower vacuum-drying 12h;
(4) getting 0.2g graphene oxide is scattered in 200ml water, obtains graphene oxide membrane with the trevira membrane filtration of 0.45 μm, and at 40 degrees Celsius of lower vacuum-drying 8h, the graphene oxide film thickness obtained is 5 μm;
(5) get in 10ml hydroiodic acid HI and 30ml ethanol mixing loading 500ml air-tight bottle, graphene oxide membrane is outstanding inner with air-tight bottle, but do not contact mixed solution, under 80 degree of oil bath closed environments, react 20h obtain graphene film, after the graphene film water obtained and ethanol are rinsed repeatedly, naturally dry, the specific conductivity measuring gained graphene film through four probe method is 2.8*10
4s/m, substantially exceeds the specific conductivity of the Graphene that traditional method obtains.
The photo of graphene oxide membrane (the right) prepared by the present embodiment and graphene film (left side) as shown in Figure 1, graphene oxide membrane presents brownish black, and after hydroiodic acid HI reduction, present bright metallic luster, this is because the increase of specific conductivity and the reflection enhancement to visible ray cause.
The stress-strain curve of the tensile strength test of graphene oxide membrane prepared by the present embodiment and graphene film as shown in Figure 2, as can be seen from Figure, the tensile strength of the graphene film obtained after reduction reaches 124MPa, than the tensile strength of graphene oxide membrane (92MPa) beyond 32MPa, elongation at break also has simultaneously significantly increases; This illustrates that graphene film not only has higher intensity, has better snappiness simultaneously after reduction.
As shown in Figure 3, as seen from Figure 3, the characteristic peak of graphene oxide (001) has appeared at 10.5 degree to the XRD figure of the graphene oxide that the present embodiment obtains and Graphene, and now the interlamellar spacing of graphene oxide is
the graphene oxide that more common Hummer legal system is standby (interlamellar spacing is
) there is obvious increase, illustrate that the degree of oxidation of the graphene oxide that the present embodiment obtains is higher; After hydroiodic acid HI reduction, sharp-pointed graphene oxide characteristic peak disappears, and occurs faint Graphene (002) characteristic peak at about 26.4 degree, and illustrating that graphene oxide reduces comparatively thoroughly becomes Graphene.
Graphene TEM that the present embodiment obtains schemes as shown in Figure 4, and TEM sample is that graphene film scrapes that rear dispersion is ultrasonic in ethanol to be obtained, and as seen from Figure 4, obtained graphene film area is comparatively large, and evenly overall, extent of exfoliation is high.
Graphene AFM that the present embodiment obtains schemes as shown in Figure 5, and it is ultrasonic in ethanol that AFM sample is that graphene film scrapes rear dispersion, then drops in sheet mica dries to obtain, and as seen from Figure 5, the graphene sheet layer area of preparation is comparatively large, and thickness is at about 0.8nm.
Embodiment 2:
The same with embodiment 1 of other step of the present embodiment, only become the volume ratio of hydroiodic acid HI and ethanol for 1:1, the specific conductivity of the graphene film obtained is 1.7*10
4s/m.
Embodiment 3:
The same with embodiment 1 of other step of the present embodiment, only the volume ratio of hydroiodic acid HI and ethanol is become 1:5, the specific conductivity of the graphene film obtained is 2.1*10
4s/m.
Embodiment 4:
The same with embodiment 1 of other step of the present embodiment, only the time of graphene oxide membrane reduction reaction is become 12h, the specific conductivity of the graphene film obtained is 1.8*10
4s/m.
Embodiment 5:
The same with embodiment 1 of other step of the present embodiment, only the time of graphene oxide membrane reduction reaction is become 40h, the specific conductivity of the graphene film obtained is 2.6*10
4s/m, can be seen by embodiment, and by improving the graphene oxide membrane that Hummer method obtains, after hydroiodic acid HI and alcohol mixeding liquid reduction, specific conductivity has compared with the Graphene that conventional oxidation reduction method obtains and significantly promotes, and has broad application prospects.
Claims (3)
1. a preparation method for high-electroconductivity graphene film, is characterized in that specifically comprising the following steps:
(1) the Hummer legal system passing through to improve under the protectant existence of phosphoric acid is for graphene oxide:
A. first natural flake graphite and potassium permanganate are added in there-necked flask according to the ratio that weight ratio is 1:6, and add the mixing acid of the vitriol oil and strong phosphoric acid, stir 30min; Wherein, the vitriol oil in nitration mixture: the volume ratio of strong phosphoric acid is 9:1; The ratio of natural flake graphite and nitration mixture is 1g:120ml;
B. the stirred in water bath reaction 12h again there-necked flask being moved to 50 degrees Celsius obtains graphite oxide solution;
C. then preparation distilled water and hydrogen peroxide volume ratio are be frozen into ice cube after the solution of 20:1, the graphite oxide solution be obtained by reacting is poured in the distilled water containing hydrogen peroxide and dissolve rear filtration completely to ice cube, be the dilute hydrochloric acid washing of 10% again by weight percent concentration, finally wash with water to pH value of solution=7, obtain graphene oxide at 40 degrees Celsius of lower vacuum-drying 12h; Wherein, the corresponding 100ml distilled water of every 1g natural flake graphite;
(2) graphene oxide membrane is obtained by trevira membrane filtration: first the graphene oxide that step (1) obtains is distributed in water the graphene oxide water solution being mixed with 0.5-3mg/ml; Graphene oxide water solution obtains graphene oxide membrane by trevira filter membrane vacuum filtration; Again by for subsequent use after 40 degrees Celsius of lower vacuum-drying 8-12h for the graphene oxide membrane obtained;
(3) graphene oxide membrane is reduced and is obtained graphene film under hydroiodic acid HI alcohol mixeding liquid: first prepare hydroiodic acid HI with ethanol contend than the mixed solution for 1:1-1:10, mixed solution is put into air-tight bottle, again graphene oxide membrane is suspended in inside air-tight bottle, but do not contact the mixed solution of hydroiodic acid HI and ethanol, then under airtight condition, reaction 12-40h is carried out in 80 degrees Celsius of oil baths; After reaction terminates, rinsed with in water and ethanol successively by the graphene film of reduction, room temperature is dried, and namely prepares high-electroconductivity graphene film.
2. the preparation method of high-electroconductivity graphene film according to claim 1, it is characterized in that the weight percent concentration of described hydrogen peroxide is 30%, the weight percent concentration of hydroiodic acid HI is 55%.
3. the preparation method of high-electroconductivity graphene film according to claim 1, it is characterized in that the thickness by the volume of controlled oxidization graphene aqueous solution and the size controlled oxidization graphene film of trevira filter membrane, the graphene oxide membrane prepared be 1 μm-10 μm.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104878590A (en) * | 2015-05-21 | 2015-09-02 | 南京理工大学 | Preparation method of conductive graphene nanofiber membrane |
| CN105523547A (en) * | 2016-01-25 | 2016-04-27 | 浙江大学 | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film |
| CN105731434A (en) * | 2016-01-25 | 2016-07-06 | 浙江伟星新型建材股份有限公司 | Graphene film for light efficient electromagnetic shielding and preparation method thereof |
| CN105731435A (en) * | 2016-01-25 | 2016-07-06 | 浙江碳谷上希材料科技有限公司 | High-strength flexible graphene composite heat conduction film and preparation method thereof |
| CN106474819A (en) * | 2016-10-24 | 2017-03-08 | 上海电力学院 | A kind of gas filtration cotton containing graphene oxide and preparation method thereof |
| CN107324316A (en) * | 2017-06-30 | 2017-11-07 | 杭州高烯科技有限公司 | A kind of preparation method of graphene film positive electrode and its application in aluminium ion battery |
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| CN110818033A (en) * | 2019-11-20 | 2020-02-21 | 德蓝水技术股份有限公司 | Preparation method and application of graphene gas diffusion electrode in electro-Fenton system |
| CN110865115A (en) * | 2019-11-07 | 2020-03-06 | 杭州电子科技大学 | HA-graphene flexible electrode and preparation method and application thereof |
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| CN104878590A (en) * | 2015-05-21 | 2015-09-02 | 南京理工大学 | Preparation method of conductive graphene nanofiber membrane |
| CN105731434B (en) * | 2016-01-25 | 2018-08-31 | 浙江伟星新型建材股份有限公司 | A kind of efficient and light weight electromagnetic shielding graphene film and preparation method thereof |
| CN105523547A (en) * | 2016-01-25 | 2016-04-27 | 浙江大学 | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film |
| CN105731434A (en) * | 2016-01-25 | 2016-07-06 | 浙江伟星新型建材股份有限公司 | Graphene film for light efficient electromagnetic shielding and preparation method thereof |
| CN105731435A (en) * | 2016-01-25 | 2016-07-06 | 浙江碳谷上希材料科技有限公司 | High-strength flexible graphene composite heat conduction film and preparation method thereof |
| CN105523547B (en) * | 2016-01-25 | 2017-09-29 | 浙江大学 | A kind of super flexible high heat conduction graphene film and preparation method thereof |
| CN105731435B (en) * | 2016-01-25 | 2017-11-28 | 浙江碳谷上希材料科技有限公司 | A kind of high tensile flexible graphene composite heat conduction film and preparation method thereof |
| CN106474819A (en) * | 2016-10-24 | 2017-03-08 | 上海电力学院 | A kind of gas filtration cotton containing graphene oxide and preparation method thereof |
| CN107324316A (en) * | 2017-06-30 | 2017-11-07 | 杭州高烯科技有限公司 | A kind of preparation method of graphene film positive electrode and its application in aluminium ion battery |
| CN108249424A (en) * | 2018-01-23 | 2018-07-06 | 浙江大学 | A kind of preparation method of the highly conductive ultra-thin graphene film of bromine doping |
| CN108249424B (en) * | 2018-01-23 | 2020-01-10 | 长兴德烯科技有限公司 | Preparation method of bromine-doped high-conductivity ultrathin graphene film |
| CN109300705A (en) * | 2018-09-07 | 2019-02-01 | 常州大学 | CeO2-MnO2The preparation of graphene and the application in supercapacitor |
| CN110865115A (en) * | 2019-11-07 | 2020-03-06 | 杭州电子科技大学 | HA-graphene flexible electrode and preparation method and application thereof |
| CN110818033A (en) * | 2019-11-20 | 2020-02-21 | 德蓝水技术股份有限公司 | Preparation method and application of graphene gas diffusion electrode in electro-Fenton system |
| CN111318176A (en) * | 2020-03-02 | 2020-06-23 | 西南科技大学 | Graphene-based conductive filter membrane and preparation method thereof |
| CN111847434A (en) * | 2020-07-30 | 2020-10-30 | 德州智南针机械科技有限公司 | Preparation process of environment-friendly graphene |
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