CN104817071A - Size grading method for graphene material - Google Patents
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Abstract
The invention relates to a graphene oxide size grading method. The method includes the steps of: 1) dispersing a graphene material in a solvent to obtain a graphene material dispersion liquid; 2) under the condition of an externally applied force, passing the graphene material dispersion liquid through a porous membrane to obtain filtrate and trapped fluid, and conducting separation to obtain graphene materials with different size ranges. Based on the correlation of graphene material size and separation membrane pore size, the method disturbs the graphene material solution to prevent pore channel blockage, and realizes physical one-step method size grading of the graphene material (e.g. graphene oxide). By selecting multiple pore sizes and separation number of times, the graphene material can be separated into a lot of grades according to size. The one-step method for size grading of graphene material is simple, effective, cheap and environment-friendly, and can be used on a large scale. At the same time, the filter membrane for separation can be used repeatedly, thus saving cost.
Description
Technical field
The invention belongs to grapheme material technical field, be specifically related to a kind of size classification method of grapheme material.
Background technology
Graphene, i.e. mono-layer graphite are by sp
2hydbridized carbon atoms is interconnected to form the new carbon of monolayers thick bi-dimensional cellular shape structure.The distinctive electricity of Graphene, light, machinery, thermal characteristics, make it in electronics, structured material, energy storage material, sensing material, catalytic material and matrix material etc., have huge application prospect.In the process of regulation and control Graphene performance and application, the size of graphene film plays a crucial role.The widespread use in the preparation process of tridimensional network, the stacking laminate structure of sequential 2 D and photoelectric device of big size graphene sheet; And in the field that bio-sensing, medicament slow release etc. are higher to biocompatibility requirement, molecular level Graphene is subject to extensive favor due to its high functionalization surface.Therefore, the application tool of size controlled synthesis to Graphene is of great significance.At present, preparing the most widely used in the method for Graphene is on a large scale redox graphene, utilizes strong acid intercalation, strong oxidizer graphite oxide, introduces a large amount of containing oxygen affinity water function group at graphite flake layer, through peeling off, obtain dispersibling the single-layer graphene oxide in the aqueous solution.But after peroxidation, ultrasonic and sequential hydrolysis, graphene oxide sheet dissociates and forms many distribution of sizes.The graphene oxide of gentle preparation reduction can realize size regulation and control to a certain degree, but effect is not remarkable, and controllability is not strong.Therefore, the graphene oxide that effectively, preparation in macroscopic quantity size is controlled still needs further exploration.
In the method for rear synthesizing mean regulation and control Graphene size, someone adopts chemical method to be separated, utilize the Zeta potential of graphene oxide and the dependency of distribution of sizes, be separated by adding exogenous agent, comprise regulation and control pH (J.Am.Chem.Soc.2011,133,6338) and utilize organic solvent (RSC Adv 2015,5,146) etc.The problem of this method is the introduction of impurity, follow-uply also needs the work carrying out Impurity removal, consuming time and uneconomical.The more important thing is that the novel substance added may have impact to graphene oxide structure, therefore chemical method be separated and inadvisable.
Physical is centrifugal methods involving mainly, such as the graphene film of density gradient ultra rate centrifugal method (ACS Nano 2010,4,3381.) separation different size.But the centrifugation rate of superelevation, less preparation batch, special gradient separations medium limit the scale operation of size controllable oxidization Graphene.Common centrifugal method also can carry out size classification, but due to the functionality of its separating effect and graphene oxide, concentration of aqueous solution, rotating speed, time correlation, be difficult to set up contacting of direct distribution of sizes and experiment condition, and centrifugal energy consumption is high, should not be integrated with preparation method.Therefore, the size means of simple and easy, extensive regulation and control graphene oxide lamella are still urgently to be resolved hurrily.
The simplest separation method is the membrane sepn carrying out based on size exclusion to graphene oxide in theory, because this technology relative energy consumption is low, to can be mass-produced and can be integrated with preparation link.But up to the present, also not about utilizing porous-film to carry out bibliographical information or the patent of apart to graphene oxide sheet.Reason or problem mainly contain following 2 points: 1, common filtering membrane pore structure interweaves, duct is longer and pore size distribution is homogeneous not, graphene oxide can be caused to remain in duct and block duct, cannot be separated big or small slice graphene oxide; Even if 2 have selected suitable mould material avoid the problems referred to above, graphene oxide, due to the two-dimentional lamella character of itself, also easily carries out stacking on film surface, causes from clogging duct, the surface of film.
Summary of the invention
The object of the present invention is to provide a kind of size classification method of grapheme material.
The size classification method of grapheme material provided by the present invention, comprises the steps:
1) by grapheme material dispersion in a solvent, grapheme material dispersion liquid is obtained;
2) under the condition applying external force, described grapheme material dispersion liquid is passed through porous-film, obtain filtered liquid (being less than porous-film aperture) and trapped fluid (being greater than porous-film aperture), the i.e. separable grapheme material obtaining different size scope.
In above-mentioned preparation method, step 1) in, described grapheme material specifically can be graphene oxide, and described graphene oxide specifically prepares by Hummers method.
Certainly, the dimensional thinlayer material of other grapheme materials (as: Graphene etc.) and non-graphite alkene material or particulate material also reach the object of size classification by above-mentioned size classification method.
Described solvent can be any one in water, ethanol, ethylene glycol, tetrahydrofuran (THF), Virahol, DMF or N-Methyl pyrrolidone, specifically can be water.
In described grapheme material dispersion liquid, the concentration of grapheme material is 0.001mg/mL-100.0mg/mL, specifically can be 0.1mg/mL-1.0mg/mL, is preferably 0.2mg/mL.
In above-mentioned preparation method, step 1) in, in order to obtain stable grapheme material dispersion liquid, also comprise the step to the ultrasonic stripping of described grapheme material.
In above-mentioned preparation method, step 1) in, also comprise the step that described grapheme material dispersion liquid is dialysed, to remove the impurity such as metal ion and mineral acid that may remain.
In above-mentioned preparation method, step 2) in, described external force specifically can be disturbance (as: stirring) and/or cross flow filter etc.
The material of described porous-film is selected from mineral membrane or polymeric membrane.
The shape of described porous-film is any one in the shape of flat sheet membrane, tubular membrane, rolled film and hollow-fibre membrane.
The forming hole method of described porous-film specifically can by stripping method (dry-wet method), stretching hole forming method, phase inversion process, thermic phase method, in dip coating, irradiation method, surface chemical modification method, nuclear track etching method, power forming method, sol-gel method, sintering process and chemical precipitation method any one and prepare.
The aperture of described porous-film is 1nm-500 μm.
Described porous-film is preferably track etching (forming hole method) film, and its aperture is 1 μm-20 μm, specifically can be polycarbonate track etching film, as: polycarbonate plate track etching film, buy purchased from the sincere company of Beijing Sheng He.
Certainly, as long as method for drilling is track etching, hole shape looks are that track etching (forming hole method) film of other materials columniform is suitable for too.
In above-mentioned preparation method, step 2) in, described grapheme material dispersion liquid repeatedly (as: can be continuously separated twice) by porous-film, obtain the more homogeneous grapheme material of particle diameter (as: graphene oxide), also by the porous-film (as: 3.5 μm and 11.0 μm) of different pore size, the grapheme material of different classification is obtained.
In one embodiment, adopt and described graphene oxide dispersion (CGO) filter membrane of 3.5 μm, aperture with 11.0 μm is successively separated, obtain more than 90% size below 7 μm, 7-17 μm, the graphene oxide of three kinds of particle size range of more than 13.0 μm, called after SGO, MGO and LGO respectively, wherein, the size of graphene oxide refers to the average length and width value of graphene oxide lamella, physical size has certain deviation due to the flexibility of graphene oxide lamella, is not to be separated in strict accordance with hole dimension.
Now, adopt the method for suction filtration film forming, prepare non-classification and classification component SGO, MGO, LGO tri-kinds of graphene oxide membrane respectively, thickness is 1-10 μm; What obtain after spending the night by 57% hydroiodic acid HI solution soaking and reducing is conventional film, can obtain individual layer and multi-layer graphene film, prepare large size graphene oxide membrane possess higher tensile strength and elongation at break through vacuum filtration.The film of chemical reduction method redox graphene, big size graphene film has higher electroconductibility.
In above-mentioned preparation method, step 2) in, when described grapheme material dispersion liquid is by porous-film, to not pass through the described grapheme material dispersion liquid of the residue 5-10% amount of solution of porous-film as trapped fluid, because the described grapheme material dispersion liquid of residue 5-10% amount of solution is difficult to by described porous-film.
In above-mentioned preparation method, step 2) in, also comprise and suction filtration film forming is carried out to described filtered liquid and described trapped fluid and naturally to dry or by cryodesiccated step, to obtain the graphene oxide of described different size scope.
Compared with prior art, the present invention has following beneficial effect:
1) method of simple, rapid, effective, cheap foundation size classification graphene oxide sheet is realized by simple physics membrane sepn, this step size classification magnanimity ground regulates and controls graphene oxide lamella size, and can be integrated with source graphene oxide preparation method;
2) be successively separated by the filter membrane of employing 3.5 μm, aperture with 11.0 μm, the three kinds of graphite oxide olefinic constituents obtained possess significant distribution of sizes difference, the lamella mean sizes of SGO, MGO and LGO component is respectively ~ and 2.3 μm, 10.0 μm and 18.6 μm, there is significant apart effect;
3) the filter membrane use water after being separated rinses, can Reusability, and it is remaining that the film after flushing there is no any graphene oxide;
4) size has a great impact the electricity of graphene oxide and reduzate thereof, mechanical property tool, can be realized the controlled separation of graphene oxide, and then can realize the regulation and control to its performance by the present invention.
5) the present invention is by preferably suitable separatory membrane, avoid common filtering membrane pore structure intertexture, duct is longer and pore size distribution is homogeneous not, graphene oxide can be caused to remain in duct and block duct, the problem of big or small slice graphene oxide cannot be separated; Stirring by applying suitable external force, avoiding the film surface with two-dimentional lamella character graphene oxide and carrying out stacking, and then avoiding clogging filtration duct, the surface of film.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of multi-level hierarchical method in embodiment 1.
Fig. 2 is 3.5 μm and 11.0 μm of aperture separatory membranes stereoscan photograph before use using in embodiment 1, and wherein, a, b and c are 3.5 μm of aperture separatory membranes, and d, e and f are 11.0 μm of aperture separatory membranes.
Fig. 3 is 3.5 μm of using in embodiment 1 and the 11.0 μm of aperture separatory membranes stereoscan photograph after a procedure and after cleaning, and wherein, a, b and c are 3.5 μm of aperture separatory membranes, and d, e and f are 11.0 μm of aperture separatory membranes.
Fig. 4 is stereoscan photograph and the correspondingly-sized statistics of non-classification and the three classification components prepared in embodiment 1.
Fig. 5 is the further data analysis of the XPS of the three classification components of carrying out in embodiment 1, infrared, Raman characterization result and correspondence.
Fig. 6 is the XRD of the three classification component graphene oxide membrane that embodiment 1 is carried out, graphene oxide takes out film time, film toughness relevant characterization result.
Fig. 7 be XPS, Raman, XRD of reduzate corresponding to three classification components prepared by embodiment 1 and Conductivity Ratio comparatively.
Fig. 8 is the stereoscan photograph of 3.5 μm of two classification component of preparation in embodiment 2.
Fig. 9 is the stereoscan photograph of 5.5 μm of two classification component of preparation in embodiment 3.
Figure 10 be in embodiment 3 use 5.5 μm of aperture separatory membranes before use after stereoscan photograph.
Figure 11 is the stereoscan photograph of 11.0 μm of two classification component of preparation in embodiment 4.
Embodiment
Be described method of the present invention below by specific embodiment, but the present invention is not limited thereto, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, foundation size classification graphene oxide sheet:
1) preparation of graphene oxide: 1.0g 325 order natural graphite powder, mix in ice-water bath with the vitriol oil of 23mL 96-98wt%, slowly add 9.0g potassium permanganate after stirring.System is warming up to 35 DEG C, maintains after stablizing half an hour and add 50mL deionized water, continue stirring 15 minutes, add 150mL deionized water, 5mL 3wt%H
2o
2.Obtained bright yellow solution is filtered and uses the 100mL HCl aqueous solution (wherein, the volume ratio of hydrochloric acid and water is 1:9) to wash.Gained solid is dry rear dilution in atmosphere, and after the week of dialysing in deionized water, through ultrasonic stripping, and 3000rpm 30min two times centrifugal removes substrate, obtains the dispersion liquid of single-layer graphene oxide;
2) according to size classification graphene oxide sheet: by step 1) obtained by the dispersion liquid of single-layer graphene oxide through being diluted to about 0.2mg/mL further, and under the disturbances such as stirring or utilize cross flow filter principle to make this solution by filter membrane, the solution of general each reservation original solution 5-10% is as trapped fluid; Again by the solution dilution of membrane retention to starting most the about half adding solution original volume, then be separated once, stay about 10% solution as trapped fluid, namely obtain graphene oxide solution that is that separated product is greater than certain size and that be less than certain size.Also naturally dry by suction filtration film forming or obtain graphene oxide by lyophilize again, utilize different hole dimension filter membrane and repeatedly use this method can obtain multi-stage oxidizing Graphene;
The separation process figure of foundation size classification graphene oxide sheet as shown in Figure 1, utilize the filter membrane-polycarbonate plate track etching film (corresponding SEM figure as shown in Figure 2) of 3.5 μm and 11.0 μm, be separated SGO, MGO and LGO tri-kinds of components obtained from small to large.Isolated rear water flushing membrane can Reusability, and as shown in Figure 3, it is remaining that the film after flushing there is no any graphene oxide.
Prepare graphene oxide self-supported membrane: naturally dry after dispersion liquid tetrafluoroethylene (PTFE) porous-film (diameter 50mm, aperture the is 0.22 μm) suction filtration of single-layer graphene oxide, graphene oxide self-supported membrane can be obtained.
To be separated the three kinds of different size scopes obtained graphene oxide (SGO, MGO and LGO) characterize:
A () Electronic Speculum characterizes: by SGO, the rare dispersant liquid drop of ethanol of MGO and LGO tri-kinds of graphene oxides is coated on silicon chip (surperficial one deck 300nm silicon-dioxide), pattern is characterized by Electronic Speculum after drying, simultaneously, also corresponding size is added up, its corresponding characterization data as shown in Figure 4, upper row figure in Fig. 4 is shape appearance figure, lower row figure in Fig. 4 is corresponding graphene oxide size and distribution plan thereof, can find out from shape appearance figure: unassorted graphene oxide (CGO) pattern is mixed and disorderly, size heterogeneity, and the three kinds of graphene oxides (SGO after three grades of classifications, MGO with LGO) pattern is all relative with size homogeneous, can find out from size and distribution plan thereof: SGO component more than 90% is less than 7 μm, MGO component more than 90% is between 7-17 μm, and LGO component more than 90% is greater than 13 μm, corresponding maximum distribution size is respectively 2.3 μm, 10.0 μm and 18.6 μm, half high Tile Width is respectively 4.5 μm, 6.0 μm and 12.4 μm, can conclude that this separation method effectively achieves three sections of apart for graphene oxide from above result,
B () XPS tests and infrared, Raman sign:
X-ray photoelectron spectroscopic analysis (XPS) is carried out as accompanying drawing 5a-c to the graphene oxide dry film obtained through solution suction filtration.Characterization result shows: along with the increase of graphene oxide size, C/O atomic ratio increase (as Fig. 5 a), in meticulous spectrum, high combination can reduce (as Fig. 5 b) by oxygen-containing functional group partly, the ratio of corresponding C=O and O-C=O also decreases (as Fig. 5 c), illustrate that actual small pieces have higher degree of oxidation, sheet then degree of oxidation is on the low side;
Infrared, Raman characterizes: in infrared spectra (as Fig. 5 d), 1620 wave numbers of C=C and the 1740 strong ratios in wave number peak of C=O increase along with graphene oxide lamella and increase.C=O is mainly present in edge, illustrates that the edge of small pieces is more than sheet, meets expection; The D/G peak intensity ratio (as Fig. 5 e and 5f) of Raman spectrum also increases with graphene oxide size and increases, and description architecture integrity is better, and D/G is increased to 0.94 than from 0.86, and corresponding average defect distance is elevated to 1.40nm from 1.35nm.
C () takes out membrane process to three kinds of graphene oxides (SGO, MGO and LGO) and mould material characterizes:
XRD analysis: the graphene oxide self-supported membrane that SGO, MGO and LGO component suction filtration is obtained, carry out XRD characterization test (as Fig. 6 a), LGO distribution is the narrowest, and diffraction angle is maximum, and d-space is minimum, and lamella is stacking the most closely; SGO distribution is the widest, and diffraction angle is minimum, and d-space is maximum, and the stacking relative randomness of lamella is large, therefore increases with size, and lamella is stacking more orderly, and distance is less;
Take out membrane process research: the time required for graphene oxide membrane that SGO, MGO and LGO component suction filtration obtains is respectively 5,13 and 21h (as Fig. 6 b), reason is that small pieces stacked relative is more not tight, and path is relatively shorter and more, otherwise it is large stretch of, this graphene oxide separatory membrane for the different permeability of research provides condition, little penetration speed is fast, and large distance is long, good separating effect (as Fig. 6 c);
Film stretching performance is tested: self-supported membrane physical strength prepared by suction filtration and elongation at break all increase with size and increase (as Fig. 6 d and Fig. 6 e), reason is many-sided, more closely stacking, lamella is more complete and interlayer juncture is the major cause that large piece performance is better than small pieces less.
D () is reduced through 57% hydroiodic acid HI soaked overnight the mould material (rSGO, rMGO and rLGO) obtained to three kinds of graphene oxides (SGO, MGO and LGO) and is characterized:
XPS characterizes: XPS spectrum display C/O increases than increasing along with lamella (as Fig. 7 a), residual carboxyl should be ascribed to and carbonyl exists more (as Fig. 7 b) in a panel;
Raman characterizes: in Raman collection of illustrative plates (as Fig. 7 c), the obvious comparatively graphene oxide of D/G strength ratio increases to some extent, proves that three is all effectively reduced;
XRD characterizes: have minimizing trend from small pieces to large sheet interlayer spacing in XRD figure spectrum (as Fig. 7 d), but this effect is also not as so strong in graphene oxide membrane, removes because most of functional group has been reduced;
Reduction membrane conductivity test: as Fig. 7 e, the rSGO membrane conductivity after reduction is 186 ± 9S/cm; And the rLGO membrane conductivity after reducing equally reaches 409 ± 8S/cm, the notable difference of the two electric conductivity depends primarily on juncture (the bringing resistance) number of the interlayer in rSGO film higher than rLGO film.
Embodiment 2, foundation size classification graphene oxide sheet:
With the dispersion liquid of the single-layer graphene oxide of preparation in embodiment 1 for raw material, be diluted to 0.2mg/mL, and only carry out two Component seperation with the film of 3.5 μm, the result obtained as shown in Figure 8, the two component size differences obtained are obvious, 3.5 μm of distribution of sizes more than 90% filtered are less than 7 μm, and retain more than 90% is greater than 6 μm.
Embodiment 3, foundation size classification graphene oxide sheet:
With the dispersion liquid of the single-layer graphene oxide of preparation in embodiment 1 for raw material, be diluted to 0.2mg/mL, and only carry out two Component seperation with the film of 5.5 μm, the result obtained as shown in Figure 9, the two component size differences obtained are obvious, 5.5 μm of distribution of sizes more than 90% filtered are less than 11 μm, and retain more than 90% is greater than 9 μm;
And, rinse through simple solvent (as water and ethanol etc.) after a procedure, filter membrane can Reusability, there is no graphene oxide (GO) remaining (as Figure 10), in Figure 10, upper row figure be the SEM figure without the filter membrane used, and in Figure 10, lower row figure used and the SEM of filter membrane after flushing schemes.
Embodiment 4, foundation size classification graphene oxide sheet:
With the dispersion liquid of the single-layer graphene oxide of preparation in embodiment 1 for raw material, be diluted to 0.2mg/mL, and only carry out two Component seperation with the film of 11.0 μm, the result obtained as shown in figure 11, the two component size differences obtained are obvious, 11.0 μm of distribution of sizes more than 90% filtered are less than 20 μm, and retain more than 90% is greater than 15 μm.
Claims (8)
1. a size classification method for grapheme material, comprises the steps:
1) by grapheme material dispersion in a solvent, grapheme material dispersion liquid is obtained;
2) under the condition applying external force, by described grapheme material dispersion liquid by porous-film, filtered liquid and trapped fluid is obtained, i.e. the separable grapheme material obtaining different size scope.
2. size classification method according to claim 1, is characterized in that: step 1) in, described grapheme material is graphene oxide;
Described solvent is any one in water, ethanol, ethylene glycol, tetrahydrofuran (THF), Virahol, DMF or N-Methyl pyrrolidone;
In described grapheme material dispersion liquid, the concentration of grapheme material is 0.001mg/mL-100.0mg/mL.
3. size classification method according to claim 1 and 2, is characterized in that: step 1) in, also comprise the step to the ultrasonic stripping of described grapheme material;
Step 1) in, also comprise the step that described grapheme material dispersion liquid is dialysed.
4. the size classification method according to any one of claim 1-3, is characterized in that: step 2) in, described external force is disturbance and/or cross flow filter;
The material of described porous-film is selected from mineral membrane or polymeric membrane;
The shape of described porous-film is any one in the shape of flat sheet membrane, tubular membrane, rolled film and hollow-fibre membrane;
The forming hole method of described porous-film presses stripping method, stretching hole forming method, phase inversion process, thermic phase method, in dip coating, irradiation method, surface chemical modification method, nuclear track etching method, power forming method, sol-gel method, sintering process and chemical precipitation method any one and prepare;
The aperture of described porous-film is 1nm-500 μm.
5. size classification method according to claim 4, is characterized in that: step 2) in, described porous-film is track etching film, and aperture is 1 μm-20 μm.
6. the size classification method according to any one of claim 1-5, is characterized in that: step 2) in, described grapheme material dispersion liquid by porous-film repeatedly and/or by the porous-film of different pore size.
7. the size classification method according to any one of claim 1-6, it is characterized in that: step 2) in, described grapheme material dispersion liquid is successively be separated by the filter membrane of 3.5 μm, aperture with 11.0 μm by described grapheme material dispersion liquid by porous-film, wherein, described grapheme material is graphene oxide.
8. the size classification method according to any one of claim 1-7, is characterized in that: step 2) in, also comprise and suction filtration film forming is carried out to described filtered liquid and described trapped fluid and naturally to dry or by cryodesiccated step.
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| CN107352533A (en) * | 2017-07-10 | 2017-11-17 | 中国石油大学(北京) | Flexible heat conducting film using more particle diameter graphenes synergy and preparation method thereof |
| CN107441956A (en) * | 2017-09-05 | 2017-12-08 | 景德镇陶瓷大学 | A kind of preparation method of adjustable asymmetric graphene oxide composite membrane of passage and its obtained product |
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| CN108996497A (en) * | 2018-07-24 | 2018-12-14 | 华侨大学 | A method of it is dialysed using multilayer and carries out the separation of grapheme material size |
| CN110127684A (en) * | 2019-05-16 | 2019-08-16 | 南京工业大学 | Method for size grading of flow type continuous stripping graphite oxide and graphene oxide |
| CN113924268A (en) * | 2019-06-13 | 2022-01-11 | 2599218 安大略公司 | Apparatus, method, and system for manufacturing graphene film |
| CN113924268B (en) * | 2019-06-13 | 2024-03-08 | 2599218 安大略公司 | Apparatus, method and system for manufacturing graphene film |
| CN110420567A (en) * | 2019-07-12 | 2019-11-08 | 中国工程物理研究院材料研究所 | A kind of preparation method of graphene hydrophobic membrane and the application method of membrane distillation |
| CN110772994A (en) * | 2019-11-08 | 2020-02-11 | 成都石大力盾科技有限公司 | Mixed graphene oxide nanofiltration membrane, preparation method and application thereof |
| CN110772994B (en) * | 2019-11-08 | 2021-09-24 | 成都石大力盾科技有限公司 | Mixed graphene oxide nanofiltration membrane, preparation method and application thereof |
| CN111391424A (en) * | 2020-03-26 | 2020-07-10 | 浙江浙能技术研究院有限公司 | Double-sided graphene film and preparation method thereof |
| CN112110441A (en) * | 2020-09-24 | 2020-12-22 | 东莞钜蕾实业有限公司 | Graphene high-energy catalytic physical stripping preparation device and method |
| CN112110441B (en) * | 2020-09-24 | 2021-10-29 | 东莞钜蕾实业有限公司 | Graphene high-energy catalytic physical stripping preparation device and method |
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