CN104961124A - Method for manufacturing graphene paper - Google Patents
Method for manufacturing graphene paper Download PDFInfo
- Publication number
- CN104961124A CN104961124A CN201510341808.0A CN201510341808A CN104961124A CN 104961124 A CN104961124 A CN 104961124A CN 201510341808 A CN201510341808 A CN 201510341808A CN 104961124 A CN104961124 A CN 104961124A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- substrate
- graphene
- oxide film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a method for manufacturing graphene paper. The method includes manufacturing graphene oxide thin films by the aid of a solvent evaporation-induced self-assembly process; reducing the graphene oxide thin films by the aid of an electrochemical reduction process to obtain reduced graphene oxide thin films; peeling the reduced graphene oxide thin films from substrates to obtain the graphene paper. The method has the advantages that the specific surface area of the graphene paper manufactured by the aid of the method can reach 105m<2>/g, the electric conductivity of the graphene paper can reach 12S/m as tested by four-point probes, and accordingly the graphene paper with the high specific surface area and the high electric conductivity has a great prospect in the aspect of energy storage.
Description
(1) technical field
This belongs to graphene paper preparing technical field, relates to a kind of preparation method of novel graphite alkene paper.
(2) background technology
Graphene forms, has the carbon materials of bi-dimensional cellular shape crystalline structure by individual layer a large amount of sp2 hydbridized carbon atoms close-packed arrays.The structure of its uniqueness makes it have the excellent physical properties such as the ultrafast electronic mobility of high theoretical specific surface area, high Young's modulus, high strength and high heat conductance.Based on the advantageous property of above grapheme material, grapheme material has more wide application prospect in fields such as energy storage, catalysis, sensor and functional composite materials, especially in following nano electron device, matrix material, solar cell, ultracapacitor, has very large application prospect.Relatively and conventional physical method prepare grapheme material, chemical method prepares Graphene, and to have productive rate higher, and preparation method is comparatively easy, and lower-cost advantage, therefore becomes a kind of conventional method prepared by Graphene.
Current preparation graphene paper mainly contains following three kinds of methods: the gentle liquid level self-assembly of vacuum filtration, liquid phase electrophoretic deposition.The people such as He (He G.Y., Chen H.Q., Zhu J.W., Bei F.L., Sun X.Q., Wang X., J.Mater.Chem., 2011,21 (38), 14631-14638) first with hydrazine hydrate solution be reductive agent, obtain the rare dispersion liquid of different reducing degree graphite by the chemical conversion process of liquid-phase reduction graphene oxide dispersion, the rare paper electrode material of graphite that electroconductibility that employing vacuum filtration legal system is standby is subsequently different.The people such as Niu (NiuZ.Q., ChenJ., HngH.H., MaJ., ChenX.D., Adv.Mater., 2012,24 (30), 4144-4150) graphene oxide dispersion first supersound process obtained obtains paper material by vacuum filtration, then prepares the rare paper of graphite with the reduction of hydrazine hydrate steam.Although the research that vacuum filtration prepares graphene paper is more, there is high, the consuming time length of suction filtration process energy consumption and the problem such as paper material and filter membrane separation difficulty in this method.2009 Nian Yangquanhong seminar (Chen C.m., Yang Q.H., Yang Y.G., Lv W., Wen Y.F., Du H.D., Zhu Z.P., Yang Q.H., Kang F.Y., J.Mater.Chem., 2011,2I (10), 3359-3364) propose a kind of short-cut method preparing graphene oxide paper material, namely obtain large-area graphene oxide papery by self-assembly on graphite oxide rare dispersion liquid liquid-gas interface, and on the basis of previous work, prepare graphene oxide and Graphene composite paper material and graphene oxide and carbon pipe paper material.These work are that theoretical basis has been established in the research of the rare paper material of big area graphite.But the preparation flow of these graphene films is usually comparatively loaded down with trivial details, and cost is higher, and the film quality prepared is poor hinders it and apply on a large scale.
Therefore those skilled in the art is devoted to prepare a kind of big area self-supporting, and the graphene paper material that electric property is excellent.
(3) summary of the invention
The object of the invention is to overcome above-mentioned technical problem, realize easy, high quality, repeatably self-supporting graphene paper preparation.
To achieve these goals, the invention provides a kind of preparation method of novel graphite alkene paper, namely the method for solvent evaporates induction self-assembly is first adopted to prepare graphene oxide film, then by the method for electrochemical reduction, graphene oxide film is reduced into oxidation graphene film, finally oxidation graphene film is peeled off from substrate, obtained graphene paper.
The present invention adopts following technical scheme:
A preparation method for graphene paper, described preparation method carries out as follows:
The preparation of (a) graphene oxide film: graphite oxide is added in solvent Virahol, ultrasonic stripping 2 ~ 3h, obtain graphene oxide Virahol dispersion liquid, gained graphene oxide Virahol dispersion liquid being added bottom is covered with in the container of substrate, and this container is placed in 30 ~ 40 DEG C of climatic chamber 8 ~ 12h, until the solvent Virahol in graphene oxide Virahol dispersion liquid volatilizees completely, namely substrate surface in a reservoir forms one deck graphene oxide film; In described graphene oxide Virahol dispersion liquid, the concentration of graphene oxide is 0.05 ~ 0.15g/L; Described substrate is copper sheet, ito glass or Pt sheet;
The reduction of (b) graphene oxide film: get the substrate that surface coverage that step (a) obtains has graphene oxide film, graphene oxide film erasing on the end face of substrate one end is reserved a segment base basal surface, then platinized platinum is got, platinized platinum drips gel electrolyte, the substrate of graphene oxide film surface coverage is had to fit on platinized platinum, between platinized platinum and substrate, form layer of gel ionogen, and substrate is coated with graphene oxide film one facing to platinized platinum and gel electrolyte adhesion, the substrate of graphene oxide film is had for working electrode with surface coverage, platinized platinum is to electrode, the one end and the platinized platinum that substrate are reserved a segment base basal surface access electrochemical workstation respectively, in-10 ~ 0V potential range, with the sweep velocity scan cycle volt-ampere of 0.05v/s, and obtain corresponding cyclic voltammetric collection of illustrative plates, when the reduction peak in cyclic voltammetric collection of illustrative plates between-5V ~-6V disappears, graphene oxide film reduction is described completely, substrate is removed from platinized platinum, obtain the substrate that surface coverage has oxidation graphene film, and on oxidation graphene film, remain gel electrolyte, described gel electrolyte is: with the swelling polymethylmethacrylate of propylene carbonate for matrix, take lithium perchlorate as the gel electrolyte that supporting electrolyte is formed,
The preparation of (c) graphene paper: get the substrate that surface coverage that step (b) obtains has oxidation graphene film, put into dehydrated alcohol and soak 8 ~ 12min, after gel electrolyte solidification residual on graphene oxide film to be restored, take the gel electrolyte of solidification off, surface coverage there is the substrate of oxidation graphene film to put into deionized water again and soak 10 ~ 20min, after graphene oxide film to be restored is separated completely with substrate, deionized water is replaced by dehydrated alcohol, take out graphene film, dry, flatten, namely described graphene paper is obtained.
Preparation method of the present invention, is characterized in that, described graphite oxide is standby by the Hummers legal system of improvement, and is washed till neutrality with deionized water, obtains described graphite oxide; The Hummers method of described improvement is the method preparing graphite oxide well known in the art.
In step (a), in preferred described graphene oxide Virahol dispersion liquid, the concentration of graphene oxide is 0.1g/L.
In step (a), preferably ultrasonic power is 53KHz.
In step (a), the container described in recommendation is culture dish.
In step (a), preferably described substrate is ito glass, and described ito glass is cleaned ito glass, the method of described cleaning is: ito glass is used respectively 0.1M KOH solution, deionized water, ethanol, acetone, toluene, ethanol, acetone ultrasonic cleaning 15min successively, finally be put in acetone and preserve, take out during use, and dry up with nitrogen, stand-by.
In step (b), preferably between platinized platinum and substrate, form the thick layer of gel ionogen of 1 ~ 3mm.
In step (b), concrete, described gel electrolyte prepares as follows: add in reaction vessel by polymethylmethacrylate and propylene carbonate, sealed reaction vessel is placed on 18h in the baking oven of steady temperature 70 DEG C, make polymethylmethacrylate swelling in propylene carbonate, then lithium perchlorate and acetonitrile are added in reaction vessel, and be placed in the ultrasonic 10h in ultrasonic pond by uncovered for reaction vessel, until material dissolution is in acetonitrile, obtain gel electrolyte, encapsulate stand-by; The mass ratio of described acetonitrile and propylene carbonate, polymethylmethacrylate, lithium perchlorate is 70:20:7:3; The molecular-weight average of described polymethylmethacrylate is 120000g/mol.
It should be noted that: in the preparation process of gel electrolyte, acetonitrile uses as electroanalysis solvent, obtained gel electrolyte is in the use procedure of preparation method's step (b) of described graphene paper, acetonitrile can vapor away, acetonitrile just plays the effect of dissolving ionogen (lithium perchlorate) when preparing gel electrolyte, after acetonitrile volatilization, electrolyte lithium perchlorate is stored in the gel of the swelling polymethylmethacrylate of propylene carbonate.
Compared with prior art, beneficial effect of the present invention is: the specific surface area of the graphene paper utilizing preparation method of the present invention to obtain can reach 105m
2/ g, tests its specific conductivity up to 12S/m by four point probe.The graphene paper obtained due to the present invention has higher specific surface area and specific conductivity, makes it in energy storage, have very large prospect.
(4) accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention prepares graphene paper;
Fig. 2 is the device sketch of electrochemical reduction oxidation graphene film, in figure: 1-Pt sheet, 2-gel electrolyte, 3-are coated with the substrate of graphene oxide film, 4-electrochemical workstation, 5-to electrode, 6-reference electrode, 7-working electrode.
(5) embodiment
Below by specific embodiment, the present invention is further detailed, but protection scope of the present invention is not limited in this.
Embodiment 1
(1) utilize the Hummers legal system of improvement for graphite oxide, and centrifuge washing is extremely neutral repeatedly with deionized water.Get graphite oxide (0.05g) to mix with isopropanol solvent (500mL), in ultrasonic pond, be 53KHz in power, temperature is ultrasonic 3h under the condition of 42 DEG C, obtains graphene oxide Virahol dispersion liquid, and its concentration is 0.1g/l.
(2) bottom a culture dish, copper sheet is put into as substrate, pour the graphene oxide Virahol dispersion liquid 50ml of above-mentioned preparation into, being put in temperature is set in the climatic chamber of 35 DEG C, volatilization process 12h, solvent Virahol in graphene oxide Virahol dispersion liquid volatilizees completely, namely forms one deck graphene oxide film on copper sheet surface.
(3) take out the copper sheet being coated with graphene oxide film of above-mentioned preparation, the graphene oxide film of its one end paper handkerchief being moistened with deionized water is wiped.Then platinized platinum is got, platinized platinum drips gel electrolyte (1mL), the copper sheet of graphene oxide film surface coverage is had to fit on platinized platinum, between platinized platinum and copper sheet, form one deck 1mm thick gel ionogen, and copper sheet is coated with graphene oxide film one facing to platinized platinum and gel electrolyte adhesion.Have the copper sheet of graphene oxide film for working electrode with surface coverage, platinized platinum is to electrode, and electrochemical workstation is accessed respectively in one end of copper sheet surface erasing graphene oxide film and platinized platinum.In the voltage range of-10-0V, sweep speed for 0.05V/s, the number of turns and be set to scan cycle volt-ampere under the condition of 10 circles, to be scanned complete after be electrochemically reduced to oxidation graphene film by graphene oxide film.Copper sheet is removed from platinized platinum, obtains the copper sheet that surface coverage has oxidation graphene film, and remain gel electrolyte on oxidation graphene film
(4) copper sheet being coated with oxidation graphene film of above-mentioned preparation is taken out put into dehydrated alcohol and soak 10min, treat that gel residual on graphene film solidifies completely, carefully take the gel had cured with tweezers off.Put it in deionized water again and soak 15min, graphene film is separated completely with copper sheet substrate.Deionized water is outwelled, adds dehydrated alcohol, carefully press from both sides out the graphene film peeled off with tweezers, dry.Put between two layers of filter paper and flatten, namely obtain graphene paper.
Embodiment 2
(1) utilize the Hummers legal system of improvement for graphite oxide, and centrifuge washing is extremely neutral repeatedly with deionized water.Get graphite oxide (0.05g) to mix with isopropanol solvent (500mL), in ultrasonic pond, be 53KHz in power, temperature is ultrasonic 3h under the condition of 42 DEG C, obtains graphene oxide Virahol dispersion liquid, and its concentration is 0.1g/l.
(2) bottom a culture dish, ito glass is put into as substrate, pour the graphene oxide Virahol dispersion liquid 50ml of above-mentioned preparation into, being put in temperature is set in the climatic chamber of 35 DEG C, volatilization process 12h, solvent Virahol in graphene oxide Virahol dispersion liquid volatilizees completely, namely forms one deck graphene oxide film on ito glass surface.
(3) take out the ito glass being coated with graphene oxide film of above-mentioned preparation, the graphene oxide film of its one end paper handkerchief being moistened with deionized water is wiped.Then platinized platinum is got, platinized platinum drips gel electrolyte (2mL), the ito glass of graphene oxide film surface coverage is had to fit on platinized platinum, between platinized platinum and ito glass, form one deck 2mm thick gel ionogen, and ito glass is coated with graphene oxide film one facing to platinized platinum and gel electrolyte adhesion.Have the ito glass of graphene oxide film for working electrode with surface coverage, platinized platinum is to electrode, and electrochemical workstation is accessed respectively in one end of ito glass surface erasing graphene oxide film and platinized platinum.In the voltage range of-10-0V, sweep speed for 0.05V/s, the number of turns and be set to scan cycle volt-ampere under the condition of 10 circles, to be scanned complete after be electrochemically reduced to oxidation graphene film by graphene oxide film.Ito glass is removed from platinized platinum, obtains the ito glass that surface coverage has oxidation graphene film, and remain gel electrolyte on oxidation graphene film
(4) taken out by the ito glass being coated with oxidation graphene film of above-mentioned preparation and put into dehydrated alcohol and soak 10min, gel residual on graphene oxide film to be restored solidifies completely, carefully takes the gel had cured with tweezers off.Put it in deionized water again and soak 15min, oxidation graphene film is separated completely with ito glass substrate.Deionized water is outwelled, adds dehydrated alcohol, carefully press from both sides out the graphene film peeled off with tweezers, dry.Put between two layers of filter paper and flatten, namely obtain graphene paper.
Embodiment 3
(1) utilize the Hummers legal system of improvement for graphite oxide, and centrifuge washing is extremely neutral repeatedly with deionized water.Get graphite oxide (0.05g) to mix with isopropanol solvent (500mL), in ultrasonic pond, be 53KHz in power, temperature is ultrasonic 3h under the condition of 42 DEG C, obtains graphene oxide Virahol dispersion liquid, and its concentration is 0.1g/l.
(2) bottom a culture dish, Pt sheet A is put into as substrate, pour the graphene oxide Virahol dispersion liquid 50ml of above-mentioned preparation into, being put in temperature is set in the climatic chamber of 35 DEG C, volatilization process 12h, solvent Virahol in graphene oxide Virahol dispersion liquid volatilizees completely, namely forms one deck graphene oxide film on Pt sheet A surface.
(3) take out the Pt sheet A being coated with graphene oxide film of above-mentioned preparation, the graphene oxide film of its one end paper handkerchief being moistened with deionized water is wiped.Then Pt sheet B is separately got, Pt sheet B drips gel electrolyte (3mL), the Pt sheet A of graphene oxide film surface coverage is had to fit on Pt sheet B, form one deck 3mm thick gel ionogen between the two, and Pt sheet A is coated with graphene oxide film one facing to Pt sheet B and gel electrolyte adhesion.Have the Pt sheet A of graphene oxide film for working electrode with surface coverage, platinized platinum B is to electrode, and electrochemical workstation is accessed respectively in one end of Pt sheet A surface erasing graphene oxide film and Pt sheet B.In the voltage range of-10-0V, sweep speed for 0.05V/s, the number of turns and be set to scan cycle volt-ampere under the condition of 10 circles, to be scanned complete after be electrochemically reduced to oxidation graphene film by graphene oxide film.Pt sheet A is removed from Pt sheet B, obtains the Pt sheet A that surface coverage has oxidation graphene film, and remain gel electrolyte on oxidation graphene film
(4) dehydrated alcohol is put in the Pt sheet A taking-up being coated with oxidation graphene film of above-mentioned preparation and soak 10min, treat that the gel on graphene film solidifies completely, carefully take the gel had cured with tweezers off.Put it in deionized water again and soak 15min, graphene film is separated completely with Pt sheet A substrate.Deionized water is outwelled, adds dehydrated alcohol, carefully press from both sides out the graphene film peeled off with tweezers, dry.Put between two layers of filter paper and flatten, namely obtain graphene paper.
In prior art, the method preparing graphene oxide paper adopts suction method mostly, uses hydrazine hydrate reduction graphene oxide, obtains graphene paper.And the present invention adopts solvent evaporates to induce autonomous dress method first to prepare graphene oxide film, then by electrochemical method, it is reduced, thus preparation graphene paper.The present invention compared with the existing methods, first there is novelty (adopting solvent evaporates induction independently to fill method) in the method for film forming, secondly the present invention utilizes the method for electrochemical reduction, the reducing degree making reductive agent compared to hydrazine hydrate is higher, also can be reflected by the good electroconductibility of material.
Claims (7)
1. a preparation method for graphene paper, is characterized in that, described preparation method carries out as follows:
The preparation of (a) graphene oxide film: graphite oxide is added in solvent Virahol, ultrasonic stripping 2 ~ 3h, obtain graphene oxide Virahol dispersion liquid, gained graphene oxide Virahol dispersion liquid being added bottom is covered with in the container of substrate, and this container is placed in 30 ~ 40 DEG C of climatic chamber 8 ~ 12h, until the solvent Virahol in graphene oxide Virahol dispersion liquid volatilizees completely, namely substrate surface in a reservoir forms one deck graphene oxide film; In described graphene oxide Virahol dispersion liquid, the concentration of graphene oxide is 0.05 ~ 0.15g/L; Described substrate is copper sheet, ito glass or Pt sheet;
The reduction of (b) graphene oxide film: get the substrate that surface coverage that step (a) obtains has graphene oxide film, graphene oxide film erasing on the end face of substrate one end is reserved a segment base basal surface, then platinized platinum is got, platinized platinum drips gel electrolyte, the substrate of graphene oxide film surface coverage is had to fit on platinized platinum, between platinized platinum and substrate, form layer of gel ionogen, and substrate is coated with graphene oxide film one facing to platinized platinum and gel electrolyte adhesion, the substrate of graphene oxide film is had for working electrode with surface coverage, platinized platinum is to electrode, the one end and the platinized platinum that substrate are reserved a segment base basal surface access electrochemical workstation respectively, in-10 ~ 0V potential range, with the sweep velocity scan cycle volt-ampere of 0.05v/s, and obtain corresponding cyclic voltammetric collection of illustrative plates, when the reduction peak in cyclic voltammetric collection of illustrative plates between-5V ~-6V disappears, graphene oxide film reduction is described completely, substrate is removed from platinized platinum, obtain the substrate that surface coverage has oxidation graphene film, and on oxidation graphene film, remain gel electrolyte, described gel electrolyte is: with the swelling polymethylmethacrylate of propylene carbonate for matrix, take lithium perchlorate as the gel electrolyte that supporting electrolyte is formed,
The preparation of (c) graphene paper: get the substrate that surface coverage that step (b) obtains has oxidation graphene film, put into dehydrated alcohol and soak 8 ~ 12min, after gel electrolyte solidification residual on graphene oxide film to be restored, take the gel electrolyte of solidification off, surface coverage there is the substrate of oxidation graphene film to put into deionized water again and soak 10 ~ 20min, after graphene oxide film to be restored is separated completely with substrate, deionized water is replaced by dehydrated alcohol, take out graphene film, dry, flatten, namely described graphene paper is obtained.
2. preparation method as claimed in claim 1, it is characterized in that, in step (a), in described graphene oxide Virahol dispersion liquid, the concentration of graphene oxide is 0.1g/L.
3. preparation method as claimed in claim 1, it is characterized in that, in step (a), ultrasonic power is 53KHz.
4. preparation method as claimed in claim 1, it is characterized in that, in step (a), described container is culture dish.
5. preparation method as claimed in claim 1, it is characterized in that, in step (a), described substrate is ito glass, and described ito glass is cleaned ito glass, and the method for described cleaning is: ito glass is used respectively 0.1M KOH solution, deionized water, ethanol, acetone, toluene, ethanol, acetone ultrasonic cleaning 15min successively, finally be put in acetone and preserve, take out during use, and dry up with nitrogen, stand-by.
6. preparation method as claimed in claim 1, is characterized in that, in step (b), forms the thick layer of gel ionogen of 1 ~ 3mm between platinized platinum and substrate.
7. preparation method as claimed in claim 1, it is characterized in that, in step (b), described gel electrolyte prepares as follows: add in reaction vessel by polymethylmethacrylate and propylene carbonate, sealed reaction vessel is placed on 18h in the baking oven of steady temperature 70 DEG C, make polymethylmethacrylate swelling in propylene carbonate, then lithium perchlorate and acetonitrile are added in reaction vessel, and be placed in the ultrasonic 10h in ultrasonic pond by uncovered for reaction vessel, until material dissolution is in acetonitrile, obtain gel electrolyte, encapsulate stand-by; The mass ratio of described acetonitrile and propylene carbonate, polymethylmethacrylate, lithium perchlorate is 70:20:7:3; The molecular-weight average of described polymethylmethacrylate is 120000g/mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341808.0A CN104961124B (en) | 2015-06-18 | 2015-06-18 | A kind of preparation method of graphene paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341808.0A CN104961124B (en) | 2015-06-18 | 2015-06-18 | A kind of preparation method of graphene paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104961124A true CN104961124A (en) | 2015-10-07 |
| CN104961124B CN104961124B (en) | 2017-07-28 |
Family
ID=54215257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510341808.0A Active CN104961124B (en) | 2015-06-18 | 2015-06-18 | A kind of preparation method of graphene paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104961124B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967172A (en) * | 2016-05-06 | 2016-09-28 | 电子科技大学 | Preparation method of foldable graphene thin film of large area |
| CN106604558A (en) * | 2017-01-16 | 2017-04-26 | 王奉瑾 | Preparation method of graphene circuit board |
| CN106604559A (en) * | 2017-01-16 | 2017-04-26 | 王奉瑾 | Preparation method of multilayer graphene circuit board |
| CN106698405A (en) * | 2017-01-12 | 2017-05-24 | 东南大学 | Method for preparing large-area graphene paper by utilizing hydroiodic acid |
| CN108275673A (en) * | 2018-04-07 | 2018-07-13 | 蒋黎婷 | A kind of preparation method of high-performance porous graphene film |
| CN108706571A (en) * | 2018-06-06 | 2018-10-26 | 丽水学院 | Method for the splicing of fragment graphene oxide |
| CN110068595A (en) * | 2019-05-20 | 2019-07-30 | 北京航空航天大学 | A kind of liquid sensor and its preparation method and application |
| CN110482534A (en) * | 2019-09-12 | 2019-11-22 | 安徽省聚科石墨烯科技股份公司 | A kind of controllable porous structure graphene paper |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844760A (en) * | 2010-04-29 | 2010-09-29 | 中国科学院化学研究所 | Preparation method and application of redox graphene |
| WO2012137156A1 (en) * | 2011-04-04 | 2012-10-11 | Efacec Engenharia E Sistemas, S.A. | Catalytic and transparent electrode of graphene, preparation method and applications thereof |
| CN104698717A (en) * | 2015-03-12 | 2015-06-10 | 浙江工业大学 | Gelatinous polymer electrolyte and preparation method for solid electrochromism device based on conductive polymer |
-
2015
- 2015-06-18 CN CN201510341808.0A patent/CN104961124B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844760A (en) * | 2010-04-29 | 2010-09-29 | 中国科学院化学研究所 | Preparation method and application of redox graphene |
| WO2012137156A1 (en) * | 2011-04-04 | 2012-10-11 | Efacec Engenharia E Sistemas, S.A. | Catalytic and transparent electrode of graphene, preparation method and applications thereof |
| CN104698717A (en) * | 2015-03-12 | 2015-06-10 | 浙江工业大学 | Gelatinous polymer electrolyte and preparation method for solid electrochromism device based on conductive polymer |
Non-Patent Citations (4)
| Title |
|---|
| SHAW YONG TOH ET AL.: "Graphene production via electrochemical reduction of graphene oxide: Synthesis and characterisation", 《CHEMICAL ENGINEERING JOURNAL》 * |
| SIYANG LIU ET AL.: "Reduced graphene oxide paper by supercritical ethanol treatment and its electrochemical properties", 《APPLIED SURFACE SCIENCE》 * |
| ZHANG XIONG ET AL.: "Electrochemical reduction of graphene oxide films: Preparation,characterization and their electrochemical properties", 《 CHIN SCI BULL》 * |
| 李文有 等: "电化学法制备部分还原氧化石墨烯薄膜及其光电性能", 《物理化学学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967172A (en) * | 2016-05-06 | 2016-09-28 | 电子科技大学 | Preparation method of foldable graphene thin film of large area |
| CN105967172B (en) * | 2016-05-06 | 2018-06-19 | 电子科技大学 | A kind of preparation method of the foldable graphene film of large area |
| CN106698405A (en) * | 2017-01-12 | 2017-05-24 | 东南大学 | Method for preparing large-area graphene paper by utilizing hydroiodic acid |
| CN106604558A (en) * | 2017-01-16 | 2017-04-26 | 王奉瑾 | Preparation method of graphene circuit board |
| CN106604559A (en) * | 2017-01-16 | 2017-04-26 | 王奉瑾 | Preparation method of multilayer graphene circuit board |
| CN108275673A (en) * | 2018-04-07 | 2018-07-13 | 蒋黎婷 | A kind of preparation method of high-performance porous graphene film |
| CN108706571A (en) * | 2018-06-06 | 2018-10-26 | 丽水学院 | Method for the splicing of fragment graphene oxide |
| CN110068595A (en) * | 2019-05-20 | 2019-07-30 | 北京航空航天大学 | A kind of liquid sensor and its preparation method and application |
| CN110068595B (en) * | 2019-05-20 | 2021-03-09 | 北京航空航天大学 | Liquid sensor and preparation method and application thereof |
| CN110482534A (en) * | 2019-09-12 | 2019-11-22 | 安徽省聚科石墨烯科技股份公司 | A kind of controllable porous structure graphene paper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104961124B (en) | 2017-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104961124A (en) | Method for manufacturing graphene paper | |
| KR101775468B1 (en) | Electrode for the super capacitor and method of the same | |
| CN103545121B (en) | A kind of electrode material for super capacitor preparation method based on three-dimensional grapheme | |
| Liu et al. | Three-dimensional tubular arrays of MnO 2–NiO nanoflakes with high areal pseudocapacitance | |
| CN102923697B (en) | Method for preparing graphene energy storing material through electrochemical cathodic disbonding | |
| CN103219164B (en) | Ultra-thin, self-supporting, flexibility, all-solid-state supercapacitor and preparation method thereof | |
| CN104134788B (en) | A kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application | |
| CN111508724B (en) | MOFs composite electrode material for supercapacitor, preparation method and working electrode | |
| CN105023768A (en) | Foam-nickel-basenickel oxide electrode material and preparation method thereof | |
| CN105118688A (en) | Preparation and application of bacterial cellulose/active carbon fiber/graphene film material | |
| CN108400023A (en) | A kind of three-dimensional nitrogen-doped carbon foam combination electrode material and preparation method thereof | |
| CN103971954A (en) | Manufacturing method for combined electrode of sponge supercapacitor | |
| CN106206082B (en) | The preparation method and application of nickel oxide/graphene combination electrode with electrochemical capacitance energy storage characteristic | |
| CN106629720A (en) | Method for preparing heteroatom co-doped porous carbon materials based on direct ionic liquid carbonization method | |
| CN106207090B (en) | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery and one one-step preparation method | |
| CN109904004A (en) | A kind of preparation method of SiC nano-array film and its application in electrode of super capacitor | |
| CN109216045A (en) | CC@ZIF-67/8-PPY composite material and preparation method and application based on carbon cloth growth in situ | |
| CN105895385A (en) | Titanium oxide columnar array/two-dimensional lamellar titanium carbide electrode material and preparation and application thereof | |
| CN108364799A (en) | A kind of flexible super capacitor and preparation method thereof | |
| CN108531954A (en) | The electrochemical preparation method of polyaniline/two-dimensional layer carbonization titanium composite material | |
| CN103456521A (en) | Method for preparing cobaltous hydroxide/bismuth sulfide composite nanowire electrode material of super-capacitor | |
| CN104966835A (en) | Method for manufacturing AgVO<3> thin films on Ag substrates by means of electrolysis | |
| CN105355463A (en) | Flexible supercapacitor electrode and device preparation method | |
| CN103258646A (en) | Preparation method for light flexible electrochemical capacitor electrodes | |
| CN104882291B (en) | A kind of electrode material for super capacitor and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |