CN106185901B - A kind of high resiliency graphene film - Google Patents
A kind of high resiliency graphene film Download PDFInfo
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- CN106185901B CN106185901B CN201610559607.2A CN201610559607A CN106185901B CN 106185901 B CN106185901 B CN 106185901B CN 201610559607 A CN201610559607 A CN 201610559607A CN 106185901 B CN106185901 B CN 106185901B
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- graphite alkene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a kind of high resiliency graphene film, which is obtained by graphene oxide by solution film forming and chemical reduction step.The graphene film is made up of macroscopical multilayered fold graphene with micro-scale fold physical crosslinking；In macro-scale, film is made of many macrofolds, therefore with high horizontal stretch elasticity.The film has fabulous flexibility, does not leave folding line doubling 100,000 times or more repeatedly.This high flexibility graphene heat conducting film is resistant to bend repeatedly 100,000 times or more, and elastic failure elongation is 20-50%, conductivity 600-1000S/cm, can be used as high-elastic compliant conductive device.
Description
Technical field
The present invention relates to elastic graphite alkene membrane material and preparation method thereof more particularly to a kind of high resiliency graphene films.
Background technique
2010, two professor Andre GeiM and Konstantin Novoselov of Univ Manchester UK because
It is successfully separated out stable graphene for the first time and obtains Nobel Prize in physics, has started the upsurge that graphene is studied in the whole world.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ Vs), heating conduction (5000W/ outstanding
MK), extraordinary specific surface area (2630 M2/ g), Young's modulus (1100GPa) and breaking strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, while graphene has the advantages that corrosion-and high-temp-resistant, and its good machinery
Performance and lower density more allow it to have the potentiality in thermo electric material field substituted metal.
Macroscopic view assembling graphene oxide membrane is an important application form of nanoscale graphite alkene, and common preparation method is
Suction method scrapes embrane method, spin-coating method, spray coating method and dip coating etc..
However, prepared graphene film does not have the high high fold of stretching at present, cannot be obtained in terms of high fold device
Using.16 years professors Shi Gaoquan create many huge folds in graphene membrane surface with the method for macroscopical template assemblies, do
The high fold for having arrived graphene film stretches, but it needs elastic substrates, and operation is more troublesome, and the deficiency of Design of Membrane Structure
So that its flexibility is still not clear, its application in terms of flexible device is limited.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of high resiliency graphene film.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of high resiliency graphene film, by the following method
It is prepared:
(1) 20-100 parts by weight are added in the graphene oxide solution that the concentration of 100 parts by weight is 1~2mg/mL
Organic precipitant；It after ultrasonic disperse, is poured on Die and mould plate, naturally dry is at graphite oxide at relative air humidity 50-80%
Alkene film, so that most (> 90wt%) solvent volatilizations, then remove residual solvent under (60-100 DEG C) at high temperature；
(2) by step 1, treated that graphene oxide film restores in hydroiodic acid solution.
(3) graphene film after restoring, which is placed in ethyl alcohol, to be impregnated, and to wash away surface hydroiodic acid, then naturally dry, is obtained
Graphene elastic film.
Further, the solvent is acetone, tetrahydrofuran, ethyl alcohol, ethylene glycol, water, DMF, NMP；The organic deposition
Agent is methanol, ethyl acetate, n-hexane, ether, petroleum ether.
Further, the hydriodic acid aqueous solution HI content in the step 2 is 15-35wt%, and reduction temperature is 70-
100 degrees Celsius, recovery time 4-8h.
The beneficial effects of the present invention are: the present invention is by being added organic precipitant, so that graphene oxide sheet forms pleat
Wrinkle；In the drying process, precipitating reagent volatilizees at high temperature, film shrunk, forms macrofold；After electronation, and
Every tunic has the spherical fold of fluctuating to constitute, and pleated structure can be all presented by cutting its internal every graphene, makes it possible to
All with high horizontal stretch elasticity and flexibility in horizontal direction.
Its high flexibility graphene heat conducting film is resistant to bend repeatedly 100,000 times or more, and horizontal resiliency elongation at break is 10-
30%, conductivity 600-1000S/cm can be used as high-elastic conductive devices.
Detailed description of the invention
Fig. 1 is the exterior view of elastic graphite alkene film.
Fig. 2 is the stress strain curve of elastic graphite alkene film.
Fig. 3 is the section surface sweeping Electronic Speculum of elastic graphite alkene film.
Fig. 4 is the structural schematic diagram of graphene film of the invention.
Specific embodiment
As shown in figs. 1 and 4, the high resiliency graphene film is by macroscopical multilayered fold graphene with micro-scale fold
It is made up of physical crosslinking；In macro-scale, film is made of many macrofolds.It makes it possible to and all has in the horizontal direction
There are high horizontal stretch elasticity and flexibility.
The invention will be further described with reference to the accompanying drawings and embodiments.The present embodiment be served only for being the present invention into
The explanation of one step should not be understood as limiting the scope of the invention, and those skilled in the art is according in foregoing invention
Appearance makes some nonessential changes and adjustment, all belongs to the scope of protection of the present invention.
Embodiment 1
A kind of high resiliency graphene film, is prepared by the following method to obtain:
(1) the acetic acid second of 20 parts by weight is added in the graphene oxide water solution that the concentration of 100 parts by weight is 1mg/mL
Ester；It after ultrasonic disperse, is poured on Die and mould plate, naturally dry is at graphene oxide membrane under relative air humidity 70%, so that absolutely
Most of (> 90wt%) solvent volatilization, then removes residual solvent at 60 DEG C；
(2) by step 1, treated that graphene oxide film restores in hydroiodic acid solution.The HI content of hydroiodic acid solution
As shown in table 1, reduction temperature is 70 degrees Celsius, recovery time 8h.
(3) graphene film after restoring, which is placed in ethyl alcohol, to be impregnated, and to wash away surface hydroiodic acid, then naturally dry, is obtained
Graphene elastic film.
Table 1: the performance of product under different hydriodic acid concentrations
As can be seen from the above table, under low-concentration hydrogen acid iodide (15%), graphene oxide membrane crosslinking dynamics is inadequate, is not enough to
So that graphene film forms continuous cavernous structure, therefore without stretching and the elasticity of compression；With mentioning for hydriodic acid concentration
Height, cavernous structure molding, and also aperture is increasing, and fold surface density is higher and higher, therefore its Compression and Expansion performance is gradually
It improves；It is more than after 37% in hydroiodic acid, performance is declined instead, can be attributed to excessively high hydriodic acid concentration and be made surface
It restores transitional effects hydroiodic acid to enter inside graphene oxide membrane, so that membrane material is uneven, and then damage performance.
Embodiment 2
A kind of high resiliency graphene film, is prepared by the following method to obtain:
(1) petroleum of 100 parts by weight is added in the graphene oxide ethanol solution that the concentration of 100 parts by weight is 2mg/mL
Ether；It after ultrasonic disperse, is poured on Die and mould plate, naturally dry is at graphene oxide membrane under relative air humidity 80%, so that absolutely
Most of (> 90wt%) solvent volatilization, then removes residual solvent at 100 DEG C；
(2) by step 1, treated that graphene oxide film restores in hydroiodic acid solution.Hydriodic acid aqueous solution HI content
For 20wt%, reduction temperature is 100 degrees Celsius, recovery time 4h.
(3) graphene film after restoring, which is placed in ethyl alcohol, to be impregnated, and to wash away surface hydroiodic acid, then naturally dry, is obtained
Graphene elastic film.
As shown in Fig. 1,3,4, the high resiliency graphene film is crosslinked by multi-layer graphene film, the graphene film table
It is made up of macroscopical multilayered fold graphene with micro-scale fold physical crosslinking；In macro-scale, film is by very much
Macrofold is constituted.It makes it possible in the horizontal direction all with high horizontal stretch elasticity and flexibility.Fig. 2 is elasticity
The stress strain curve of graphene film, elastic failure elongation be 20%, in addition, this high flexibility graphene heat conducting film be resistant to repeatedly it is curved
It rolls over 100,000 times or more, conductivity 964S/cm, can be used as high-elastic compliant conductive device.
Embodiment 3
A kind of high resiliency graphene film, is prepared by the following method to obtain:
(1) second of 40 parts by weight is added in the graphene oxide DMF solution that the concentration of 100 parts by weight is 1.8mg/mL
Acetoacetic ester；It after ultrasonic disperse, is poured on Die and mould plate, naturally dry makes at graphene oxide membrane under relative air humidity 50%
Most (> 90wt%) solvents volatilizations are obtained, then remove residual solvent at 80 DEG C；
(2) by step 1, treated that graphene oxide film restores in hydroiodic acid solution.Hydriodic acid aqueous solution HI content
For 20wt%, reduction temperature is 100 degrees Celsius, recovery time 4h.
(3) graphene film after restoring, which is placed in ethyl alcohol, to be impregnated, and to wash away surface hydroiodic acid, then naturally dry, is obtained
Graphene elastic film.
This high flexibility graphene heat conducting film is resistant to bend repeatedly 100,000 times or more, and elastic failure elongation is 38%, conductive
Rate is 852S/cm, can be used as high-elastic compliant conductive device.
Claims (2)
1. a kind of elastic graphite alkene film, which is characterized in that be prepared by the following method to obtain:
(1) the organic heavy of 20-100 parts by weight is added in the graphene oxide solution that the concentration of 100 parts by weight is 1 ~ 2 mg/mL
Shallow lake agent；It after ultrasonic disperse, is poured on Die and mould plate, naturally dry makes at graphene oxide membrane at relative air humidity 50-80%
It obtains the solvent greater than 90wt% to volatilize, then in 60-100oResidual solvent is removed at a high temperature of C；The organic precipitant is selected from first
Alcohol, ethyl acetate, n-hexane, ether, petroleum ether；
(2) by step 1, treated that graphene oxide film restores in hydroiodic acid solution；Hydriodic acid aqueous solution HI content is
15-35wt%, reduction temperature are 70-100 degrees Celsius, recovery time 4-8h；
(3) graphene film after restoring, which is placed in ethyl alcohol, to be impregnated, and to wash away surface hydroiodic acid, then naturally dry, obtains graphite
Alkene elastic film.
2. elastic graphite alkene film according to claim 1, which is characterized in that the solvent is acetone, tetrahydrofuran, second
Alcohol, ethylene glycol, water, DMF or NMP.
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| RU2753510C1 (en) * | 2017-10-13 | 2021-08-17 | Чжэцзян Юниверсити | Independent freely located graphene film and method for production thereof |
| CN107651673B (en) * | 2017-10-13 | 2020-01-10 | 长兴德烯科技有限公司 | Nano-scale thickness independent self-supporting folded graphene film and preparation method thereof |
| CN107651670B (en) * | 2017-10-13 | 2019-10-15 | 杭州高烯科技有限公司 | A kind of preparation method of no folding line elastic graphite alkene film |
| CN110127666A (en) * | 2019-04-23 | 2019-08-16 | 宁波昕科工贸有限公司 | A kind of multi-folded high resiliency graphene film and preparation method thereof |
| CN111058107B (en) * | 2019-12-12 | 2024-03-05 | 杭州高烯科技有限公司 | Graphene oxide stretchable solution and preparation method and application thereof |
| CN111263568B (en) * | 2020-01-22 | 2022-03-11 | Oppo广东移动通信有限公司 | Heat dissipation material, preparation method thereof and electronic equipment |
| CN114163712B (en) * | 2021-12-27 | 2022-09-23 | 安徽联嘉祥特种电缆有限公司 | Graphene composite PE material and preparation method thereof |
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| CN101702345A (en) * | 2009-11-27 | 2010-05-05 | 南京邮电大学 | Preparation method for laminated graphene conductive film |
| CN104261391A (en) * | 2014-09-23 | 2015-01-07 | 浙江碳谷上希材料科技有限公司 | Self-supported graphene hydrogel membrane and preparation method thereof |
| CN105733516A (en) * | 2016-01-25 | 2016-07-06 | 浙江大学 | Graphene-based composite phase-change membrane and preparation method thereof |
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| KR101623571B1 (en) * | 2014-08-27 | 2016-05-23 | 성균관대학교산학협력단 | Graphene quantum dot and preparing method of the same |
| JP6350220B2 (en) * | 2014-10-30 | 2018-07-04 | 株式会社デンソー | Method for producing graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101702345A (en) * | 2009-11-27 | 2010-05-05 | 南京邮电大学 | Preparation method for laminated graphene conductive film |
| CN104261391A (en) * | 2014-09-23 | 2015-01-07 | 浙江碳谷上希材料科技有限公司 | Self-supported graphene hydrogel membrane and preparation method thereof |
| CN105733516A (en) * | 2016-01-25 | 2016-07-06 | 浙江大学 | Graphene-based composite phase-change membrane and preparation method thereof |
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Effective date of registration: 20190903 Address after: 313199 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang University |