CN105776185A - Preparation method of graphene paper with high thermal conductivity and electrical conductivity - Google Patents
Preparation method of graphene paper with high thermal conductivity and electrical conductivity Download PDFInfo
- Publication number
- CN105776185A CN105776185A CN201410816514.4A CN201410816514A CN105776185A CN 105776185 A CN105776185 A CN 105776185A CN 201410816514 A CN201410816514 A CN 201410816514A CN 105776185 A CN105776185 A CN 105776185A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- paper
- graphene
- conductivity
- 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.)
- Pending
Links
Abstract
The invention discloses a preparation method of graphene paper with high thermal conductivity and electrical conductivity. The method comprises the following steps: dispersing graphene oxide into a solvent to obtain a graphene oxide dispersion; preparing graphene oxide paper from the graphene oxide dispersion by a scrape coating or casting method; and finally reducing the graphene oxide paper by the use of a chemical reductant or through high-temperature reduction so as to obtain the graphene paper with high thermal conductivity and electrical conductivity. The preparation method of the graphene paper has simple process, is green and environmentally friendly, and is suitable for batch production. In addition, the graphene paper obtained has controllable size and better performance.
Description
Technical field
The invention belongs to Graphene macroscopic material preparation field, the preparation method being specifically related to a kind of high heat-conductivity conducting graphene paper.
Background technology
Graphene is by the two-dimensional sheet nano material of monolayer carbon atomic building, is that carbon atom is with sp2Hydridization bonding forms the flat film with hexagonal honeycomb lattice structure, and the molecular structure of its almost Perfect is which provide the performances such as the mechanics of excellence, electricity, calorifics.Graphene is the thinnest is the hardest nano material also, and its hot strength is up to 130GPa, and Young's modulus reaches 1TPa；It is almost fully transparent, only absorbs the light of 2.3%；Heat conductivity is up to 5,300W/ (m K), higher than CNT and diamond；Under room temperature, its electron mobility is more than 15,000cm2/ (V s) is higher than CNT or silicon single crystal again；Its resistivity about 10-6Ω m, lower than copper and Yin Geng, minimum for being currently known resistivity material；Graphene also has the specific surface area (2,630m of super large2/ g).
Graphene has heat conduction and the electric conductivity of excellence concurrently, provides wide application prospect for it at electronic device and field of radiating.How the performance of single-layer graphene expressed by macroscopic material and then used by people, become a critically important research topic.The intrinsic preparation that two-dimensional characteristics is Graphene two dimension paper of Graphene provides condition.The preparation method of current graphene film is broadly divided into following three kinds: (1) utilizes the method for chemical vapour deposition (CVD) direct growth in particular substrate to go out ultra-thin graphene film with gas for raw material；(2) with graphene oxide for raw material, first graphene oxide is reduced to Graphene, then Graphene is prepared into graphene paper by machining process；(3) with graphene oxide dispersion for raw material, utilize the method for vacuum aided sucking filtration to prepare graphene oxide paper, then be reduced into graphene paper.
Prepared graphene paper size is limited at present, and the big multi load of thin film prepared by chemical vapour deposition technique is in substrate, it is difficult to form the thin film of self-supporting；Redox graphene has limited dispersibility, and the graphene paper uniformity prepared is not so good；Vacuum aided suction method is consuming time, power consumption height, it is more difficult to obtain the graphene paper that large scale is uniformly complete.
Summary of the invention
It is an object of the invention to: the preparation method that the defect existed for above-mentioned prior art provides a kind of high heat-conductivity conducting graphene paper.Described this preparation method to solve the technical problem being difficult to obtain the complete heat-conductivity conducting graphene paper of Large-Area-Uniform in prior art.
The technical solution of the present invention is that it comprises the following steps:
(1) graphene oxide is dispersed in water, methanol, ethanol, N, N '-dimethyl Methanamide, N-Methyl pyrrolidone or wherein in both mixed liquors, prepare the homogeneous dispersion liquid of graphene oxide of 0.1 ~ 40mg/mL；
(2) by graphene oxide dispersion blade coating or casting, the graphene oxide paper of self-supporting after natural drying, is obtained；
(3) a, reduces graphene oxide paper in vitamin C, hydrazine hydrate, hydroiodic acid or its mixture, and reduction temperature is 60 ~ 120 DEG C；Recovery time is 1 ~ 720 minute；B, reduces graphene oxide paper in hydrogen and argon, helium, nitrogen or its gaseous mixture, and in gaseous mixture, hydrogen accounts for 1% ~ 30%, and flow is 1 ~ 50cm3/ min, high temperature reduction temperature is 300 ~ 1000 DEG C, and the time is 1 ~ 300 minute；Finally give the self-supporting graphene paper of heat-conductivity conducting.
The preparation method that the invention have the advantage that the heat-conductivity conducting graphene paper providing a kind of simplicity, with homodisperse graphene oxide for raw material, it is ensured that the uniformity of products therefrom；Industrial available blade coating and casting method is utilized to obtain large-area graphene paper, it is achieved thereby that the preparation of Large-Area-Uniform graphene paper.Follow-up electronation and thermal reduction have recovered the heat-conductivity conducting performance that graphene paper is good, have paved road for its subsequent applications.
Detailed description of the invention
Further illustrate the technical solution of the present invention below in conjunction with specific embodiment, these embodiments are not to be construed as the restriction to technical scheme.
Embodiment 1:
(1) 1g graphene oxide is dispersed in 25mL water, prepares the graphene oxide dispersion of 40mg/mL；
(2) graphene oxide dispersion blade coating is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 1000 μm of self-supportings；
(3) by graphene oxide paper in vitamin C 60 DEG C reduce 720 minutes, obtaining heat conductivity is 400W/ (mK), and conductivity is the self-supporting graphene paper of 10S/m.
Embodiment 2:
(1) 1g graphene oxide is dispersed in 10L methanol, prepares the graphene oxide dispersion of 0.1mg/mL；
(2) graphene oxide dispersion casting is obtained Graphene gel film, after natural drying, obtain the graphene oxide paper that thickness is 2 μm of self-supportings；
(3) by graphene oxide paper in hydrazine hydrate 90 DEG C reduce 1 minute, obtaining heat conductivity is 600W/ (mK), and conductivity is the self-supporting graphene paper of 300S/m.
Embodiment 3:
(1) 1g graphene oxide is dispersed in 100mL ethanol, prepares the graphene oxide dispersion of 10mg/mL；
(2) graphene oxide dispersion blade coating is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 10 μm of self-supportings；
(3) again by graphene oxide paper in hydroiodic acid 60 DEG C reduce 60 minutes, obtaining heat conductivity is 800W/ (mK), and conductivity is the self-supporting graphene paper of 500S/m.
Embodiment 4:
(1) 1g graphene oxide is dispersed in 50mLN, in N '-dimethyl Methanamide, prepares the graphene oxide dispersion of 20mg/mL；
(2) graphene oxide dispersion blade coating is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper of 300 μm of self-supportings of thickness；
(3) again by graphene oxide paper in vitamin C 120 DEG C reduce 1 minute, obtaining heat conductivity is 600W/ (mK), and conductivity is the self-supporting graphene paper of 650S/m.
Embodiment 5:
(1) 1g graphene oxide is dispersed in 100mLN-methyl pyrrolidone or in, prepare the graphene oxide dispersion of 10mg/mL；
(2) graphene oxide dispersion casting is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 200 μm of self-supportings；
(3) again graphene oxide paper 1000 DEG C of reduction in argon and hydrogen (1%) gaseous mixture being obtained the self-supporting graphene paper of heat-conductivity conducting for 1 minute, gas flow is 50cm3/min.The heat conductivity of graphene paper is 900W/ (mK), and conductivity is 850S/m.
Embodiment 6:
(1) 1g graphene oxide is dispersed in 50mL water and 50mL alcohol mixed solvent, prepares the graphene oxide dispersion of 10mg/mL；
(2) graphene oxide dispersion blade coating is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 500 μm of self-supportings；
(3) again by graphene oxide paper in helium and hydrogen (30%) gaseous mixture 300 DEG C reduce 300 minutes, obtain the self-supporting graphene paper of heat-conductivity conducting, gas flow is 1cm3/min.The thermal conductivity of graphene paper is 600W/ (mK), and conductivity is 550S/m.
Embodiment 7:
(1) 1g graphene oxide is dispersed in 25mLN, N '-dimethyl Methanamide and in 25mLN-methyl pyrrolidone mixed solvent, prepare the graphene oxide dispersion of 20mg/mL；
(2) graphene oxide dispersion casting is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 700 μm of self-supportings；
(3) again by graphene oxide paper in nitrogen and hydrogen (10%) gaseous mixture 800 DEG C reduce 10 minutes, obtain the self-supporting graphene paper of heat-conductivity conducting, gas flow is 10cm3/min.The heat conductivity of graphene paper is 800W/ (mK), and conductivity is 750S/m.
Embodiment 8:
(1) 1g graphene oxide is dispersed in 25mLN-methyl pyrrolidone, prepares the graphene oxide dispersion of 40mg/mL；
(2) graphene oxide dispersion blade coating is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 800 μm of self-supportings；
(3) again by graphene oxide paper in argon, nitrogen and hydrogen (3%) gaseous mixture 500 DEG C reduce 120 minutes, obtain the self-supporting graphene paper of heat-conductivity conducting, gas flow is 30cm3/min.Graphene paper heat conductivity is 600W/ (mK), and conductivity is 500S/m.
Embodiment 9:
(1) 1g graphene oxide is dispersed in 50mL ethanol, prepares the graphene oxide dispersion of 20mg/mL；
(2) graphene oxide dispersion casting is obtained graphene oxide gel film, after natural drying, obtain the graphene oxide paper that thickness is 50 μm of self-supportings；
(3) again by graphene oxide paper in argon and hydrogen (1%) gaseous mixture 1000 DEG C reduce 10 minutes, obtain the self-supporting graphene paper of heat-conductivity conducting, gas flow is 50cm3/min.Graphene paper heat conductivity is 1000W/ (mK), and conductivity is 1000S/m.
Accompanying drawing illustrates:
Fig. 1 is the photo of a 200mm*150mm heat-conductivity conducting graphene paper
Fig. 2 is graphene paper cross section layer structure
Fig. 3 is the thermal conductivity test result of graphene paper.
Claims (7)
1. the preparation method of a high heat-conductivity conducting graphene paper, it is characterized in that, graphene oxide paper, for graphene oxide dispersion blade coating or casting are obtained graphene oxide paper, is obtained high heat-conductivity conducting graphene paper by chemical reducing agent or high temperature reduction by described method afterwards.
2. the method for claim 1, it is characterised in that described graphene oxide dispersion is disperseed to obtain in a solvent by graphene oxide.
3. the method as described in claim 1 and 2, it is characterised in that described solvent includes water, methanol, ethanol, N, N '-dimethyl Methanamide, N-Methyl pyrrolidone and wherein both mixed liquors；The concentration of described graphene oxide dispersion is 0.1 ~ 40mg/mL；The thickness of described graphene oxide paper is 2 ~ 1000 μm.
4. the method as described in claim 1 ~ 3, it is characterised in that described chemical reducing agent includes vitamin C, hydrazine hydrate, hydroiodic acid and mixture thereof；Described reduction temperature is 60 ~ 120 DEG C；The described recovery time is 1 ~ 720 minute.
5. the method as described in claim 1 ~ 3, it is characterised in that described high temperature reduction carries out in reducing atmosphere；Described high temperature reduction temperature is 300 ~ 1000 DEG C, and the time is 1 ~ 300 minute.
6. the method as described in claim 1 ~ 5, it is characterised in that described reducing atmosphere is the gaseous mixture of hydrogen and noble gas；Described noble gas is argon, helium, nitrogen and gaseous mixture thereof；In described gaseous mixture, hydrogen accounts for 1% ~ 30%, and flow is 1 ~ 50cm3/min。
7. the method as described in claim 1 ~ 6, it is characterised in that the thickness of described high heat-conductivity conducting graphene paper is 2 ~ 1000 μm, heat conductivity is 400 ~ 1000W/ (mK), and electrical conductivity is 10 ~ 1000S/m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410816514.4A CN105776185A (en) | 2014-12-25 | 2014-12-25 | Preparation method of graphene paper with high thermal conductivity and electrical conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410816514.4A CN105776185A (en) | 2014-12-25 | 2014-12-25 | Preparation method of graphene paper with high thermal conductivity and electrical conductivity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105776185A true CN105776185A (en) | 2016-07-20 |
Family
ID=56377406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410816514.4A Pending CN105776185A (en) | 2014-12-25 | 2014-12-25 | Preparation method of graphene paper with high thermal conductivity and electrical conductivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776185A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311581A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Manufacturing method for efficient composite heat sink for electronic product |
| CN106653382A (en) * | 2016-12-23 | 2017-05-10 | 深圳先进技术研究院 | Flexible electrode material and preparation method and application thereof |
| CN107342431A (en) * | 2017-03-06 | 2017-11-10 | 南京大学 | A kind of graphene-based gas-diffusion electrode of used in proton exchange membrane fuel cell and preparation method thereof |
| CN108251076A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube-graphene composite radiating film, preparation method and application |
| CN108996496A (en) * | 2018-07-23 | 2018-12-14 | 哈尔滨工业大学 | A method of preparing graphene/graphene mixed film |
| CN112520731A (en) * | 2020-12-24 | 2021-03-19 | 广东工业大学 | Preparation method and production line of graphene heat-conducting film |
| WO2021146810A1 (en) * | 2020-01-23 | 2021-07-29 | The Royal Institution For The Advancement Of Learning / Mcgill University | Electronic circuit having graphene oxide paper substrate and method of recovering parts of an electronic circuit |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070142A (en) * | 2010-12-14 | 2011-05-25 | 四川大学 | Method for preparing graphene by chemical oxidation reduction |
| CN103427088A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Making method of graphene paper collector |
| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
-
2014
- 2014-12-25 CN CN201410816514.4A patent/CN105776185A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070142A (en) * | 2010-12-14 | 2011-05-25 | 四川大学 | Method for preparing graphene by chemical oxidation reduction |
| CN103427088A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Making method of graphene paper collector |
| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311581A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Manufacturing method for efficient composite heat sink for electronic product |
| CN106653382A (en) * | 2016-12-23 | 2017-05-10 | 深圳先进技术研究院 | Flexible electrode material and preparation method and application thereof |
| CN108251076A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube-graphene composite radiating film, preparation method and application |
| CN107342431A (en) * | 2017-03-06 | 2017-11-10 | 南京大学 | A kind of graphene-based gas-diffusion electrode of used in proton exchange membrane fuel cell and preparation method thereof |
| CN108996496A (en) * | 2018-07-23 | 2018-12-14 | 哈尔滨工业大学 | A method of preparing graphene/graphene mixed film |
| WO2021146810A1 (en) * | 2020-01-23 | 2021-07-29 | The Royal Institution For The Advancement Of Learning / Mcgill University | Electronic circuit having graphene oxide paper substrate and method of recovering parts of an electronic circuit |
| CN112520731A (en) * | 2020-12-24 | 2021-03-19 | 广东工业大学 | Preparation method and production line of graphene heat-conducting film |
| CN112520731B (en) * | 2020-12-24 | 2021-09-14 | 广东工业大学 | Preparation method and production line of graphene heat-conducting film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105776185A (en) | Preparation method of graphene paper with high thermal conductivity and electrical conductivity | |
| Lin et al. | High-performance graphene-based flexible heater for wearable applications | |
| Cui et al. | Low-temperature synthesis of multilayer graphene/amorphous carbon hybrid films and their potential application in solar cells | |
| Li et al. | Flexible graphene electrothermal films made from electrochemically exfoliated graphite | |
| Chen et al. | Highly conductive and flexible paper of 1D silver-nanowire-doped graphene | |
| CN103601181B (en) | Method for preparing nitrogen-doped graphene with polydopamine as raw material | |
| Chen et al. | Flexible and transparent supercapacitor based on ultrathin Au/graphene composite electrodes | |
| Bae et al. | Large-area graphene films by simple solution casting of edge-selectively functionalized graphite | |
| Ho et al. | Self‐crack‐filled graphene films by metallic nanoparticles for high‐performance graphene heterojunction solar cells | |
| Shobin et al. | Enhancement of electrothermal performance in single-walled carbon nanotube transparent heaters by room temperature post treatment | |
| Zhang et al. | Synthesis and field emission characteristics of bilayered ZnO nanorod array prepared by chemical reaction | |
| Gan et al. | Efficient photovoltaic conversion of graphene–carbon nanotube hybrid films grown from solid precursors | |
| US20140166496A1 (en) | Method for producing shaped graphene sheets | |
| CN104973590B (en) | Method of preparing high-heat-conductive and high-electric-conductive thin film through dispersion of high-quality graphite powder and graphene with graphene oxide | |
| CN102417176A (en) | Preparation method of graphene-carbon nanotube compound film based on three-dimensional network appearance | |
| Yuan et al. | All-carbon devices based on sp2-on-sp3 configuration | |
| Cui et al. | Highly conductive nitrogen-doped vertically oriented graphene toward versatile electrode-related applications | |
| CN105274491A (en) | Preparation method for graphene-boron nitride heterogeneous phase composite thin film material | |
| Lin et al. | Hybrid structure of graphene sheets/ZnO nanorods for enhancing electron field emission properties | |
| Masikhwa et al. | High electrochemical performance of hybrid cobalt oxyhydroxide/nickel foam graphene | |
| CN101696491A (en) | In-situ method for preparing graphene/carbon nanotube composite film | |
| CN103407988A (en) | Method for preparing graphene film at low temperature | |
| Li et al. | Direct synthesis of graphene/carbon nanotube hybrid films from multiwalled carbon nanotubes on copper | |
| CN113957527A (en) | Preparation of two-dimensional Nano Cs3Cu2I5Method for producing crystalline material and use thereof | |
| Chen et al. | Harnessing light energy with a planar transparent hybrid of graphene/single wall carbon nanotube/n-type silicon heterojunction solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160720 |