CN103833027A - Preparation method of graphene paper - Google Patents
Preparation method of graphene paper Download PDFInfo
- Publication number
- CN103833027A CN103833027A CN201210491207.4A CN201210491207A CN103833027A CN 103833027 A CN103833027 A CN 103833027A CN 201210491207 A CN201210491207 A CN 201210491207A CN 103833027 A CN103833027 A CN 103833027A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- graphene paper
- suspension
- paper
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the field of graphene materials, and discloses a preparation method of a graphene paper. The preparation method comprises the following steps of: preparing graphene oxide suspension liquid by adopting graphite oxide; carrying out heating and pressurizing treatment on the graphene oxide suspension in a closed state to prepare graphene suspension liquid; carrying out vacuum filtration on the graphene suspension liquid by adopting a microporous filtering film to obtain a graphene paper sample; carrying out pre-heating treatment on the graphene paper sample at an inert atmosphere, and then carrying out reduction treatment at high temperature to obtain the graphene paper. The preparation method of the graphene paper, which is disclosed by the invention, realizes high permeability and solubility on graphene by introducing a supercutical fluid between the layer and layer of the graphene in a supercritical state by utilizing an organic solvent, achieves better dispersion effect during reduction, prevents the agglomeration of the reduced graphene and can more easily obtain the graphene paper with the graphene dispersed uniformly.
Description
Technical field
The present invention relates to grapheme material, relate in particular to a kind of preparation method of Graphene paper.
Background technology
Ultracapacitor is a kind of novel energy storing device, there is the advantages such as high power density (for the more than 10 times of common batteries), high cycle life (cycle index can reach more than 100,000 times), fast charging and discharging performance are good, be widely used in the AC-battery power source of military field, device for mobile communication, computer and electromobile etc.Conventionally mainly being assembled by electrode active material layer, ionogen, barrier film, collector, shell etc. of ultracapacitor.The energy density of existing ultracapacitor is generally lower, the influence factor of the energy density of ultracapacitor mainly contains the electric capacity of electrode materials, the voltage of system, electrode materials accounts for the proportion of the gross weight of electrode active material layer, collector, sheating material composition, therefore, the weight of the energy-storage property of increase electrode materials and each composition material of reduction device can effectively improve the performance of device.Wherein, the quality of reduction collector is a method that effectively improves energy density.
Collector is a kind of structure or part that collects electric current, and major function is that the electric current that cell active materials is produced collects, and electron channel is provided, and accelerates electric charge and shifts, and improves and discharges and recharges coulombic efficiency.Need to meet the features such as specific conductivity is high, good mechanical property, quality is light, internal resistance is little as collector.
At present, in most document or in industry, anodal aluminium foil, the negative pole of adopting of general collector adopts Copper Foil, because the density of metal collector is larger, quality is heavier, the weight of general collector accounts for the 20-25% of whole battery, and the proportion that electrode materials accounts for whole battery greatly reduces, and finally causes the energy density of ultracapacitor lower.
Graphene can be prepared into graphene film or Graphene paper by certain method, because the specific surface area of Graphene is larger, its density is lower, the lighter weight of Graphene paper, its high mechanical property and high conductivity also can meet the fundamental property index of collector application simultaneously, therefore can serve as collector based on the prepared Graphene paper of Graphene and use, and can reduce the quality of collector.
While preparing Graphene paper by the method for graphene suspension direct filtration, often the Graphene paper of preparation is even not, or more difficult film forming is summed up its reason and is mainly and is more difficult to get stable graphene suspension.Because the specific surface area of Graphene is large, interlaminar action van der Waals interaction, cause it to be easier to reunite, be difficult for disperseing.
Summary of the invention
Problem to be solved by this invention is to provide the preparation method of the finely dispersed Graphene paper of a kind of Graphene.
Technical scheme of the present invention is as follows:
A preparation method for Graphene paper, comprises the steps:
Graphite oxide is added in solvent, be configured to the graphite oxide solution that concentration is 0.25-1mg/ml, and to graphite oxide solution supersound process, obtain homodisperse graphene oxide suspension;
After putting into reactor in described graphene oxide suspension, seal, then to reactor heat, pressure treatment, obtain stable graphene suspension;
Adopt graphene suspension described in millipore filtration vacuum filtration, and after filtering by filtration cakes torrefaction processing, then screening is taken off from microporous membrane surface, obtains Graphene pattern product;
Described Graphene pattern product are placed in to inert atmosphere, at 200 ℃, are incubated 5 minutes thermal pretreatment, be then warming up to 500-1000 ℃ reduce process 0.5-2h, cooling after, obtain Graphene paper.
The preparation method of described Graphene paper, wherein, in described graphite oxide solution preparation, solvent used is at least one in water, liquefied ammonia, Virahol, ethanol and methyl alcohol.
The preparation method of described Graphene paper, wherein, to the graphene oxide solution supersound process time be 0.5-3h.
The preparation method of described Graphene paper wherein, is 150 ℃-400 ℃ to the temperature of described graphene oxide suspension heat treated.
The preparation method of described Graphene paper, wherein, is 5-25MPa to the pressure of described graphene oxide suspension pressure treatment, and the pressurization time length is 0.5-5h.
The preparation method of described Graphene paper wherein, is to carry out in the baking oven of 40 ℃ to the drying treatment of the filter cake obtaining after millipore filtration vacuum filtration.
The preparation method of described Graphene paper, wherein, the preheating treatment procedure of described Graphene is: under the air-flow that is 50-70ml/min at inert gas flow, be warming up to 200 ℃ with the temperature rise rate of 1-5 ℃/min, be then incubated 5 minutes.
The preparation method of described Graphene paper, wherein, the reduction treatment process of described Graphene is: with the temperature rise rate of 5-10 ℃/min, be slowly warming up to 500-1000 ℃, pass into subsequently reducing gas reduce process 0.5-2h.
The preparation method of described Graphene paper, wherein, described reducing gas is that volume ratio is the argon gas of 90 ~ 95:5 ~ 10 and the gas mixture of hydrogen.
The preparation method of Graphene paper provided by the invention, utilize organic solvent under supercritical state, make supercutical fluid enter Graphene between layers, realize hypertonicity and solvability to Graphene, in reduction, reach good dispersion effect, avoid the reunion of the Graphene after reduction, can be easier to obtain the Graphene paper that graphene uniform disperses.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of Graphene paper of the present invention.
Embodiment
Preparation technology's flow process of the present embodiment Graphene paper is as follows:
S1, prepare graphene oxide suspension: graphite oxide is added in solvent, be configured to the graphite oxide solution that concentration is 0.25-1mg/ml, and to graphite oxide solution supersound process 0.5-3h, obtain homodisperse graphene oxide suspension; Wherein solvent is: the aqueous solvent of critical temperature more than 100 ℃, liquefied ammonia, Virahol, ethanol, methyl alcohol etc.;
S2, prepare graphene suspension: after putting into reactor (preferably high-temperature high-pressure reaction kettle) in described graphene oxide suspension, seal, then, to reactor heating, pressure treatment, obtain stable graphene suspension;
Preferably, the temperature of heat treated is 150 ℃-400 ℃; The pressure of pressure treatment is 5-25MPa, and the pressurization time length is 0.5-5h;
S3, prepare Graphene pattern product: adopt graphene suspension described in millipore filtration vacuum filtration, after filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then screening is taken off from microporous membrane surface, obtains Graphene pattern product;
S4, prepare Graphene paper: described graphene oxide paper is placed in to inert atmosphere and (can comprises nitrogen, argon gas or the mixed gas of the two, preferably argon gas), at 200 ℃, be incubated 5 minutes thermal pretreatment, then be warming up to 500-1000 ℃ reduce process 0.5-2h, after cooling, obtain Graphene paper;
Preferably, preheating treatment procedure is: under the air-flow that is 50-70ml/min at inert gas flow, be warming up to 200 ℃ with the temperature rise rate of 1-5 ℃/min, be then incubated 5 minutes;
Preferably, reduction treatment process is: with the temperature rise rate of 5-10 ℃/min, be slowly warming up to 500-1000 ℃, pass into subsequently reducing gas reduce process 0.5-2h;
Preferably, described reducing gas is that volume ratio is the argon gas of 90 ~ 95:5 ~ 10 and the gas mixture of hydrogen.
The preparation method of Graphene paper provided by the invention, utilize organic solvent under supercritical state, make supercutical fluid enter Graphene between layers, realize hypertonicity and solvability to Graphene, in reduction, reach good dispersion effect, avoid the reunion of the Graphene after reduction, can be easier to obtain the Graphene paper that graphene uniform disperses.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Preparation technology's flow process of the present embodiment Graphene paper is as follows:
(1) prepare graphene oxide suspension: graphite oxide is added to the water, and being configured to concentration is the ultrasonic 0.5h of graphite oxide solution of 0.25mg/ml, obtains homodisperse graphene oxide suspension;
(2) prepare graphene suspension: by putting into high-temperature high-pressure reaction kettle in obtained graphene oxide suspension, by its good seal, be then heated 400 ℃, pressure, under 25MPa, keeps 0.5h; Obtain stable graphene suspension;
(3) prepare Graphene pattern product: adopt the graphene suspension in millipore filtration vacuum filtration (2).After filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then screening is taken off from microporous membrane surface, obtains Graphene pattern product;
(4) prepare Graphene paper: by the graphene oxide paper of (3) gained, put into tube furnace, pass into argon gas and drive the air in stove away, then control the flow of argon gas at the air-flow of 50ml/min, be first warming up to 180 ℃ with the temperature rise rate of 1 ℃/min, be incubated 5 minutes, with the temperature rise rate of 5 ℃/min, be slowly warming up to 500 ℃ again, now passing into volume ratio is the argon gas of 95:5 and the mixed gas of hydrogen, at this temperature, reduce 0.5h, obtain Graphene paper.
Embodiment 2
Preparation technology's flow process of the present embodiment Graphene paper is as follows:
(1) prepare graphene oxide suspension: graphite oxide is added in liquefied ammonia, and being configured to concentration is the ultrasonic 2h of graphite oxide solution of 1mg/ml, obtains homodisperse graphene oxide suspension;
(2) prepare graphene suspension: by putting into high-temperature high-pressure reaction kettle in obtained graphene oxide suspension, by its good seal, be then heated 150 ℃, pressure, under 15MPa, keeps 1h, obtains stable graphene suspension;
(3) prepare Graphene pattern product: adopt the graphene suspension in millipore filtration vacuum filtration (2).After filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then screening is taken off from microporous membrane surface, obtains Graphene pattern product;
(4) prepare Graphene paper: by the graphene oxide paper of (3) gained, put into tube furnace, pass into argon gas and drive the air in stove away, then control the flow of argon gas at the air-flow of 70ml/min, be first warming up to 200 ℃ with the temperature rise rate of 5 ℃/min, be incubated 5 minutes, with the temperature rise rate of 10 ℃/min, be slowly warming up to 1000 ℃ again, now passing into volume ratio is the argon gas of 90:10 and the mixed gas of hydrogen, reductase 12 h at this temperature, obtains Graphene paper.
Embodiment 3
Preparation technology's flow process of the present embodiment Graphene paper is as follows:
(1) prepare graphene oxide suspension: graphite oxide is added in Virahol, and being configured to concentration is the ultrasonic 3h of graphite oxide solution of 1mg/ml, obtains homodisperse graphene oxide suspension;
(2) prepare graphene suspension: by putting into high-temperature high-pressure reaction kettle in obtained graphene oxide suspension, by its good seal, be then heated 250 ℃, pressure, under 5MPa, keeps 5h, obtains stable graphene suspension;
(3) prepare Graphene pattern product: adopt the graphene suspension in millipore filtration vacuum filtration (2).After filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then screening is taken off from microporous membrane surface, obtains Graphene pattern product;
(4) prepare Graphene paper: by the graphene oxide paper of (3) gained, put into tube furnace, pass into argon gas and drive the air in stove away, then control the flow of argon gas at the air-flow of 70ml/min, be first warming up to 200 ℃ with the temperature rise rate of 5 ℃/min, be incubated 5 minutes, with the temperature rise rate of 10 ℃/min, be slowly warming up to 1000 ℃ again, now passing into volume ratio is the argon gas of 90:10 and the mixed gas of hydrogen, reductase 12 h at this temperature, obtains Graphene paper.
The mensuration of specific conductivity
The Graphene paper that embodiment 1 is made, uses the two electrical measurement four point probe tester testing conductivities of D41-11D/ZM type under room temperature.In the time that test current is shown as probe coefficient, press electricalresistivityρ's button, screen directly shows that electricalresistivityρ is worth, and directly calculates specific conductivity according to γ=l/ ρ.
The specific conductivity of measuring Graphene paper in embodiment 1 by four probe method is 9.6*10
4s/m, illustrates that the specific conductivity of the Graphene paper after reduction is higher, can be used as collector and uses.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a preparation method for Graphene paper, is characterized in that, comprises the steps:
Graphite oxide is added in solvent, be configured to the graphite oxide solution that concentration is 0.25-1mg/ml, and to graphite oxide solution supersound process, obtain homodisperse graphene oxide suspension;
After putting into reactor in described graphene oxide suspension, seal, then to reactor heat, pressure treatment, obtain stable graphene suspension;
Adopt graphene suspension described in millipore filtration vacuum filtration, and after filtering by filtration cakes torrefaction processing, then screening is taken off from microporous membrane surface, obtains Graphene pattern product;
Described Graphene pattern product are placed in to inert atmosphere, at 200 ℃, are incubated 5 minutes thermal pretreatment, be then warming up to 500-1000 ℃ reduce process 0.5-2h, cooling after, obtain Graphene paper.
2. the preparation method of Graphene paper according to claim 1, is characterized in that, in described graphite oxide solution preparation, solvent used is at least one in water, liquefied ammonia, Virahol, ethanol and methyl alcohol.
3. the preparation method of Graphene paper according to claim 1, is characterized in that, to the graphene oxide solution supersound process time be 0.5-3h.
4. the preparation method of Graphene paper according to claim 1, is characterized in that, is 150 ℃-400 ℃ to the temperature of described graphene oxide suspension heat treated.
5. the preparation method of Graphene paper according to claim 1, is characterized in that, is 5-25MPa to the pressure of described graphene oxide suspension pressure treatment, and the pressurization time length is 0.5-5h.
6. the preparation method of Graphene paper according to claim 1, is characterized in that, is to carry out in the baking oven of 40 ℃ to the drying treatment of the filter cake obtaining after millipore filtration vacuum filtration.
7. the preparation method of Graphene paper according to claim 1, it is characterized in that, the preheating treatment procedure of described Graphene is: under the air-flow that is 50-70ml/min at inert gas flow, be warming up to 200 ℃ with the temperature rise rate of 1-5 ℃/min, be then incubated 5 minutes.
8. the preparation method of Graphene paper according to claim 1, is characterized in that, the reduction treatment process of described Graphene is: with the temperature rise rate of 5-10 ℃/min, be slowly warming up to 500-1000 ℃, pass into subsequently reducing gas reduce process 0.5-2h.
9. the preparation method of Graphene paper according to claim 8, is characterized in that, described reducing gas is that volume ratio is the argon gas of 90 ~ 95:5 ~ 10 and the gas mixture of hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491207.4A CN103833027A (en) | 2012-11-27 | 2012-11-27 | Preparation method of graphene paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491207.4A CN103833027A (en) | 2012-11-27 | 2012-11-27 | Preparation method of graphene paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103833027A true CN103833027A (en) | 2014-06-04 |
Family
ID=50796975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210491207.4A Pending CN103833027A (en) | 2012-11-27 | 2012-11-27 | Preparation method of graphene paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103833027A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254920A (en) * | 2015-09-21 | 2016-01-20 | 武汉理工大学 | Preparation method of graphene paper prepreg |
| CN108314012A (en) * | 2017-01-16 | 2018-07-24 | 山东恒华新材料有限公司 | Ammonia heat method batch prepares the production technology of graphene |
| CN113376915A (en) * | 2021-06-28 | 2021-09-10 | 绍兴迪飞新材料有限公司 | Graphene-polyaniline composite electrochromic intelligent dynamic dimming glass |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
| CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
| JP2011144060A (en) * | 2010-01-13 | 2011-07-28 | Sekisui Chem Co Ltd | Method for producing dispersion liquid of flaked graphite, method for producing flaked graphite and method for producing composite material |
| CN102583340A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | High-conductivity graphene material with low-temperature gas-phase reduction and preparation method thereof |
-
2012
- 2012-11-27 CN CN201210491207.4A patent/CN103833027A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011144060A (en) * | 2010-01-13 | 2011-07-28 | Sekisui Chem Co Ltd | Method for producing dispersion liquid of flaked graphite, method for producing flaked graphite and method for producing composite material |
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
| CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
| CN102583340A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | High-conductivity graphene material with low-temperature gas-phase reduction and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254920A (en) * | 2015-09-21 | 2016-01-20 | 武汉理工大学 | Preparation method of graphene paper prepreg |
| CN105254920B (en) * | 2015-09-21 | 2018-04-20 | 武汉理工大学 | A kind of preparation method of graphene paper prepreg |
| CN108314012A (en) * | 2017-01-16 | 2018-07-24 | 山东恒华新材料有限公司 | Ammonia heat method batch prepares the production technology of graphene |
| CN113376915A (en) * | 2021-06-28 | 2021-09-10 | 绍兴迪飞新材料有限公司 | Graphene-polyaniline composite electrochromic intelligent dynamic dimming glass |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103887502B (en) | A kind of Delanium lithium ion battery negative material and preparation method thereof | |
| CN101367516B (en) | High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses | |
| CN104091944B (en) | The preparation method of LiFePO4 | |
| CN105000553B (en) | A kind of method that thermo-contact formula prepares nano aperture Graphene | |
| CN104103812A (en) | Composite flexible electrode material as well as preparation method and application thereof | |
| CN103456520B (en) | A kind of preparation method and applications of graphene/carbon nanotube composite film | |
| CN106602062A (en) | Preparation method of graphene aerogel positive electrode material and application of graphene aerogel positive electrode material in aluminum ion battery | |
| CN105152170A (en) | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor | |
| CN108658119A (en) | A kind of cryogenic vulcanization technology is used to prepare the methods and applications of Nano slices of copper sulphide and its compound | |
| CN104649267A (en) | Preparation method of activated carbon for making supercapacitors | |
| CN103681000A (en) | A method for producing graphene paper | |
| CN105529444A (en) | Preparation method and application of negative electrode material for lithium ion battery | |
| CN108807888A (en) | A kind of three-dimensional porous copper silicon-carbon composite integrated polarizing electrode and preparation method thereof | |
| CN103779083A (en) | Nitrogen-doped graphene/metal composite current collector and preparation method thereof | |
| WO2018095074A1 (en) | Ultra-high-temperature resistant, high-conductivity porous aromatic framework compound and method for preparation thereof, and application thereof in proton-exchange membrane fuel cell | |
| CN102569810A (en) | Graphene modified lithium ion battery anode material and preparation method thereof | |
| CN103833011A (en) | Graphene/carbon black composite material, preparation method and application thereof | |
| CN103833027A (en) | Preparation method of graphene paper | |
| CN103903876A (en) | Preparation method for flexible current collector | |
| CN105016337B (en) | A kind of absorbent charcoal material and preparation method thereof can be used for electrode of super capacitor | |
| CN104167298A (en) | Graphene-protein derived carbon supercapcaitor material and preparation method thereof | |
| CN108565409B (en) | Lithium iron phosphate composite material and preparation method thereof | |
| CN103903874A (en) | Graphene current collector and preparing method thereof | |
| CN103647082A (en) | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material | |
| CN103680970A (en) | Graphene paper as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140604 |