CN103700513A - Graphene paper and preparation method and application thereof - Google Patents

Graphene paper and preparation method and application thereof Download PDF

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CN103700513A
CN103700513A CN201310743046.8A CN201310743046A CN103700513A CN 103700513 A CN103700513 A CN 103700513A CN 201310743046 A CN201310743046 A CN 201310743046A CN 103700513 A CN103700513 A CN 103700513A
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paper
preparation
graphene
graphene paper
graphite
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CN103700513B (en
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卢锡洪
于明浩
童叶翔
方萍萍
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Sun Yat Sen University
National Sun Yat Sen University
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    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses graphene paper and a preparation method and application thereof. According to the preparation method disclosed by the invention, the preparation of the graphene paper is performed by taking conventional graphite paper as a basal body. The preparation method comprises the following specific steps: S1, performing oxidation stripping on the graphite paper by using a mixed oxidizing agent with strong oxidizing property, and then, cleaning and drying; S2, performing high-temperature calcination reduction on oxide graphene paper under an inert gas atmosphere to obtain the graphene paper. The preparation method is simple in process and low in cost, and suitable for large-scale volume industrial production. A paper form is kept by the prepared graphene paper, so that the graphene paper is very high in stripping degree, excellent in electrical conductivity and superhigh in specific surface area and very good in electrochemical capacitance performance. Compared with a traditional powder operation method, the preparation method is more convenient. The graphene paper product can be directly used as an electrode material of a supercapacitor, and is broad in application prospect in the energy storage aspect.

Description

A kind of Graphene paper and its preparation method and application
Technical field
The invention belongs to capacitor material field, be specifically related to a kind of Graphene paper and its preparation method and application.
Background technology
Along with social development and scientific and technological development, continually developing and utilizing of various novel energies requires to develop Efficient Conversion and the utilization that different types of energy accumulating device is realized new forms of energy.Ultracapacitor (supercapacitors) is as a kind of novel, efficient, practical energy storing device between battery and traditional capacitor, there is many merits, as high in power density, the speed that discharges and recharges is fast, long service life, environmental friendliness, serviceability temperature window are wide etc.At present ultracapacitor has been widely used in electronic equipment stand-by power supply, signal lamp power supply is thought with the compound electrical source of power as electric automobile of electrokinetic cell such as fuel cell, lithium battery etc., has boundless application prospect.Ultracapacitor has now been put in the < < medium-term and long-term scientific and technological development outline > > of country (2005-2020).Along with going deep into that ultracapacitor is studied, heightened awareness is to the performance that will improve ultracapacitor for researchers, and key is to find high performance energy storage electrode material.Current conventional electrode material has take active carbon as main porous carbon materials, transition metal and conducting polymer etc.In various electrode materials, material with carbon element is because of aboundresources, low price, and the advantages such as good stability are acknowledged as desirable electrochemical capacitance material and are commercially produced in a large number, but because the problems such as its theoretical capacitance is low have greatly limited its application.Therefore design specific area large, the material with carbon element of porous three-dimensional structure becomes current research emphasis.
Graphene (Graphene) is a kind of monatomic graphite material, and its lattice is the two-dimentional honeycomb structure that carbon atom forms.The method of first passage mechanical stripping in 2004 obtains the graphene sheet layer of fewer layer, and finds that it can stable existence in external environment.The chemical constitution of Graphene uniqueness makes it show very excellent performance, and for example its specific area is up to 2630 m 2g -1, sign mobility is up to 200000 cm 2v -1s -1-, much 1.0 TPa of Young's modulus, thermal conduction constant is 5000 Wm -1k -1, optical transmittance is up to 97.7%, and its conductivity is also very excellent, has almost reached the electric conductivity of metal simple-substance.These characteristics that Graphene shows make it in various fields such as electronics, optics, inductions, show extraordinary application prospect.Wherein, because Graphene has superhigh specific surface area and excellent electric conductivity, be applicable to being very much designed for the three-dimensional porous carbon electrode of ultracapacitor.Method for the production of Graphene is mainly oxidized graphite powder by strong oxidizers such as sulfuric acid, nitric acid, potassium permanganate at present, thereby make by oxygen-containing functional group, to be strutted the object that reaches lamella separation between graphite flake layer, and then the method by electronation obtains Graphene.Yet current this method usually occurs in the aqueous solution, there is to the reunion of graphene sheet layer in strong model ylid bloom action power between tending to due to graphene sheet layer in the process of Graphene separation, thereby greatly reducing its specific area and capacitive property thereof.In addition this method is difficult to scale and prepares large Graphene electrodes.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation method of Graphene paper is provided, be particularly suitable for extensive industrial production in batches.
Another object of the present invention is to provide the Graphene paper product being made by preparation method of the present invention, and this product remains with the form of paper shape, can be directly as electrochemical capacitance material and there is excellent capacitive property.
A further object of the invention is to provide the application of Graphene paper product of the present invention in preparing capacitance material.
Preparation method of the present invention adopts conventional graphite paper as matrix, to carry out the preparation of Graphene paper, the graphite paper that this routine graphite paper is current widespread commercial, and cheap, cost is cheap.Chemical oxidization method by design is processed graphite paper, finally obtains complete Graphene paper, and this Graphene paper shows extraordinary electrochemical capacitance performance.In addition, this method is simple to operate, and easily scale, for suitability for industrialized production has in the future been laid solid theory and practice basis.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A preparation method for Graphene paper, comprises the steps:
S1. prepare the hybrid oxidant of the concentrated sulfuric acid, red fuming nitric acid (RFNA) and potassium permanganate, in described hybrid oxidant, the amount ratio of the concentrated sulfuric acid, nitric acid and potassium permanganate is 35 ~ 45mL:10 ~ 15mL:5 ~ 7g;
S2. graphite paper is added and in the hybrid oxidant of step S1 preparation, carry out chemical oxidation and peel off 2 ~ 3h, clean, dryly obtain graphene oxide paper, the amount ratio of described graphite paper and hybrid oxidant is 1.5 ~ 2.5g:45 ~ 60mL;
S3. graphene oxide paper is inserted to inert gas atmosphere, carry out high-temperature calcination reduction at 800 ~ 1000 ℃ and make Graphene paper product.
As a kind of most preferably scheme, in described hybrid oxidant, the amount ratio of the concentrated sulfuric acid, nitric acid and potassium permanganate is 40mL:10mL:6g, and the amount ratio of described graphite paper and hybrid oxidant is 2g:50mL, and the time that described chemical oxidation is peeled off is 2h.
The present invention adopts the concentrated sulfuric acid (18.4 mol/L), red fuming nitric acid (RFNA) (14.5 mol/L) and the composite hybrid oxidant that makes of potassium permanganate, it has specific oxidation susceptibility to graphite paper, during oxidation, can between graphite flake layer, form oxygen-containing functional group, thereby reach the effect of exfoliated graphite, guarantee oxidizability can not cross strong simultaneously and destroy graphite paper, as Graphene paper breaks.The described concentrated sulfuric acid, red fuming nitric acid (RFNA) and potassium permanganate are the analytical reagent that the direct business in this area is bought.
Described in step S2, clean as using successively hydrogen peroxide, hydrochloric acid (3 mol/L), distilled water to clean, first adopt hydrogen peroxide and hydrochloric acid can effectively remove unnecessary oxidant and the heteroion of graphite paper remained on surface, finally adopt distilled water to be washed till neutrality.
Described in step S2, dry object is away the moisture on Graphene paper surface, be beneficial to follow-up calcining reduction and process, and in order not destroy structure and the pattern of Graphene paper in dry run, as a kind of preferred version, described being dried as freeze drying.
The effect that the present invention calcines under inert gas atmosphere is by the method for high temperature, graphene oxide to be reduced, thereby prepares the Graphene paper of high conductivity, so in step S3, the time of calcining is for fully reducing graphene oxide paper.
In order to control energy consumption, as a kind of preferred version, the temperature of described calcining is preferably 800 ~ 900 ℃, and calcination time is preferably 2 ~ 3 h.
Described inert gas can be selected the conventional inert gases such as nitrogen, helium, argon gas, and as a kind of preferred version, described inertia is selected nitrogen, reduces preparation cost.
Carbon precursor of the present invention is business-like graphite paper, and thickness is 1mm, and it is produced by large-scale commercial, cheap.
The Graphene paper that prepared method makes according to the present invention can be used as capacitance material, it has solved the problem of easily meeting again in Graphene preparation process in conventional method, thereby effectively improved the specific area of Graphene, and preparation method of the present invention is applicable to extensive industrial production in batches.
The Graphene paper that prepared method makes according to the present invention has excellent capacitive property, its pattern is the three-dimensional porous structure that individual layer or few layer graphite flake form, this material has specific area high, the advantages such as electric conductivity excellence, also because of these advantages, this Graphene paper shows extraordinary capacitive property aspect electrochemical capacitance.
In technical scheme of the present invention, by setting suitable hybrid oxidant and oxidization time, graphite paper is oxidized and is peeled off, thereby obtain the graphene oxide of individual layer or few layer; By setting suitable calcining heat and calcination time, reach the object of redox graphene.
Compared with prior art, the present invention has following beneficial effect:
(1) in preparation method of the present invention, graphite flake layer peel off the surface that occurs in graphite paper, Graphene after peeling off is still attached to graphite paper around, so easily depart from water, overcome existing preparation when Graphene being migrated out from solution phase in Graphene process, due to the strong model ylid bloom action power between graphene molecules layer, can there is the phenomenon of meeting again, cause the Graphene of originally having peeled away that polymerization occurs again, specific area declines greatly, and the characteristic of Graphene is also subject to certain shortcoming of damaging.
(2) preparation method's technique of the present invention is simple, with low cost, is applicable to extensive suitability for industrialized production in batches.
(3) product that the present invention prepares is the form that Graphene paper remains with paper shape, more convenient to operate with respect to traditional powder, product can be directly as the electrode material of ultracapacitor.
(4) the Graphene paper product that the present invention makes has good electrochemical capacitance performance, aspect energy storage, has great application prospect.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) picture of embodiment 1 Graphene paper under different multiples;
Fig. 2 is transmission electron microscope (TEM) picture of embodiment 1 Graphene paper under different multiples;
Fig. 3 is the electrochemical property test of embodiment 1 Graphene paper;
Fig. 4 is ESEM (SEM) picture of comparative example 1 Graphene paper under different multiples.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, in embodiment, related reagent, method is the conventional reagent in this area and method.
embodiment 1
(1) first carry out the preparation of hybrid oxidant.Under condition of ice bath, the 40 mL concentrated sulfuric acids are mixed with 10 mL red fuming nitric acid (RFNA)s, and be constantly stirred to evenly.Then in mixed solution, slowly add 6g potassium permanganate, continue to stir.
(2) by thickness, be that the graphite paper of 1 mm carries out cutting, be cut into 4*4cm, quality is 1.5 g, and is dropped in hybrid oxidant.Stop stirring, and by whole system as for waiting for 2 hours in room temperature.Take out the graphite paper after oxidation, with hydrogen peroxide, 3 mol/L hydrochloric acid solutions, distilled water, clean to neutral successively, and it is carried out to freeze drying.
(3) dried graphene oxide paper is inserted in tube furnace, under nitrogen atmosphere, high-temperature calcination is 1 hour, and calcining heat is controlled at 800 ℃.
(4) performance test:
A, the Graphene paper making has been carried out to field emission scanning electron microscope figure, result as shown in Figure 1.
The Scanning Electron Microscope photos reveal of Fig. 1 goes out graphite flake height to be peeled off, and simultaneously numerous graphene film plies distributions are superimposed as three-dimensional porous structure, and (BET specific area is 116 m 2g -1).
B, the Graphene paper making has been carried out to a transmission electron microscope picture, result as shown in Figure 2.
Graphene paper is comprised of the Graphene of individual layer or less layer as can be seen from Figure 2.In the form of sheets, and shape is complete for Graphene.
C, the Graphene paper making has been carried out to electrochemical property test, and its capacitive property has been studied.Adopted cyclic voltammetry and the constant current charge-discharge in electrochemical method to test to study its electrochemical capacitance performance, result as shown in Figure 3.
Cyclic voltammetry curve by Fig. 3 can find out, its curve shows extraordinary invertibity, and the figure that curve surrounds is approximate rectangular, and occurs a pair of reversible redox peak.By calculating the high specific electric capacity of this Graphene paper stock, be 500 mF cm -2, be far longer than current commercial carbon-based material (100 ~ 200 mF cm -2).Same constant current charge-discharge curve also shows extraordinary invertibity and capacitive character.In addition, prepared Graphene paper also has extraordinary conductivity, records the conductance of Graphene paper up to 15 S m by four electrode method -1.In sum, this Graphene paper shows very good electrochemical capacitance performance, and the application aspect energy storage has very large prospect.
embodiment 2 ~ 7
The preparation method of embodiment 2-7 and embodiment 1, difference is the proportioning of hybrid oxidant and the time of calcining and temperature.The concrete proportioning of hybrid oxidant is, the results are shown in table 1 and table 2 of the time of calcining and temperature and each embodiment.
The oxidation regulation and control of table 1. graphite paper
? Oxidant sulfuric acid amount Oxidant nitric acid amount Oxidant potassium permanganate Oxidization time Presentation of results Specific area m 2g -1 Conductance S m -1 High specific electric capacity mF cm -2
Embodiment 2 35 mL 10 mL 5 g 2h Graphene extent of exfoliation is slightly on the low side 83 17 411
Embodiment 3 45 mL 15 mL 7 g 2h Graphene extent of exfoliation is higher, has breakage 121 23 489
Embodiment 4 35 mL 15 mL 6 g 2h Graphene extent of exfoliation is slightly on the low side 101 18 425
Embodiment 5 45 mL 10 mL 6 g 2h Graphene extent of exfoliation is higher, has breakage 138 27 474
Table 2. Graphene paper reduction regulation and control
? treatment temperature processing time presentation of results
embodiment 6 800 ℃ 2 h reduction is better similar with 800 ℃
embodiment 7 900 ℃ 1 h reduction effect is similar with 800 ℃, but energy consumption is higher.
Although the Graphene paper product maximum capacitor in table 1 in embodiment 1 ~ 5 is the product lower than embodiment 1 than performance, all can realize the object of the invention, product is the flake graphite alkene paper with higher capacitance performance and conductivity.
From the results shown in Table 2, the temperature and time of calcining also can affect the performance of Graphene paper product.The calcining heat that the present invention is claimed and time all can be realized the object of the invention, are technical scheme preferably.
comparative example 1 ~ 9
The preparation method of comparative example 1 ~ 9 is identical with embodiment 1, and difference is the proportioning of hybrid oxidant and the time of calcining and temperature.The concrete proportioning of hybrid oxidant is, the results are shown in table 3 and table 4 of the time of calcining and temperature and each embodiment.
The oxidation regulation and control of table 3. graphite paper
? oxidant sulfuric acid amount oxidant nitric acid amount oxidant potassium permanganate oxidization time presentation of results
comparative example 1 30 mL 10 mL 6 g 2h graphene oxide is peeled off insufficient.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 2 60 mL 10 mL 6 g 2h graphene oxide paper is broken, can not become as a whole, and degree of oxidation is too high.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 3 40 mL 5 mL 6 g 2h nitric acid quantity not sufficient, oxidizability is not strong, and extent of exfoliation is poor.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 4 40 mL 20 mL 6 g 2h salpeter solution is on the high side, and Graphene paper breaks.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 5 40 mL 10 mL 4 g 2h potassium permanganate quantity not sufficient, Graphene extent of exfoliation is not enough.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 6 40 mL 10 mL 8 g 2h potassium permanganate amount is too much, and Graphene paper breaks.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 7 40 mL 10 mL 6 g 1h oxidization time is not enough, and Graphene extent of exfoliation is not enough.From electron microscopic observation, can judge and can not realize goal of the invention.
comparative example 8 40 mL 10 mL 6 g 4h oxidization time is long, and Graphene paper breaks.From electron microscopic observation, can judge and can not realize goal of the invention.
Table 4. Graphene paper reduction regulation and control
? treatment temperature processing time presentation of results
comparative example 9 600 ℃ 1 h temperature is on the low side, and reduction effect is poor, still exists a large amount of graphene oxides can judge and can not realize goal of the invention from electron microscopic observation.
From the results shown in Table 3, the proportioning of hybrid oxidant and oxidization time need to be controlled in specific scope, otherwise the extent of exfoliation of Graphene paper is poor, insufficient or break because oxidizability causes excessively by force Graphene paper, by electron microscopy observation, can judge that the capacitive property of this Graphene paper cannot reach goal of the invention (accompanying drawing 4).
From the results shown in Table 4, the temperature and time of calcining also can affect the performance of Graphene paper product.Temperature is too low, and the processing time can cause a large amount of graphene oxides of product residue not.

Claims (8)

1. a preparation method for Graphene paper, is characterized in that, comprises the steps:
S1. prepare the hybrid oxidant of the concentrated sulfuric acid, red fuming nitric acid (RFNA) and potassium permanganate, in described hybrid oxidant, the amount ratio of the concentrated sulfuric acid, nitric acid and potassium permanganate is 35 ~ 45mL:10 ~ 15mL:5 ~ 7g;
S2. graphite paper is added and in the hybrid oxidant of step S1 preparation, carry out chemical oxidation and peel off 2 ~ 3h, clean, dryly obtain graphene oxide paper, the amount ratio of described graphite paper and hybrid oxidant is 1.5 ~ 2.5g:45 ~ 60mL;
S3. graphene oxide paper is inserted to inert gas atmosphere, carry out high-temperature calcination reduction at 800 ~ 1000 ℃ and make Graphene paper product.
2. preparation method according to claim 1, it is characterized in that, in described hybrid oxidant, the amount ratio of the concentrated sulfuric acid, nitric acid and potassium permanganate is 40mL:10mL:6g, and the amount ratio of described graphite paper and hybrid oxidant is 2g:50mL, and the time that described chemical oxidation is peeled off is 2h.
3. preparation method according to claim 1, is characterized in that, the temperature of described calcining is 800 ~ 900 ℃, and calcination time is 2 ~ 3 h.
4. preparation method according to claim 1, is characterized in that described being dried as freeze drying.
5. preparation method according to claim 1, is characterized in that, cleans as using successively hydrogen peroxide, 3 mol/L hydrochloric acid, distilled water cleaning described in step S2.
6. preparation method according to claim 1, is characterized in that, described inert gas is nitrogen, helium or argon gas.
7. a Graphene paper, is characterized in that, described Graphene paper is made by preparation method described in claim 1 to 6 any one.
8. the application of Graphene paper in preparing capacitance material described in claim 7.
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Cited By (7)

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CN103935994A (en) * 2014-04-28 2014-07-23 上海交通大学 Self-supported reduced graphene oxide paper and preparation method thereof
CN104261387A (en) * 2014-09-16 2015-01-07 中山大学 Method for large-area preparation of graphene based carbon paper and graphene based carbon paper prepared thereby
CN105000553A (en) * 2015-07-31 2015-10-28 中国科学技术大学 Method for preparing nanometer hole graphene in heat contact mode
CN107337199A (en) * 2017-07-17 2017-11-10 山西大学 A kind of preparation method of the graphene film electrode material of ultracapacitor
CN107902641A (en) * 2017-09-19 2018-04-13 太原理工大学 A kind of preparation method of functionalization reduced graphene
CN109133923A (en) * 2018-08-21 2019-01-04 大同新成新材料股份有限公司 A kind of method that graphene oxide-special graphite powder prepares special graphite paper
CN115231564A (en) * 2021-04-22 2022-10-25 宁波材料所杭州湾研究院 Graphene thermal interface material and preparation method and application thereof

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CN103935994A (en) * 2014-04-28 2014-07-23 上海交通大学 Self-supported reduced graphene oxide paper and preparation method thereof
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CN105000553B (en) * 2015-07-31 2017-06-16 中国科学技术大学 A kind of method that thermo-contact formula prepares nano aperture Graphene
CN107337199A (en) * 2017-07-17 2017-11-10 山西大学 A kind of preparation method of the graphene film electrode material of ultracapacitor
CN107902641A (en) * 2017-09-19 2018-04-13 太原理工大学 A kind of preparation method of functionalization reduced graphene
CN109133923A (en) * 2018-08-21 2019-01-04 大同新成新材料股份有限公司 A kind of method that graphene oxide-special graphite powder prepares special graphite paper
CN109133923B (en) * 2018-08-21 2020-10-30 大同新成新材料股份有限公司 Method for preparing special graphite paper from graphene oxide-special graphite powder
CN115231564A (en) * 2021-04-22 2022-10-25 宁波材料所杭州湾研究院 Graphene thermal interface material and preparation method and application thereof

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