CN103700513B - A kind of graphene paper and its preparation method and application - Google Patents
A kind of graphene paper and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 30
- 239000007800 oxidant agent Substances 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 238000004299 exfoliation Methods 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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
- 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
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Abstract
Open graphene paper of the present invention and its preparation method and application.Preparation method of the present invention employing ordinary graphite paper carries out the preparation of graphene paper, the specifically first step and uses the hybrid oxidant of strong oxidizing property that graphite paper carries out oxidation stripping, then cleaning-drying as matrix；Second step high-temperature calcination redox graphene paper under inert gas atmosphere obtains graphene paper.Preparation method technique is simple, with low cost, is suitable for extensive bulk industrial and produces.The graphene paper prepared remains with the form of paper-like, there is the highest extent of exfoliation, show electric conductivity and the specific surface area of superelevation of excellence, show extraordinary electrochemical capacitance performance, more convenient to operate relative to traditional powder, product can have great application prospect in terms of energy storage directly as the electrode material of ultracapacitor.
Description
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 development and the development of science and technology of society, difference is developed in the requirement of continually developing and utilize of various novel energies
The energy accumulating device of kind realizes Efficient Conversion and the utilization of new forms of energy.Ultracapacitor (supercapacitors) is made
For a kind of novel, efficient, practical energy storing device between battery and traditional capacitor, there is many merits, as
Power density is high, charge/discharge rates fast, length in service life, environmental friendliness, use temperature window width etc..Ultracapacitor is at present
Be widely used in electronic equipment stand-by power supply, signal lights power supply thinks and the electrokinetic cell such as fuel cell, lithium battery is combined conduct
The electrical source of power etc. of electric automobile, has boundless application prospect.Ultracapacitor has been put into " national medium-term and long-term section
Learn and technology development outline " in (2005-2020).Along with going deep into ultracapacitor research, researchers recognize the most deeply
Know the performance to ultracapacitor to be improved, it is critical only that the high performance energy storage electrode material of searching.The most conventional electrode material
Material has porous carbon materials, transition metal and the conducting polymer etc. based on activated carbon.In various electrode materials, material with carbon element
Because of aboundresources, low price, the advantage such as good stability is acknowledged as preferable electrochemical capacitance material and by a large amount of business metaplasias
Produce, but owing to the problems such as its theoretical capacitance is low significantly limit its application.Therefore design specific surface area is big, porous three
The material with carbon element of dimension structure becomes current research emphasis.
Graphene (Graphene) is a kind of monatomic graphite material, and its lattice is the two-dimentional Nidus Vespae knot that carbon atom is constituted
Structure.The method of first passage mechanical stripping in 2004 obtains the graphene sheet layer of fewer layer, and finds that it is in external environment
Can stable existence.The chemical constitution of Graphene uniqueness makes it show the most excellent performance, such as its specific surface area up to
2630 m2 g-1, sign mobility is up to 200000 cm2v-1 s-1, much 1.0 TPa of Young's modulus, thermal conduction constant is
5000 Wm-1 K-1, optical transmittance is up to 97.7%, and its electric conductivity is the most excellent, has nearly reached metal simple-substance
Electric conductivity.These characteristics that Graphene shows make it show extraordinary in various fields such as electronics, optics, sensings
Application prospect.Wherein there are superhigh specific surface area and excellent electric conductivity due to Graphene, are especially suitable for being designed for super
The three-dimensional porous carbon electrode of capacitor.The method being currently used for producing Graphene is mainly strong by sulphuric acid, nitric acid, potassium permanganate etc.
Graphite powder is aoxidized by oxidant, reaches, so that being strutted by oxygen-containing functional group between graphite flake layer, the purpose that lamella separates,
Method followed by electronation obtains Graphene.But current this method usually occurs in aqueous solution, inciting somebody to action
Often graphene sheet layer is there is due to model ylid bloom action power strong between graphene sheet layer in Graphene during separating
Meet again, thus greatly reduce its specific surface area and capacitive property thereof.The most this method is difficult to scale and prepares big stone
Ink alkene electrode.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, it is provided that the preparation method of a kind of graphene paper, special
It is not suitable for extensive volume industrial to produce.
It is a further object to provide the graphene paper product prepared by preparation method of the present invention, this product retains
There is the form of paper-like, can be directly as electrochemical capacitance material the capacitive property having excellence.
It is also an object of the present invention to provide the graphene paper product of the present invention application in preparing capacitance material.
Preparation method of the present invention uses ordinary graphite paper to carry out the preparation of graphene paper as matrix, and this ordinary graphite paper is
The graphite paper of widespread commercial at present, cheap, cost is cheap.By design chemical oxidization method to graphite paper at
Reason, finally obtains complete graphene paper, and this graphene paper shows extraordinary electrochemical capacitance performance.Additionally, this method
Simple to operate, easy scale, lay solid theory and practice basis for industrialized production in the future.
The above-mentioned purpose of the present invention is achieved by following technical solution:
The preparation method of a kind of graphene paper, comprises the steps:
S1. the hybrid oxidant of concentrated sulphuric acid, concentrated nitric acid and potassium permanganate is prepared, concentrated sulphuric acid, nitre in described hybrid oxidant
The amount ratio of acid and potassium permanganate is 35 ~ 45mL:10 ~ 15mL:5 ~ 7g；
S2. graphite paper is added and the hybrid oxidant of step S1 preparation carries out chemical oxidation stripping 2 ~ 3h, clean, do
The dry graphene oxide paper that obtains, described graphite paper is 1.5 ~ 2.5g:45 ~ 60mL with the amount ratio of hybrid oxidant；
S3. graphene oxide paper is inserted inert gas atmosphere, carry out high-temperature calcination reduction at 800 ~ 1000 DEG C and prepare stone
Ink alkene paper product.
As one most preferably scheme, in described hybrid oxidant, the amount ratio of concentrated sulphuric acid, nitric acid and potassium permanganate is
40mL:10mL:6g, 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 uses compounding the preparing of concentrated sulphuric acid (18.4 mol/L), concentrated nitric acid (14.5 mol/L) and potassium permanganate to mix
Closing oxidant, it has specific oxidation susceptibility, can form oxygen-containing functional group during oxidation between graphite flake layer graphite paper,
Thus reach the effect of exfoliated graphite, ensure that oxidisability will not be too strong and destroy graphite paper, as graphene paper ruptures simultaneously.Institute
State concentrated sulphuric acid, concentrated nitric acid and potassium permanganate and be the analytical reagent that this area is the most commercially available.
Clean as to use hydrogen peroxide, hydrochloric acid (3 mol/L), distilled water to clean successively described in step S2, first use dioxygen
Water and hydrochloric acid can effectively remove unnecessary oxidant and the heteroion of graphite paper remained on surface, in finally using distilled water to be washed till
Property.
The purpose being dried described in step S2 is away the moisture on graphene paper surface, beneficially subsequent calcination reduction treatment,
In order to dry run is not destroyed structure and the pattern of graphene paper, as a kind of preferred version, described it is dried as lyophilization.
The effect that the present invention calcines under inert gas atmosphere is that graphene oxide is reduced by the method by high temperature,
Thus prepare the graphene paper of high conductivity, therefore in step S3, the time of calcining fully reduces for making graphene oxide paper
?.
In order to control energy consumption, as a kind of preferred version, the temperature of described calcining is preferably 800 ~ 900 DEG C, calcination time
It is preferably 2 ~ 3 h.
Described noble gas can be selected for the conventional noble gases such as nitrogen, helium, argon, as a kind of preferred version, described
Inertia selects nitrogen, reduces preparation cost.
Carbon precursor of the present invention is business-like graphite paper, and thickness is 1mm, and it is by large-scale commercial
Produce, cheap.
Can be used as capacitance material according to the graphene paper that method prepared by the present invention prepares, which solve stone in conventional method
The problem easily met again in ink alkene preparation process, thus it is effectively increased the specific surface area of Graphene, and the preparation side of the present invention
Method is suitable for extensive volume industrial and produces.
Having excellent capacitive property according to the graphene paper that method prepared by the present invention prepares, its pattern is monolayer or few layer
The three-dimensional porous structure of graphite flake composition, this material has specific surface area high, and the advantages such as electric conductivity is excellent, also because these are excellent
Point, this graphene paper shows extraordinary capacitive property in terms of electrochemical capacitance.
In technical scheme, by setting suitable hybrid oxidant and oxidization time, graphite paper is carried out
Oxidation is peeled off, thus obtains monolayer or the graphene oxide of few layer；Come by setting suitable calcining heat and calcination time
Reach the purpose of redox graphene.
Compared with prior art, there is advantages that
(1), in preparation method of the present invention, peeling off of graphite flake layer occurs on the surface of graphite paper, and the Graphene after stripping is still
So being attached to around graphite paper, so being easily separated from aqueous phase, overcoming existing preparation Graphene during Graphene from solution
The when that phase transfer going out, the phenomenon met again can occur due to the strong model ylid bloom action power between graphene molecules layer, cause former
The Graphene peeled away is polymerized again, and specific surface area is greatly reduced, and the characteristic of Graphene is the most necessarily damaged
Shortcoming.
(2) the preparation method technique of the present invention is simple, with low cost, is suitable for extensive bulk industrial and produces.
(3) product that the present invention prepares is the form that graphene paper remains with paper-like, relative to traditional powder behaviour
Making convenient, product can be directly as the electrode material of ultracapacitor.
(4) the graphene paper product that the present invention prepares has excellent electrochemical capacitance performance, has the biggest in terms of energy storage
Application prospect.
Accompanying drawing explanation
Fig. 1 is embodiment 1 graphene paper scanning electron microscope (SEM) picture under different multiples；
Fig. 2 is embodiment 1 graphene paper transmission electron microscope (TEM) picture under different multiples；
Fig. 3 is the electrochemical property test of embodiment 1 graphene paper；
Fig. 4 is comparative example 1 graphene paper scanning electron microscope (SEM) picture under different multiples.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further explained, but specific embodiment is not to the present invention
It is limited in any way.Unless stated otherwise, involved in embodiment reagent, method are reagent commonly used in the art and method.
Embodiment 1
(1) preparation of hybrid oxidant is first carried out.Under condition of ice bath, 40 mL concentrated sulphuric acids and 10 mL concentrated nitric acids are mixed
Close, and be constantly stirred until homogeneous.Then in mixed solution, it is slowly added to 6g potassium permanganate, continues to stir.
(2) graphite paper that thickness is 1 mm being carried out cutting, be cut into 4*4cm, quality is 1.5 g, and is put into mixed
Close in oxidant.Stop stirring, and whole system is waited 2 hours as in room temperature.Take out the graphite paper after oxidation, use successively
Hydrogen peroxide, 3 mol/L hydrochloric acid solutions, distilled water clean to neutral, and it is carried out lyophilization.
(3) dried graphene oxide paper is inserted in tube furnace, in a nitrogen atmosphere high-temperature calcination 1 hour, forge
Burn temperature to control at 800 DEG C.
(4) performance test:
A, prepared graphene paper having been carried out field emission scanning electron microscope figure, result is as shown in Figure 1.
The scanning electron microscope (SEM) photograph of Fig. 1 demonstrates that graphite flake height is peeled off, and the most numerous graphene sheet layer overlap population are superimposed as
(BET specific surface area is 116 m to three-dimensional porous structure2g-1)。
B, prepared graphene paper having carried out Flied emission transmission electron microscope figure, result is as shown in Figure 2.
Graphene paper is made up of the Graphene of monolayer or small layers as can be seen from Figure 2.Graphene in the form of sheets, and
Shape is complete.
C, prepared graphene paper is carried out electrochemical property test, and its capacitive property has been studied.Use
Cyclic voltammetry and constant current charge-discharge test in electrochemical method carry out studying its electrochemical capacitance performance, result such as Fig. 3 institute
Show.
By the cyclic voltammetry curve of Fig. 3 it can be seen that its curve shows extraordinary reversibility, the figure that curve surrounds
Shape is approximate rectangular, and a pair reversible oxidoreduction peak occurs.By being calculated the high specific electric capacity of this Graphene paper stock
It is 500 mF cm-2, it is far longer than current commercial carbon-based material (100 ~ 200 mF cm-2).Same constant current charge-discharge curve is also
Show extraordinary reversibility and capacitive character.It addition, prepared graphene paper also has extraordinary electric conductivity, pass through
Four electrode method records the conductivity of graphene paper and is up to 15 S m-1.In sum, this graphene paper shows the most excellent
Electrochemical capacitance performance, the application in terms of energy storage has the biggest prospect.
Embodiment 2 ~ 7
The preparation method of embodiment 2-7 and embodiment 1, difference be the proportioning of hybrid oxidant and the time of calcining and
Temperature.The result of the concrete proportioning of hybrid oxidant, the time of calcining and temperature and each embodiment is listed in Tables 1 and 2.
The oxidation regulation and control of table 1. graphite paper
| Oxidant sulfuric acid amount | Oxidant nitric acid amount | Oxidant potassium permanganate | Oxidization time | Result explanation | Specific surface area m2g-1 | Conductivity S m-1 | High specific electric capacity mF cm-2 | |
| Embodiment 2 | 35 mL | 10 mL | 5 g | 2h | Graphene extent of exfoliation is the most 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 the most 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 |
The reduction regulation and control of table 2. graphene paper
| Treatment temperature | The process time | Result explanation | |
| Embodiment 6 | 800℃ | 2 h | Reduction is preferably similar to 800 DEG C |
| Embodiment 7 | 900℃ | 1 h | Reduction effect is similar to 800 DEG C, but energy consumption is higher. |
Although the graphene paper product maximum capacitor in embodiment 1 ~ 5 is less than the product of embodiment 1 than performance in table 1, but
Being all to realize the object of the invention, product is the flake graphite alkene paper with higher capacitance performance and electric conductivity.
From the results shown in Table 2, the temperature and time of calcining also can affect the performance of graphene paper product.The present invention
Claimed calcining heat and time all can realize the object of the invention, for preferably technical scheme.
Comparative example 1 ~ 9
The preparation method of comparative example 1 ~ 9 is same as in Example 1, difference be the proportioning of hybrid oxidant and calcining time
Between and temperature.The result of the concrete proportioning of hybrid oxidant, the time of calcining and temperature and each embodiment is listed in table 3 and table 4
In.
The oxidation regulation and control of table 3. graphite paper
| Oxidant sulfuric acid amount | Oxidant nitric acid amount | Oxidant potassium permanganate | Oxidization time | Result explanation | |
| Comparative example 1 | 30 mL | 10 mL | 6 g | 2h | Graphene oxide is peeled off insufficient.May determine that from electron microscopic observation and can not realize goal of the invention. |
| Comparative example 2 | 60 mL | 10 mL | 6 g | 2h | Graphene oxide paper crushes, it is impossible to becoming an entirety, degree of oxidation is the highest.May determine that from electron microscopic observation and can not realize goal of the invention. |
| Comparative example 3 | 40 mL | 5 mL | 6 g | 2h | Nitric acid amount is not enough, and oxidisability is not strong, and extent of exfoliation is poor.May determine that from electron microscopic observation 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 ruptures.May determine that from electron microscopic observation and can not realize goal of the invention. |
| Comparative example 5 | 40 mL | 10 mL | 4 g | 2h | Potassium permanganate amount is not enough, and Graphene extent of exfoliation is not enough.May determine that from electron microscopic observation 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 ruptures.May determine that from electron microscopic observation 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.May determine that from electron microscopic observation 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 ruptures.May determine that from electron microscopic observation and can not realize goal of the invention. |
The reduction regulation and control of table 4. graphene paper
| Treatment temperature | The process time | Result explanation | |
| Comparative example 9 | 600℃ | 1 h | Temperature is on the low side, and reduction effect is poor, still suffers from a large amount of graphene oxide and may determine that from electron microscopic observation and can not realize goal of the invention. |
From the results shown in Table 3, the proportioning of hybrid oxidant and oxidization time need to control in the range of specific,
Otherwise the extent of exfoliation of graphene paper is poor, insufficient or cause graphene paper to rupture owing to oxidisability is too strong, is seen by Electronic Speculum
Survey and i.e. can determine whether that the capacitive property of this graphene paper is unable to 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 mistake
Low, the process time can cause a large amount of graphene oxide of product residue not.
Claims (6)
1. the preparation method of a graphene paper, it is characterised in that comprise the steps:
S1. prepare the hybrid oxidant of concentrated sulphuric acid, concentrated nitric acid and potassium permanganate, concentrated sulphuric acid in described hybrid oxidant, nitric acid and
The amount ratio of potassium permanganate is 35 ~ 45mL:10 ~ 15mL:5 ~ 7g；
S2. graphite paper is added and the hybrid oxidant of step S1 preparation carries out chemical oxidation stripping 2 ~ 3h, clean, be dried
To graphene oxide paper, described graphite paper is 1.5 ~ 2.5g:45 ~ 60mL with the amount ratio of hybrid oxidant；
S3. graphene oxide paper is inserted inert gas atmosphere, carry out high-temperature calcination reduction at 800 ~ 900 DEG C and prepare Graphene
Paper product；
Wherein, described noble gas is nitrogen, helium or argon, and the time of described calcining is 2 ~ 3 h.
Preparation method the most according to claim 1, it is characterised in that concentrated sulphuric acid, nitric acid and Gao Meng in described hybrid oxidant
The amount ratio of acid potassium is 40mL:10mL:6g, and described graphite paper is 2g:50mL with the amount ratio of hybrid oxidant, described chemical oxygen
The time changing stripping is 2h.
Preparation method the most according to claim 1, it is characterised in that described be dried as lyophilization.
Preparation method the most according to claim 1, it is characterised in that clean described in step S2 for use successively hydrogen peroxide, 3
Mol/L hydrochloric acid, distilled water clean.
5. a graphene paper, it is characterised in that described graphene paper is by preparation method system described in any one of Claims 1-4
?.
6. the application in preparing capacitance material of the graphene paper described in claim 5.
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| CN103700513B true CN103700513B (en) | 2016-09-14 |
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| CN103935994B (en) * | 2014-04-28 | 2015-09-09 | 上海交通大学 | A kind of self-supporting redox graphene paper and preparation method thereof |
| CN104261387B (en) * | 2014-09-16 | 2016-06-01 | 中山大学 | A kind of big area prepares the method for Graphene carbon paper and the Graphene carbon paper of preparation thereof |
| 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 |
| 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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| CN102153077A (en) * | 2011-05-12 | 2011-08-17 | 北京工业大学 | Method for preparing single-layer graphene with high carbon-oxygen ratio |
| CN103137342A (en) * | 2013-02-06 | 2013-06-05 | 燕山大学 | Grapheme-polyaniline super capacitor electrode material and preparation method thereof |
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| US20130295374A1 (en) * | 2010-12-02 | 2013-11-07 | Jie Tang | Graphene sheet film connected with carbon nanotubes, method for producing same, and graphene sheet capacitor using same |
| KR101240276B1 (en) * | 2011-01-25 | 2013-03-07 | 한국과학기술연구원 | A preparation method for reduced graphene oxide using the sulfonyl hydrazide-based reducing agent and optoelectronic devices thereof |
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| CN103137342A (en) * | 2013-02-06 | 2013-06-05 | 燕山大学 | Grapheme-polyaniline super capacitor electrode material and preparation method thereof |
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