CN104192836B - The solution hot preparation method of self-supporting porous graphene base film - Google Patents

The solution hot preparation method of self-supporting porous graphene base film Download PDF

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CN104192836B
CN104192836B CN201410471401.5A CN201410471401A CN104192836B CN 104192836 B CN104192836 B CN 104192836B CN 201410471401 A CN201410471401 A CN 201410471401A CN 104192836 B CN104192836 B CN 104192836B
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CN104192836A (en
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贾铮
李程远
刘道庆
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The solution hot preparation method of self-supporting porous graphene base film, the present invention relates to the preparation method of graphene-based thin film.The present invention is to solve the graphene-based film dimensions of existing self-supporting and finite thickness, in chemical reduction procedure, graphene film interlayer is compound seriously causes the technical problem of chemical property difference.Preparation method: be dispersed in water by graphite oxide, is not added with or adds doping material with carbon element, sprawling film forming, obtain graphene oxide film after concentration；The solution of solution heat treatment it is formulated for by acid or alkali solute, graphene oxide film is put into and has in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, after airtight for reactor, carry out heat treatment, obtain self-supporting porous graphene base film.Self-supporting porous graphene base film is arranged in parallel and formed by graphene sheet layer high-sequential ground, and graphene film interlayer exists hole, can be used in the electrochemical energy storage devices such as ultracapacitor.

Description

The solution hot preparation method of self-supporting porous graphene base film
Technical field
The present invention relates to the preparation method of graphene-based thin film.
Background technology
Ultracapacitor is a kind of novel electrochemical energy storage device, have ultrahigh speed charging and discharging capabilities, overlength cycle life, The advantages such as good high temperature performance, are suitable for the wide spectrums such as electric vehicle power sources, accumulation power supply and electronic equipment power source.Wherein, Flexible super capacitor wearable, that can wind is particularly subject to market and pays close attention to.In order to improve the energy density of ultracapacitor, Realize the wound performance of ultracapacitor, graphene-based for self-supporting thin film is used as gluing without collector, nothing of ultracapacitor Knot agent electrode becomes current study hotspot.
The preparation method of the graphene-based thin-film material of self-supporting being used as electrode material for super capacitor mainly includes electronation Graphene oxide film method, the vacuum filtration method of graphene dispersing solution and chemical gaseous phase depositing process, but these sides Method all has respective limitation.
The preparation method of electronation graphene oxide film generally uses vacuum filtration method to prepare graphene oxide film, then leads to Cross the chemical reducing agent such as hydrazine hydrate, hydroiodic acid and graphene oxide film is reduced into graphene film, or by high-temperature hot Graphene oxide film is reduced into graphene film by the method for reason；Vacuum filtration graphene dispersing solution prepares graphene film Method is then first to use the chemical reducing agent redox graphene dispersion liquid such as hydrazine hydrate, ascorbic acid, and generation can stably divide The graphene dispersing solution dissipated, then graphene dispersing solution is carried out vacuum filtration, obtain graphene film.
Above two method have the drawback that (1) during vacuum filtration, along with the shape of (oxidation) graphene film Becoming and thicken, the solvent in (oxidation) graphene dispersing solution passes thin film and filter membrane and becomes more and more difficult, sucking filtration process without Method continues, and the thickness of (oxidation) graphene film that therefore can reach exists the limit, generally below several microns, difficult To obtain thicker thin film, this will reduce energy per unit area density and volume energy density (the thickest stone of ultracapacitor Ink alkene thin film has the biggest electrode active material/capacitor casing ratio)；(2) area of the graphene film that can prepare It is limited to the size of vacuum filtration funnel, it is difficult to obtain large-area graphene film；(3) through the reduction of chemical reducing agent Electrostatic row or after the reduction of high-temperature heat treatment, the oxygen-containing functional group on graphene oxide lamella gradually removes, between negative charge Scolding declines, the π-π sucking action between lamella big π key strengthens, and easily occurs to stack (restacking) again between lamella Closely it is combined between phenomenon, i.e. graphene sheet layer, causes hole between graphene sheet layer little, even atresia, specific surface area Little, thus lower than electric capacity, and high rate performance is poor.
Therefore, need development technology process at present badly simply efficient, there is the graphene-based thin film material of controlled dimensions and abundant hole The preparation method of material.
Summary of the invention
The present invention is to solve the graphene-based film dimensions of existing self-supporting and finite thickness, graphene film interlayer in reduction process It is combined serious and causes the technical problem of chemical property difference, and then the self-supporting porous graphene of electrochemical performance is provided The solution hot preparation method of base film.
The solution hot preparation method of the self-supporting porous graphene base film of the present invention sequentially includes the following steps:
One, it is 0.01mg mL by the concentration of graphite oxide-1～0.5mg mL-1, graphite oxide is added to the water, in frequency It is ultrasonic stripping under the ultrasound condition of 20～100KHz, dispersion 0.5～10h, obtains graphene oxide aqueous dispersions；
Two, under conditions of temperature is 20 DEG C～100 DEG C, graphene oxide aqueous dispersions step one obtained reduces pressure Evaporation or atmospheric evaporation concentrate；
Three, graphene oxide aqueous dispersions step 2 concentrated is at flat base upper berth generated film, after drying at room temperature, and will Thin film and matrix stripping, obtain graphene oxide film；
Four, it is 0.01mol L by solute concentration-1～20mol L-1It is formulated for the solution of solution heat treatment, wherein said Solute is a kind of or the most several mixture in sulphuric acid, hydrochloric acid, phosphoric acid and boric acid, or solute is potassium hydroxide, hydrogen A kind of or the most several mixture in sodium oxide and Lithium hydrate；The graphene oxide film obtained in step 3 is put into Have in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, will reaction Heat treatment is carried out after still is airtight；Washing the thin film after solution heat treatment to washing liquid is neutrality, obtains self-supporting porous graphene Base film.
Wherein, in step 2, the concentration of graphene oxide aqueous dispersions is concentrated into 0.5～200mg mL-1。
Step 3 uses the oxidation stone that step 2 is concentrated by knife coating, the tape casting, nebulization, spin-coating method or drop-coating Ink alkene aqueous dispersions is at flat base upper berth generated film.
In step 3 obtained by graphene oxide film be by the mutual close parallel of graphene oxide lamella rearrange thin Film, thin film has a higher mechanical strength, and thin film color even also increases with film thickness that gradually added plutonic by brown color brown Color.
The condition of the solution heat treatment described in step 4 is that reactor heats 1～24h at 100～170 DEG C.
The solution by the use of thermal means used in step 4 is that a kind of to use acidity or alkaline aqueous solution be the hydrothermal method of medium, both retains The high temperature of light water by the use of thermal means (employing pure water is medium) and spontaneous condition of high voltage, make use of again the thin film of solute in solution Stability Analysis of Structures effect.Using solution by the use of thermal means to process graphene oxide film, the most suitable temperature and pressure can remove Part oxygen-containing functional group on graphene oxide, has recovered the conjugated structure of big π key on graphene sheet layer to a certain extent, Improve the electric conductivity of material；On the other hand, under high temperature and spontaneous high pressure effect, it is thin that hydrone is inserted into graphene oxide Between graphene oxide lamella in film, thus cause between lamella, forming abundant hole, it is to avoid the graphite that reduction produces Occur between alkene lamella closely to stack phenomenon again, it is provided that high-specific surface area and high porous volume, improve its chemical property； Meanwhile, the solute in solution hot solution also has the holding constitutionally stable effect of graphene film, can be described as membrane structure steady Determine agent.Specifically, using water as medium if adopted, graphene oxide film being carried out common hydrothermal treatment consists, due to oxygen There is strong electrostatic repulsion between oxygen-containing functional group electronegative on functionalized graphene lamella, insert graphite at hydrone Under release effect between alkene lamella, graphene sheet layer can disintegrate, and loses original membrane structure；On the contrary, if adopted By acid solution hot solution, graphene oxide film is carried out solution heat treatment, oxygen-containing functional group on graphene oxide lamella The negative charge carried is because of same H+In conjunction with and reduce, the electrostatic repulsion between negative charge weakens, and between lamellaπ-π Sucking action rises to mastery reaction, and the trend and the stable trend that so separate reach dynamic equilibrium, can produce sheet interlayer Hole, thin film also can be made to keep completely in solution thermal process, be unlikely to because hydrone inserts the stripping between graphene sheet layer Make thin film disintegrate from effect, gained graphene film shows obvious metallic luster；If using the solution of alkalescence Hot solution, carries out solution heat treatment to graphene oxide film, and the oxygen-containing functional group on graphene oxide lamella is adequately ionized, Thus electronegative, with there is electrostatic attraction effect between cation positively charged in solution hot solution, cation is embedded into By electrostatic attraction effect, graphene oxide lamella is connected with each other between graphene oxide lamella, the trend so separated Reach dynamic equilibrium with stable trend, the hole of sheet interlayer can be produced, also can make graphene film in solution thermal process Keep complete, be unlikely to make thin film disintegrate because hydrone inserts the release effect between graphene sheet layer；It addition, by Cation in alkaline solution hot solution can be embedded between graphene sheet layer, the graphite obtained in alkaline solution hot solution The graphene film obtained in the graphene sheet layer gap ratio acid solution hot solution of alkene thin film is big, therefore alkaline solution hot solution In the graphene film that obtains thicker, its pore-size is bigger.For reaching the portfolio effect of above-mentioned solution heat effect, solution heat The selection of solute in solution, and suitable solution heat treatment temperature and the time most important.
Use self-supporting porous graphene prepared by the solution hot preparation method of the self-supporting porous graphene base film of the present invention Base film is arranged in parallel and formed by graphene sheet layer high-sequential ground, and the Graphene that graphene film interlayer exists hole is thin Film；Film thickness is 10nm～1mm；Film size can reach infinitely great in theory, is dependent only on used base Body size and the size of film-forming apparatus；Under suitable solution heat treatment temperature and time conditions, gained self-supporting porous stone Mertenyl thin film is with the oxygen-containing functional group of higher level, and these surface functional groups can occur quick oxidation-reduction reaction, Thus Faraday pseudo-capacitance is provided, improve total ratio capacitance values.
The solution hot preparation method of the self-supporting porous graphene base film of the present invention can also sequentially include the following steps:
One, it is 0.01mg mL by the concentration of graphite oxide-1～0.5mg mL-1, graphite oxide is added to the water, in frequency It is ultrasonic stripping under the ultrasound condition of 20～100KHz, dispersion 0.5～10h, obtains graphene oxide aqueous dispersions；
Two, in the graphene oxide aqueous dispersions that step one obtains, add doping material with carbon element, be 20～100KHz in frequency Ultrasound condition under ultrasonic disperse 0.5～10h so that each component is uniformly dispersed in water, obtains graphite oxide thiazolinyl moisture Dissipate liquid；
Three, under conditions of temperature is 20 DEG C～100 DEG C, graphite oxide thiazolinyl aqueous dispersions step 2 obtained subtracts Pressure evaporation or atmospheric evaporation, to improve the concentration of each component in graphite oxide thiazolinyl aqueous dispersions；
Four, graphite oxide thiazolinyl aqueous dispersions step 3 concentrated, will after drying at room temperature at flat base upper berth generated film Thin film and matrix stripping, obtain graphene oxide base film；
Five, it is 0.01mol L by solute concentration-1～20mol L-1It is formulated for the solution of solution heat treatment, wherein said Solute is sulphuric acid, a kind of or the most several mixture in hydrochloric acid, phosphoric acid and boric acid, or solute be potassium hydroxide, A kind of or the most several mixture in sodium hydroxide and Lithium hydrate；The graphene oxide base film that will obtain in step 4 Put into and have in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, will Heat treatment is carried out after reactor is airtight；Washing the thin film after solution heat treatment to washing liquid is neutrality, obtains self-supporting porous stone Mertenyl thin film.
Wherein, the doping material with carbon element described in step 2 is CNT, white carbon black, graphite powder, carbon fiber, activated carbon, mould A kind of or the most several mixture in plate porous carbon, carbide-derived carbon, graphene oxide and the quality of doping material with carbon element Ratio is 1:(0.0001～0.5).
In step 3, in graphite oxide thiazolinyl aqueous dispersions, the concentration of graphene oxide is concentrated into 0.5～200mg mL-1。
Step 4 uses the oxidation stone that step 3 is concentrated by knife coating, the tape casting, nebulization, spin-coating method or drop-coating Mertenyl aqueous dispersions is at flat base upper berth generated film.
Graphene oxide base film obtained by step 4 is to be formed by the arrangement of graphene oxide lamella mutual close parallel , doping material with carbon element be embedded in the thin film between graphene oxide lamella, thin film has higher mechanical strength, its color with Film thickness, the increase of doping material with carbon element content are gradually added plutonic black by brown color.
The condition of the solution heat treatment described in step 5 is that reactor heats 1～24h at 100～170 DEG C.
The solution by the use of thermal means that step 5 uses is that a kind of to use acidity or alkaline aqueous solution be the hydrothermal method of medium, both remains The high temperature of light water by the use of thermal means (employing pure water is medium) and spontaneous condition of high voltage, make use of again the thin film of solute in solution to tie Structure Stabilization.Using solution by the use of thermal means to process graphene oxide base film, the most suitable temperature and pressure can remove Part oxygen-containing functional group on graphene oxide, has recovered the conjugated structure of big π key on graphene sheet layer to a certain extent, Improve the electric conductivity of material；On the other hand, under high temperature and spontaneous high pressure effect, hydrone is inserted into graphite oxide thiazolinyl Between graphene oxide lamella in thin film, thus cause between lamella, forming abundant hole, it is to avoid the stone that reduction produces Occur closely to stack phenomenon again between ink alkene lamella, it is provided that high-specific surface area and high porous volume, improve its chemical property； Meanwhile, the solute in solution hot solution also maintains the effect that graphene-based membrane structure is stable, can be described as membrane structure Stabilizer.Specifically, use water as medium if adopted, graphene oxide base film is carried out common hydrothermal treatment consists, by There is strong electrostatic repulsion between oxygen-containing functional group electronegative on graphene oxide lamella, insert at hydrone Under release effect between graphene sheet layer, graphene sheet layer can disintegrate, and loses original membrane structure；On the contrary, as Fruit uses acid solution hot solution, and graphene oxide base film carries out solution heat treatment, oxygen-containing on graphene oxide lamella The negative charge that functional group is carried is because of same H+In conjunction with and reduce, the electrostatic repulsion between negative charge weakens, and between lamella π-π sucking action rise to mastery reaction, so separate trend and stable trend reach dynamic equilibrium, can produce The hole of sheet interlayer, also can make thin film keep completely in solution thermal process, be unlikely to because of hydrone insert graphene sheet layer it Between release effect and make thin film disintegrate, the graphene-based thin film of gained shows obvious metallic luster；If employing alkali The solution hot solution of property, carries out solution heat treatment, the oxygen-containing functional group on graphene oxide lamella to graphene oxide base film It is adequately ionized, thus electronegative, with there is electrostatic attraction effect between cation positively charged in solution hot solution, sun Ion is embedded between graphene oxide lamella and is connected with each other by graphene oxide lamella by electrostatic attraction effect, so The trend and the stable trend that separate reach dynamic equilibrium, can produce the hole of sheet interlayer, graphene film also can be made molten Liquid thermal process keeps complete, be unlikely to make because hydrone inserts the release effect between graphene sheet layer thin film divide collapse from Analysis；Further, since the cation in alkaline solution hot solution can be embedded between graphene sheet layer, alkaline solution hot solution In the graphene-based thin film that obtains in the graphene sheet layer gap ratio acid solution hot solution of graphene-based thin film that obtains big, because of The graphene-based thin film obtained in this alkaline solution hot solution is thicker, and its pore-size is bigger.For reaching above-mentioned solution heat effect Portfolio effect, the selection of solute in solution hot solution, and suitable solution heat treatment temperature and the time most important.
Use self-supporting porous graphene prepared by the solution hot preparation method of the self-supporting porous graphene base film of the present invention Base film is arranged in parallel and formed by graphene sheet layer high-sequential ground, and doping material with carbon element is embedded between graphene sheet layer , there is the Graphene/doping material with carbon element laminated film of hole in graphene film interlayer, wherein, doping material with carbon element is carbon nanometer A kind of or the most several in pipe, white carbon black, graphite powder, carbon fiber, activated carbon, templated porous carbon, carbide-derived carbon Mixture, Graphene is 1:(0.0002～1 with the mass ratio of doping material with carbon element)；Film thickness is 10nm～1mm；Thin film Area can reach infinitely great in theory, is dependent only on used matrix size and the size of film-forming apparatus；Suitably Solution heat treatment temperature and time conditions under, gained self-supporting porous graphene base film is with the oxygen-containing sense of higher level Group, these surface functional groups can occur quick oxidation-reduction reaction, thus provide Faraday pseudo-capacitance, improve total Compare capacitance values.
The solution hot preparation method of the self-supporting porous graphene base film of the present invention, compared with existing preparation technology, has following Advantage: it is thin that (1) this method uses knife coating, the tape casting, nebulization, spin-coating method or drop-coating to prepare graphite oxide thiazolinyl Film, then uses solution by the use of thermal means to carry out reduction and obtains graphene-based thin film, and technical process is simple, and manufacturing cycle is short, Production efficiency is high, it is easy to accomplish large-scale commercial produces；(2) the solution thermal reduction method that this method uses is with common change Learn method of reducing or thermal reduction method is compared, owing to solution thermal process playing lamella between hydrone insertion graphene sheet layer Release effect, it is possible to avoid stacking phenomenon again between graphene sheet layer, produces abundant hole, institute at graphene film interlayer Obtain graphene-based thin film and there is high specific capacitance and high rate capability；(3) the solution thermal reduction method that this method uses is with common Hydrothermal reduction method is compared, and the solute in solution hot solution can play the effect maintaining graphene-based membrane structure stable, both Create the abundant hole of graphene film interlayer, it also avoid the destruction of membrane structure；(4) this method is by adjusting oxidation stone The concentration of graphene oxide and filming technology parameter in mertenyl aqueous dispersions, it is possible to achieve big from 10nm to 1mm Scope film thickness adjusts.Especially can obtain thickness that other method is difficult to the prepare thick film more than 10 μm easily, from And improve surface density and the energy per unit area density of thin film, it is advantageously implemented the film type electrochemical energy storage of high-energy-density Device；(5) this method is by selecting masking matrix and the size of corresponding film-forming apparatus, can prepare arbitrary area in theory The self-supporting porous graphene base film of size, especially can obtain large-area graphene-based thin film, and be assembled into accordingly Large-area film type electrochemical energy storage device.
Use self-supporting porous graphene prepared by the solution hot preparation method of the self-supporting porous graphene base film of the present invention Base film, compared with existing graphene-based thin film, has the advantage that self-supporting porous graphene prepared by (1) this method Base film possesses good pliability and mechanical strength, can arbitrarily crimp, and can be used for assembling the electrochemical energy storage of special shape Device, such as cylindrical winding type super capacitor etc.；(2) hydrone is made to insert between graphene sheet layer due to solution heat treatment Playing limellar stripping effect, in the self-supporting porous graphene base film that therefore prepared by this method, graphene film interlamellar spacing is relatively big, Having abundant hole between lamella, consequent high-specific surface area and high porous volume provide place and the electricity of charge buildup Solve the passage of liquid transmission, therefore show good chemical property, well should have in terms of ultracapacitor and battery Use prospect；(3) by selecting temperature and the time of solution heat treatment, the self-supporting porous prepared by this method of solution heat treatment Graphene-based thin film is with the oxygen-containing functional group of higher level, and these surface functional groups can occur quick oxidation-reduction anti- Should, thus Faraday pseudo-capacitance is provided, improve total ratio capacitance values；(4) what prepared by this method includes doping material with carbon element Self-supporting porous graphene base film further increase the chemical property of material: doped carbon nanometer pipe, white carbon black, graphite Powder, the self-supporting porous graphene base film of carbon fiber are retaining Faraday pseudo-capacitance same that a large amount of oxygen-containing functional groups provide Time, it is possible to significantly improve the electron conduction of thin film, when the electrode active material of ultracapacitor, both there is high specific capacitance, There is again high rate capability；Dopped activated carbon, templated porous carbon, the self-supporting porous graphene base film of carbide-derived carbon Not only comprise the hole between graphene sheet layer, also comprise activated carbon, that templated porous carbon, carbide-derived carbon provide is abundant Hole, further increases the ratio electric capacity of thin film, has expanded the transmission channel of electrolyte, shown high specific capacitance and high magnification Performance.
The porous graphene based film material of the present invention can be used in the electrochemical energy storage devices such as ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the digital photograph of the graphene oxide film of preparation in test one；
Fig. 2 is scanning electron microscope (SEM) photo on the graphene oxide film surface of preparation in test one；
Fig. 3 is the digital photograph of the graphene film of preparation in test one；
Fig. 4 is the digital photograph after the graphene film bending of preparation in test one；
Fig. 5 is scanning electron microscope (SEM) photo on the graphene film surface of preparation in test one；
Fig. 6 is the ultracapacitor of the graphene film assembling of preparation in test one ratio electric capacity under different electric current densities；
Fig. 7 is the ultracapacitor of the graphene film assembling of preparation in test one equivalent series under different electric current densities Resistance；
Fig. 8 is the digital photograph of the graphene film of preparation in test two；
Fig. 9 is the digital photograph after the graphene film bending of preparation in test two；
Figure 10 is scanning electron microscope (SEM) photo on the graphene film surface of preparation in test two；
Figure 11 is the ultracapacitor of the graphene film assembling of preparation in test two ratio electric capacity under different electric current densities；
Figure 12 is the ultracapacitor of the graphene film assembling of preparation in test two equivalent series under different electric current densities Resistance；
Figure 13 is the digital photograph of the graphene-based thin film of preparation in test three；
Figure 14 is the digital photograph after the graphene-based thin film bending of preparation in test three；
Figure 15 is scanning electron microscope (SEM) photo of the graphene-based film surface of preparation in test three；
Figure 16 is scanning electron microscope (SEM) photo of the graphene-based film sections of preparation in test three；
Figure 17 is the ultracapacitor of the graphene-based thin film assembling of preparation in test three circulation volt under different scanning speed The ratio capacitance-voltage curve that peace Curve transform becomes；
Figure 18 is the ultracapacitor of the graphene-based thin film assembling of preparation in test three ratio electricity under different electric current densities Hold；
Figure 19 is the ultracapacitor of the graphene-based thin film assembling of preparation in test three equivalent string under different electric current densities Connection resistance；
Figure 20 is the digital photograph of the graphene-based thin film of preparation in test four；
Figure 21 is the digital photograph after the graphene-based thin film bending of preparation in test four；
Figure 22 is scanning electron microscope (SEM) photo of the graphene-based film surface of preparation in test four；
Figure 23 is the ultracapacitor of the graphene-based thin film assembling of preparation in test four ratio electricity under different electric current densities Hold；
Figure 24 is the ultracapacitor of the graphene-based thin film assembling of preparation in test four equivalent string under different electric current densities Connection resistance；
Figure 25 is graphene oxide film digital photograph after hydrothermal treatment consists in pure water in contrast test.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes appointing between each detailed description of the invention Meaning combination.
Detailed description of the invention one: the solution hot preparation method of the self-supporting porous graphene base film of present embodiment presses following step Suddenly carry out:
One, it is 0.01mg mL by the concentration of graphite oxide-1～0.5mg mL-1, graphite oxide is added to the water, in frequency It is ultrasonic stripping under the ultrasound condition of 20～100KHz, dispersion 0.5～10h, obtains graphene oxide aqueous dispersions；
Two, under conditions of temperature is 20 DEG C～100 DEG C, graphene oxide aqueous dispersions step one obtained reduces pressure Evaporation or atmospheric evaporation concentrate；
Three, graphene oxide aqueous dispersions step 2 concentrated is at flat base upper berth generated film, by thin after drying at room temperature Film and matrix stripping, obtain graphene oxide film；
Four, it is 0.01mol L by solute concentration-1～20mol L-1It is formulated for the solution of solution heat treatment, wherein said Solute is a kind of or the most several mixture in sulphuric acid, hydrochloric acid, phosphoric acid and boric acid, or solute is potassium hydroxide, hydrogen A kind of or the most several mixture in sodium oxide, Lithium hydrate；The graphene oxide film obtained in step 3 is put into Have in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, will reaction Heat treatment is carried out after still is airtight；Washing the thin film after solution heat treatment to washing liquid is neutrality, obtains self-supporting porous graphene Base film.
The solution hot preparation method of the self-supporting porous graphene base film of present embodiment, compared with existing preparation technology, has Advantages below: (1) this method uses knife coating, the tape casting, nebulization, spin-coating method or drop-coating to prepare graphene oxide Base film, then uses solution by the use of thermal means to carry out reduction and obtains graphene-based thin film, and technical process is simple, manufacturing cycle Short, production efficiency is high, it is easy to accomplish large-scale commercial produces；(2) the solution thermal reduction method that this method uses is with common Chemical reduction method or thermal reduction method compare, owing in solution thermal process, hydrone inserts between graphene sheet layer and plays Limellar stripping effect, it is possible to avoid stacking phenomenon again between graphene sheet layer, produces abundant hole at graphene film interlayer, The graphene-based thin film of gained has high specific capacitance and high rate capability；(3) the solution thermal reduction method that this method uses is with common Hydrothermal reduction method compare, the solute in solution hot solution can play and maintain the stable effect of graphene-based membrane structure, Both create the abundant hole of graphene film interlayer, it also avoid the destruction of membrane structure；(4) this method is aoxidized by adjustment The concentration of graphene oxide and filming technology parameter in Graphene aqueous dispersions, it is possible to achieve big from 10nm to 1mm Scope film thickness adjusts.Especially can obtain thickness that other method is difficult to the prepare thick film more than 10 μm easily, from And improve surface density and the energy per unit area density of thin film, it is advantageously implemented the film type electrochemical energy storage of high-energy-density Device；(5) this method is by selecting masking matrix and the size of corresponding film-forming apparatus, can prepare arbitrary area in theory The self-supporting porous graphene base film of size, especially can obtain large-area graphene-based thin film, and be assembled into accordingly Large-area film type electrochemical energy storage device.
Detailed description of the invention two: present embodiment is the graphite oxide described in step one unlike detailed description of the invention one Preparation method is as follows: adding 120mL mass percentage concentration in dry beaker is the H of 98%2SO4, then by beaker It is placed in ice-water bath, adds 5g graphite and 2.5g NaNO3, stir with the speed of 50～500 revs/min, be gradually added into simultaneously 15g powder KMnO4, under ice-water bath, stirring condition, continue reaction 2h；Beaker is moved into the constant temperature oil bath of 35 ± 1 DEG C Groove continues reaction 2h；After being slowly added to 360mL distilled water under the stirring condition that rotating speed is 50～500 revs/min, control Temperature constant, in 75 DEG C, continues isothermal reaction 1h；Add the distilled water that 1000mL temperature is 40 DEG C, add 50mL matter Amount percentage concentration is the hydrogen peroxide of 30%, then vacuum filtration；Filter cake is cleaned, directly with the hydrochloric acid that mass percentage concentration is 5% Without SO to filtrate4 2-Ion, then use distilled water filtering and washing；Take out filter cake, the air dry oven of 50 DEG C be dried 24h, Obtain graphite oxide.Other is identical with detailed description of the invention one.
SO in present embodiment4 2-Ion can use BaCl2Solution detects.
Detailed description of the invention three: present embodiment decompression described in step 2 unlike detailed description of the invention one or two is steamed Send out be temperature be 40 DEG C～90 DEG C, vacuum be-0.07MPa～-0.1Mpa, rotating speed be 20 revs/min～500 revs/min Decompression rotary evaporation.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment normal pressure described in step 2 unlike detailed description of the invention one or two steams Sending out is the normal heating evaporation under the conditions of temperature is 60 DEG C～100 DEG C.Other is identical with detailed description of the invention one or two.
Detailed description of the invention five: graphite oxide in present embodiment step 2 unlike one of detailed description of the invention one to four The concentration of alkene aqueous dispersions is concentrated into 0.5～200mg mL-1.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: graphite oxide in present embodiment step 2 unlike one of detailed description of the invention one to four The concentration of alkene aqueous dispersions is concentrated into 2～50mg mL-1.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention seven: by step 2 in present embodiment step 3 unlike one of detailed description of the invention one to six The graphene oxide aqueous dispersions concentrated is knife coating in the method for flat base upper berth generated film.Other and specific embodiment party One of formula one to six is identical.
The knife coating of present embodiment is: use manual coating device or automatic spray device, will be concentrated by the scraper at the uniform velocity moved After graphene oxide aqueous dispersions be coated on flat base, the thickness of gained graphene oxide film by scraper and matrix it Between distance regulation and control.
Detailed description of the invention eight: by step 2 in present embodiment step 3 unlike one of detailed description of the invention one to six The graphene oxide aqueous dispersions concentrated is the tape casting in the method for flat base upper berth generated film.Other and specific embodiment party One of formula one to six is identical.
The tape casting of present embodiment is: scraper maintains static, and is positioned at the flat base below scraper under the drive of motor At the uniform velocity moving, the graphene oxide aqueous dispersions after concentrating is coated on flat base, the thickness of gained graphene oxide film Spend and regulated and controled by the distance between scraper and matrix.
Detailed description of the invention nine: by step 2 in present embodiment step 3 unlike one of detailed description of the invention one to six The graphene oxide aqueous dispersions concentrated is nebulization in the method for flat base upper berth generated film.Other and specific embodiment party One of formula one to six is identical.
The nebulization of present embodiment is: use air pressure spray gun, utilizes pressure-air to be atomized by graphene oxide aqueous dispersions, Droplet arrives flat base surface under the promotion of load gas, and deposit, film forming, gained graphene oxide film Thickness is regulated and controled by concentration and the spray time of graphene oxide aqueous dispersions.
Detailed description of the invention ten: by step 2 in present embodiment step 3 unlike one of detailed description of the invention one to six The graphene oxide aqueous dispersions concentrated is spin-coating method in the method for flat base upper berth generated film.Other and specific embodiment party One of formula one to six is identical.
The spin-coating method of present embodiment is: the graphene oxide aqueous dispersions dropping after concentrating is at the flat base of high speed rotating On, utilize the centrifugal force rotating generation that major part graphene oxide aqueous dispersions is thrown away matrix, and make the graphite oxide of residual Alkene aqueous dispersions uniformly spreads out and overlays on flat base, and the thickness of gained graphene oxide film is by graphene oxide aqueous dispersions Concentration and the rotation speed regulating and controlling of flat base.
Detailed description of the invention 11: by step in present embodiment step 3 unlike one of detailed description of the invention one to six The graphene oxide aqueous dispersions that two have concentrated is drop-coating in the method for flat base upper berth generated film.Other be embodied as One of mode one to six is identical.
The drop-coating of present embodiment is: the graphene oxide aqueous dispersions after concentrating drops on flat base, stands one section Making graphene oxide aqueous dispersions spread on flat base after time, the thickness of gained graphene oxide film is by graphite oxide The concentration regulation and control of alkene aqueous dispersions.
Detailed description of the invention 12: present embodiment is unlike one of detailed description of the invention one to ten one described in step 4 The condition of solution heat treatment be that reactor heats 1～24h at 100～170 DEG C.Other is with detailed description of the invention one to ten One of one identical.
Detailed description of the invention 13: present embodiment obtains in step 4 unlike one of detailed description of the invention one to ten two The thickness of self-supporting porous graphene base film be 10nm～1mm；Other and one of detailed description of the invention one to ten two phase With.
The self-supporting porous graphene base film of present embodiment is arranged in parallel and formed by graphene sheet layer high-sequential ground , there is hole in graphene film interlayer；Self-supporting porous graphene base film with oxygen-containing functional group, these surface functional groups Quick oxidation-reduction reaction can occur, thus Faraday pseudo-capacitance is provided, improve total ratio capacitance values；Pellicular front Amass and can reach infinitely great in theory, be dependent only on used matrix size and the size of film-forming apparatus.
Detailed description of the invention 14: the solution hot preparation method of the self-supporting porous graphene base film of present embodiment is by following Step is carried out:
One, it is 0.01mg mL by the concentration of graphite oxide-1～0.5mg mL-1, graphite oxide is added to the water, in frequency It is ultrasonic stripping under the ultrasound condition of 20～100KHz, dispersion 0.5～10h, obtains graphene oxide aqueous dispersions；
Two, in the graphene oxide aqueous dispersions that step one obtains, add doping material with carbon element, be 20～100KHz in frequency Ultrasound condition under ultrasonic disperse 0.5～10h so that each component is uniformly dispersed in water, obtains graphite oxide thiazolinyl moisture Dissipate liquid；
Three, under conditions of temperature is 20 DEG C～100 DEG C, graphite oxide thiazolinyl aqueous dispersions step 2 obtained subtracts Pressure evaporation or atmospheric evaporation, to improve the concentration of each component in graphite oxide thiazolinyl aqueous dispersions；
Four, graphite oxide thiazolinyl aqueous dispersions step 3 concentrated, will after drying at room temperature at flat base upper berth generated film Thin film and matrix stripping, obtain graphene oxide base film；
Five, it is 0.01mol L by solute concentration-1～20mol L-1It is formulated for the solution of solution heat treatment, wherein said Solute is a kind of or the most several mixture in sulphuric acid, hydrochloric acid, phosphoric acid and boric acid；Or solute is potassium hydroxide, hydrogen A kind of or the most several mixture in sodium oxide and Lithium hydrate；The graphene oxide base film obtained in step 4 is put Enter to have in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, will be anti- Heat treatment is carried out after answering still airtight；Washing the thin film after solution heat treatment to washing liquid is neutrality, obtains self-supporting porous graphite Thiazolinyl thin film.
The solution hot preparation method of the self-supporting porous graphene base film of present embodiment, compared with existing preparation technology, has Advantages below: (1) this method uses knife coating, the tape casting, nebulization, spin-coating method or drop-coating to prepare graphene oxide Base film, then uses solution by the use of thermal means to carry out reduction and obtains graphene-based thin film, and technical process is simple, manufacturing cycle Short, production efficiency is high, it is easy to accomplish large-scale commercial produces；(2) the solution thermal reduction method that this method uses is with common Chemical reduction method or thermal reduction method compare, owing in solution thermal process, hydrone inserts between graphene sheet layer and plays Limellar stripping effect, it is possible to avoid stacking phenomenon again between graphene sheet layer, produces abundant hole at graphene film interlayer, The graphene-based thin film of gained has high specific capacitance and high rate capability；(3) the solution thermal reduction method that this method uses is with common Hydrothermal reduction method compare, the solute in solution hot solution can play and maintain the stable effect of graphene-based membrane structure, Both create the abundant hole of graphene film interlayer, it also avoid the destruction of membrane structure；(4) this method is aoxidized by adjustment The concentration of graphene oxide and filming technology parameter in graphene-based aqueous dispersions, it is possible to achieve from 10nm to 1mm Film thickness adjusts on a large scale.Especially can obtain thickness that other method is difficult to the prepare thick film more than 10 μm easily, Thus improve surface density and the energy per unit area density of thin film, it is advantageously implemented the film type electrochemistry storage of high-energy-density Can device；(5) this method is by selecting masking matrix and the size of corresponding film-forming apparatus, can prepare arbitrary face in theory The self-supporting porous graphene base film of long-pending size, especially can obtain large-area graphene-based thin film, and assemble accordingly Become large-area film type electrochemical energy storage device.
Detailed description of the invention 15: present embodiment is the oxidation stone described in step one unlike detailed description of the invention 14 The preparation method of ink is as follows: adding 120mL mass percentage concentration in dry beaker is the H of 98%2SO4, then will Beaker is placed in ice-water bath, adds 5g graphite and 2.5g NaNO3, stir with the speed of 50～500 revs/min, the most gradually Add 15g powder KMnO4, under ice-water bath, stirring condition, continue reaction 2h；Beaker is moved into the constant temperature of 35 ± 1 DEG C Oil bath continues reaction 2h；After being slowly added to 360mL distilled water under the stirring condition that rotating speed is 50～500 revs/min, Control temperature constant, in 75 DEG C, continues isothermal reaction 1h；Add the distilled water that 1000mL temperature is 40 DEG C, add 50mL Mass percentage concentration is the hydrogen peroxide of 30%, then vacuum filtration；Filter cake is cleaned with the hydrochloric acid that mass percentage concentration is 5%, Until without SO in filtrate4 2-Ion, then use distilled water filtering and washing；Take out filter cake, be dried in the air dry oven of 50 DEG C 24h, obtains graphite oxide.Other is identical with detailed description of the invention 14.
SO in present embodiment4 2-Ion can use BaCl2Solution detects.
Detailed description of the invention 16: present embodiment is unlike detailed description of the invention 14 or 15 described in step 2 Doping material with carbon element is in CNT, white carbon black, graphite powder, carbon fiber, activated carbon, templated porous carbon, carbide-derived carbon A kind of or the most several mixture, graphene oxide with doping material with carbon element mass ratio be 1:(0.0001～0.5).Other Identical with detailed description of the invention 14 or 15.
Detailed description of the invention 17: institute in present embodiment step 3 unlike one of detailed description of the invention ten four to ten six The reduction vaporization stated be temperature be 40 DEG C～90 DEG C, vacuum be-0.07MPa～-0.1Mpa, rotating speed be 20 revs/min～ The decompression rotary evaporation of 500 revs/min.Other is identical with one of detailed description of the invention ten four to ten six.
Detailed description of the invention 18: institute in present embodiment step 3 unlike one of detailed description of the invention ten four to ten six The atmospheric evaporation stated is the normal heating evaporation under the conditions of temperature is 60 DEG C～100 DEG C.Other with detailed description of the invention 14 to One of 16 identical.
Detailed description of the invention 19: oxygen in present embodiment step 3 unlike one of detailed description of the invention ten four to ten eight In graphite thiazolinyl aqueous dispersions, the concentration of graphene oxide is concentrated into 0.5～200mg mL-1.Other and detailed description of the invention One of ten four to ten eight identical.
Detailed description of the invention 20: oxygen in present embodiment step 3 unlike one of detailed description of the invention ten four to ten eight In graphite thiazolinyl aqueous dispersions, the concentration of graphene oxide is concentrated into 2～50mg mL-1.Other is with detailed description of the invention ten One of four to ten eight identical.
Detailed description of the invention 21: in present embodiment step 4 unlike one of detailed description of the invention ten four to two ten Graphite oxide thiazolinyl aqueous dispersions step 3 concentrated is knife coating in the method for flat base upper berth generated film.Other with One of detailed description of the invention ten four to two ten is identical.
The knife coating of present embodiment is: use manual coating device or automatic spray device, will be concentrated by the scraper at the uniform velocity moved After graphite oxide thiazolinyl aqueous dispersions be coated on flat base, the thickness of gained graphene oxide base film is by scraper and base Distance regulation and control between body.
Detailed description of the invention 22: in present embodiment step 4 unlike one of detailed description of the invention ten four to two ten Graphite oxide thiazolinyl aqueous dispersions step 3 concentrated is the tape casting in the method for flat base upper berth generated film.Other with One of detailed description of the invention ten four to two ten is identical.
The tape casting of present embodiment is: scraper maintains static, and is positioned at the flat base below scraper under the drive of motor At the uniform velocity moving, the graphite oxide thiazolinyl aqueous dispersions after concentrating is coated on flat base, gained graphene oxide base film Thickness by between scraper and matrix distance regulate and control.
Detailed description of the invention 23: in present embodiment step 4 unlike one of detailed description of the invention ten four to two ten Graphite oxide thiazolinyl aqueous dispersions step 3 concentrated is nebulization in the method for flat base upper berth generated film.Other with One of detailed description of the invention ten four to two ten is identical.
The nebulization of present embodiment is: use air pressure spray gun, utilizes pressure-air to be atomized by graphite oxide thiazolinyl aqueous dispersions, Droplet arrives flat base surface under the promotion of load gas, and deposit, film forming, gained graphene oxide base film Thickness by the concentration of graphite oxide thiazolinyl aqueous dispersions and spray time regulation and control.
Detailed description of the invention 24: in present embodiment step 4 unlike one of detailed description of the invention ten four to two ten Graphite oxide thiazolinyl aqueous dispersions step 3 concentrated is spin-coating method in the method for flat base upper berth generated film.Other with One of detailed description of the invention ten four to two ten is identical.
The spin-coating method of present embodiment is: the graphite oxide thiazolinyl aqueous dispersions dropping after concentrating is at the flat board base of high speed rotating On body, utilize the centrifugal force rotating generation that major part graphite oxide thiazolinyl aqueous dispersions is thrown away matrix, and make the oxidation of residual Graphene-based aqueous dispersions uniformly spreads out and overlays on flat base, and the thickness of gained graphene oxide base film is by graphite oxide thiazolinyl The concentration of aqueous dispersions and the rotation speed regulating and controlling of flat base.
Detailed description of the invention 25: in present embodiment step 4 unlike one of detailed description of the invention ten four to two ten Graphite oxide thiazolinyl aqueous dispersions step 3 concentrated is drop-coating in the method for flat base upper berth generated film.Other with One of detailed description of the invention ten four to two ten is identical.
The drop-coating of present embodiment is: the graphite oxide thiazolinyl aqueous dispersions after concentrating drops on flat base, stands one Making graphite oxide thiazolinyl aqueous dispersions spread on flat base after the section time, the thickness of gained graphene oxide base film is by oxygen The concentration regulation and control of graphite thiazolinyl aqueous dispersions.
Detailed description of the invention 26: step 5 unlike one of present embodiment and detailed description of the invention ten four to two 15 Described in the condition of solution heat treatment be that reactor heats 1～24h at 100～170 DEG C.Other and detailed description of the invention One of ten four to two ten five identical.
Detailed description of the invention 27: step 5 unlike one of present embodiment and detailed description of the invention ten four to two 16 In the self-supporting porous graphene base film that obtains comprises doping material with carbon element, wherein said doping material with carbon element is carbon nanometer A kind of or the most several in pipe, white carbon black, graphite powder, carbon fiber, activated carbon, templated porous carbon, carbide-derived carbon Mixture.Other is one of ten four to two ten six identical with detailed description of the invention.
Detailed description of the invention 28: step 5 unlike one of present embodiment and detailed description of the invention ten four to two 17 In in the self-supporting porous graphene base film that obtains, Graphene is 1:(0.0002～1 with the mass ratio of doping material with carbon element).Its It is one of ten four to two ten seven identical with detailed description of the invention.
Detailed description of the invention 29: step 5 unlike one of present embodiment and detailed description of the invention ten four to two 18 In the thickness of self-supporting porous graphene base film that obtains be 10nm～1mm.Other is with detailed description of the invention ten four to two One of 18 identical.
The self-supporting porous graphene base film obtained in present embodiment is arranged in parallel by graphene sheet layer high-sequential ground And formed, doping material with carbon element is embedded between graphene sheet layer, and graphene film interlayer exists the Graphene/doping of hole Material with carbon element laminated film；Self-supporting porous graphene base film is with oxygen-containing functional group, and these surface functional groups can occur soon The oxidation-reduction reaction of speed, thus Faraday pseudo-capacitance is provided, improve total ratio capacitance values；Film size in theory may be used To reach infinitely great, it is dependent only on used matrix size and the size of film-forming apparatus.
By following verification experimental verification beneficial effects of the present invention:
Test one: the solution hot preparation method of the self-supporting porous graphene base film of this test one sequentially includes the following steps:
One, it is 0.1mg mL by the concentration of graphite oxide-1, graphite oxide is added to the water, is the super of 40KHz in frequency Ultrasonic stripping under the conditions of sound, dispersion 1h, obtain graphene oxide aqueous dispersions；
Two, temperature be 80 DEG C, vacuum is-0.09MPa, under conditions of rotating speed is 70 revs/min, step one obtained Graphene oxide aqueous dispersions carry out reduce pressure rotary evaporation, its concentration is concentrated into 20mg mL-1；
Three, graphene oxide aqueous dispersions step 2 concentrated scratches film forming on glass plate matrix, after drying at room temperature By thin film and matrix stripping, obtain graphene oxide film；
Four, preparation 5mol L-1KOH solution as the solution for solution heat treatment；The oxidation that will obtain in step 3 Graphene film is put into be had in teflon-lined reactor, and with can submergence thin film be as the criterion addition solution heat treatment use Solution, by after airtight for reactor at 160 DEG C heat treated 6h；By after solution heat treatment thin film wash to washing liquid in Property, obtain self-supporting porous graphene thin film.
Wherein, in step 3, the spacing controlled between coating device scraper and glass basis is the oxidation obtained during 1.0mm The digital photograph of graphene film is as it is shown in figure 1, graphene oxide film is dark brown brown；Change coating device scraper and glass When spacing between matrix is 0.5mm, the graphene oxide film obtained is sundown, and this explanation is scratched by control The thickness of wet film can obtain the graphene oxide dry film of different-thickness；And the thickest film or thin film, film surface All quite flat smooth.
Fig. 2 is scanning electron microscope (SEM) photo on the graphene oxide film surface of preparation in step 3, it can be seen that thin film Surface is also the most smooth on microcosmic, there is also the bulge-structure of some sheet simultaneously, thin film is described on flat surface Formed by graphene oxide lamella is arranged in parallel, owing to graphene oxide sheet interlayer exists strong electrostatic repulsion, Therefore sheet Coating combination is the tightst, there is large pitch.
Fig. 3 is the digital photograph of graphene film of preparation in test one, it can be seen that molten through in KOH solution Liquid heat treatment, thin film color transition becomes black, illustrates that the graphene oxide in thin film has been partially reduced, changes into part The graphene film of reduction；It addition, compared with the graphene oxide film before reduction, surface has become the most coarse, cloth Full a large amount of folds, the graphene sheet layer illustrated in thin film under solution heat effect occurs the most rugosity, is formed big between lamella Metering-orifice gap.Fig. 4 is the digital photograph after the graphene film bending of preparation in test one, it can be seen that thin film bends 180 ° There is not any destruction in rear structure, illustrates that thin film has good pliability.
Fig. 5 is scanning electron microscope (SEM) photo on the graphene film surface of preparation in test one, it can be seen that composition thin film Graphene sheet layer really occur the most rugosity, therefore sheet interlayer can form a large amount of hole.
The disk of 2 a diameter of 14mm is gone out, as two electrodes, with matter with the graphene film of preparation in test one Measuring the KOH solution that percentage composition is 30% is electrolyte, with polypropylene screen as barrier film, assembles CR2025 type button super Capacitor, and capacitor is carried out electrochemical property test.
The ultracapacitor assembling the graphene film of preparation in test one is carried out under different electric current density between 0～1V Constant current charge-discharge test, thus calculate the ratio electric capacity under different electric current density, as shown in Figure 6.Can from figure Going out, under 0.2A/g electric current density, the electric discharge quality of capacitor is up to 192F/g than electric capacity；When electric current density increases 10 times, When reaching 2A/g, electric discharge still can reach 96F/g than electric capacity.The highest ratio electric capacity shows, exists in this graphene film Abundant hole, therefore has higher specific surface area, it is possible to provide higher electric double layer capacitance, it addition, the stone of partial reduction There is substantial amounts of oxygen-containing functional group in ink alkene surface, quick oxidation-reduction reaction can occur, thus provide extra faraday Fake capacitance.
The ultracapacitor assembling the graphene film of preparation in test one is carried out under different electric current density between 0～1V Constant current charge-discharge test, the ohm voltage drop part of discharge curve calculate the equivalent series electricity under different electric current density Resistance, as shown in Figure 7.During due to low current density, ohm voltage drop is little, and its error is big, it equivalent series electricity calculated Resistance error is the biggest；And when electric current density is bigger, ohm voltage drop, beyond the scope of 1V discharge voltage, now calculates Equivalent series resistance also have bigger error.Therefore, the numerical value only taking 1.5A/g to 5A/g scope is averaged, and obtains Equivalent series resistance is 120.7m Ω g.
Test two: the solution hot preparation method of the self-supporting porous graphene base film of this test two sequentially includes the following steps:
One, it is 0.1mg mL by the concentration of graphite oxide-1, graphite oxide is added to the water, is the super of 40KHz in frequency Ultrasonic stripping under the conditions of sound, dispersion 1h, obtain graphene oxide aqueous dispersions；
Two, temperature be 80 DEG C, vacuum is-0.09MPa, under conditions of rotating speed is 70 revs/min, step one obtained Graphene oxide aqueous dispersions carry out reduce pressure rotary evaporation, its concentration is concentrated into 20mg mL-1；
Three, graphene oxide aqueous dispersions step 2 concentrated scratches film forming on glass plate matrix, after drying at room temperature By thin film and matrix stripping, obtain graphene oxide film；
Four, preparation 5mol L-1Phosphoric acid solution as the solution for solution heat treatment；The oxidation stone that will obtain in step 3 Ink alkene thin film is put into and is had in teflon-lined reactor, and can be as the criterion and add solution heat treatment by submergence thin film Solution, by after airtight for reactor at 160 DEG C heat treated 6h；By after solution heat treatment thin film wash to washing liquid be neutrality, Obtain self-supporting porous graphene thin film.
Fig. 8 is the digital photograph of the graphene film of preparation in test two, it can be seen that through the solution in phosphoric acid solution Heat treatment, thin film color transition becomes black, and demonstrates obvious metallic luster, the graphene oxide in thin film has been described It is partially reduced, changes into the graphene film of partial reduction；It addition, compared with the graphene oxide film before reduction, table Face has become relatively rough, manifests certain fold, and the graphene sheet layer illustrated in thin film under solution heat effect occurs certain Degree rugosity, forms a large amount of hole between lamella.Fig. 9 is that the number after the graphene film bending of preparation in test two shines Sheet, it can be seen that after thin film bends 180 °, structure does not occur any destruction, illustrates that thin film has good pliability.
Figure 10 is scanning electron microscope (SEM) photo on the graphene film surface of preparation in test two, it can be seen that form thin The graphene sheet layer of film occurs a certain degree of rugosity really, and display sheet interlayer forms a large amount of hole.
The disk of 2 a diameter of 14mm is gone out, as two electrodes, with matter with the graphene film of preparation in test two Measuring the KOH solution that percentage composition is 30% is electrolyte, with polypropylene screen as barrier film, assembles CR2025 type button super Capacitor, and capacitor is carried out electrochemical property test.
The ultracapacitor assembling the graphene film of preparation in test two is carried out under different electric current density between 0～1V Constant current charge-discharge test, thus calculate the ratio electric capacity under different electric current density, as shown in figure 11.From figure permissible Finding out, under 0.2A/g electric current density, the electric discharge quality of capacitor is up to 144F/g than electric capacity；When electric current density increases 50 Times, when reaching 10A/g, electric discharge still can reach 55F/g than electric capacity.The highest ratio electric capacity shows, in this graphene film There is abundant hole, therefore there is higher specific surface area, it is possible to provide higher electric double layer capacitance, it addition, partial reduction Graphenic surface there is substantial amounts of oxygen-containing functional group, quick oxidation-reduction reaction can occur, thus extra method is provided Draw fake capacitance.
The ultracapacitor assembling the graphene film of preparation in test two is carried out under different electric current density between 0～1V Constant current charge-discharge test, the ohm voltage drop part of discharge curve calculate the equivalent series electricity under different electric current density Resistance, as shown in figure 12.During due to low current density, ohm voltage drop is little, and its error is big, it equivalent series calculated Resistance error is the biggest.Therefore, the numerical value only taking 1.5A/g to 10A/g scope is averaged, and obtains equivalent series resistance For 55.8m Ω g.
Test three: the solution hot preparation method of the self-supporting porous graphene base film of this test three sequentially includes the following steps:
One, it is 0.1mg mL by the concentration of graphite oxide-1, graphite oxide is added to the water, is the super of 40KHz in frequency Ultrasonic stripping under the conditions of sound, dispersion 1h, obtain graphene oxide aqueous dispersions；
Two, in the graphene oxide aqueous dispersions that step one obtains, CNT is added as doping material with carbon element, graphite oxide Alkene is 1:0.05 with the mass ratio of CNT；Ultrasonic disperse 1h under the ultrasound condition that frequency is 40KHz so that each group Divide and be uniformly dispersed in water, obtain graphite oxide thiazolinyl aqueous dispersions；
Three, temperature be 80 DEG C, vacuum is-0.09MPa, under conditions of rotating speed is 70 revs/min, step 2 obtained Graphite oxide thiazolinyl aqueous dispersions carry out reduce pressure rotary evaporation, the concentration of wherein graphene oxide is concentrated into 20 mg·mL-1；
Four, graphite oxide thiazolinyl aqueous dispersions step 3 concentrated scratches film forming, drying at room temperature on glass plate matrix After by thin film and matrix stripping, obtain graphene oxide base film；
Five, preparation 5mol L-1KOH solution as the solution for solution heat treatment；The oxidation that will obtain in step 4 Graphene-based thin film is put into be had in teflon-lined reactor, and with can submergence thin film be as the criterion addition solution heat treatment Solution, by after airtight for reactor at 160 DEG C heat treated 6h；By after solution heat treatment thin film wash to washing liquid in Neutrality, obtains self-supporting porous graphene base film.
Figure 13 is the digital photograph of the graphene-based thin film of preparation in test three, it can be seen that through in KOH solution Solution heat treatment, thin film color transition becomes black, illustrates that the graphene oxide in thin film has been partially reduced, changes into The graphene-based thin film of partial reduction；It addition, compared with the graphene oxide base film before reduction, surface has become suitable Coarse, be covered with a large amount of fold, the graphene sheet layer that illustrates in thin film under solution heat effect occurs the most rugosity, lamella it Between form a large amount of hole.Figure 14 is the digital photograph after the graphene-based thin film bending of preparation in test three, it can be seen that After thin film bends 180 ° there is not any destruction in structure, illustrates that thin film has good pliability.
Figure 15 is scanning electron microscope (SEM) photo of the graphene-based film surface of preparation in test three, it can be seen that composition The graphene sheet layer of thin film occurs the most rugosity really, and therefore sheet interlayer can form a large amount of hole.
Figure 16 is scanning electron microscope (SEM) photo of the graphene-based film sections of preparation in test three, it can be seen that graphite Alkene lamella high-sequential ground is arranged in parallel thus constitutes graphene-based thin film, and between the most visible graphene sheet layer, existence is enriched Hole, additionally as in figure arrow mark, CNT is embedded between graphene sheet layer.
The disk of 2 a diameter of 14mm is gone out with the graphene-based thin film of preparation in test three, as two electrodes, with Weight/mass percentage composition be the KOH solution of 30% be electrolyte, with polypropylene screen as barrier film, assemble CR2025 type button surpass Level capacitor, and capacitor is carried out electrochemical property test.
The ultracapacitor assembling the graphene-based thin film of preparation in test three carries out different scanning speed between 0～1V Under cyclic voltammetry, electric current is converted into ratio and after electric capacity, obtains ratio capacitance-voltage curve, as shown in figure 17.From figure 17 it can be seen that under relatively low scanning speed, curve is in close proximity to rectangle, at the immediate current of scanning voltage commutation Reindexing immediately, shows extraordinary capacitance characteristic；When scanning speed is up to 500mV/s, curve shape still than Being closer to rectangle, decline less than capacitance, illustrate that this graphene-based thin film has splendid high rate capability, this should be With thin film, there is abundant hole and embed electric conductivity after CNT at graphene film interlayer and significantly improve close pass System；Moreover, it is noted that higher than capacitance at lower voltages, and more relatively low than capacitance under high voltages, and this says This graphene-based thin film bright not only has electric double layer capacitance, and has Faraday pseudo-capacitance, and this is oxygen-containing by graphenic surface Functional group will definitely provide by inverse oxidation-reduction reaction.
The ultracapacitor assembling the graphene-based thin film of preparation in test three carries out different electric current density between 0～1V Under constant current charge-discharge test, thus calculate the ratio electric capacity under different electric current density, as shown in figure 18.Can from figure To find out, under 0.2A/g electric current density, the electric discharge quality of capacitor is up to 195F/g than electric capacity；When electric current density increases 50 times, when reaching 10A/g, electric discharge still can reach 128F/g than electric capacity.The highest ratio electric capacity shows, this is graphene-based Thin film exists abundant hole, therefore there is higher specific surface area, it is possible to provide higher electric double layer capacitance, it addition, portion There is substantial amounts of oxygen-containing functional group in the graphenic surface dividing reduction, quick oxidation-reduction reaction can occur, thus provide volume Outer Faraday pseudo-capacitance.Compared with the pure graphene film of preparation in test one, in this test three, preparation comprises carbon nanometer The graphene-based thin film of pipe shows much better high rate capability, and this is primarily due to the carbon being embedded between graphene sheet layer Nanotube significantly improves the electric conductivity of thin film.
The ultracapacitor assembling the graphene-based thin film of preparation in test three carries out different electric current density between 0～1V Under constant current charge-discharge test, the ohm voltage drop part of discharge curve calculate the equivalent series electricity under different electric current density Resistance, as shown in figure 19.During due to low current density, ohm voltage drop is little, and its error is big, it equivalent series calculated Resistance error is the biggest.Therefore, the numerical value only taking 2A/g to 10A/g scope is averaged, and obtains equivalent series resistance and is 16.5mΩ·g.Compared with the equivalent series resistance of the pure graphene film up to 120.7m Ω g of preparation in test one, this examination Test the equivalent series resistance of the graphene-based thin film comprising CNT of preparation in three to be greatly reduced, illustrate to embed graphene film CNT between Ceng improves the electron conduction of thin film dramatically, realizes high rate capability for graphene-based thin film Provide essential condition.
Test four: the solution hot preparation method of the self-supporting porous graphene base film of this test four sequentially includes the following steps:
One, it is 0.1mg mL by the concentration of graphite oxide-1, graphite oxide is added to the water, is the super of 40KHz in frequency Ultrasonic stripping under the conditions of sound, dispersion 1h, obtain graphene oxide aqueous dispersions；
Two, in the graphene oxide aqueous dispersions that step one obtains, CNT is added as doping material with carbon element, graphite oxide Alkene is 1:0.05 with the mass ratio of CNT；Ultrasonic disperse 1h under the ultrasound condition that frequency is 40KHz so that each group Divide and be uniformly dispersed in water, obtain graphite oxide thiazolinyl aqueous dispersions；
Three, temperature be 80 DEG C, vacuum is-0.09MPa, under conditions of rotating speed is 70 revs/min, step 2 obtained Graphite oxide thiazolinyl aqueous dispersions carry out reduce pressure rotary evaporation, the concentration of wherein graphene oxide is concentrated into 20 mg·mL-1；
Four, graphite oxide thiazolinyl aqueous dispersions step 3 concentrated scratches film forming, drying at room temperature on glass plate matrix After by thin film and matrix stripping, obtain graphene oxide base film；
Five, preparation 5mol L-1Phosphoric acid solution as the solution for solution heat treatment；The oxidation stone that will obtain in step 4 Mertenyl thin film is put into be had in teflon-lined reactor, and with can submergence thin film be as the criterion addition solution heat treatment use Solution, by after airtight for reactor at 160 DEG C heat treated 6h；By after solution heat treatment thin film wash to washing liquid in Property, obtain self-supporting porous graphene base film.
Figure 20 is the digital photograph of the graphene-based thin film of preparation in test four, it can be seen that through in phosphoric acid solution Solution heat treatment, thin film color transition becomes black, and demonstrates obvious metallic luster, the graphene oxide in thin film is described It is partially reduced, has changed into the graphene-based thin film of partial reduction；It addition, with the graphene oxide base film before reduction Comparing, surface has become relatively rough, manifests certain fold, and the graphene sheet layer in thin film under solution heat effect is described Occur a certain degree of rugosity, between lamella, form a large amount of hole.Figure 21 is that in test four, the graphene-based thin film of preparation is curved Digital photograph after folding, it can be seen that after thin film bends 180 °, structure does not occur any destruction, illustrates that thin film has good Good pliability.
Figure 22 is scanning electron microscope (SEM) photo of the graphene-based film surface of preparation in test four, it can be seen that composition The graphene sheet layer of thin film occurs a certain degree of rugosity really, and therefore sheet interlayer can form a large amount of hole.
The disk of 2 a diameter of 14mm is gone out with the graphene-based thin film of preparation in test four, as two electrodes, with Weight/mass percentage composition be the KOH solution of 30% be electrolyte, with polypropylene screen as barrier film, assemble CR2025 type button surpass Level capacitor, and capacitor is carried out electrochemical property test.
The ultracapacitor assembling the graphene-based thin film of preparation in test four carries out different electric current density between 0～1V Under constant current charge-discharge test, thus calculate the ratio electric capacity under different electric current density, as shown in figure 23.Can from figure To find out, under 0.2A/g electric current density, the electric discharge quality of capacitor is up to 176F/g than electric capacity；When electric current density increases 50 times, when reaching 10A/g, electric discharge still can reach 91F/g than electric capacity.The highest ratio electric capacity shows, this is graphene-based thin Film exists abundant hole, therefore there is higher specific surface area, it is possible to provide higher electric double layer capacitance, it addition, part There is substantial amounts of oxygen-containing functional group in the graphenic surface of reduction, quick oxidation-reduction reaction can occur, thus provide extra Faraday pseudo-capacitance.Compared with the pure graphene film of preparation in test two, in this test four, preparation comprises CNT Graphene-based thin film show much better high rate capability, this carbon being primarily due to be embedded between graphene sheet layer is received Mitron significantly improves the electric conductivity of thin film.
The ultracapacitor assembling the graphene-based thin film of preparation in test four carries out different electric current density between 0～1V Under constant current charge-discharge test, the ohm voltage drop part of discharge curve calculate the equivalent series electricity under different electric current density Resistance, as shown in figure 24.During due to low current density, ohm voltage drop is little, and its error is big, it equivalent series calculated Resistance error is the biggest.Therefore, the numerical value only taking 2A/g to 10A/g scope is averaged, and obtains equivalent series resistance and is 19.6mΩ·g.Compared with the equivalent series resistance of the pure graphene film up to 55.8m Ω g of preparation in test two, this test In four, the equivalent series resistance of the graphene-based thin film comprising CNT of preparation is greatly reduced, and illustrates to embed graphene sheet layer Between CNT improve the electron conduction of thin film dramatically, realize high rate capability for graphene-based thin film and carry Supply essential condition.
Test five: the solution hot preparation method of the self-supporting porous graphene base film of this test five sequentially includes the following steps:
One, it is 0.1mg mL by the concentration of graphite oxide-1, graphite oxide is added to the water, is the super of 40KHz in frequency Ultrasonic stripping under the conditions of sound, dispersion 1h, obtain graphene oxide aqueous dispersions；
Two, in the graphene oxide aqueous dispersions that step one obtains, activated carbon is added as doping material with carbon element, graphene oxide It is 1:0.2 with the mass ratio of activated carbon；Ultrasonic disperse 1h under the ultrasound condition that frequency is 40KHz so that each component is at water In be uniformly dispersed, obtain graphite oxide thiazolinyl aqueous dispersions；
Three, temperature be 80 DEG C, vacuum is-0.09MPa, under conditions of rotating speed is 70 revs/min, step 2 obtained Graphite oxide thiazolinyl aqueous dispersions carry out reduce pressure rotary evaporation, the concentration of wherein graphene oxide is concentrated into 20 mg·mL-1；
Four, graphite oxide thiazolinyl aqueous dispersions step 3 concentrated scratches film forming, drying at room temperature on glass plate matrix After by thin film and matrix stripping, obtain graphene oxide base film；
Five, preparation 5mol L-1KOH solution as the solution for solution heat treatment；The oxidation that will obtain in step 4 Graphene-based thin film is put into be had in teflon-lined reactor, and with can submergence thin film be as the criterion addition solution heat treatment Solution, by after airtight for reactor at 160 DEG C heat treated 6h；By after solution heat treatment thin film wash to washing liquid in Neutrality, obtains self-supporting porous graphene base film.
The disk of 2 a diameter of 14mm is gone out with the graphene-based thin film of preparation in test five, as two electrodes, with Weight/mass percentage composition be the KOH solution of 30% be electrolyte, with polypropylene screen as barrier film, assemble CR2025 type button surpass Level capacitor, and capacitor is carried out electrochemical property test.
The ultracapacitor assembling the graphene-based thin film of preparation in test five carries out different electric current density between 0～1V Under constant current charge-discharge test, thus calculate the ratio electric capacity under different electric current density.Under 0.2A/g electric current density, The electric discharge quality of capacitor is up to 212F/g than electric capacity；When electric current density increases 10 times, when reaching 2A/g, electric discharge is than electricity Hold and still can reach 107F/g.The highest ratio electric capacity shows, there is abundant hole, therefore have in this graphene-based thin film There is higher specific surface area, it is possible to provide higher electric double layer capacitance, it addition, the graphenic surface of partial reduction exists substantial amounts of Oxygen-containing functional group, can occur quick oxidation-reduction reaction, thus provide extra Faraday pseudo-capacitance.Meanwhile, Compared with the pure graphene film of preparation in test one, the graphene-based thin film performance comprising activated carbon of preparation in this test five Going out higher electric discharge than electric capacity, this activated carbon being primarily due to be embedded between graphene sheet layer has higher specific surface Long-pending, using the teaching of the invention it is possible to provide higher electric double layer capacitance, Graphene and activated carbon act on jointly, it is provided that electric capacity is compared in higher electric discharge.
Contrast test: contrast test process sequentially includes the following steps:
One, it is 0.1mg mL by the concentration of graphite oxide-1, graphite oxide is added to the water, is the super of 40KHz in frequency Ultrasonic stripping under the conditions of sound, dispersion 1h, obtain graphene oxide aqueous dispersions；
Two, temperature be 80 DEG C, vacuum is-0.09MPa, under conditions of rotating speed is 70 revs/min, step one obtained Graphene oxide aqueous dispersions carry out reduce pressure rotary evaporation, its concentration is concentrated into 20mg mL-1；
Three, graphene oxide aqueous dispersions step 2 concentrated scratches film forming on glass plate matrix, after drying at room temperature By thin film and matrix stripping, obtain graphene oxide film；
Four, the graphene oxide film obtained in step 3 is put into have in teflon-lined reactor, and with energy Submergence thin film is as the criterion addition pure water, by after airtight for reactor at 160 DEG C heat treated 6h；Thin film after hydrothermal treatment consists is washed Washing to washing liquid is neutrality, obtains hydrothermal product.
Figure 25 is graphene oxide film digital photograph after hydrothermal treatment consists in pure water in contrast test, it can be seen that water Hot is the most no longer the shape of thin film, but there occurs disintegrating of graphene sheet layer.This is because at pure water oxygen On functionalized graphene lamella, the negative electrostatic charge repulsive interaction of oxygen-containing functional group is the strongest, and in hydrothermal treatment consists, hydrone inserts Graphene Under release effect between lamella, thin film cannot continue to keep stable structure, disintegrates between graphene sheet layer, occurs Structural rearrangement.
In sum, test one is to solution hot preparation method and the existing preparation of the self-supporting porous graphene base film of test five Technique is compared, and has the advantage that (1) this method uses knife coating to prepare graphene oxide base film, then uses solution By the use of thermal means carries out reduction and obtains graphene-based thin film, and technical process is simple, and manufacturing cycle is short, and production efficiency is high, it is easy to Realize large-scale commercial to produce；(2) the solution thermal reduction method that this method uses is with common chemical reduction method or heat Method of reducing is compared, owing to playing limellar stripping effect between hydrone insertion graphene sheet layer in solution thermal process, it is possible to keep away Exempting to stack phenomenon again between graphene sheet layer, produce abundant hole at graphene film interlayer, the graphene-based thin film of gained has There are high specific capacitance and high rate capability；(3) the solution thermal reduction method that this method uses is compared with common hydrothermal reduction method, Solute in solution hot solution can play the effect maintaining graphene-based membrane structure stable, had both created graphene film interlayer Abundant hole, it also avoid the destruction of membrane structure；(4) this method is by adjusting oxygen in graphite oxide thiazolinyl aqueous dispersions The concentration of functionalized graphene and filming technology parameter, it is possible to achieve the film thickness on a large scale from 10nm to 1mm adjusts. Especially can obtain thickness that other method is difficult to the prepare thick film more than 10 μm easily, thus improve the surface density of thin film And energy per unit area density, it is advantageously implemented the film type electrochemical energy storage device of high-energy-density；(5) this method is led to Cross and select masking matrix and the size of corresponding film-forming apparatus, the self-supporting porous stone of arbitrary area size can be prepared in theory Mertenyl thin film, especially can obtain large-area graphene-based thin film, and be assembled into large-area film type electrification accordingly Learn energy storage device.
Self-supporting prepared by employing test one to the solution hot preparation method of the self-supporting porous graphene base film of test five is many The graphene-based thin film in hole, compared with existing graphene-based thin film, has the advantage that self-supporting prepared by (1) this method is many The graphene-based thin film in hole possesses good pliability and mechanical strength, can arbitrarily crimp, and can be used for assembling the electricity of special shape Chemical energy storage device, such as cylindrical winding type super capacitor etc.；(2) hydrone is made to insert Graphene due to solution heat treatment Limellar stripping effect is played, graphene film interlayer in the self-supporting porous graphene base film that therefore prepared by this method between lamella Away from relatively big, having abundant hole between lamella, consequent high-specific surface area and high porous volume provide charge buildup Place and the passage of electrolyte transmission, therefore show good chemical property, have in terms of ultracapacitor and battery Well application prospect；(3) by selecting the temperature of solution heat treatment and the time of solution heat treatment, this method prepare from Supporting the porous graphene base film oxygen-containing functional group with higher level, these surface functional groups can occur quickly to aoxidize -reduction reaction, thus Faraday pseudo-capacitance is provided, improve total ratio capacitance values；(4) including that prepared by this method is mixed The self-supporting porous graphene base film of miscellaneous material with carbon element further increases the chemical property of material: doped carbon nanometer pipe from Support porous graphene base film while retaining the Faraday pseudo-capacitance that a large amount of oxygen-containing functional groups provide, it is possible to significantly improve The electron conduction of thin film, had both had high specific capacitance when the electrode active material of ultracapacitor, had had again high power forthright Energy；The self-supporting porous graphene base film of dopped activated carbon not only comprises the hole between graphene sheet layer, also comprises activity The abundant hole that charcoal provides, further increases the ratio electric capacity of thin film, has expanded the transmission channel of electrolyte, shows high ratio Electric capacity and high rate capability.

Claims (10)

1. the solution hot preparation method of self-supporting porous graphene base film, it is characterised in that the method sequentially includes the following steps:
One, it is 0.01mg mL by the concentration of graphite oxide-1～0.5mg mL-1, graphite oxide is added to the water, in frequency is Ultrasonic stripping under the ultrasound condition of 20～100KHz, dispersion 0.5～10h, obtain graphene oxide aqueous dispersions；
Two, under conditions of temperature is 20 DEG C～100 DEG C, graphene oxide aqueous dispersions step one obtained reduces pressure Evaporation or atmospheric evaporation concentrate；
Three, graphene oxide aqueous dispersions step 2 concentrated is at flat base upper berth generated film, by thin after drying at room temperature Film and matrix stripping, obtain graphene oxide film；
Four, it is 0.01mol L by solute concentration-1～20mol L-1Being formulated for the solution of solution heat treatment, wherein said is molten Matter is a kind of or the most several mixture in sulphuric acid, hydrochloric acid, phosphoric acid and boric acid；Or solute is potassium hydroxide, hydrogen-oxygen Change a kind of or the most several mixture in sodium, Lithium hydrate；The graphene oxide film obtained in step 3 is put into tool Have in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, by reactor Heat treatment is carried out after airtight；Washing the thin film after solution heat treatment to washing liquid is neutrality, obtains self-supporting porous graphite thiazolinyl Thin film.
The solution hot preparation method of self-supporting porous graphene base film the most according to claim 1, it is characterised in that step In rapid two, the concentration of graphene oxide aqueous dispersions is concentrated into 0.5～200mg mL-1。
The solution hot preparation method of self-supporting porous graphene base film the most according to claim 1 and 2, its feature exists Graphene oxide aqueous dispersions step 2 concentrated in step 3 is blade coating in the method for flat base upper berth generated film Method, the tape casting, nebulization, spin-coating method or drop-coating.
The solution hot preparation method of self-supporting porous graphene base film the most according to claim 1 and 2, its feature exists Condition in the solution heat treatment described in step 4 is that reactor heats 1～24h at 100～170 DEG C.
The solution hot preparation method of self-supporting porous graphene base film the most according to claim 1 and 2, its feature exists The thickness of the self-supporting porous graphene base film obtained in step 4 is 10nm～1mm.
6. the solution hot preparation method of self-supporting porous graphene base film, it is characterised in that the method sequentially includes the following steps:
One, it is 0.01mg mL by the concentration of graphite oxide-1～0.5mg mL-1, graphite oxide is added to the water, in frequency is Ultrasonic stripping under the ultrasound condition of 20～100KHz, dispersion 0.5～10h, obtain graphene oxide aqueous dispersions；
Two, in the graphene oxide aqueous dispersions that step one obtains, add doping material with carbon element, be 20～100KHz in frequency Ultrasound condition under ultrasonic disperse 0.5～10h so that each component is uniformly dispersed in water, obtains graphite oxide thiazolinyl moisture Dissipate liquid；
Three, under conditions of temperature is 20 DEG C～100 DEG C, graphite oxide thiazolinyl aqueous dispersions step 2 obtained subtracts Pressure evaporation or atmospheric evaporation, to improve the concentration of each component in graphite oxide thiazolinyl aqueous dispersions；
Four, graphite oxide thiazolinyl aqueous dispersions step 3 concentrated, will after drying at room temperature at flat base upper berth generated film Thin film and matrix stripping, obtain graphene oxide base film；
Five, it is 0.01mol L by solute concentration-1～20mol L-1Being formulated for the solution of solution heat treatment, wherein said is molten Matter is a kind of or the most several mixture in sulphuric acid, hydrochloric acid, phosphoric acid and boric acid；Or solute is potassium hydroxide, hydrogen-oxygen Change a kind of or the most several mixture in sodium and Lithium hydrate；The graphene oxide base film obtained in step 4 is put into Have in teflon-lined reactor, and the solution of the addition solution heat treatment that is as the criterion with energy submergence thin film, will reaction Heat treatment is carried out after still is airtight；Washing the thin film after solution heat treatment to washing liquid is neutrality, obtains self-supporting porous graphene Base film.
The solution hot preparation method of self-supporting porous graphene base film the most according to claim 6, it is characterised in that step Doping material with carbon element described in rapid two is CNT, white carbon black, graphite powder, carbon fiber, activated carbon, templated porous carbon, carbon A kind of or the most several mixture in compound derived carbon, graphene oxide with the mass ratio of doping material with carbon element is 1:(0.0001～0.5).
8., according to the solution hot preparation method of the self-supporting porous graphene base film described in claim 6 or 7, its feature exists In step 3, in graphite oxide thiazolinyl aqueous dispersions, the concentration of graphene oxide is concentrated into 0.5～200mg mL-1。
9., according to the solution hot preparation method of the self-supporting porous graphene base film described in claim 6 or 7, its feature exists Graphene oxide aqueous dispersions step 3 concentrated in step 4 is blade coating in the method for flat base upper berth generated film Method, the tape casting, nebulization, spin-coating method or drop-coating.
10. according to the solution hot preparation method of the self-supporting porous graphene base film described in claim 6 or 7, its feature The condition being the solution heat treatment described in step 5 is that reactor heats 1～24h at 100～170 DEG C.
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