CN103011138B - Graphene with composite pore structure, preparation method thereof and application in super capacitor - Google Patents
Graphene with composite pore structure, preparation method thereof and application in super capacitor Download PDFInfo
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Abstract
The invention provides graphene with a composite pore structure and a preparation method thereof. The lamellar structure of the graphene comprises micropores with pore diameters of 0.1-10nm and macropores with pore diameters of greater than 50nm. Semiconductor oxide nano particles are combined with graphene oxide; in the mixed dispersion liquid thereof, the conjugate microcells of the graphene oxide absorb photons to generate electrons and holes through an ultraviolet irradiation method, and the electrons and holes react with oxygen-containing groups of a non-conjugate area to generate macropores; and the semiconductor oxide nano particles absorb photons to generate electrons and holes, and the graphene oxide of the microcells in direct contact with the semiconductor oxide nano particles is oxidized to generate micropores. When serving as an electrode material, the graphene has a high specific surface area and also can enable electrolyte to enter a narrow space between the lamellas of the graphene to form an effective double layer so as to increase the effective specific surface area of the grapheme, thereby obtaining a device with a high specific capacitance value.
Description
Technical field
The present invention relates to grapheme material and ultracapacitor field, relate in particular to a kind of Graphene, its preparation method and application in ultracapacitor with composite pore structural.
Background technology
Graphene is the Novel Carbon Nanomaterials of the monatomic bed thickness of a kind of two dimension, due to the specific surface area of its superelevation specific conductivity and super large, has been subject to high attention in the last few years in energy storage material field.
Ultracapacitor is a kind of novel energy storage device, and its structure can be considered two blocks of parallel porous electrode plates that are suspended in electrolytic solution.In the time of extra electric field, the ion in electrolytic solution is to porous electrode plate surface transport, and positive charge is assembled on negative plate, and negative charge is assembled on positive plate, thereby forms two double layer capacitors in parallel.Ultracapacitor, with respect to classic flat-plate electrical condenser, has and exceeds 2 energy densities more than order of magnitude; With respect to chemical cell, also there is higher power density, thereby be expected to replace traditional chemical battery, become main flow accumulator system in the future.
Energy density is one of principal element of restriction ultracapacitor large-scale application at present.The energy density of ultracapacitor is mainly determined by effective ratio area and the electrostatic double layer positive and negative charge width between centers of electrode materials.Effective ratio area refers to that unit mass electrode materials can form the value of the surface-area of electrostatic double layer in the time of charging.Electrostatic double layer positive and negative charge width between centers is relevant with composition with concentration of electrolyte, not in the present invention discusses scope.
The theoretical specific surface area of single-layer graphene is 2675m
2/ g.Because existing preparation method is difficult to obtain pure single-layer graphene, the Graphene specific surface area of bibliographical information is generally 100 to 1000m
2within the scope of/g.2011, R.S.Ruoff and co-worker thereof (Y.W.Zhu, et al.Science, 2011,332,1537-1541) develop the technology that micropore (0～10nm) Graphene is prepared in a kind of KOH activation, make the specific surface area of Graphene break through theoretical value, reached 3100m
2/ g.But the ratio capacitance that is assembled into ultracapacitor using this Graphene as electrode materials is not high, be only 166F/g, far below the theory of Graphene than capacitance 550F/g, trace it to its cause is mainly in electrode production process, between graphene film because the model ylid bloom action power having compared with strong is assembled Graphene mutually, the small space that causes electrolytic solution in process of charging to be difficult to enter graphene film interlayer forms effective electric double layer capacitance, although therefore the specific surface of this micropore Graphene is very high, its effective ratio area is but very low.
Therefore, for there being stronger model ylid bloom action power between graphene film, in electrode production process, be difficult to the problem of avoiding Graphene to assemble, need badly and improve existing micropore graphene-structured, make electrolytic solution can enter the small space of graphene film interlayer with the effective ratio area of raising Graphene, thereby improve the ratio capacitance of ultracapacitor.
Summary of the invention
Technical purpose of the present invention is for above-mentioned the deficiencies in the prior art, a kind of Graphene with composite pore structural is provided, in this graphene sheet layer structure, both comprised micropore, comprise again macropore, described micropore size is 0.1nm～10nm, described macropore diameter is more than 50nm, to be preferably 50nm～500nm.
The Graphene of composite pore structural provided by the invention had both retained existing microvoid structure, had high-specific surface area; Also there is macroporous structure simultaneously, the small space that when it is used as electrode materials, electrolytic solution can enter this graphene film interlayer forms effective electrostatic double layer, thereby improve the effective ratio area of Graphene, therefore, while assembling ultracapacitor using this Graphene as electrode materials, can obtain having the device of high specific capacitance value.
There is the Graphene of composite pore structural in order to prepare the present invention, need in graphene sheet layer structure, obtain micropore and macropore.Document: Y.Matsumoto, et al.J.Phys.Chem.C2011, in 115,19280-19286, having recorded graphene oxide can autocatalyzed oxidation under ultraviolet lighting, generates the graphene oxide containing a large amount of macropores.Contriver has used for reference the method, through long-term experimental study, obtain a kind of semiconductor nanoparticle that adopts in conjunction with graphene oxide, in its mixed dispersion liquid, pass through ultraviolet lighting, obtain having concurrently the composite pore structural Graphene of micropore and macropore, concrete preparation comprises the steps:
The preparation of step 1, conductor oxidate or sulfide nano-particle combined oxidation graphene dispersing solution:
By graphene oxide and appropriate conductor oxidate and/or sulfide nano-particle is ultrasonic is dispersed in solvent, under induction stirring, 50～180 DEG C are heated 1～24 hour, make conductor oxidate and/or sulfide nano-particle be dispersed in graphene oxide surface, obtain the dispersion liquid of conductor oxidate and/or sulfide nano-particle combined oxidation Graphene;
Wherein, conductor oxidate and sulfide have following characteristics: energy gap is between 3.1eV～6.2eV, and grain size is 0.5nm～20nm;
Step 2, the dispersion liquid in step 1 is placed under UV-light to illumination reaction 0.5～48 hour under induction stirring state;
Step 3, first, adds excessive mineral acid in the dispersion liquid obtaining after step 2 reaction, and induction stirring is to dissolve conductor oxidate and/or sulfide nano-particle;
Then, filter, join in deionized water with excessive deionized water and washing with alcohol filter residue, taking-up filter residue, with ammoniacal liquor regulator solution PH to 10～12, graphene oxide is re-dispersed in water solution supersound process, obtain composite pore structural graphene oxide dispersion liquid; Or, filter, with joining in organic solvent after excessive deionized water and washing with alcohol filter residue, taking-up filter residue, graphene oxide is re-dispersed in organic solvent solution supersound process, obtain composite pore structural graphene oxide dispersion liquid;
Step 4: the composite pore structural graphene oxide dispersion liquid that adopts hydrothermal reduction method or chemical reduction method reduction step 3 to obtain, makes composite pore structural graphene dispersing solution;
Step 5: the composite pore structural graphene dispersing solution that adopts freeze-drying or filtration method treatment step 4 to obtain, obtains composite pore structural Graphene solid.
In described step 1, when graphene oxide and conductor oxidate and/or sulfide nano-particle is ultrasonic is dispersed in solvent, under stirring heating condition, because the atoms metal in the Sauerstoffatom in graphene oxide and conductor oxidate and/or sulfide nano-particle has very strong electrostatic attraction, make conductor oxidate and/or sulfide nano-particle can be dispersed in graphene oxide surface;
Wherein, conductor oxidate or sulfide include but not limited to ZnO, SnO, TiO
2, SiTiO
3, one or more mixing in ZnS etc.; The mass ratio of conductor oxidate and/or sulfide nano-particle and graphene oxide is preferably 1:200～1:2; In conductor oxidate and/or sulfide nano-particle and graphene oxide dispersion liquid, solvent includes but not limited to water, ethanol, acetone, N-Methyl pyrrolidone, N ' N, the mixing of one or more in-dimethyl formamide.
In described step 2, in the time that the dispersion liquid of conductor oxidate and/or sulfide nano-particle and graphene oxide is carried out to ultraviolet lighting, graphene oxide autocatalysis oxidation, be that graphene oxide conjugation microcell absorbs photon generation electronics and hole, react with the oxy radical in non-conjugated region, generate macropore; Meanwhile, conductor oxidate and/or sulfide nano-particle absorb photon and produce electronics and hole, the graphene oxide of the tiny area that oxidation directly contacts with this conductor oxidate and/or sulfide nano-particle, thus produce micropore;
Wherein, described ultraviolet lamp power is preferably 1～500W.
In described step 3, organic solvent is ethanol, acetone, N-Methyl pyrrolidone, N, N, the combination of one or more in-dimethyl formamide; Mineral acid includes but not limited to one or more the mixing in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; The supersound process time is preferably 1～120 minute.
In described step 4, hydrothermal method is prior art, includes but not limited to adopt document Y.Zhong, et al.Chem.Mater.2009, the method in 21,2950-2956; In described step 4, chemical reduction method is prior art, includes but not limited to adopt document H.C.Schniepp, et al.J.Phys.Chem.B2006, the method in 110,8535 – 8539.
In described step 5, Freeze Drying Technique is prior art, and including but not limited to adopt application number is the disclosed technology of Chinese patent application of CN201010179339.4.
Shown in step 5, filtering technique is prior art, includes but not limited to adopt document D.Li, et al.NatNanotechnol.2008, the method in 3,101-105.
In sum, the invention provides a kind of composite pore structural Graphene and preparation method thereof.In the laminated structure of this composite pore structural Graphene, not only comprise macropore but also comprise micropore, the small space that therefore can also make electrolytic solution enter graphene film interlayer in the time having high-specific surface area in the time that this Graphene uses as electrode materials forms effective electrostatic double layer, thereby improve the effective ratio area of Graphene, therefore, while assembling ultracapacitor taking this Graphene as electrode materials, can obtain having the device of high specific capacitance value.The preparation method of this composite pore structural Graphene adopts the mixture of conductor oxidate and/or sulfide nano particle and graphene oxide, its dispersion liquid is carried out to ultraviolet lighting, pickling, reduction, filter, obtain after dry the Graphene of composite pore structural, and tool has the following advantages:
(1) conductor oxidate and/or sulfide nano particle diameter are controlled and can be dispersed in graphene oxide lamella body structure surface, carry out forming the adjustable microvoid structure in aperture after ultraviolet lighting;
(2) due under ultraviolet lighting, the catalytic oxidation of the autocatalyzed oxidation of graphene oxide and conductor oxidate and/or sulfide nano particle carries out simultaneously, and macropore and micropore can generate simultaneously;
(3) adopt liquid phase environment to carry out ultraviolet lighting, after being uniformly dispersed by conductor oxidate or sulfide nano particle and graphene oxide liquid phase, carry out ultraviolet lighting, multi-disc can be generated simultaneously has the Graphene of composite pore structural, therefore can enhance productivity, reduce production costs, realize scale operation.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of graphene oxide-zinc oxide nano-particle mixture of making of the embodiment of the present invention 1;
Fig. 2 (a) is the transmission electron microscope photo of the composite pore structural Graphene that makes of the embodiment of the present invention 1;
Fig. 2 (b) is the enlarged view of Fig. 2 (a);
Fig. 3 is the atomic force microscopy of the composite pore structural Graphene that makes of the embodiment of the present invention 1;
Fig. 4 is the composite pore structural Graphene that makes of the embodiment of the present invention 1 as the ultracapacitor of electrode materials assembling than electric capacity with sweeping fast variation diagram.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Embodiment 1:
In the present embodiment, have in the graphene sheet layer structure of composite pore structural and both comprised micropore, comprise again macropore, this micropore size is 0.1nm～10nm, and macropore diameter is 50nm～100nm.
The preparation method of the above-mentioned Graphene with composite pore structural is as follows:
(1) after 40ml is contained to ultrasonic the mixing of aqueous dispersion liquid of 6mg zinc oxide nano-particle (median size 4nm) containing the aqueous dispersion liquid of 100mg graphene oxide with 160ml, in the lower 90 DEG C of heating of induction stirring 5 hours, make zinc oxide nano-particle be dispersed in graphene oxide surface, obtain the dispersion liquid of zinc oxide nano-particle combined oxidation Graphene;
(2) dispersion liquid of zinc oxide nano-particle and graphene oxide is placed under 24W ultraviolet lamp to illumination 12 hours under induction stirring state;
(3) in the dispersion liquid obtaining after step (2) reaction, adding 2.1ml massfraction is 37% hydrochloric acid, stir 1 hour, then use millipore filtration vacuum filtration, with after 25ml deionized water wash filter residue 3 times, filter residue is joined to the ammoniacal liquor containing 0.75ml, in the 200ml deionized water of PH=11, supersound process 1 hour in ultrasonic cleaning machine (180W), obtains composite pore structural graphene oxide dispersion liquid;
(4) dispersion liquid step (3) being obtained is transferred in pyroreaction still, and 180 DEG C are reacted 5 hours; By reacted dispersion liquid lyophilize, obtain composite pore structural Graphene solid.
Fig. 1 is transmission electron microscope (TEM) photo of graphene oxide-zinc oxide nano-particle mixture of obtaining of above-mentioned steps (1), and as can be seen from the figure zinc oxide nano-particle is comparatively evenly dispersed in graphene oxide surface.
Fig. 2 is the transmission electron microscope photo of the composite pore structural Graphene that obtains of above-mentioned steps (4), can find out that from Fig. 2 (a) Graphene surface exists the macropore of 50～100nm, can find out that from enlarged view Fig. 2 (b) Graphene surface also exists the micropore of 0.1～10nm.
Fig. 3 is atomic force microscope (AFM) photo of the composite pore structural Graphene that obtains of above-mentioned steps (4), can clearly see micropore and the macropore on Graphene surface from figure.
Using 6M KOH as electrolytic solution, the composite pore structural Graphene that above-mentioned steps (4) is obtained is assembled into ultracapacitor as electrode materials, its than capacitance with sweeping fast variation relation figure as shown in Figure 4, can see low and sweeping under speed, this grapheme material has represented very high ratio capacitance, in the time of 10mV/s, up to 350F/g, this is the high specific capacitance value of grapheme material reported up to now.
Embodiment 2:
In the present embodiment, the graphene sheet layer structure with composite pore structural is identical with the graphene sheet layer structure of composite pore structural in embodiment 1.
The preparation method of the above-mentioned Graphene with composite pore structural is as follows:
(1) after 40ml is contained to ultrasonic the mixing of N-Methyl pyrrolidone phase dispersant liquid of 25mg zinc oxide nano-particle (median size 4nm) containing the N-Methyl pyrrolidone phase dispersant liquid of 100mg graphene oxide with 200ml, in the lower 90 DEG C of heating of induction stirring 5 hours, make zinc oxide nano-particle be dispersed in graphene oxide surface, obtain the dispersion liquid of zinc oxide nano-particle combined oxidation Graphene;
(2) dispersion liquid of zinc oxide nano-particle and graphene oxide is placed under 24W ultraviolet lamp to illumination 35 hours under induction stirring state;
(3) in the dispersion liquid obtaining after step (2) reaction, adding 10ml massfraction is 0.37% hydrochloric acid, stir 1 hour, then use millipore filtration vacuum filtration, after respectively washing filter residue 3 times with 25ml ethanol and 25ml deionized water, filter residue is joined to the ammoniacal liquor containing 0.75ml, in the 200ml deionized water of PH=12, in ultrasonic cleaning machine (180W) ultrasonic 1 hour, obtain composite pore structural graphene oxide dispersion liquid;
(4) dispersion liquid step (3) being obtained is transferred in pyroreaction still, and 180 DEG C are reacted 5 hours.By reacted dispersion liquid lyophilize, also can obtain having the Graphene solid of composite pore structural.
The transmission electron microscope photo of graphene oxide-zinc oxide nano-particle mixture that the transmission electron microscope photo of graphene oxide-zinc oxide nano-particle mixture that above-mentioned steps (1) obtains obtains to step (1) in embodiment 1 is similar, and as can be seen from the figure zinc oxide nano-particle is comparatively evenly dispersed in graphene oxide surface.
The transmission electron microscope photo of the composite pore structural Graphene that above-mentioned steps (4) obtains is similar to the transmission electron microscope photo of the composite pore structural Graphene that in embodiment 1, step (4) obtains, as can be seen from the figure there is the macropore of 50～100nm in Graphene surface, can find out that from enlarged view Graphene surface also exists the micropore of 0.1～10nm.
The atomic force microscopy of the composite pore structural Graphene that above-mentioned steps (4) obtains is similar to the atomic force microscopy of the composite pore structural Graphene that in embodiment 1, step (4) obtains, and can clearly see micropore and the macropore on Graphene surface from figure.
Using 6M KOH as electrolytic solution, the composite pore structural Graphene that above-mentioned steps (4) is obtained is assembled into ultracapacitor as electrode materials, its than capacitance with shown in the Fig. 4 sweeping in fast variation relation figure similar embodiment 1, can see low and sweeping under speed, this grapheme material has represented high specific capacitance value.
Embodiment 3:
In the present embodiment, the graphene sheet layer structure with composite pore structural is identical with the graphene sheet layer structure of composite pore structural in embodiment 1.
The preparation method of the above-mentioned Graphene with composite pore structural is as follows:
(1) after 40ml is contained to ultrasonic the mixing of N-Methyl pyrrolidone phase dispersant liquid of 12.5mg zinc oxide nano-particle (median size 4nm) containing the N-Methyl pyrrolidone phase dispersant liquid of 100mg graphene oxide with 160ml, in the lower 90 DEG C of heating of induction stirring 5 hours, make zinc oxide nano-particle be dispersed in graphene oxide surface, obtain the dispersion liquid of zinc oxide nano-particle combined oxidation Graphene;
(2) dispersion liquid of zinc oxide nano-particle and graphene oxide is placed under 24W ultraviolet lamp to illumination 35 hours under induction stirring state;
(3) in the dispersion liquid obtaining after step (2) reaction, adding 10ml massfraction is 0.37% hydrochloric acid, stir 1 hour, then use millipore filtration vacuum filtration, after respectively washing filter residue 3 times with 25ml ethanol and 25ml deionized water, filter residue is joined to the ammoniacal liquor containing 0.75ml, in the 200ml deionized water of PH=10, in ultrasonic cleaning machine (180W) ultrasonic 1 hour, obtain composite pore structural graphene oxide dispersion liquid;
(4) dispersion liquid step (3) being obtained is transferred in there-necked flask, adds 1ml hydrazine hydrate, and 90 DEG C are reacted 24 hours, by reacted dispersion liquid lyophilize, obtain having the Graphene solid of composite pore structural.
The transmission electron microscope photo of graphene oxide-zinc oxide nano-particle mixture that the transmission electron microscope photo of graphene oxide-zinc oxide nano-particle mixture that above-mentioned steps (1) obtains obtains to step (1) in embodiment 1 is similar, and as can be seen from the figure zinc oxide nano-particle is comparatively evenly dispersed in graphene oxide surface.
The transmission electron microscope photo of the composite pore structural Graphene that above-mentioned steps (4) obtains is similar to the transmission electron microscope photo of the composite pore structural Graphene that in embodiment 1, step (4) obtains, as can be seen from the figure there is the macropore of 50～100nm in Graphene surface, can find out that from enlarged view Graphene surface also exists the micropore of 0.1～10nm.
The atomic force microscopy of the composite pore structural Graphene that above-mentioned steps (4) obtains is similar to the atomic force microscopy of the composite pore structural Graphene that in embodiment 1, step (4) obtains, and can clearly see micropore and the macropore on Graphene surface from figure.
Using 6M KOH as electrolytic solution, the composite pore structural Graphene that above-mentioned steps (4) is obtained is assembled into ultracapacitor as electrode materials, its than capacitance with shown in the Fig. 4 sweeping in fast variation relation figure similar embodiment 1, can see low and sweeping under speed, this grapheme material has represented high specific capacitance value.
Embodiment 4:
In the present embodiment, the graphene sheet layer structure with composite pore structural is identical with the graphene sheet layer structure of composite pore structural in embodiment 1.
The preparation method of the above-mentioned Graphene with composite pore structural is as follows:
(1) after 40ml is contained to ultrasonic the mixing of aqueous dispersion liquid of 6mg zinc sulphide containing 6mg zinc oxide nano-particle (median size 4nm) with 160ml with 160ml containing the aqueous dispersion liquid of 100mg graphene oxide, in the lower 90 DEG C of heating of induction stirring 5 hours, make zinc oxide nano-particle and Zinc sulfide nano-particle be dispersed in graphene oxide surface, obtain the dispersion liquid of zinc oxide/Zinc sulfide nano-particle combined oxidation Graphene;
(2) dispersion liquid of zinc oxide/Zinc sulfide nano-particle combined oxidation Graphene is placed under 24W ultraviolet lamp under induction stirring state to illumination 12 hours;
(3) in the dispersion liquid obtaining after step (2) reaction, adding 1ml massfraction is 37% hydrochloric acid, stir 1 hour, then use millipore filtration vacuum filtration, with after 25ml deionized water wash filter residue 3 times, filter residue is joined to the ammoniacal liquor containing 0.75ml, in the 200ml deionized water of PH=11, in ultrasonic cleaning machine (180W) ultrasonic 1 hour, obtain composite pore structural graphene oxide dispersion liquid;
(4) dispersion liquid step (3) being obtained is transferred in pyroreaction still, and 180 DEG C are reacted 5 hours, by reacted dispersion liquid lyophilize, obtain composite pore structural Graphene solid.
The transmission electron microscope photo of graphene oxide-zinc oxide/Zinc sulfide nano-particle mixture that the transmission electron microscope photo of graphene oxide-zinc oxide nano-particle mixture that above-mentioned steps (1) obtains obtains to step (1) in embodiment 1 is similar, and as can be seen from the figure zinc oxide/Zinc sulfide nano-particle is comparatively evenly dispersed in graphene oxide surface.
The transmission electron microscope photo of the composite pore structural Graphene that above-mentioned steps (4) obtains is similar to the transmission electron microscope photo of the composite pore structural Graphene that in embodiment 1, step (4) obtains, as can be seen from the figure there is the macropore of 50～100nm in Graphene surface, can find out that from enlarged view Graphene surface also exists the micropore of 0.1～10nm.
The atomic force microscopy of the composite pore structural Graphene that above-mentioned steps (4) obtains is similar to the atomic force microscopy of the composite pore structural Graphene that in embodiment 1, step (4) obtains, and can clearly see micropore and the macropore on Graphene surface from figure.
Using 6M KOH as electrolytic solution, the composite pore structural Graphene that above-mentioned steps (4) is obtained is assembled into ultracapacitor as electrode materials, its than capacitance with shown in the Fig. 4 sweeping in fast variation relation figure similar embodiment 1, can see low and sweeping under speed, this grapheme material has represented high specific capacitance value.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any amendments of making within the scope of principle of the present invention, supplement or similar fashion substitute etc., within all should being included in protection scope of the present invention.
Claims (7)
1. the preparation method with the Graphene of composite pore structural, is characterized in that: in described graphene sheet layer structure, both comprised micropore, and comprised again macropore, described micropore size is 0.1nm～10nm, and described macropore diameter is more than 50nm; Preparation method comprises the steps:
Step 1, by graphene oxide and appropriate conductor oxidate nanoparticle and/or sulfide nano-particle is ultrasonic is dispersed in solvent, under induction stirring, 50～180 DEG C are heated 1～24 hour, make conductor oxidate nanoparticle and/or sulfide nano-particle be dispersed in graphene oxide surface, obtain the dispersion liquid of conductor oxidate nanoparticle and/or sulfide nano-particle combined oxidation Graphene;
Wherein, the energy gap of conductor oxidate and sulfide is 3.1eV～6.2eV, and grain size is 0.5nm～20nm;
Step 2, the dispersion liquid in step 1 is placed under UV-light to illumination reaction 0.5～48 hour under induction stirring state;
Step 3, first, adds excessive mineral acid in the dispersion liquid obtaining after step 2 reaction, and induction stirring is to dissolve conductor oxidate nanoparticle and/or sulfide nano-particle;
Then, filter, join in deionized water with excessive deionized water and washing with alcohol filter residue, taking-up filter residue, with ammoniacal liquor regulator solution pH to 10～12, graphene oxide is re-dispersed in water solution supersound process, obtain composite pore structural graphene oxide dispersion liquid; Or, filter, with joining in organic solvent after excessive deionized water and washing with alcohol filter residue, taking-up filter residue, graphene oxide is re-dispersed in organic solvent solution supersound process, obtain composite pore structural graphene oxide dispersion liquid;
Step 4: the composite pore structural graphene oxide dispersion liquid that adopts hydrothermal reduction method or chemical reduction method reduction step 3 to obtain;
Step 5: the composite pore structural graphene dispersing solution that adopts freeze-drying or filtration method treatment step 4 to obtain, obtains composite pore structural Graphene solid.
2. the preparation method of the Graphene with composite pore structural according to claim 1, is characterized in that: described conductor oxidate and sulfide comprise ZnO, SnO, TiO
2, one or more mixing in ZnS.
3. the preparation method of the Graphene with composite pore structural according to claim 1, is characterized in that: in described step 1, the mass ratio of conductor oxidate and/or sulfide and graphene oxide is 1:200～1:2.
4. the preparation method of the Graphene with composite pore structural according to claim 1, it is characterized in that: in described step 1, in the dispersion liquid of conductor oxidate or sulfide nano-particle and graphene oxide, solvent is water, ethanol, acetone, N-Methyl pyrrolidone, N, N, the combination of one or more in-dimethyl formamide.
5. the preparation method of the Graphene with composite pore structural according to claim 1, is characterized in that: in described step 2, ultraviolet lamp power is 1～500W.
6. the preparation method of the Graphene with composite pore structural according to claim 1, is characterized in that: in described step 3, mineral acid comprises one or more the mixing in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid.
7. the preparation method of the Graphene with composite pore structural according to claim 1, is characterized in that: in described step 3, organic solvent is ethanol, acetone, N-Methyl pyrrolidone, N, N, the mixing of one or more in-dimethyl formamide.
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| CN107021475B (en) * | 2017-03-20 | 2019-07-23 | 上海大学 | Ultraviolet light solidifies the method for preparing mesoporous graphene |
| CN110831896A (en) * | 2017-05-05 | 2020-02-21 | 加利福尼亚大学董事会 | Purification and drying of graphene oxide |
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| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
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