CN103011138A - 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, because the specific surface area of its superelevation specific conductivity and super large had been subject to high attention in the energy storage material field in the last few years.
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 the electrolytic solution.When extra electric field, the ion in the electrolytic solution is to porous electrode plate surface transport, and positive charge is assembled at negative plate, and negative charge is assembled at positive plate, thereby forms the double layer capacitor of two parallel connections.Ultracapacitor has the energy density that exceeds more than 2 orders of magnitude with respect to the classic flat-plate electrical condenser; With respect to chemical cell, also have higher power density, thereby be expected to replace the 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 the unit mass electrode materials can form the value of the surface-area of electrostatic double layer when 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
2In/g the scope.2011, R.S.Ruoff and co-worker thereof (Y.W.Zhu, et al.Science, 2011,332,1537-1541) developed a kind of KOH activation preparation micropore (technology of 0～10nm) Graphene, so that the specific surface area of Graphene has broken through theoretical value, reached 3100m
2/ g.Yet it is not this Graphene is high as the ratio capacitance that electrode materials is assembled into ultracapacitor, only be 166F/g, far below the theory of Graphene than capacitance 550F/g, trace it to its cause mainly is in electrode production process, owing to having stronger model ylid bloom action power Graphene is assembled mutually between graphene film, the small space that causes electrolytic solution in the process of charging to be difficult to enter the 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 avoid the problem of Graphene gathering, 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, namely both comprised micropore on this graphene sheet layer structure, comprise again macropore, described micropore size is 0.1nm～10nm, described macropore diameter is more than the 50nm, to be preferably 50nm～500nm.
The Graphene of composite pore structural provided by the invention had both kept existing microvoid structure, had high-specific surface area; Also has simultaneously macroporous structure, the small space that electrolytic solution can enter this graphene film interlayer when it was used as electrode materials forms effective electrostatic double layer, thereby improve the effective ratio area of Graphene, therefore, when this Graphene is assembled ultracapacitor as electrode materials, can access the device with high specific capacitance value.
The Graphene that has composite pore structural in order to prepare the present invention need to obtain micropore and macropore in the graphene sheet layer structure.Document: Y.Matsumoto, et al.J.Phys.Chem.C2011, having put down in writing graphene oxide among 115, the 19280-19286 can autocatalyzed oxidation under ultraviolet lighting, generates the graphene oxide that contains a large amount of macropores.The contriver has used for reference the method, experimental study through long-term obtains a kind of employing semiconductor nanoparticle in conjunction with graphene oxide, passes through ultraviolet lighting in its mixed dispersion liquid, 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:
With graphene oxide and an amount of conductor oxidate and/or sulfide nano-particle ultra-sonic dispersion in solvent, 50～180 ℃ were heated 1～24 hour under induction stirring, make conductor oxidate and/or sulfide nano-particle be dispersed in the 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 the step 1 is placed under the UV-light, illumination reaction is 0.5～48 hour under the induction stirring state;
Step 3, at first adds excessive mineral acid in the dispersion liquid that obtains after step 2 reaction, induction stirring is with dissolving conductor oxidate and/or sulfide nano-particle;
Then, filter, join in the 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 the water solution supersound process, obtain composite pore structural graphene oxide dispersion liquid; Perhaps, filter, with joining in the organic solvent behind excessive deionized water and washing with alcohol filter residue, the taking-up filter residue, graphene oxide is re-dispersed in the 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 the 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 the described step 1, when graphene oxide and conductor oxidate and/or sulfide nano-particle ultra-sonic dispersion in solvent, under the stirring heating condition, because the Sauerstoffatom in the graphene oxide and the atoms metal in conductor oxidate and/or the sulfide nano-particle have very strong electrostatic attraction, make conductor oxidate and/or sulfide nano-particle can be dispersed in the graphene oxide surface;
Wherein, conductor oxidate or sulfide include but not limited to ZnO, SnO, TiO
2, SiTiO
3, one or more the mixing among the ZnS etc.; The mass ratio of conductor oxidate and/or sulfide nano-particle and graphene oxide is preferably 1:200～1:2; Solvent includes but not limited to water, ethanol, acetone, N-Methyl pyrrolidone, N ' N, the mixing of one or more the in-dimethyl formamide in conductor oxidate and/or sulfide nano-particle and the graphene oxide dispersion liquid.
In the described step 2, when the dispersion liquid to conductor oxidate and/or sulfide nano-particle and graphene oxide carries out ultraviolet lighting, the graphene oxide autocatalysis oxidation, be that graphene oxide conjugation microcell absorbs photon generation electronics and hole, oxy radical reaction with non-conjugated zone generates macropore; Simultaneously, conductor oxidate and/or sulfide nano-particle absorb photon and produce electronics and hole, the graphene oxide of the tiny area that oxidation and this conductor oxidate and/or sulfide nano-particle directly contact, thereby generation micropore;
Wherein, described ultraviolet lamp power is preferably 1～500W.
In the described step 3, organic solvent is ethanol, acetone, N-Methyl pyrrolidone, N, N, the combination of one or more the in-dimethyl formamide; Mineral acid includes but not limited to one or more the mixing in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid; The supersound process time is preferably 1～120 minute.
In the described step 4, hydrothermal method is prior art, includes but not limited to adopt document Y.Zhong, et al.Chem.Mater.2009, the method among 21, the 2950-2956; In the 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 among 110,8535 – 8539.
In the 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 the step 5, filtering technique is prior art, includes but not limited to adopt document D.Li, et al.NatNanotechnol.2008, the method among 3, the 101-105.
In sum, the invention provides a kind of composite pore structural Graphene and preparation method thereof.Not only comprise macropore but also comprise micropore on the laminated structure of this composite pore structural Graphene, the small space that therefore can also make electrolytic solution enter the graphene film interlayer when having high-specific surface area when this Graphene uses as electrode materials forms effective electrostatic double layer, thereby improve the effective ratio area of Graphene, therefore, when assembling ultracapacitor take this Graphene as electrode materials, can access the device with 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 ultraviolet lighting, the Graphene of composite pore structural is filtered, obtains after the drying in pickling, reduction, has following advantage:
(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 behind the ultraviolet lighting;
(2) because under ultraviolet lighting, the catalytic oxidation of the autocatalyzed oxidation of graphene oxide and conductor oxidate and/or sulfide nano particle carries out simultaneously, macropore and micropore can generate simultaneously;
(3) adopt liquid phase environment to carry out ultraviolet lighting, be about to carry out ultraviolet lighting after conductor oxidate or sulfide nano particle and graphene oxide liquid phase are uniformly dispersed, can generate simultaneously the Graphene that multi-disc has composite pore structural, therefore can enhance productivity, reduce production costs, realize scale operation.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the graphene oxide that makes of the embodiment of the invention 1-zinc oxide nano-particle mixture;
Fig. 2 (a) is the transmission electron microscope photo of the composite pore structural Graphene that makes of the embodiment of the 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 invention 1;
Fig. 4 is the composite pore structural Graphene that makes of the embodiment of the invention 1 as the ultracapacitor of electrode materials assembling than electric capacity with the variation diagram of sweeping speed.
Embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing, 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 any restriction effect.
Embodiment 1:
In the present embodiment, have on 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 above-mentioned Graphene with composite pore structural is as follows:
(1) 40ml is contained the aqueous dispersion liquid of 100mg graphene oxide and ultrasonic the mixing of aqueous dispersion liquid that 160ml contains 6mg zinc oxide nano-particle (median size 4nm) after, in the lower 90 ℃ of heating of induction stirring 5 hours, make zinc oxide nano-particle be dispersed in the graphene oxide surface, obtain the dispersion liquid of zinc oxide nano-particle combined oxidation Graphene;
(2) dispersion liquid with zinc oxide nano-particle and graphene oxide places under the 24W ultraviolet lamp, and illumination is 12 hours under the induction stirring state;
(3) adding 2.1ml massfraction is 37% hydrochloric acid in the dispersion liquid that obtains after step (2) reaction, stirred 1 hour, then use the millipore filtration vacuum filtration, contain 0.75ml ammoniacal liquor with behind the 25ml deionized water wash filter residue 3 times filter residue being joined, in the 200ml deionized water of PH=11, supersound process is 1 hour in ultrasonic cleaning machine (180W), obtains composite pore structural graphene oxide dispersion liquid;
(4) dispersion liquid that step (3) is obtained is transferred in the pyroreaction still, and 180 ℃ were reacted 5 hours; With reacted dispersion liquid lyophilize, namely obtain composite pore structural Graphene solid.
Fig. 1 is transmission electron microscope (TEM) photo of the graphene oxide that obtains of above-mentioned steps (1)-zinc oxide nano-particle mixture, and as can be seen from the figure zinc oxide nano-particle comparatively is evenly dispersed in the 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) there is the macropore of 50～100nm in the Graphene surface, can find out that from enlarged view Fig. 2 (b) also there is the micropore of 0.1～10nm in the Graphene surface.
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.
With 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 the speed, this grapheme material has represented very high ratio capacitance, up to 350F/g, this is the high specific capacitance value of grapheme material of reporting up to now when 10mV/s.
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 among the embodiment 1.
The preparation method of above-mentioned Graphene with composite pore structural is as follows:
(1) 40ml is contained the N-Methyl pyrrolidone phase dispersant liquid of 100mg graphene oxide and ultrasonic the mixing of N-Methyl pyrrolidone phase dispersant liquid that 200ml contains 25mg zinc oxide nano-particle (median size 4nm) after, in the lower 90 ℃ of heating of induction stirring 5 hours, make zinc oxide nano-particle be dispersed in the graphene oxide surface, obtain the dispersion liquid of zinc oxide nano-particle combined oxidation Graphene;
(2) dispersion liquid with zinc oxide nano-particle and graphene oxide places under the 24W ultraviolet lamp, and illumination is 35 hours under the induction stirring state;
(3) adding 10ml massfraction is 0.37% hydrochloric acid in the dispersion liquid that obtains after step (2) reaction, stirred 1 hour, then use the millipore filtration vacuum filtration, respectively wash behind the filter residue 3 times filter residue joined with 25ml ethanol and 25ml deionized water and contain 0.75ml ammoniacal liquor, 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 that step (3) is obtained is transferred in the pyroreaction still, and 180 ℃ were reacted 5 hours.With reacted dispersion liquid lyophilize, also can obtain having the Graphene solid of composite pore structural.
The transmission electron microscope photo of the graphene oxide that step (1) obtains among the transmission electron microscope photo of the graphene oxide that above-mentioned steps (1) obtains-zinc oxide nano-particle mixture and the embodiment 1-zinc oxide nano-particle mixture is similar, and as can be seen from the figure zinc oxide nano-particle comparatively is evenly dispersed in the graphene oxide surface.
The transmission electron microscope photo of the composite pore structural Graphene that step (4) obtains among the transmission electron microscope photo of the composite pore structural Graphene that above-mentioned steps (4) obtains and the embodiment 1 is similar, as can be seen from the figure there is the macropore of 50～100nm in the Graphene surface, can find out that from enlarged view also there is the micropore of 0.1～10nm in the Graphene surface.
The atomic force microscopy of the composite pore structural Graphene that step (4) obtains among the atomic force microscopy of the composite pore structural Graphene that above-mentioned steps (4) obtains and the embodiment 1 is similar, can clearly see micropore and the macropore on Graphene surface from figure.
With 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 shown in Figure 4 in the fast variation relation figure similar embodiment 1, can see low and sweeping under the speed, this grapheme material has represented the 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 among the embodiment 1.
The preparation method of above-mentioned Graphene with composite pore structural is as follows:
(1) 40ml is contained the N-Methyl pyrrolidone phase dispersant liquid of 100mg graphene oxide and ultrasonic the mixing of N-Methyl pyrrolidone phase dispersant liquid that 160ml contains 12.5mg zinc oxide nano-particle (median size 4nm) after, in the lower 90 ℃ of heating of induction stirring 5 hours, make zinc oxide nano-particle be dispersed in the graphene oxide surface, obtain the dispersion liquid of zinc oxide nano-particle combined oxidation Graphene;
(2) dispersion liquid with zinc oxide nano-particle and graphene oxide places under the 24W ultraviolet lamp, and illumination is 35 hours under the induction stirring state;
(3) adding 10ml massfraction is 0.37% hydrochloric acid in the dispersion liquid that obtains after step (2) reaction, stirred 1 hour, then use the millipore filtration vacuum filtration, respectively wash behind the filter residue 3 times filter residue joined with 25ml ethanol and 25ml deionized water and contain 0.75ml ammoniacal liquor, 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 that step (3) is obtained is transferred in the there-necked flask, adds the 1ml hydrazine hydrate, and 90 ℃ were reacted 24 hours, and with reacted dispersion liquid lyophilize, obtained having the Graphene solid of composite pore structural.
The transmission electron microscope photo of the graphene oxide that step (1) obtains among the transmission electron microscope photo of the graphene oxide that above-mentioned steps (1) obtains-zinc oxide nano-particle mixture and the embodiment 1-zinc oxide nano-particle mixture is similar, and as can be seen from the figure zinc oxide nano-particle comparatively is evenly dispersed in the graphene oxide surface.
The transmission electron microscope photo of the composite pore structural Graphene that step (4) obtains among the transmission electron microscope photo of the composite pore structural Graphene that above-mentioned steps (4) obtains and the embodiment 1 is similar, as can be seen from the figure there is the macropore of 50～100nm in the Graphene surface, can find out that from enlarged view also there is the micropore of 0.1～10nm in the Graphene surface.
The atomic force microscopy of the composite pore structural Graphene that step (4) obtains among the atomic force microscopy of the composite pore structural Graphene that above-mentioned steps (4) obtains and the embodiment 1 is similar, can clearly see micropore and the macropore on Graphene surface from figure.
With 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 shown in Figure 4 in the fast variation relation figure similar embodiment 1, can see low and sweeping under the speed, this grapheme material has represented the 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 among the embodiment 1.
The preparation method of above-mentioned Graphene with composite pore structural is as follows:
(1) 40ml is contained the aqueous dispersion liquid of 100mg graphene oxide and 160ml and contains 6mg zinc oxide nano-particle (median size 4nm) and contain ultrasonic the mixing of aqueous dispersion liquid of 6mg zinc sulphide with 160ml after, in the lower 90 ℃ of heating of induction stirring 5 hours, make zinc oxide nano-particle and Zinc sulfide nano-particle be dispersed in the 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 was placed under the 24W ultraviolet lamp under the induction stirring state illumination 12 hours;
(3) adding 1ml massfraction is 37% hydrochloric acid in the dispersion liquid that obtains after step (2) reaction, stirred 1 hour, then use the millipore filtration vacuum filtration, contain 0.75ml ammoniacal liquor with behind the 25ml deionized water wash filter residue 3 times filter residue being joined, 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 that step (3) is obtained is transferred in the pyroreaction still, and 180 ℃ were reacted 5 hours, and with reacted dispersion liquid lyophilize, obtained composite pore structural Graphene solid.
The transmission electron microscope photo of graphene oxide-zinc oxide that step (1) obtains among the transmission electron microscope photo of the graphene oxide that above-mentioned steps (1) obtains-zinc oxide nano-particle mixture and the embodiment 1/Zinc sulfide nano-particle mixture is similar, and as can be seen from the figure zinc oxide/Zinc sulfide nano-particle comparatively is evenly dispersed in the graphene oxide surface.
The transmission electron microscope photo of the composite pore structural Graphene that step (4) obtains among the transmission electron microscope photo of the composite pore structural Graphene that above-mentioned steps (4) obtains and the embodiment 1 is similar, as can be seen from the figure there is the macropore of 50～100nm in the Graphene surface, can find out that from enlarged view also there is the micropore of 0.1～10nm in the Graphene surface.
The atomic force microscopy of the composite pore structural Graphene that step (4) obtains among the atomic force microscopy of the composite pore structural Graphene that above-mentioned steps (4) obtains and the embodiment 1 is similar, can clearly see micropore and the macropore on Graphene surface from figure.
With 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 shown in Figure 4 in the fast variation relation figure similar embodiment 1, can see low and sweeping under the speed, this grapheme material has represented the high specific capacitance value.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that the above only is specific embodiments of the invention; be not limited to the present invention; all any modifications of in principle scope of the present invention, making, replenish or similar fashion substitutes etc., all should be included within protection scope of the present invention.
Claims (10)
1. Graphene with composite pore structural, it is characterized in that: both comprised micropore on the described graphene sheet layer structure, and comprised again macropore, described micropore size is 0.1nm～10nm, and described macropore diameter is more than the 50nm.
2. according to right 1 described Graphene with composite pore structural, it is characterized in that: described macropore diameter is 50nm～500nm.
3. according to right 1 described preparation method with Graphene of composite pore structural, it is characterized in that: comprise the steps:
Step 1, with graphene oxide and an amount of conductor oxidate nanoparticle and/or sulfide nano-particle ultra-sonic dispersion in solvent, 50～180 ℃ were heated 1～24 hour under induction stirring, make conductor oxidate nanoparticle and/or sulfide nano-particle be dispersed in the 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 the step 1 is placed under the UV-light, illumination reaction is 0.5～48 hour under the induction stirring state;
Step 3, at first adds excessive mineral acid in the dispersion liquid that obtains after step 2 reaction, induction stirring is with dissolving conductor oxidate nanoparticle and/or sulfide nano-particle;
Then, filter, join in the 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 the water solution supersound process, obtain composite pore structural graphene oxide dispersion liquid; Perhaps, filter, with joining in the organic solvent behind excessive deionized water and washing with alcohol filter residue, the taking-up filter residue, graphene oxide is re-dispersed in the 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.
4. require described preparation method with Graphene of composite pore structural according to right 3, it is characterized in that: described conductor oxidate and sulfide comprise ZnO, SnO, TiO
2, SiTiO
3, one or more the mixing among the ZnS.
5. require described preparation method with Graphene of composite pore structural according to right 3, it is characterized in that: in the described step 1, the mass ratio of conductor oxidate and/or sulfide and graphene oxide is 1:200～1:2.
6. require described preparation method with Graphene of composite pore structural according to right 3, it is characterized in that: in the described step 1, solvent is water, ethanol, acetone, N-Methyl pyrrolidone, N in the dispersion liquid of conductor oxidate or sulfide nano-particle and graphene oxide, N, the combination of one or more the in-dimethyl formamide.
7. require described preparation method with Graphene of composite pore structural according to right 3, it is characterized in that: in the described step 2, ultraviolet lamp power is 1～500W.
8. require described preparation method with Graphene of composite pore structural according to right 3, it is characterized in that: in the described step 3, mineral acid comprises one or more the mixing in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
9. require described preparation method with Graphene of composite pore structural according to right 3, it is characterized in that: in the described step 3, organic solvent is ethanol, acetone, N-Methyl pyrrolidone, N, N, the mixing of one or more the in-dimethyl formamide.
10. ultracapacitor, it is characterized in that: electrode materials is the Graphene with composite pore structural described in claim 1 or 2.
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| CN107021475A (en) * | 2017-03-20 | 2017-08-08 | 上海大学 | The method that ultraviolet light solidification prepares mesoporous graphene |
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| US10988383B2 (en) * | 2017-05-05 | 2021-04-27 | The Regents Of The University Of California | Purification and drying of graphene oxide |
| US11787698B2 (en) | 2017-05-05 | 2023-10-17 | The Regents Of The University Of California | Purification and drying of graphene oxide |
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