CN105161310A - Graphene-based composite electrode material and preparation method thereof - Google Patents
Graphene-based composite electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a graphene-based composite electrode material. The composite electrode material comprises a graphene base body and a polymer component. The graphene base body has a three-dimensional porous structure formed by self assembling of a laminated structure of a graphene derivative in an overlap joint, wherein the porosity is 10% to 95%. The porous structure of the graphene base body is filled with the polymer component and in-situ polymerization of the polymer component and the graphene base body is realized. In addition, the invention also provides a manufacturing method of the graphene-based composite electrode material.
Description
Technical field
The present invention relates to the technical field of electrode material for super capacitor and preparation thereof, specifically, graphene-based combination electrode material relating to a kind of high-volume and capacity ratio and preparation method thereof.
Background technology
The Graphene feature that specific area is large, electron conduction is high because having, mechanical property is good and become desirable capacitance material, but the theoretical capacity of Graphene is not high, in graphene-based electrode production process, easily there is stacking phenomenon, cause material specific surface area and ionic conductivity to decline.At present, the preparation of graphene-based electrode mainly through Graphene is modified or and conducting polymer materials forms graphene combination electrode material, thus raising capacitance.
But, because Graphene is relative with the density of conducting polymer materials all lower, make the density of the two composite material formed also lower, cause the specific discharge capacity of composite material and volume and capacity ratio all lower.In addition, existing document also there are some metal oxide based composites of report and some two-dimensional layer thin-film materials have very high volume and capacity ratio.Such as Ti
3c
2and MoS
2the volume and capacity ratio of lamella can reach 900F/cm
3and 700F/cm
3, this density ratio mainly owing to them is higher, and so their specific discharge capacity is relatively low is respectively 245F/g and 280F/g, and if the electrode of these metal oxide based composites does thick, its ion and/or electronics can not effectively transmit; And two-dimensional layer thin-film electrode material is not because have effective ion transfer passage, the thickness of electrode of these two-dimensional layer materials can not be done thick.
Summary of the invention
In view of above content, be necessary graphene-based combination electrode material that a kind of high-volume and capacity ratio is provided and preparation method thereof.
A kind of graphene-based combination electrode material, it comprises graphene base body and polymers compositions.Described graphene base body is overlapped by the lamellar structure self assembly of Graphene derivative to form three-dimensional loose structure, and porosity is 10% ~ 95%.Described polymers compositions is filled in the loose structure of described graphene base body, and with described graphene base body in-situ polymerization.
A preparation method for graphene-based combination electrode material, it comprises the steps:
Graphene derivative solution is carried out hydrothermal treatment consists, obtains the graphene base body with three-dimensional loose structure;
The graphene base body that above-mentioned reaction obtains being immersed in is dissolved with in the solution of polymers compositions, makes the sheet surfaces of described graphene base body adsorb described polymers compositions; Add oxidant subsequently, make, between described polymers compositions and described graphene base body, home position polymerization reaction occurs, obtain graphene composite material;
The graphene composite material obtained by above-mentioned reaction and reducing agent carry out reduction reaction, add washed with de-ionized water, and through vacuum drying treatment, obtain graphene combination electrode material after having reacted.
Compare prior art, the preparation of above-mentioned graphene-based combination electrode material, the graphene base body and polymers compositions with three-dimensional loose structure are carried out home position polymerization reaction, obtain graphene-based composite material, wherein this graphene base body carries out hydrothermal treatment consists by Graphene derivative to obtain, in hydrothermal treatment consists processing procedure, the lamellar structure meeting self assembly of this Graphene derivative is overlapped to form the network configuration of three-dimensional porous, thus achieves the tight assembling of two kinds of low density materials.Further, there is volume contraction through vacuumize in above-mentioned graphene-based composite material, thus form highdensity graphene-based combination electrode material.The graphene-based combination electrode material that the present invention makes has important application in the ultracapacitor of high-volume and capacity ratio and high-quality specific capacity, it can not only provide good Electronic Mail Network and ion transfer passage, and the thickness of electrode plates can also be made to be increased.
Accompanying drawing explanation
Fig. 1 is the pictorial diagram before the graphene composite material of embodiment 1 preparation is dried.
Fig. 2 is the scintigram before the graphene composite material of embodiment 1 preparation is dried.
Fig. 3 is the pictorial diagram after the graphene composite material of embodiment 1 preparation is dried.
Fig. 4 is the scintigram after the graphene composite material of embodiment 1 preparation is dried.
Embodiment
Graphene combination electrode material of the present invention, it contains graphene composite material and auxiliary element.This graphene composite material comprises graphene base body and polymers compositions.Described graphene base body has three-dimensional porous structure, and this graphene base body is overlapped by the lamellar structure self assembly of Graphene derivative to form, and porosity is 10% ~ 95%.Described polymers compositions is for filling the pore structure of described graphene base body, and it aggregates into graphene composite material by situ aggregation method and described graphene base body.
Understandable, in order to allow described polymers compositions and described graphene base body overlap crosslinked more fully, this Graphene derivative preferably has the functionalization graphene containing oxygen functional group.This Graphene derivative is selected from least one in graphene oxide, modified graphene.The sheet number of plies of described Graphene derivative is 1 ~ 1000, and planar dimension radius is 1nm ~ 1cm.
In an embodiment of the present invention, this Graphene derivative preferential oxidation Graphene.
Described polymers compositions is that polymer monomer is or/and polymer.Described polymer monomer is selected from least one in thiophene, pyrroles, aniline.Described polymer is selected from least one in polythiophene, polypyrrole, polyaniline.
In an embodiment of the present invention, described polymers compositions is film like structures, and described polymers compositions can grow along the sheet surfaces of described Graphene derivative, and is connected by chemical bond between described graphene base body with described polymers compositions.
Understandable, this auxiliary element is such as conductive agent.Described helper component is selected from least one in conductive black, carbon nano-tube, super conductive carbon, Ketjen black, electrically conductive graphite.The mass percentage of this auxiliary element in described graphene-based combination electrode material is less than or equal to 0.2wt%.
The thickness of described graphene-based combination electrode material is 10 μm ~ 400 μm, and the mass fraction in described graphene-based combination electrode material shared by graphene base body is 20% ~ 99%.
The preparation method of graphene combination electrode material of the present invention, it comprises the steps:
(1) graphene base body is prepared.
Graphite derivative joined in deionized water, under ice-water bath, ultrasonic disperse obtains Graphene derivative solution.
Preferably, this Graphene derivative is selected from graphene oxide.
Graphene derivative solution good for ultrasonic disperse is put in water heating kettle and carries out hydrothermal treatment consists, obtain the graphene base body with three-dimensional porous structure.
It will be appreciated by those skilled in the art that, the lamellar structure self assembly that hydrothermal treatment consists is conducive to Graphene derivative is overlapped to form three-dimensional porous network configuration, and thus obtained graphene base body has higher specific area and a large amount of oxygen-containing functional groups, therefore be conducive to polymers compositions and be adsorbed onto Graphene derivative sheet surfaces, and described polymers compositions can be made along the superficial growth of Graphene derivative lamella, to realize effective compound of graphene base body and polymers compositions, thus obtain graphene composite material.In addition, because graphene base body has three-dimensional porous network configuration, can provide good ion transfer passage and Electronic Mail Network, and the thickness of electrode utilizing described graphene composite material to prepare can reach 400 μm, can meet the demand of electrochemical energy storing device practical application.
The temperature of hydrothermal treatment consists is 90 DEG C ~ 200 DEG C.
Preferably, the temperature of hydrothermal treatment consists is 180 DEG C.
The time of hydrothermal treatment consists is 2-24 hour.
Preferably, the time of hydrothermal treatment consists is 6 hours.
(2) graphene composite material is prepared.
Above-mentioned obtained graphene base body being immersed in is dissolved with in the hydrochloric acid solution of polymers compositions, add oxidant subsequently, make polymerization reaction take place between described polymers compositions, between described polymers compositions and described graphene base body, obtain graphene composite material.
Described oxidant is selected from the one in ferric trichloride, hydrogen peroxide, potassium bichromate, aluminate, ammonium persulfate.
Preferably, described oxidant is selected from ammonium persulfate.
Described polymers compositions be polymer monomer or/and polymer, described polymer monomer is selected from least one in thiophene, pyrroles, aniline, and described polymer is selected from least one in polythiophene, polypyrrole, polyaniline.
Preferably, polymers compositions is selected from polymer monomer, the preferred aniline of this polymer monomer.
In an embodiment of the present invention, the concentration of described polymers compositions is 0.013-0.32mol/L.
Preferably, the concentration of described polymers compositions is 0.16mol/L.
In an embodiment of the present invention, described graphene base body soak time is 0.5-24 hour.
Preferably, described graphene base body soak time is 12 hours.
In an embodiment of the present invention, the time of polymerization reaction is 1-24 hour.
Preferably, the time of polymerization reaction is 2 hours.
The mol ratio of oxidant and polymers compositions is 1:1 ~ 8:1.
Preferably, the mol ratio of described oxidant and polymers compositions is 4:1.
(3) graphene combination electrode material is prepared.
The graphene composite material obtain above-mentioned reaction and excessive reducing agent carry out reduction reaction, add washed with de-ionized water after having reacted, and in vacuum drying chamber dry 24 hours, obtain high-density graphite alkene/polyaniline composite electrode material.
Those skilled in the art can understand, and owing to having capillarity between graphene base body and hydrone, can impel whole graphene composite material, in vacuum drying process, volume contraction occurs, thus form a highdensity electrode material.
In an embodiment of the present invention, the time of reduction reaction is 1-12 hour.
Preferably, the time of reduction reaction is 4 hours.
It will be appreciated by those skilled in the art that, the time of vacuum drying treatment is not limited to 24 hours, when keeping constancy of volume in the process of graphene composite material in vacuum drying treatment prepared, can stop vacuum drying treatment.Preferably, the time of vacuum drying treatment is 24 hours.
The temperature of described vacuum drying treatment is 50-60 DEG C.
Preferably, the temperature of described vacuum drying treatment is 55 DEG C.
Described reducing agent is selected from the one in hydrazine hydrate, hydroiodic acid, natrium citricum, sodium hydrogensulfite.
Preferably, described reducing agent is selected from hydrazine hydrate or hydroiodic acid.
Below by specific embodiment and above-mentioned accompanying drawing, the present invention is described in further detail, and following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
In an embodiment of the present invention, polymers compositions is selected from aniline monomer; Graphene derivative is selected from graphene oxide; Oxidant is selected from ammonium persulfate; Reducing agent is selected from hydroiodic acid or hydrazine hydrate.
Embodiment 1
(1) three-dimensional porous graphene base body is prepared.
The graphite oxide taking 170mg joins in 85mL deionized water, and under ice-water bath, ultrasonic disperse obtains the graphene oxide solution of 2mg/mL.The graphene oxide water solution of above-mentioned obtained homogeneous dispersion is placed in the hydrothermal reaction kettle of 100mL, then hydrothermal reaction kettle is put into the Muffle furnace constant temperature 6h of temperature 180 DEG C, obtain three-dimensional porous graphene base body.
(2) grapheme/polyaniline composite material is prepared.
What the graphene base body that above-mentioned reaction obtains is immersed in 20mL1mol/L is dissolved with 12h in the hydrochloric acid solution of aniline monomer, and the concentration of described aniline monomer is 0.16mol/L.The graphene base body being adsorbed with aniline monomer is immersed in the hydrochloric acid solution being dissolved with ammonium persulfate again and reacts 2h, obtain grapheme/polyaniline composite material.The mol ratio of described ammonium persulfate and described aniline monomer is 4:1.
(3) graphene/polyaniline combination electrode material is prepared.
The grapheme/polyaniline composite material above-mentioned reaction obtained carries out reduction reaction with excessive hydroiodic acid, uses washed with de-ionized water after having reacted.Finally dry 24h in vacuum drying chamber, obtains high-density graphite alkene/polyaniline composite electrode material.
See also Fig. 1-4, compare pictorial diagram and the scintigram thereof of graphene composite material oven dry front and back prepared by embodiment 1, can find out that the volume after the oven dry of described graphene composite material obviously shrinks and (narrow down to about 70mm by original highly about 270mm, diameter is about 200mm and is reduced into about 50mm), this is owing to having capillarity between graphene base body and hydrone, impel whole graphene composite material, in vacuum drying process, volume contraction occurs, thus form a high density material.
Embodiment 2
(1) three-dimensional porous graphene base body is prepared.
The graphite oxide taking 170mg joins in 85mL deionized water, and under ice-water bath, ultrasonic disperse obtains the graphene oxide solution of 2mg/mL.The graphene oxide water solution of above-mentioned obtained homogeneous dispersion is placed in the hydrothermal reaction kettle of 100mL, then hydrothermal reaction kettle is put into the Muffle furnace constant temperature 6h of temperature 180 DEG C, obtain three-dimensional grapheme matrix.
(2) grapheme/polyaniline composite material is prepared.
What the graphene base body that above-mentioned reaction obtains is immersed in 1mol/L is dissolved with 12h in the hydrochloric acid solution of aniline monomer, and the concentration of described aniline monomer is 0.013mol/L.The graphene base body being adsorbed with aniline monomer is immersed in the hydrochloric acid solution being dissolved with ammonium persulfate again and reacts 2h, obtain grapheme/polyaniline composite material.The mol ratio of described ammonium persulfate and aniline monomer is 4:1.
(3) graphene/polyaniline combination electrode material is prepared.
The grapheme/polyaniline composite material above-mentioned reaction obtained carries out reduction reaction with excessive hydroiodic acid, uses washed with de-ionized water after having reacted.Finally dry 24h in vacuum drying chamber, obtains high-density graphite alkene/polyaniline composite electrode material.
Embodiment 3
(1) three-dimensional porous graphene base body is prepared.
The graphite oxide taking 170mg joins in 85mL deionized water, and under ice-water bath, ultrasonic disperse obtains the graphene oxide solution of 2mg/mL.The graphene oxide water solution of above-mentioned obtained homogeneous dispersion is placed in the hydrothermal reaction kettle of 100mL, then Muffle furnace constant temperature 6h hydrothermal reaction kettle being put into temperature 180 DEG C obtains three-dimensional grapheme matrix.
(2) grapheme/polyaniline composite material is prepared.
What the graphene base body that above-mentioned reaction obtains is immersed in 20mL1mol/L is dissolved with 12h in the hydrochloric acid solution of aniline monomer, and the concentration of described aniline monomer is 0.16mol/L.The graphene base body being adsorbed with aniline monomer is immersed in the hydrochloric acid solution being dissolved with ammonium persulfate again and reacts 2h, obtain grapheme/polyaniline composite material.The mol ratio of described ammonium persulfate and aniline monomer is 1:1.
(3) graphene/polyaniline combination electrode material is prepared.
The grapheme/polyaniline composite material above-mentioned reaction obtained carries out reduction reaction with excessive hydroiodic acid, uses washed with de-ionized water after having reacted.Finally dry 24h in vacuum drying chamber, obtains high-density graphite alkene/polyaniline composite electrode material.
Embodiment 4
(1) three-dimensional porous graphene base body is prepared.
The graphite oxide taking 170mg joins in 85mL deionized water, and under ice-water bath, ultrasonic disperse obtains the graphene oxide solution of 2mg/mL.The graphene oxide water solution of above-mentioned obtained homogeneous dispersion is placed in the hydrothermal reaction kettle of 100mL, then Muffle furnace constant temperature 6h hydrothermal reaction kettle being put into temperature 180 DEG C obtains three-dimensional grapheme matrix.
(2) grapheme/polyaniline composite material is prepared.
What the graphene base body that above-mentioned reaction obtains is immersed in 20mL1mol/L is dissolved with 30min in the hydrochloric acid solution of aniline monomer, and the concentration of described aniline monomer is 1mol/L.The graphene base body being adsorbed with aniline monomer is immersed in the hydrochloric acid solution being dissolved with ammonium persulfate again and reacts 2h, obtain grapheme/polyaniline composite material.The mol ratio of described ammonium persulfate and aniline monomer is 4:1.
(3) graphene/polyaniline combination electrode material is prepared.
The grapheme/polyaniline composite material above-mentioned reaction obtained carries out reduction reaction with excessive hydroiodic acid, uses washed with de-ionized water after having reacted.Finally dry 24h in vacuum drying chamber, obtains high-density graphite alkene/polyaniline composite electrode material.
Comparative example
(1) three-dimensional porous graphene base body is prepared.
The graphite oxide taking 170mg joins in 85mL deionized water, and under ice-water bath, ultrasonic disperse obtains the graphene oxide solution of 2mg/mL.The graphene oxide water solution of above-mentioned obtained homogeneous dispersion is placed in the hydrothermal reaction kettle of 100mL, then Muffle furnace constant temperature 6h hydrothermal reaction kettle being put into temperature 180 DEG C obtains three-dimensional grapheme matrix.
(2) grapheme/polyaniline composite material is prepared.
What the graphene base body that above-mentioned reaction obtains is immersed in 20mL1mol/L is dissolved with 12h in the hydrochloric acid solution of aniline monomer, and the concentration of described aniline monomer is 0.16mol/L.The graphene base body being adsorbed with aniline monomer is immersed in the hydrochloric acid solution being dissolved with ammonium persulfate again and reacts 2h, obtain grapheme/polyaniline composite material.The mol ratio of described ammonium persulfate and aniline monomer is 4:1.
(3) graphene/polyaniline combination electrode material is prepared.
The grapheme/polyaniline composite material above-mentioned reaction obtained reduces with excessive hydroiodic acid, and reaction, uses washed with de-ionized water after having reacted.Finally dry 24h in freeze drier, obtains graphene/polyaniline combination electrode material.
Performance test
The mass fraction that graphene/polyaniline combination electrode material prepared by embodiment 1-4 and comparative example is shared in described graphene/polyaniline combination electrode material to density, thickness and polyaniline is respectively tested, and test result is as shown in following table one.
Table one
As shown in Table 1, the density that the graphene/polyaniline combination electrode material that prepared by embodiment 1-4 records is higher than 1.3g/cm
3.Therefore, test result illustrates and utilizes graphene/polyaniline combination electrode material preparation method of the present invention can obtain highdensity electrode material.The density that graphene/polyaniline combination electrode material prepared by comparative example records is 0.7g/cm
3.Therefore, test result illustrates that its density of graphene/polyaniline combination electrode material that grapheme/polyaniline composite material utilizes vacuum drying treatment to obtain is relatively high.
Graphene/polyaniline combination electrode material prepared by embodiment 1-4 and comparative example is ground respectively, fully pulverize last, add graphene/polyaniline combination electrode material, helper component and binding agent respectively, and respectively according to mass ratio be 90:5:5 mixing, and in alcohol solvent ultrasonic disperse.Described binding agent is such as polytetrafluoroethylene (PTEE).Then rolled circular pole piece to be respectively pressed on stainless (steel) wire and to carry out electro-chemical test, also namely test its specific discharge capacity and volume and capacity ratio respectively, test result is as shown in following table two.Attention: above performance test is that thickness that graphene/polyaniline combination electrode material embodiment 1-4 and comparative example prepared makes electrode plates is 35 μm and tests, the thickness that the graphene/polyaniline combination electrode material simultaneously prepared embodiment 1 makes electrode plates is 200 μm to be tested.
Table two
As shown in Table 2, the specific discharge capacity that graphene/polyaniline combination electrode material prepared by embodiment 1 and comparative example records is the same is 550F/g, the specific capacity that the volume and capacity ratio that right embodiment 1 records records apparently higher than comparative example.Therefore, test result illustrate grapheme/polyaniline composite material its specific discharge capacity of graphene/polyaniline combination electrode material of utilizing vacuum drying treatment to obtain and volume and capacity ratio relatively high.
The graphene/polyaniline combination electrode material prepared according to embodiment 1 method forms electrode plates, and when the thickness of electrode plates is 200 μm, the specific discharge capacity of electrode still has 335Fg
-1, volume and capacity ratio is 400Fcm
-3.Therefore, the graphene/polyaniline combination electrode material that prepared by the present invention has better ion transmission performance and electric conductivity.
Table three
Note list of references specifying information is as follows:
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Table three illustrates specific discharge capacity and the volume and capacity ratio value of other material with carbon element of reporting and C-base composte material on graphene combination electrode material and document prepared by embodiments of the invention 1.As can be seen from above-mentioned table, the density of the material with carbon element that list of references [3], [4] are reported is relatively high, and its volume and capacity ratio reaches 900F/cm respectively
3and 442F/cm
3, so the specific discharge capacity of its correspondence is relatively low is respectively 245F/g
3and 130F/g
3, this is mainly higher owing to the material with carbon element density ratio selected.In addition, the specific discharge capacity of C-base composte material reported of list of references [9] and volume and capacity ratio reach 790F/g respectively
3and 205F/cm
3, so its density is relatively low is 0.26g/cm
3.Show from above-mentioned comparing, its density of carbon-based composite electrode material prepared by the present invention is relatively high, and specific discharge capacity and volume and capacity ratio are also relatively high.Therefore, the present invention passes through the in-situ polymerization of more low-density three-dimensional porous graphene base body and polymers compositions, and adopt vacuum drying treatment can obtain the electrode material of high density, high-volume and capacity ratio and high-quality volume, it has important application in ultracapacitor, good Electronic Mail Network and ion transfer passage can not only be provided, when the thickness of electrode plates can also be made to increase, still there is preferable quality specific capacity and volume and capacity ratio.
Above-described embodiment is the present invention's preferably execution mode, but embodiments of the present invention are not restricted to the described embodiments, and above execution mode is only for explaining claims.Right protection scope of the present invention is not limited to specification.Anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, the change that can expect easily or replacement, be included within protection scope of the present invention.
Claims (12)
1. a graphene-based combination electrode material, comprises graphene base body and polymers compositions, it is characterized in that, described graphene base body is overlapped by the lamellar structure self assembly of Graphene derivative to form three-dimensional loose structure, and porosity is 10% ~ 95%; Described polymers compositions is filled in the loose structure of described graphene base body, and with described graphene base body in-situ polymerization.
2. a kind of graphene-based combination electrode material as claimed in claim 1, be is characterized in that, be connected between described graphene base body with described polymers compositions by chemical bond.
3. a kind of graphene-based combination electrode material as claimed in claim 1, it is characterized in that, the thickness of described graphene-based combination electrode material is 10 μm ~ 400 μm, and the mass fraction in described graphene-based combination electrode material shared by graphene base body is 20% ~ 99%.
4. a kind of graphene-based combination electrode material as claimed in claim 1, is characterized in that, the density of described graphene combination electrode material is 1.2 ~ 1.5g/cm
3.
5. a kind of graphene-based combination electrode material as claimed in claim 1, is characterized in that, also comprises binding agent and helper component in described graphene-based combination electrode material, and described binding agent is polytetrafluoroethylene; Described helper component is selected from least one in conductive black, carbon nano-tube, super conductive carbon, Ketjen black, electrically conductive graphite, and the mass percentage of described helper component in described graphene-based combination electrode material is less than or equal to 0.2wt%.
6. a kind of graphene-based combination electrode material as claimed in claim 1, it is characterized in that, described Graphene derivative has containing oxygen functional group, this Graphene derivative is selected from least one in graphene oxide, modified graphene, the sheet number of plies of described Graphene derivative is 1 ~ 1000, and planar dimension radius is 1nm ~ 1cm.
7. a kind of graphene-based combination electrode material as claimed in claim 1, it is characterized in that, described polymers compositions is that polymer monomer is or/and polymer, described polymer monomer is selected from least one in thiophene, pyrroles, aniline, and described polymer is selected from least one in polythiophene, polypyrrole, polyaniline.
8. a kind of graphene-based combination electrode material as claimed in claim 1, it is characterized in that, the concentration of described polymers compositions is 0.013-0.32mol/L, and described polymers compositions is film like structures, and described polymers compositions grows along the sheet surfaces of described Graphene derivative.
9. a preparation method for graphene-based combination electrode material, is characterized in that, comprises the steps:
Graphene derivative solution is carried out hydrothermal treatment consists, obtains the graphene base body with three-dimensional loose structure;
The graphene base body that above-mentioned reaction obtains being immersed in is dissolved with in the solution of polymers compositions, makes the sheet surfaces of described graphene base body adsorb described polymers compositions; Add oxidant subsequently, make, between described polymers compositions and described graphene base body, home position polymerization reaction occurs, obtain graphene composite material;
The graphene composite material obtained by above-mentioned reaction and reducing agent carry out reduction reaction, add washed with de-ionized water, and through vacuum drying treatment, obtain graphene combination electrode material after having reacted.
10. the preparation method of graphene-based combination electrode material as claimed in claim 9, it is characterized in that, the concentration of described polymers compositions is 0.013-0.32mol/L, described polymers compositions is that polymer monomer is or/and polymer, described polymer monomer is selected from least one in thiophene, pyrroles, aniline, and described polymer is selected from least one in polythiophene, polypyrrole, polyaniline.
The preparation method of 11. graphene-based combination electrode materials as claimed in claim 9, it is characterized in that, described oxidant is selected from the one in ferric trichloride, hydrogen peroxide, potassium bichromate, aluminate, ammonium persulfate.
The preparation method of 12. graphene-based combination electrode materials as claimed in claim 9, it is characterized in that, described reducing agent is selected from the one in hydrazine hydrate, hydroiodic acid, natrium citricum, sodium hydrogensulfite.
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| CN105552333A (en) * | 2016-01-01 | 2016-05-04 | 三峡大学 | Preparation method of graphene/silicon/conducting polymer composite anode material |
| CN105543991A (en) * | 2016-01-13 | 2016-05-04 | 郑州大学 | Graphene fibers of helical structure and preparation method and application of graphene fibers |
| CN105543991B (en) * | 2016-01-13 | 2018-06-01 | 郑州大学 | A kind of helical structure graphene fiber and its preparation method and application |
| CN105513826A (en) * | 2016-01-18 | 2016-04-20 | 西安科技大学 | Preparation method of pyrrole-o-toluidine copolymer with porous structure |
| CN105513826B (en) * | 2016-01-18 | 2017-11-17 | 西安科技大学 | A kind of preparation method of loose structure pyrroles o-toluidine copolymer |
| CN105869924A (en) * | 2016-05-06 | 2016-08-17 | 清华大学深圳研究生院 | Preparation method of graphene-based thick and dense electrode |
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| CN110354700A (en) * | 2018-04-11 | 2019-10-22 | 广州墨羲科技有限公司 | A kind of polymer graphite alkene composite filtering film |
| CN109767923A (en) * | 2018-12-24 | 2019-05-17 | 上海交通大学 | Structure-function integration supercapacitor and preparation method thereof |
| CN109801793A (en) * | 2018-12-26 | 2019-05-24 | 中国电子科技集团公司第十八研究所 | Preparation method of graphene/polypyrrole composite material for lithium ion capacitor cathode material |
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