CN102558772A - Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof - Google Patents
Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN102558772A CN102558772A CN201110419526XA CN201110419526A CN102558772A CN 102558772 A CN102558772 A CN 102558772A CN 201110419526X A CN201110419526X A CN 201110419526XA CN 201110419526 A CN201110419526 A CN 201110419526A CN 102558772 A CN102558772 A CN 102558772A
- Authority
- CN
- China
- Prior art keywords
- sulfonated graphene
- enedioxy thiophene
- graphene composite
- preparation
- composite water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for preparing poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel with a porous structure through supramolecular self-assembly. The method comprises the following steps of: dissolving sodium polystyrene sulfonate and sulfonated graphene in water, stirring, performing ultrasonic dispersion to ensure that the sodium polystyrene sulfonate and the sulfonated graphene are dissolved, adding a 3,4-ethylenedioxythiophene monomer, uniformly stirring, adding polyvalent iron salt, standing at room temperature and reacting to obtain blocky poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel. The poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel with a controllable and porous structure is prepared by using the interaction and electrostatic action of a hydrogen bond and a pi-pi bond among the sulfonated graphene, the sodium polystyrene sulfonate and 3,4-ethylenedioxythiophene through supramolecular self-assembly. The prepared composite hydrogel has high electrical conductivity and mechanical strength, and high specific capacitance and cycle stability in electroactive electrolyte.
Description
Technical field
The present invention relates to the conducting polymer composite material field, be specifically related to electrode of super capacitor and use field of compound material.
Background technology
Performances such as its excellent electricity, optics, redox have been given in conductive polymers particular chemical composition, conjugated structure and unique doping/dedoping behavior.The late nineteen eighties, the conductive polymers with high-voltage window begins to receive people's attention as the electrode active material of ultracapacitor, like polyaniline (PANI), polypyrrole (PPy), Polythiophene, gather benzene etc.Higher than electric capacity with conductive polymers as the pseudo-capacitance device of electrode materials, but specific surface is little, poorly conductive, and material use efficiency is reduced.And the conducting polymer rerum natura is crisp, mechanical strength is low, thereby in doping/dedoping process, can experience swelling, shrinks, breaks or destroy the variation that causes material volume, finally can cause the decay of conductive polymers specific conductivity and cyclical stability.
Gather (3,4-enedioxy thiophene) (hereinafter to be referred as: PEDOT) introduce ethylene two oxies 3 and 4 of thiophene, make polymer molecular chain more regular in order, make its conductiving doping state more stable as the representative of thiophene-based conductive polymer.Utilize the PEDOT hydrogel of supramolecule self-assembly preparation to be applied to the electrode materials of ultracapacitor very early, but because its lower electroconductibility and mechanical strength, the PEDOT hydrogel can only obtain lower ratio electric capacity and cyclical stability (referring to Dai TY; Qing XT, Lu Y, Xia YY. Conducting hydrogels with enhanced mechanical strength. Polymer; 2009; 50:5236-5241. Aouada MR, Moura EM, Girotto AF; Rubira EC. Muniz EG. The synthesis and capacitive properties of poly (3; 4-ethylene dioxythiophene)/and poly (styrene-sulfonate) and poly (acrylamide) conducting hydrogels. e-Polymers, 2007,81.).PEDOT hydrogel and polymkeric substance can be improved its physical strength and cyclical stability after compound.PEDOT composite water gel is improved its mechanical strength because of the introducing of a large amount of Lewatits and polymkeric substance, but the quick decay of conductivity can't obtain higher ratio electric capacity when making it as electrode material for super capacitor.
Summary of the invention
In order to overcome the above problems, the objective of the invention is that micro-sulfonated graphene is introduced PEDOT and prepare the composite water gel, the composite water gel that is prepared by this method has controllable porous structure, high mechanical strength and high conductivity.(1MH in electroactive ionogen
2SO
4+ 0.1MK
3Fe (CN)
6) showing good ultracapacitor characteristic, this kind method is not appeared in the newspapers both at home and abroad as yet.
In order to realize above-mentioned goal of the invention, the technical scheme that the present invention adopts is following:
A kind of preparation method who prepares PEDOT/ sulfonated graphene composite water gel, its characterization step is following:
(1) Lewatit and sulfonated graphene is soluble in water, stir and utilize ultrasonic dispersing, form dispersion liquid.The concentration of Lewatit is 20.6-500.2g/L, and the concentration of sulfonated graphene solution is 6.7-333mg/L, is preferably 50-250mg/L, is more preferred from 50-100mg/L,
(2) with 3,4-enedioxy thiophene (hereinafter to be referred as EDOT) monomer adds in the dispersion liquid of step (1), stirs and utilize ultrasonic dispersing; The monomeric volumetric molar concentration of EDOT is 33-600mmol/L, and preferable scope is 400-550mmol/L;
(3) iron salt dissolved is processed solution in water, the reaction system that disposable adding step (2) forms mixes.Described molysite is Fe (NO
3)
39H
2O or FeCl
36H
2O or Fe (NO
3)
39H
2O and Fe (NO
3)
26H
2The mixture of O or Fe (NO
3)
39H
2O and FeCl
24H
2The mixture of O, the monomeric mol ratio of molysite and EDOT is 5:1;
(4) standing and reacting 6-24h with the product that obtains cleaning and balance in a large amount of zero(ppm) water, carries out the purified product of gained promptly to obtain PEDOT/ sulfonated graphene composite water gel of the present invention after the lyophilize.Clarification time is 2-7 days, and every 24h changes primary water, and sublimation drying is 24h.
Sulfonated graphene is by a kind of carbonaceous novel material of the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline structure, has such as lower production cost high-specific surface area, good mechanical performance and superior advantages such as conductivity.The conduction of sulfonated graphene and compound sulfonated graphene capable of using of conductive polymers and conductive polymers conjugated structure acted synergistically improve conductivity, but the enhancing of implementation structure again simultaneously.Sulfonated graphene/conductive polymers combination electrode material can be inherited the two advantage as the representative of electrostatic double layer/pseudo-capacitance combination electrode material, and material is a nanoscale, and specific surface is high, and flourishing pore structure and conductive network are arranged.The add-on of sulfonated graphene is to the significant effects that is being formed with of PEDOT hydrogel network structure; The adding of trace sulfonated graphene (concentration is low to moderate 6.7mg/L) can improve the ratio electric capacity of matrix material; But the affiliation that adds of too much sulfonated graphene (concentration surpasses 333mg/L) makes hydrogel be difficult to moulding, and the concentration of sulfonated graphene is controlled at 50-100mg/L for best.
The present invention utilizes polyvalent cation Fe under normal temperature leaves standstill condition
3+, Fe
2+As polymerization oxidation agent and ion crosslinking agent, gelation reaction and polyreaction take place simultaneously.Realize that by following three kinds of reactive forces functionalization graphene and PEDOT, many group members of Lewatit, multi-level supramolecule self-assembly obtain the adjustable PEDOT/ sulfonated graphene composite water gel micrometer structure in duct: the sulfonated graphene surface-SO
3The hydrogen bond that the C=O of H and EDOT forms; π key between the benzene ring structure of Lewatit and the EDOT thiphene ring, between sulfonated graphene skeleton and the EDOT thiphene ring; Electrostatic interaction between EDOT positively charged ion and the polystyrolsulfon acid root negatively charged ion.
Positively effect of the present invention is following:
1, the sulfonated graphene of trace is introduced PEDOT; Adopt molysite to do the PEDOT/ sulfonated graphene composite water gel that the linking agent preparation has three-dimensional porous structure; Add-on through regulating sulfonated graphene can be regulated and control the vesicular structure of composite water gel easily, does not at home and abroad appear in the newspapers as yet in the document.
2, the composite water gel electrode material of the present invention preparation (for example contains Fe (CN) containing the acidic electrolyte bath of redox couple
6 3-/41MH
2SO
4) in have higher ratio electric capacity (chemical property as electrode material for super capacitor has excellence be with a wide range of applications for 215F/g, current density=5A/g) and good cyclical stability (circulation 5000 circles are not seen decay than electric capacity).
3, the present invention carries out polyreaction under normal temperature, static state, and equipment is simple, processing ease, enlargement of scale production easily.
Description of drawings
Fig. 1 a is the sulfonated graphene/PEDOTF composite water gel SEM photo of embodiment 2 preparations;
Fig. 1 b is the SEM photo of the PEDOT/ sulfonated graphene composite water gel of embodiment 1 preparation;
Fig. 2 is the cyclic voltammetry curve of the PEDOT/ sulfonated graphene composite water gel of the embodiment of the invention 1 preparation;
Fig. 3 is the charging and discharging curve of the PEDOT/ sulfonated graphene composite water gel of the embodiment of the invention 1 preparation;
Fig. 4 is the cycle life figure of the PEDOT/ sulfonated graphene composite water gel of the embodiment of the invention 1 preparation.
Visible by Fig. 1 a, the composite water gel shows as three-dimensional network-like structure, and the aperture is 200nm-3 μ m, and (1-3 μ m) is in the majority with the micron hole.(magnification is 10,000 times)
Fig. 1 b is the SEM photo of the PEDOT/ sulfonated graphene composite water gel of embodiment 1 preparation; Aperture by the visible composite aquogel of Fig. 1 b is 100nm-2 μ m, and the micron hole number obviously reduces, with sub-micron pore (100-500nm) in the majority (magnification is 10,000 times)
Fig. 1 a, 1b all adopt JSM-5610 type ESEM (Japanese JEOL company) to test, and sample is gold,platinized before test.
Visible by Fig. 2, the CV curve (ionogen: 1MH of composite water gel electrode in electroactive ionogen
2SO
4,Add 0.1MK
3Fe (CN)
6, sweep speed=10mV/s) maybe be owing to doping/dedoping process of PEDOT at a pair of redox peak at 403 and 516 mV current potential places, the redox peak here with at 1MH
2SO
4Comparing in the ionogen skew has taken place, possibly be because K
3Fe (CN)
6Introducing also play simultaneously doping effect to the composite water gel.Except this a pair of redox peak, with the 199mV place another redox peak good to peak shape has appearred at current potential 122, and its apparent electropotential is 160.5mV, and this a pair of peak is attributable to Fe (CN)
6 4-/ Fe (CN)
6 3-Between conversion.
Fig. 3 is the charging and discharging curve (electrolytic solution: 1MH of the PEDOT/ sulfonated graphene composite water gel of the embodiment of the invention 1 preparation
2SO
4+ 0.1MK
3Fe (CN)
6, current density=5A/g).Visible by Fig. 3, two steps appear in the discharge curve of composite water gel in this electroactive ionogen, be attributable to Fe (CN)
6 4-/ Fe (CN)
6 3-Between conversion.Can calculate according to following formula than electric capacity:
Fig. 4 is the cycle life figure (electrolytic solution: 1MH of the PEDOT/ sulfonated graphene composite water gel of the embodiment of the invention 1 preparation
2SO
4+ 0.1MK
3Fe (CN)
6, current density=5A/g).Visible by figure, the composite water gel phenomenon than the electric capacity reduction occurs about 300 circles before charge and discharge cycles, two peak values after this occur, is respectively 270F/g and 300F/g, and this possibly be the process that the composite water gel is activated in active electrolyte.About 4000 circles, tend towards stability than electric capacity, remain on about 260F/g, be higher than initially than electric capacity (232F/g), this explanation composite water gel has good cyclical stability in electroactive ionogen.
When the concentration of sulfonated graphene was controlled at 67mg/L, the controllable aperture of composite water gel was built in submicron-scale, and in electroactive ionogen, good electrochemical arranged.
Embodiment
Below through concrete embodiment foregoing of the present invention is done further explain.But should this be interpreted as that content of the present invention only limits to following instance.
Embodiment 1
A kind of preparation method of PEDOT/ sulfonated graphene composite water gel, step is following:
(1) under the room temperature, (preparation method is referring to Zhao G with 0.309g Lewatit (20.6g/L is available from German Aldrich company) and 1mg sulfonated graphene (67mg/L); Jiang L, He Y, Li JX; Dong HL, Wang XK, et al. Sulfonated graphene for persistent aromatic pollutant management. Advanced Materials; 2011; 23:3959.) add in the 15mL water, stir and utilize ultrasonic dispersing, form dispersion liquid;
(2) with 770 μ L (7mmol) 3,4-enedioxy thiophene monomer (available from Suzhou Yield Pharmaceutical R&D Co., Ltd.) adds in the above-mentioned dispersion liquid, stirs and utilizes ultrasonic dispersing 1h, is uniformly dispersed;
(3) with 14.1g Fe (NO
3)
39H
2O (available from Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in the 5mL water, and the reaction system that disposable adding step (2) forms continues to stir to guarantee that reaction reagent mixes;
(4) standing and reacting 6h; With the product that obtains cleaning and balance 2 days (every 24h changes primary water) in a large amount of zero(ppm) water; The purified product of gained is carried out promptly obtaining PEDOT/ sulfonated graphene composite water gel after the lyophilize (utilize liquid nitrogen to carry out precooling earlier hydrogel, refrigerated water-setting blob of viscose is put into Vacuumdrier (intelligence automatic equipment ltd is carried in Nanjing) and vacuumized dry 24h in advance).Prepared composite type hydrogel aperture is 100nm-2 μ m, and (100-500nm) is in the majority with sub-micron pore
The preparation method of 2. 1 kinds of PEDOT/ sulfonated graphenes of embodiment composite water gel; It is that with embodiment 1 different place the concentration of Lewatit becomes 103g/L; The concentration of sulfonated graphene becomes 6.7mg/L, and standing and reacting 6h becomes 12h, and 2 days cleaning and balance time became 4 days; The aperture is 200nm-3 μ m, and (1-3 μ m) is in the majority with the micron hole.
The preparation method of 3. 1 kinds of PEDOT/ sulfonated graphenes of embodiment composite water gel, it is that with embodiment 1 different place the concentration of Lewatit becomes 206g/L, the concentration of sulfonated graphene becomes 133mg/L, 14.1g Fe (NO
3)
39H
2O becomes 9.5g Fe Cl
36H
2O (available from Chemical Reagent Co., Ltd., Sinopharm Group), standing and reacting 6h becomes 10h, and 2 days cleaning and balance time became 3 days, and the aperture is 3 μ m-10 μ m.
The preparation method of 4. 1 kinds of PEDOT/ sulfonated graphenes of embodiment composite water gel; It is that with embodiment 1 different place 770 μ L EDOT monomers (7mmol) become 55 μ L (concentration is 33mmol/L); The concentration of sulfonated graphene becomes 33mg/L, 14.1g Fe (NO
3)
39H
2O becomes 1.01g Fe (NO
3)
39H
2O, the aperture is 2-10 μ m.
The preparation method of 5. 1 kinds of PEDOT/ sulfonated graphenes of embodiment composite water gel, step is following:
(1) under the room temperature, 4.635g Lewatit (309g/L is available from German Aldrich company) and 3mg sulfonated graphene (200mg/L) are added in the 15mL water, stir and utilize ultrasonic dispersing, form dispersion liquid;
(2) with under room temperature, stirring and utilize ultrasonic dispersing 1h in the above-mentioned mixed solution of 990 μ L EDOT monomers (9mmol) adding;
(3) with 6.1g Fe (NO
3)
39H
2O is dissolved in the 2mL water, with 5.4g Fe (NO
3)
26H
2O (available from Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in the 3mL water, and the former adds the latter after stirring 5min, mixes;
(4) behind the standing and reacting 18h with the product that obtains cleaning and balance 5 days (every 24h changes primary water) in a large amount of zero(ppm) water, the product of gained is carried out promptly obtaining PEDOT/ sulfonated graphene composite water gel after the lyophilize, the aperture is 500nm-2 μ m.
The preparation method of 6. 1 kinds of PEDOT/ sulfonated graphenes of embodiment composite water gel is that with embodiment 5 different places the concentration of Lewatit becomes 500.2g/L, and the concentration of sulfonated graphene becomes 333mg/mL, 6.1g Fe (NO
3)
39H
2O becomes 4.1g Fe Cl
36H
2O (available from Chemical Reagent Co., Ltd., Sinopharm Group), standing and reacting 6h becomes 24h, and 2 days cleaning and balance time became 7 days, and the aperture is 1 μ m-5 μ m.
Claims (7)
1. one kind is gathered 3, and the preparation method of 4-(enedioxy thiophene)/sulfonated graphene composite water gel is characterized in that step is following:
(1) Lewatit and sulfonated graphene is soluble in water, stir and utilize ultrasonic dispersing to form dispersion liquid, subsequent use;
(2) with 3,4-enedioxy thiophene monomer adds in the above-mentioned dispersion liquid, stirs and utilizes ultrasonic dispersing to form reaction system, and is subsequent use;
(3) iron salt dissolved is processed solution in water, the reaction system that disposable adding step (2) forms mixes;
(4) standing and reacting 6-24h with the product that obtains cleaning and balance in zero(ppm) water, carries out lyophilize with the product after the purification of gained, obtains gathering 3,4-(enedioxy thiophene)/sulfonated graphene composite water gel.
2. gather 3 according to claim 1 is said, the preparation method of 4-(enedioxy thiophene)/sulfonated graphene composite water gel is characterized in that described molysite is Fe (NO
3)
39H
2O or FeCl
36H
2O, or Fe (NO
3)
39H
2O and Fe (NO
3)
26H
2The mixture of O or Fe (NO
3)
39H
2O and FeCl
24H
2The mixture of O.
3. gather 3 according to claim 1 is said; The preparation method of 4-(enedioxy thiophene)/sulfonated graphene composite water gel; (3, the 4-enedioxy thiophene) monomer that it is characterized in that being adopted in the step (2) and the mol ratio of the molysite in the step (3) are 1:5.
4. gather 3 according to claim 1 is said; The preparation method of 4-(enedioxy thiophene)/sulfonated graphene composite water gel, it is characterized in that: the concentration of sulfonated graphene solution is 6.7-333mg/L, the concentration of Lewatit is 20.6-500.2g/L; (3; 4-enedioxy thiophene) volumetric molar concentration of solution is 33-600mmol/L, and the cleaning and balance time of step (4) is 2-7 days, and sublimation drying is 24h.
5. gather 3 according to claim 1 is said, the preparation method of 4-(enedioxy thiophene)/sulfonated graphene composite water gel, it is characterized in that: the concentration of sulfonated graphene solution is 50-250mg/L; The concentration 20.6-500.2g/L of Lewatit; The volumetric molar concentration of gathering (3,4-enedioxy thiophene) solution is 150-260mmol/L, and the cleaning and balance time of step (4) is 2-7 days; Every 24h changes primary water, and sublimation drying is 24h.
6. gather 3 according to claim 1 is said, the preparation method of 4-(enedioxy thiophene)/sulfonated graphene composite water gel, it is characterized in that: the concentration of sulfonated graphene solution is 50-100mg/L; The concentration of Lewatit is 20.6-500.2g/L; The volumetric molar concentration of (3,4-enedioxy thiophene) solution is 150-260mmol/L, and the cleaning and balance time of step (4) is 2-7 days; Every 24h changes primary water, and sublimation drying is 24h.
7. one kind is gathered 3, and 4-(enedioxy thiophene)/sulfonated graphene composite water gel is characterized in that it being to adopt following method to prepare:
(1), Lewatit and sulfonated graphene are added in the entry, stir and utilize ultrasonic dispersing, form dispersion liquid;
(2), with 3,4-enedioxy thiophene monomer adds in the above-mentioned dispersion liquid and to stir and to utilize ultrasonic dispersing;
(3), iron salt dissolved is processed solution in water, the reaction system that disposable adding step (2) forms mixes;
(4), standing and reacting 6-24h, with the product that obtains cleaning and balance in a large amount of zero(ppm) water, the purified product of gained is carried out lyophilize, obtain gathering 3,4-(enedioxy thiophene)/sulfonated graphene composite water gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110419526 CN102558772B (en) | 2011-12-15 | 2011-12-15 | Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110419526 CN102558772B (en) | 2011-12-15 | 2011-12-15 | Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102558772A true CN102558772A (en) | 2012-07-11 |
| CN102558772B CN102558772B (en) | 2013-03-06 |
Family
ID=46405466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110419526 Expired - Fee Related CN102558772B (en) | 2011-12-15 | 2011-12-15 | Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102558772B (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325573A (en) * | 2013-05-21 | 2013-09-25 | 河海大学 | Method for preparing active conducting polymer hydrogel with oxidoreduction function |
| CN104893538A (en) * | 2015-06-04 | 2015-09-09 | 栾万强 | Waterborne antistatic coating as well as preparation method and application thereof |
| CN105331276A (en) * | 2015-08-12 | 2016-02-17 | 国网山东省电力公司临沂供电公司 | Three-phase dry type transformer |
| CN105374499A (en) * | 2015-08-16 | 2016-03-02 | 国网山东省电力公司临沂供电公司 | Solid-state insulating transformer |
| CN105368295A (en) * | 2015-08-11 | 2016-03-02 | 国网山东省电力公司临沂供电公司 | Indoor distribution box |
| CN105419618A (en) * | 2015-09-21 | 2016-03-23 | 国网山东费县供电公司 | Novel distribution box |
| CN105440932A (en) * | 2015-08-11 | 2016-03-30 | 国网山东省电力公司临沂供电公司 | High-temperature-resistant corrosion-resistant power distribution box |
| CN105461948A (en) * | 2015-11-23 | 2016-04-06 | 南京航空航天大学 | Preparation method of conductive macromolecule non-covalent functionalized graphene modified electrokinetic energy conversion polymer material |
| CN105505188A (en) * | 2015-08-10 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Noise-elimination antirust paint for communication machine room and preparation method thereof |
| CN105505186A (en) * | 2015-08-10 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Antistatic paint |
| CN105507558A (en) * | 2015-08-24 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Anti-static PVC (polyvinyl chloride) plastic floor |
| CN105505189A (en) * | 2015-08-11 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Novel power distribution cabinet |
| CN105505190A (en) * | 2015-08-12 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Novel transformer |
| CN105524542A (en) * | 2015-08-10 | 2016-04-27 | 国网山东省电力公司临沂供电公司 | Antistatic floor paint |
| CN105524543A (en) * | 2015-08-12 | 2016-04-27 | 国网山东省电力公司临沂供电公司 | Electromagnetic wire-saving arc-welding transformer |
| CN105606669A (en) * | 2015-12-24 | 2016-05-25 | 北京航空航天大学 | Preparation method for controllable graphene based microsphere and nanowire materials |
| WO2016090523A1 (en) * | 2014-11-13 | 2016-06-16 | 上海工程技术大学 | Graphene-containing composite material and preparation method and use thereof |
| CN105749825A (en) * | 2016-04-06 | 2016-07-13 | 天津工业大学 | Preparation method of graphene/polyelectrolyte compound microcapsules |
| CN105833810A (en) * | 2016-04-06 | 2016-08-10 | 天津工业大学 | A preparing method of a composite polyelectrolyte microcapsule |
| CN106810675A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN108219152A (en) * | 2016-12-09 | 2018-06-29 | 钰邦科技股份有限公司 | Polymer composite and its manufacturing method, capacitor packaging structure and its manufacturing method |
| CN110060876A (en) * | 2019-04-22 | 2019-07-26 | 杭州电子科技大学 | A kind of preparation method of NGA@PEDOT material and the super capacitor for dragonfly shape miniature drone |
| CN110349757A (en) * | 2019-05-21 | 2019-10-18 | 浙江工业大学 | A kind of graphene/poly- (3,4- ethene dioxythiophene) self-supporting film and preparation method thereof |
| CN110534352A (en) * | 2019-09-19 | 2019-12-03 | 福州大学 | A kind of preparation method and applications of poly- 3,4- ethylenedioxy thiophene cladding graphene oxide |
| CN110604560A (en) * | 2019-06-19 | 2019-12-24 | 北京大学 | Method for connecting electronic material and hydrogel substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602876A (en) * | 2009-06-23 | 2009-12-16 | 南京大学 | The multimeshed network compound water congealing glue material and the method for making thereof of high mechanical strength and electrochemical activity |
| CN101851398A (en) * | 2010-05-12 | 2010-10-06 | 北京理工大学 | Conductive polymer aerogel and preparation method thereof |
-
2011
- 2011-12-15 CN CN 201110419526 patent/CN102558772B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602876A (en) * | 2009-06-23 | 2009-12-16 | 南京大学 | The multimeshed network compound water congealing glue material and the method for making thereof of high mechanical strength and electrochemical activity |
| CN101851398A (en) * | 2010-05-12 | 2010-10-06 | 北京理工大学 | Conductive polymer aerogel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YANFEI XU: "A Hybrid Material of Graphene and Poly (3,4-ethyldioxythiophene)", 《NANO RES》, no. 2, 31 December 2009 (2009-12-31), pages 343 - 348 * |
| 王升文: "3,4-乙撑二氧噻吩(EDT)及其聚合物(PEDT)的合成与应用", 《化工中间体》, no. 3, 31 March 2006 (2006-03-31), pages 16 - 19 * |
| 郑华靖: "聚3,4-乙烯二氧噻吩聚苯乙烯磺酸复合LB膜", 《化工学报》, vol. 61, no. 6, 30 June 2010 (2010-06-30), pages 1583 - 1585 * |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325573A (en) * | 2013-05-21 | 2013-09-25 | 河海大学 | Method for preparing active conducting polymer hydrogel with oxidoreduction function |
| CN103325573B (en) * | 2013-05-21 | 2016-09-14 | 河海大学 | A kind of preparation method of the conducting polymer hydrogel with redox active |
| WO2016090523A1 (en) * | 2014-11-13 | 2016-06-16 | 上海工程技术大学 | Graphene-containing composite material and preparation method and use thereof |
| CN104893538A (en) * | 2015-06-04 | 2015-09-09 | 栾万强 | Waterborne antistatic coating as well as preparation method and application thereof |
| CN105505188A (en) * | 2015-08-10 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Noise-elimination antirust paint for communication machine room and preparation method thereof |
| CN105505186B (en) * | 2015-08-10 | 2017-10-31 | 国网山东省电力公司临沂供电公司 | A kind of antistatic coating |
| CN105505188B (en) * | 2015-08-10 | 2018-07-06 | 国网山东省电力公司临沂供电公司 | A kind of used in communication machine room noise elimination antirust paint and preparation method thereof |
| CN105505186A (en) * | 2015-08-10 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Antistatic paint |
| CN105524542B (en) * | 2015-08-10 | 2018-02-23 | 国网山东省电力公司临沂供电公司 | A kind of floor paint for possessing antistatic property |
| CN105524542A (en) * | 2015-08-10 | 2016-04-27 | 国网山东省电力公司临沂供电公司 | Antistatic floor paint |
| CN105440932A (en) * | 2015-08-11 | 2016-03-30 | 国网山东省电力公司临沂供电公司 | High-temperature-resistant corrosion-resistant power distribution box |
| CN105368295A (en) * | 2015-08-11 | 2016-03-02 | 国网山东省电力公司临沂供电公司 | Indoor distribution box |
| CN105505189B (en) * | 2015-08-11 | 2018-07-06 | 国网山东省电力公司临沂供电公司 | A kind of new type power distribution box |
| CN105505189A (en) * | 2015-08-11 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Novel power distribution cabinet |
| CN105331276A (en) * | 2015-08-12 | 2016-02-17 | 国网山东省电力公司临沂供电公司 | Three-phase dry type transformer |
| CN105524543A (en) * | 2015-08-12 | 2016-04-27 | 国网山东省电力公司临沂供电公司 | Electromagnetic wire-saving arc-welding transformer |
| CN105505190B (en) * | 2015-08-12 | 2018-06-12 | 国网山东省电力公司费县供电公司 | A kind of novel transformer |
| CN105505190A (en) * | 2015-08-12 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Novel transformer |
| CN105374499A (en) * | 2015-08-16 | 2016-03-02 | 国网山东省电力公司临沂供电公司 | Solid-state insulating transformer |
| CN105507558A (en) * | 2015-08-24 | 2016-04-20 | 国网山东省电力公司临沂供电公司 | Anti-static PVC (polyvinyl chloride) plastic floor |
| CN105507558B (en) * | 2015-08-24 | 2018-05-22 | 国网山东省电力公司临沂供电公司 | A kind of Antistatic PVC plastic floor |
| CN105419618A (en) * | 2015-09-21 | 2016-03-23 | 国网山东费县供电公司 | Novel distribution box |
| CN105461948A (en) * | 2015-11-23 | 2016-04-06 | 南京航空航天大学 | Preparation method of conductive macromolecule non-covalent functionalized graphene modified electrokinetic energy conversion polymer material |
| CN106810675A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN106810675B (en) * | 2015-11-30 | 2019-03-29 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN105606669B (en) * | 2015-12-24 | 2018-04-17 | 北京航空航天大学 | A kind of preparation method of controllable grapheme base microballoon and nano-material |
| CN105606669A (en) * | 2015-12-24 | 2016-05-25 | 北京航空航天大学 | Preparation method for controllable graphene based microsphere and nanowire materials |
| CN105833810A (en) * | 2016-04-06 | 2016-08-10 | 天津工业大学 | A preparing method of a composite polyelectrolyte microcapsule |
| CN105749825A (en) * | 2016-04-06 | 2016-07-13 | 天津工业大学 | Preparation method of graphene/polyelectrolyte compound microcapsules |
| CN108219152A (en) * | 2016-12-09 | 2018-06-29 | 钰邦科技股份有限公司 | Polymer composite and its manufacturing method, capacitor packaging structure and its manufacturing method |
| CN110060876A (en) * | 2019-04-22 | 2019-07-26 | 杭州电子科技大学 | A kind of preparation method of NGA@PEDOT material and the super capacitor for dragonfly shape miniature drone |
| CN110349757A (en) * | 2019-05-21 | 2019-10-18 | 浙江工业大学 | A kind of graphene/poly- (3,4- ethene dioxythiophene) self-supporting film and preparation method thereof |
| CN110604560A (en) * | 2019-06-19 | 2019-12-24 | 北京大学 | Method for connecting electronic material and hydrogel substrate |
| CN110534352A (en) * | 2019-09-19 | 2019-12-03 | 福州大学 | A kind of preparation method and applications of poly- 3,4- ethylenedioxy thiophene cladding graphene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102558772B (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102558772B (en) | Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof | |
| Moussa et al. | Self-assembly and cross-linking of conducting polymers into 3D hydrogel electrodes for supercapacitor applications | |
| Mawad et al. | Conductive polymer hydrogels | |
| Yang et al. | Tunable three-dimensional nanostructured conductive polymer hydrogels for energy-storage applications | |
| Ji et al. | Phytic acid assisted fabrication of graphene/polyaniline composite hydrogels for high-capacitance supercapacitors | |
| Cho et al. | Enhanced electrochemical performance of highly porous supercapacitor electrodes based on solution processed polyaniline thin films | |
| Xu et al. | High-performance Li-organic battery based on thiophene-containing porous organic polymers with different morphology and surface area as the anode materials | |
| Ma et al. | Effect of substituent position on electrodeposition, morphology, and capacitance performance of polyindole bearing a carboxylic group | |
| Mo et al. | Facile electrochemical polymerization of 2-(thiophen-2-yl) furan and the enhanced capacitance properties of its polymer in acetonitrile electrolyte containing boron trifluoride diethyl etherate | |
| Ju et al. | Synthesis and electrochemical capacitive performance of thieno [3, 4-b] pyrazine-based Donor-Acceptor type copolymers used as supercapacitor electrode material | |
| CN102627768A (en) | Preparation method of grapheme/polypyrrole nanocomposite material for super capacitor electrode | |
| Yuan et al. | Two-step method for synthesizing polyaniline with bimodal nanostructures for high performance supercapacitors | |
| Mo et al. | Alkyl functionalized bithiophene end-capped with 3, 4-ethylenedioxythiophene units: synthesis, electropolymerization and the capacitive properties of their polymers | |
| CN106910643B (en) | In-situ polymerization polyaniline-application of the sulfonated graphene composite material in electrode material | |
| CN106981374B (en) | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application | |
| Jia et al. | Pyrrole/macrocycle/MOF supramolecular co-assembly for flexible solid state supercapacitors | |
| Zhang et al. | Chain engineering-tailored microstructures and lithium storage performance of hydrothermally-synthesized linear polyimides | |
| Zhang et al. | A conjugated polymer with Electron-withdrawing cyano group enables for flexible asymmetric electrochromic supercapacitors | |
| CN106206073A (en) | ZnO thin film Polymerization of Polyaniline/carbon Nanotube combination electrode material and preparation method thereof | |
| CN106024094B (en) | A kind of compliant conductive polyaniline nano fiber bumps electrode material and preparation method thereof | |
| SE512579C2 (en) | Polymer gel electrode, and process for its preparation | |
| Ringk et al. | Electropolymerized star-shaped benzotrithiophenes yield π-conjugated hierarchical networks with high areal capacitance | |
| Li et al. | Synthesis of feather fan-like PANI electrodes for supercapacitors | |
| CN105118687B (en) | Flowers type conductive polythiophene flexible electrode and the ultracapacitor based on this flexible electrode and preparation method thereof | |
| Sidheekha et al. | Current sensing supercapacitor electrodes based on chitosan/poly-o-toluidine hydrogel composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130306 Termination date: 20161215 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |