CN103665376A - Preparation method of polypyrrole micro/nano tube - Google Patents
Preparation method of polypyrrole micro/nano tube Download PDFInfo
- Publication number
- CN103665376A CN103665376A CN201310700726.1A CN201310700726A CN103665376A CN 103665376 A CN103665376 A CN 103665376A CN 201310700726 A CN201310700726 A CN 201310700726A CN 103665376 A CN103665376 A CN 103665376A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polypyrrole
- micro
- nanotubes
- polypyrrole micro
- 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
Abstract
The invention relates to a preparation method of a polypyrrole micro/nano tube. The preparation method comprises the steps as follows: 1), an oxidant is dissolved in deionized water, and an oxidant solution with the concentration of 130-150 mmol/L is prepared; 2), methyl orange and sodium dodecyl benzene sulfonate are dissolved in deionized water according to a molar ratio of 1:(0.8-1.2), and a double micelle template solution is prepared; and 3), a pyrrole monomer is added to the double micelle template solution, and a raw material liquid is obtained; the raw material liquid is dropwise added to the oxidant solution and reacts for 10-30 h at a temperature of 0-20 DEG C; and filtration is performed, a solid is collected, cleaned and dried, and the polypyrrole micro/nano tube is obtained. The preparation method is simple, and the specific capacitance performance and the thermal stability are excellent.
Description
Technical field
The present invention relates to a kind of preparation method of polypyrrole Micro/nanotubes, belong to conductive polymers micro/nano material preparing technical field.
Background technology
Conducting polymer has many advantageous properties such as electricity, electrochemistry, mechanics, optics, magnetics, in fields such as productive life, military affairs, aerospace, all has potential application prospect.The pattern of conducting polymer composite and the size electrical property to polymkeric substance, gas sensing performance, catalytic performance produces important impact, therefore the controlledly synthesis of conductive polymers pattern, become study hotspot and difficult point (the Yongqiang Yang in the synthetic field of conducting polymer, Ruiqing Pang, Xuejiao Zhou, Yan Zhang, Haixia Wu and Shouwu Guo, Composites of chemically-reduced graphene oxide sheets and carbon nanospheres with three-dimensional network structure as anode materials for lithium ion batteries, J.Mater.Chem., 2012, 22, 23194 – 23200, S.N.Beesabathuni, J.G.Stockham, J.H.Kim, H.B.Lee, J.H.Chung and A.Q.Shen, Fabrication of conducting polyaniline microspheres using droplet microfluidics, RSC Adv., 2013, 3, 24423 – 24429), the tensio-active agent of take can be prepared particulate state as soft template, the electric polypyrrole of fibrous and tubulose, difference due to its pattern and structure, these conductive polymerss are in specific conductivity, super capacitor material and lithium ion battery material show excellent performance (Xuehua Zhang, Shasha Wang, Shan Lu, Jia Su, Tao He, Influence of doping anions on structure and properties of electro-polymerized polypyrrole counter electrodes for use in dye-sensitized solar cells, J.Power Sources, 246 (2014) 491-498, Weiyang Li, Qianfan Zhang, Guangyuan Zheng, Zhi Wei Seh, Hongbin Yao, Yi Cui, Understanding the Role of Different Conductive Polymers in Improving the Nanostructured Sulfur Cathode Performance, Nano Lett.2013,13,5534-5540).With Sodium dodecylbenzene sulfonate, conventionally obtain granular electric polypyrrole (K á tia R.L.Castagno; Viviane Dalmorob; Denise S.Azambuja; Characterization and corrosion of polypyrrole/sodium dodecylbenzene sulfonate electropolymerised on aluminum alloy1100, Materials Chemistry and Physics130 (2011) 721 – 726; Baobao Zhao, Zhaodong Nan, Formation of self-assembled nanofiber-like Ag@PPy core/shell structures induced by SDBS, Materials Science and Engineering C32 (2012) 1971 – 1975); The tubulose polypyrrole Micro/nanotubes specific conductivity that the tropeolin-D of take is prepared as template reaches 33.0S/cm; Solubility property is slightly improved (J.Upadhyay, A.Kumar, Structural, thermal and dielectric studies of polypyrrole nanotubes synthesized by reactive self degrade template method, Materials Science and Engineering B178 (2013) 982 – 989).
Chinese patent literature CN102924718A(application number: 201210463063.1) disclose a kind of preparation method with the polypyrrole of nanostructure; Comprise step: using the Manganse Dioxide with certain nanostructure pattern as reaction template, in acidic solution, react with pyrrole monomer, the pH of described acidic solution is 0～6, temperature of reaction is-10～50 ℃, molar weight ratio >=the 1:2 of pyrrole monomer and Manganse Dioxide, prepare polypyrrole, the nanostructure pattern of described polypyrrole is identical with the nanostructure pattern of described Manganse Dioxide.But this polypyrrole with nanostructure is less than electric capacity; And temperature of reaction is higher, is unfavorable for energy conservation.
At present, usining tropeolin-D and Sodium dodecylbenzene sulfonate jointly prepares electric polypyrrole as soft template and not yet has report.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of polypyrrole Micro/nanotubes.
Technical scheme of the present invention is as follows:
A preparation method for polypyrrole Micro/nanotubes, step is as follows:
(1) under agitation condition, oxygenant is dissolved in deionized water, make the oxidizing agent solution that concentration is 130～150mmol/L; Described oxygenant is ammonium persulphate;
(2), under agitation condition, by tropeolin-D and Sodium dodecylbenzene sulfonate, be 1:(0.8～1.2 in molar ratio) be dissolved in deionized water, make two micella template solution; In described two micella template solution, the concentration of tropeolin-D is 0.5～4.0mmol/L;
(3) pyrrole monomer is joined in two micella template solution, obtain stock liquid; Droplets of feed is added in oxidizing agent solution, in 0～20 ℃ of reaction 10～30h; Filter, collect solid, washing, dry, obtain polypyrrole Micro/nanotubes;
Described pyrrole monomer and the mol ratio of oxygenant are 1:(0.8～1.2).
According to the present invention, preferred, the concentration of the oxidizing agent solution described in step (1) is 144mmol/L.
According to the present invention, preferred, the mol ratio of the tropeolin-D described in step (2) and Sodium dodecylbenzene sulfonate is 1:1;
Preferably, in described two micella template solution, the concentration of tropeolin-D is 2.0～3.0mmol/L.
According to the present invention, preferred, the pyrrole monomer described in step (3) is (0.3～1) with the volume ratio of two micella template solution: 150, and more preferably 0.5:150;
Preferably, the mol ratio of described pyrrole monomer and oxygenant is 1:1;
Preferably, described temperature of reaction is 0～10 ℃, and the reaction times is 24h;
Preferably, described mode of washing for washing after alcohol wash, use washing with alcohol 2～3 times after more preferably washing 1～2 time;
Preferably, drying mode is dry 10～24h in 40～80 ℃ of air atmospheres.
According to the present invention, preferred, the speed of the stirring described in step (1) and (2) is 200～500r/min.
Tropeolin-D of the present invention and Sodium dodecylbenzene sulfonate are jointly as soft template, and the polypyrrole Micro/nanotubes of preparing is hollow thorn-like; The diameter of polypyrrole Micro/nanotubes is in about 400nm, and wall thickness is in 60nm left and right, at the Surface Creation of polypyrrole Micro/nanotubes the polypyrrole of thorn-like of granulometric composition.
The invention has the beneficial effects as follows:
1, to take the solution of tropeolin-D and Sodium dodecylbenzene sulfonate be template in the present invention, use in situ chemical oxidation method, synthesized first hollow thorn-like polypyrrole Micro/nanotubes, this polypyrrole Micro/nanotubes conductivity is significantly improved, under the current density of 0.2A/g, discharge and recharge, than electric capacity, reach 380F/g, in super capacitor material field, there is good application prospect.
2, temperature of reaction of the present invention is 0～20 ℃, neither needs very low temperature, does not also need higher temperature, and reaction conditions is gentle, and energy consumption is low; Preparation process is simple, is easy to suitability for industrialized production.
3, the polypyrrole Micro/nanotubes Heat stability is good that prepared by the present invention, than only obviously improving by the thermostability that tropeolin-D is the polypyrrole Micro/nanotubes prepared of template.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of the prepared polypyrrole Micro/nanotubes of embodiment 1.
Fig. 2 is transmission electron microscope (TEM) photo of the prepared polypyrrole Micro/nanotubes of embodiment 1.
Fig. 3 is the thermogravimetric curve figure of the prepared polypyrrole Micro/nanotubes of embodiment 1 and comparative example.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited to this.
Raw materials usedly in embodiment be conventional commercial product; Equipment used is conventional equipment, and testing method is ordinary method.
Wherein: tropeolin-D, Tianjin Kermel Chemical Reagent Co., Ltd. is on sale; Ammonium persulphate, Shanghai wide promise chemistry Science and Technology Ltd. is on sale; Sodium dodecylbenzene sulfonate, Tianjin Bo Di Chemical Co., Ltd. is on sale; Pyrrole monomer, Sa En chemical technology (Shanghai) Co., Ltd. is on sale; Dehydrated alcohol, Tianjin Bo Di Chemical Co., Ltd. is on sale.
In embodiment 1, the stereoscan photograph of prepared sample is to detect and obtain through Japanese Hitachi S-4800 field emission scanning electron microscope; Transmission electron microscope photo is to detect and obtain through Japanese JEM-1011 transmission electron microscope, and charge-discharge test is to detect and obtain through PARSTAT2263 electrochemical workstation, and the SDTQ600 of thermogravimetric curve Shi Jing U.S. TA company checks and obtains.
A preparation method for polypyrrole Micro/nanotubes, step is as follows:
(1) under 300r/min agitation condition, ammonium persulphate 7.2mmol is dissolved in 50mL deionized water, stir that it is standby to be placed in constant pressure funnel, make oxidizing agent solution;
(2) 0.3mmol tropeolin-D and 0.3mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, make two micella template solution;
(3) in two micella template solution, add 0.5mL(7.2mmol) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 0 ℃ of reaction 24h, obtains black reaction liquid; Gained reaction solution is filtered to liquids recovery, standby; Solid is through water washing, absolute ethanol washing, and in 50 ℃ of air atmospheres, dry 24h, obtains polypyrrole Micro/nanotubes.
Fig. 1 is the stereoscan photograph of the polypyrrole Micro/nanotubes prepared of the present embodiment, and Fig. 2 is the transmission electron microscope photo of the polypyrrole Micro/nanotubes prepared of the present embodiment.Polypyrrole Micro/nanotubes prepared by the present embodiment the present embodiment be hollow tubular structures, the diameter of pipe is in about 400nm, wall thickness is in 60nm left and right, at the Surface Creation of polypyrrole Micro/nanotubes the polypyrrole of thorn-like of granulometric composition.From Fig. 1,2, polypyrrole Micro/nanotubes prepared by the present embodiment is thorn-like.
Polypyrrole Micro/nanotubes prepared by the present embodiment carries out charge-discharge test, under the current density condition of 0.2A/g, discharges and recharges, and than electric capacity, be 380F/g.
Embodiment 2
A preparation method for polypyrrole Micro/nanotubes, step is with embodiment 1, different: in step (3), temperature of reaction is 10 ℃.
Polypyrrole Micro/nanotubes prepared by the present embodiment carries out charge-discharge test, under the current density condition of 0.2A/g, discharges and recharges, and than electric capacity, be 268F/g.
Embodiment 3
A preparation method for polypyrrole Micro/nanotubes, step is as follows:
(1) under 500r/min agitation condition, ammonium persulphate 7.2mmol is dissolved in 50mL deionized water, stir that it is standby to be placed in constant pressure funnel, make oxidizing agent solution;
(2) 0.1mmol tropeolin-D and 0.1mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, make two micella template solution;
(3) in two micella template solution, add 0.5mL(7.2mmol) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 0 ℃ of reaction 30h, obtains black reaction liquid; Gained reaction solution is filtered to liquids recovery, standby; Solid is through water washing, absolute ethanol washing, and in 80 ℃ of air atmospheres, dry 12h, obtains polypyrrole Micro/nanotubes.
Polypyrrole Micro/nanotubes prepared by the present embodiment carries out charge-discharge test, under the current density condition of 0.2A/g, discharges and recharges, and than electric capacity, be 312F/g.
Embodiment 4
A preparation method for polypyrrole Micro/nanotubes, step is with embodiment 3, different: in step (3), temperature of reaction is 10 ℃.
Polypyrrole Micro/nanotubes prepared by the present embodiment carries out charge-discharge test, under the current density condition of 0.2A/g, discharges and recharges, and than electric capacity, be 285F/g.
Embodiment 5
A preparation method for polypyrrole Micro/nanotubes, step is as follows:
(1) under 400r/min agitation condition, ammonium persulphate 6.5mmol is dissolved in 50mL deionized water, stir that it is standby to be placed in constant pressure funnel, make oxidizing agent solution;
(2) 0.1mmol tropeolin-D and 0.08mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, make two micella template solution;
(3) in two micella template solution, add 0.5mL(7.2mmol) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 5 ℃ of reaction 20h, obtains black reaction liquid; Gained reaction solution is filtered to liquids recovery, standby; Solid is through water washing, absolute ethanol washing, and in 70 ℃ of air atmospheres, dry 15h, obtains polypyrrole Micro/nanotubes.
Polypyrrole Micro/nanotubes prepared by the present embodiment carries out charge-discharge test, under the current density condition of 0.2A/g, discharges and recharges, and than electric capacity, be 254F/g.
Embodiment 6
A preparation method for polypyrrole Micro/nanotubes, step is as follows:
(1) under 400r/min agitation condition, ammonium persulphate 7.5mmol is dissolved in 50mL deionized water, stir that it is standby to be placed in constant pressure funnel, make oxidizing agent solution;
(2) 0.1mmol tropeolin-D and 0.12mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, make two micella template solution;
(3) in two micella template solution, add 0.5mL(7.2mmol) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 15 ℃ of reaction 12h, obtains black reaction liquid; Gained reaction solution is filtered to liquids recovery, standby; Solid is through water washing, absolute ethanol washing, and in 60 ℃ of air atmospheres, dry 20h, obtains polypyrrole Micro/nanotubes.
Polypyrrole Micro/nanotubes prepared by the present embodiment carries out charge-discharge test, under the current density condition of 0.2A/g, discharges and recharges, and than electric capacity, be 223F/g.
Comparative example
This comparative example is prepared polypyrrole Micro/nanotubes by single template solution, and step is with embodiment 1, and different is not add Sodium dodecylbenzene sulfonate in step (2), only adds tropeolin-D to make template solution.
Polypyrrole Micro/nanotubes prepared by this comparative example carries out charge-discharge test, at 0.2A/g, discharges and recharges under condition, and than electric capacity, be 177F/g.
Polypyrrole Micro/nanotubes test thermal stability prepared by embodiment 1 and comparative example, result as shown in Figure 3.As shown in Figure 3, the thermostability of the polypyrrole Micro/nanotubes of embodiment 1 preparation is than the obvious improve of comparative example.
Claims (10)
1. a preparation method for polypyrrole Micro/nanotubes, step is as follows:
(1) under agitation condition, oxygenant is dissolved in deionized water, make the oxidizing agent solution that concentration is 130～150mmol/L; Described oxygenant is ammonium persulphate;
(2), under agitation condition, by tropeolin-D and Sodium dodecylbenzene sulfonate, be 1:(0.8～1.2 in molar ratio) be dissolved in deionized water, make two micella template solution; In described two micella template solution, the concentration of tropeolin-D is 0.5～4.0mmol/L;
(3) pyrrole monomer is joined in two micella template solution, obtain stock liquid; Droplets of feed is added in oxidizing agent solution, in 0～20 ℃ of reaction 10～30h; Filter, collect solid, washing, dry, obtain polypyrrole Micro/nanotubes;
Described pyrrole monomer and the mol ratio of oxygenant are 1:(0.8～1.2).
2. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the concentration of the oxidizing agent solution described in step (1) is 144mmol/L.
3. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the mol ratio of the tropeolin-D described in step (2) and Sodium dodecylbenzene sulfonate is 1:1.
4. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, in the two micella template solution described in step (2), the concentration of tropeolin-D is 2.0～3.0mmol/L.
5. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the pyrrole monomer described in step (3) is (0.3～1) with the volume ratio of two micella template solution: 150, and more preferably 0.5:150.
6. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the mol ratio of the pyrrole monomer described in step (3) and oxygenant is 1:1.
7. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the temperature of reaction described in step (3) is 0～10 ℃, and the reaction times is 24h.
8. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the mode of washing described in step (3) for washing after alcohol wash, use washing with alcohol 2～3 times after more preferably washing 1～2 time.
9. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, in step (3), drying mode is dry 10～24h in 40～80 ℃ of air atmospheres.
10. the preparation method of polypyrrole Micro/nanotubes according to claim 1, is characterized in that, the speed of the stirring described in step (1) and (2) is 200～500r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310700726.1A CN103665376B (en) | 2013-12-18 | 2013-12-18 | A kind of preparation method of polypyrrole micro/nano tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310700726.1A CN103665376B (en) | 2013-12-18 | 2013-12-18 | A kind of preparation method of polypyrrole micro/nano tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103665376A true CN103665376A (en) | 2014-03-26 |
| CN103665376B CN103665376B (en) | 2015-11-18 |
Family
ID=50304223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310700726.1A Expired - Fee Related CN103665376B (en) | 2013-12-18 | 2013-12-18 | A kind of preparation method of polypyrrole micro/nano tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103665376B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107794600A (en) * | 2017-11-15 | 2018-03-13 | 惠州市永耐宝新材料有限公司 | A kind of preparation method of polyaniline/polythiophene composite nano tube |
| CN108250744A (en) * | 2017-12-19 | 2018-07-06 | 彭枭雄 | A kind of polyaniline/polypyrrole composite nano tube and preparation method thereof |
| CN108373535A (en) * | 2018-03-26 | 2018-08-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of Mn oxide load polypyrrole nanotube |
| CN109313090A (en) * | 2016-06-01 | 2019-02-05 | 微软技术许可有限责任公司 | Power sensing element |
| CN109851783A (en) * | 2019-01-22 | 2019-06-07 | 齐鲁工业大学 | A kind of preparation method of hollow quadrangular shape electric polypyrrole |
| CN112058187A (en) * | 2020-09-15 | 2020-12-11 | 安徽大学 | Preparation method of hollow polypyrrole microspheres |
| CN116666665A (en) * | 2023-05-29 | 2023-08-29 | 湖北文理学院 | Catalytic layer, method for producing same, and fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051401A1 (en) * | 2004-09-07 | 2006-03-09 | Board Of Regents, The University Of Texas System | Controlled nanofiber seeding |
| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
-
2013
- 2013-12-18 CN CN201310700726.1A patent/CN103665376B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051401A1 (en) * | 2004-09-07 | 2006-03-09 | Board Of Regents, The University Of Texas System | Controlled nanofiber seeding |
| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
Non-Patent Citations (2)
| Title |
|---|
| MEI LI等: "Preparation and characterization of PPy with methyl orange as soft template", 《J MATER SCI: MATER ELECTRON》 * |
| 李 亮，陈 旭，艾建连: "偶氮染料掺杂聚吡咯纳米／微米结构材料的制备", 《武汉工程大学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109313090A (en) * | 2016-06-01 | 2019-02-05 | 微软技术许可有限责任公司 | Power sensing element |
| CN109313090B (en) * | 2016-06-01 | 2021-05-04 | 微软技术许可有限责任公司 | Method of forming a force sensor, force sensor array and force sensor apparatus |
| CN107794600A (en) * | 2017-11-15 | 2018-03-13 | 惠州市永耐宝新材料有限公司 | A kind of preparation method of polyaniline/polythiophene composite nano tube |
| CN108250744A (en) * | 2017-12-19 | 2018-07-06 | 彭枭雄 | A kind of polyaniline/polypyrrole composite nano tube and preparation method thereof |
| CN108373535A (en) * | 2018-03-26 | 2018-08-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of Mn oxide load polypyrrole nanotube |
| CN109851783A (en) * | 2019-01-22 | 2019-06-07 | 齐鲁工业大学 | A kind of preparation method of hollow quadrangular shape electric polypyrrole |
| CN109851783B (en) * | 2019-01-22 | 2021-11-26 | 齐鲁工业大学 | Preparation method of hollow quadrangular-prism-shaped conductive polypyrrole |
| CN112058187A (en) * | 2020-09-15 | 2020-12-11 | 安徽大学 | Preparation method of hollow polypyrrole microspheres |
| CN116666665A (en) * | 2023-05-29 | 2023-08-29 | 湖北文理学院 | Catalytic layer, method for producing same, and fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103665376B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665376A (en) | Preparation method of polypyrrole micro/nano tube | |
| Liang et al. | A honeycomb-like porous carbon derived from pomelo peel for use in high-performance supercapacitors | |
| Shi et al. | Flexible supercapacitors | |
| CN103201216B (en) | Composite material of carbon-coated graphene oxide, preparation method and application thereof | |
| Wu et al. | Preparation of sandwich-like ternary hierarchical nanosheets manganese dioxide/polyaniline/reduced graphene oxide as electrode material for supercapacitor | |
| CN104973596B (en) | A kind of Heteroatom doping hollow ball graphene composite material and preparation method and application | |
| CN102760870B (en) | Graphene/polythiophene derivative composite material as well as preparation method and application thereof | |
| CN103787320B (en) | The Synthesis and applications of the carbon nanosheet material of one kind graphene sheet layer structure | |
| CN105502386A (en) | Preparation method of microporous carbon nanosheets | |
| CN103204497A (en) | Method for preparing graphene material and application thereof in chemical energy storage and/or conversion | |
| CN106504910B (en) | A kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof | |
| CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
| CN107045948B (en) | NaxMnO2Positive electrode, preparation method and applications | |
| Liu et al. | An enhanced capacitive storage of hybrid supercapacitor based on interconnected nitrogen-doped graphene encapsulated honeycomb cobalt manganese pyrophosphate | |
| Yang et al. | MnO 2-assisted fabrication of PANI/MWCNT composite and its application as a supercapacitor | |
| CN104072768B (en) | A kind of preparation method of hollow tubular polypyrrole film | |
| Wang et al. | Preparation of benzoxazine-based N-doped mesoporous carbon material and its electrochemical behaviour as supercapacitor | |
| CN107658147B (en) | It is a kind of to prepare graphene-manganese dioxide composite material method and its application | |
| Cao et al. | Redox-active doped polypyrrole microspheres induced by phosphomolybdic acid as supercapacitor electrode materials | |
| CN104466110A (en) | Preparation method of high-performance lithium ion battery negative electrode material | |
| CN103359796A (en) | Preparation method of supercapacitor cobaltous oxide electrode material | |
| Liu et al. | Preparation of high-performance graphene materials by adjusting internal micro-channels using a combined electrospray/electrospinning technique | |
| CN107658148A (en) | A kind of method for preparing graphene tin dioxide composite material and its application in terms of energy storage | |
| CN109809398B (en) | Preparation method and application of graphene conductive agent dispersion liquid of high-capacity supercapacitor | |
| CN107104006A (en) | A kind of graphene@cupric silicates are classified heterogeneous nano composite material and its production and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151118 Termination date: 20161218 |