CN102220664B - Preparation method and application of conducting polymer-based nanometer carbon fibers - Google Patents
Preparation method and application of conducting polymer-based nanometer carbon fibers Download PDFInfo
- Publication number
- CN102220664B CN102220664B CN 201110118733 CN201110118733A CN102220664B CN 102220664 B CN102220664 B CN 102220664B CN 201110118733 CN201110118733 CN 201110118733 CN 201110118733 A CN201110118733 A CN 201110118733A CN 102220664 B CN102220664 B CN 102220664B
- Authority
- CN
- China
- Prior art keywords
- conducting polymer
- preparation
- carbon fibre
- polymer base
- base nano
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a method for preparing conducting polymer-based nanometer carbon fibers, which comprises the following steps of: processing a conducting polymer nanometer fiber precursor in the oxidizing atmosphere to obtain a preoxidation product; and carbonizing at the temperature of between 600 and 900 DEG C in the nitrogen atmosphere to obtain the conducting polymer nanometer carbon fibers, wherein in the electrode material, the stable specific electric capacity is up to 158F/g under the condition of current density of 0.1A/g; and when the current density is gradually increased from 0.1A/g to 1A/g, the retention rate of the capacity is 75 percent. The conducting polymer-based nanometer carbon fibers have high discharge specific capacity and cyclical stability.
Description
Technical field
The present invention relates to the electrode material for super capacitor field, particularly a kind of preparation method of conducting polymer base nano carbon fibre and application.
Background technology
Ultracapacitor (supercapacitor) as a kind of model electrochemical energy storage device, has the dual-use function of electric capacity and battery concurrently, compares with battery, and super capacitor energy storage device weight has only the former 1/3, and volume has only the former 1/2.Thereby all have in fields such as power system, communication, new forms of energy, Aero-Space, electric automobiles very and use widely.Because electrode material is the core component of ultracapacitor.Therefore develop the novel electrode material that can improve ultracapacitor energy density and power out-put characteristic and become the task of top priority.
Activated carbon fiber (ACF) has bigger specific area, surperficial perforate, and large, medium and small hole connects closely; The duct is unimpeded, helps the transmission and the absorption of electrolyte, and electric conductivity is good; The resist chemical performance is good, the ability fast charging and discharging, so activated carbon fiber becomes one of research focus of electrode material for super capacitor [Xu Bin; Wu Feng, Chen Shi, et al.Activated carbon fiber cloths as electrodesfor high performance electric double layer capacitors [J] .Electrochimica Acta; 2007,52:4595-4598].Mainly contain organic fibers such as polyacrylonitrile base, asphaltic base, phenolic aldehyde base as activated carbon fiber (ACF) presoma at present.But these organic fiber precursors through after the carbonization treatment, often need activation processing to increase its specific area.Carbon fibre material average pore size through after the activation processing is 2～5nm, and specific area reaches 1500～3000m2/g.With the activated carbon fiber cloth is the ultracapacitor of electrode material preparation, reaches 80F/g than electric capacity, and energy density reaches 20.2Wh/kg [Chen Qiufei; Zhang Xuejun; The field bright red. the capacitance characteristic of asphalt activity carbon fiber [J]. Beijing University of Chemical Technology's journal, 2008,35 (2): 55-59].
In recent years, the application of nitrogenous material with carbon element aspect electrode material for super capacitor is a research focus.Seongyop Lim etc. adopt chemical vapour deposition technique on metal is Ni-based, use acetonitrile and acrylonitrile to be raw material, through controlled condition; Prepared nitrogen atom content 1～10%, diameter is the nitrogenous carbon nano-fiber of 20～60nm [Seongyop Lim, Seong-Ho Yoon; Isao Mochida.et al.Direct Synthesis and StructuralAnalysis of Nitrogen-Doped Carbon Nanofibers [J] .Langmuir; 2009,25 (14), 8268-8273].Denisa Hulicova etc. are presoma with the melamine; Prepared the carbon electrode material that is rich in nitrogen, and confirmed, nitrogen-containing functional group can improve the active carbon electrode material surface moist can also produce tangible fake capacitance [Denisa H simultaneously; Masaya K; Hiroaki H.Electrochemical performance ofnitrogen-enriched carbons in aqueous and nonaqueous supercapacitors [J] .ChemMater, 2006,18 (9): 2318].But present preparation method's technological process is complicated, and cost is higher, is unfavorable for industrialized realization.
Summary of the invention
To the problems referred to above of prior art, the purpose of this invention is to provide a kind of preparation method of conducting polymer base nano carbon fibre, make by following method:
Step 1: in the oxidizing gas atmosphere, 200 ℃～400 ℃ following pre-oxidation treatment 2～4h obtain the pre-oxidation product with the conductive polymer nanometer fiber;
Step 2: get step 1 gained pre-oxidation product, put into the high temperature carbonization stove, under inert atmosphere, progressively be heated to 600～900 ℃, insulation 1～2h promptly gets the conducting polymer base nano carbon fibre.
The further preferred version of the present invention is: said conductive polymer nanometer fiber is selected from a kind of in polyaniline, polypyrrole, polythiophene or the polyphenylene sulfide nanofiber.
The further preferred version of the present invention is: said oxidizing gas is selected from a kind of in air, carbon dioxide, sulfur dioxide or the nitrogen dioxide.
The present invention also provides a kind of electrode material for super capacitor of conducting polymer base nano carbon fibre preparation in addition.
The present invention utilizes high temperature that the conductive polymer nanometer fiber is carried out charing Processing of Preparation material with carbon element.Charing is handled and can be obtained with the carbon is main skeleton structure; Can also make simultaneously that the nitrogen atom doping on the phenyl ring is inner to phenyl ring; The nitrogen-atoms of this doping attitude has very high activity, thereby application not only helps the double layer capacitor of electrolyte infiltration raising material with carbon element with electrode material for super capacitor but also can produce than the higher fake capacitance that gets.The ultracapacitor specific discharge capacity that uses the conductive polymer nanometer carbon fiber electrode material is at 110～158Fg
-1Between, far above the specific capacity (80Fg of activated carbon fiber
-1), when current density increased to 1A/g gradually from 0.1A/g, the specific capacity conservation rate was about 75%.Good power-performance and cycle performance have been showed.
Description of drawings
Accompanying drawing 1 is the sem photograph of gained conductive polyaniline nanometer carbon fiber under 600 ℃ of carburizing temperatures.
Accompanying drawing 2 is respectively the specific discharge capacity of 600,700 and 850 times gained conductive polymer nanometer carbon fibers and the graph of relation of current density for carburizing temperature.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated:
Embodiment 1
In air atmosphere, 200 ℃ of following pre-oxidation treatment 4h obtain the pre-oxidation product with the 1g electrically conductive polyaniline nano fiber; With the pre-oxidation product, put into the high temperature carbonization stove then, heating under nitrogen atmosphere, heating rate is 1 ℃ of min
-1, being warming up to from room temperature, insulation 2h promptly gets the conducting polymer base nano carbon fibre in the time of 600 ℃.
Polyaniline carbon fiber pattern remains intact shown in accompanying drawing 1 ESEM (SEM).
2 electrochemical property test results show that this electrode material is at 0.1Ag like accompanying drawing
-1Specific discharge capacity under the current density can reach 130Fg
-1At 1Ag
-1Under the current density circulation 100 times after, specific discharge capacity can keep 110Fg
-1
Embodiment 2
In the carbon dioxide atmosphere, 300 ℃ of following pre-oxidation treatment 3h obtain the pre-oxidation product with 1g electric polypyrrole nano fiber; With the pre-oxidation product, put into the high temperature carbonization stove then, heating under nitrogen atmosphere, heating rate is 1 ℃ of min
-1, being warming up to from room temperature, insulation 1h promptly gets the conducting polymer base nano carbon fibre in the time of 700 ℃.
2 electrochemical property test results show that this electrode material is at 0.1Ag like accompanying drawing
-1Specific discharge capacity under the current density can reach 158Fg
-11Ag
-1Under the current density circulation 100 times after, specific discharge capacity can keep 110Fg
-1
Embodiment 3
In the carbon dioxide atmosphere, 400 ℃ of following pre-oxidation treatment 2h obtain the pre-oxidation product with 1g conductive polythiophene nanofiber; With the pre-oxidation product, put into the high temperature carbonization stove then, heating under nitrogen atmosphere, heating rate is 1 ℃ of min
-1, being warming up to from room temperature, insulation 1h promptly gets the conducting polymer base nano carbon fibre in the time of 850 ℃.
2 electrochemical property test results show that this electrode material is at 0.1Ag like accompanying drawing
-1Specific discharge capacity under the current density can reach 132Fg
-11Ag
-1Under the current density circulation 100 times after, specific discharge capacity can keep 123Fg
-1
Embodiment 4
The 1g conduction is gathered the polyphenylene sulfide nanofiber in the carbon dioxide atmosphere, and 350 ℃ of following pre-oxidation treatment 2h obtain the pre-oxidation product; With the pre-oxidation product, put into the high temperature carbonization stove then, heating under nitrogen atmosphere, heating rate is 1 ℃ of min
-1, being warming up to from room temperature, insulation 1h promptly gets the conducting polymer base nano carbon fibre in the time of 900 ℃.
Electrochemical property test is the result show, this electrode material is at 0.1Ag
-1Specific discharge capacity under the current density can reach 128Fg
-11Ag
-1Under the current density circulation 100 times after, specific discharge capacity can keep 115Fg
-1
Below preferred embodiment of the present invention is specified; But the present invention is not limited to said embodiment; Those of ordinary skill in the art also can make all modification that is equal to or replacement under the prerequisite of spirit of the present invention, modification that these are equal to or replacement all are included in the application's claim institute restricted portion.
Claims (4)
1. the preparation method of a conducting polymer base nano carbon fibre is characterized in that making by following method:
Step 1: in the oxidizing gas atmosphere, 200 ℃～400 ℃ following pre-oxidation treatment 2～4h obtain the pre-oxidation product with the conductive polymer nanometer fiber;
Step 2: get step 1 gained pre-oxidation product, put into the high temperature carbonization stove, under inert atmosphere, progressively be heated to 600～900 ℃, insulation 1～2h promptly gets the conducting polymer base nano carbon fibre.
2. the preparation method of conducting polymer base nano carbon fibre according to claim 1 is characterized in that: said conductive polymer nanometer fiber is selected from a kind of in polyaniline, polypyrrole, polythiophene or the polyphenylene sulfide nanofiber.
3. the preparation method of conducting polymer base nano carbon fibre according to claim 1 is characterized in that: said oxidizing gas is selected from a kind of in air, carbon dioxide, sulfur dioxide or the nitrogen dioxide.
4. electrode material for super capacitor by the said method gained of claim 1 to 3 conducting polymer base nano carbon fibre preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110118733 CN102220664B (en) | 2011-05-09 | 2011-05-09 | Preparation method and application of conducting polymer-based nanometer carbon fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110118733 CN102220664B (en) | 2011-05-09 | 2011-05-09 | Preparation method and application of conducting polymer-based nanometer carbon fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102220664A CN102220664A (en) | 2011-10-19 |
| CN102220664B true CN102220664B (en) | 2012-08-22 |
Family
ID=44777359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110118733 Expired - Fee Related CN102220664B (en) | 2011-05-09 | 2011-05-09 | Preparation method and application of conducting polymer-based nanometer carbon fibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102220664B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105839228B (en) * | 2016-05-30 | 2019-01-22 | 天津工业大学 | A kind of preparation method of polyacrylonitrile-radical conductive fiber material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661336A (en) * | 1985-11-25 | 1987-04-28 | Hitco | Pretreatment of pan fiber |
| CN1786304A (en) * | 2005-12-05 | 2006-06-14 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
| CN1908260A (en) * | 2005-08-03 | 2007-02-07 | 厦门大学 | Preparation method of polyacrylonitrile-based carbon core |
-
2011
- 2011-05-09 CN CN 201110118733 patent/CN102220664B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661336A (en) * | 1985-11-25 | 1987-04-28 | Hitco | Pretreatment of pan fiber |
| CN1908260A (en) * | 2005-08-03 | 2007-02-07 | 厦门大学 | Preparation method of polyacrylonitrile-based carbon core |
| CN1786304A (en) * | 2005-12-05 | 2006-06-14 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102220664A (en) | 2011-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bhat et al. | Low cost, catalyst free, high performance supercapacitors based on porous nano carbon derived from agriculture waste | |
| Liu et al. | Nitrogen-doped hierarchical porous carbon from wheat straw for supercapacitors | |
| Liu et al. | Highly flexible freestanding porous carbon nanofibers for electrodes materials of high-performance all-carbon supercapacitors | |
| Ju et al. | Preparation and characterization of PVA-based carbon nanofibers with honeycomb-like porous structure via electro-blown spinning method | |
| Inagaki et al. | Carbon nanofibers prepared via electrospinning | |
| Chen et al. | Synthesis of nitrogen-doped porous carbon nanofibers as an efficient electrode material for supercapacitors | |
| Chen et al. | Thiourea-induced N/S dual-doped hierarchical porous carbon nanofibers for high-performance lithium-ion capacitors | |
| Simotwo et al. | Polyaniline-carbon based binder-free asymmetric supercapacitor in neutral aqueous electrolyte | |
| He et al. | Influence of KOH/coke mass ratio on properties of activated carbons made by microwave-assisted activation for electric double-layer capacitors | |
| WO2021027100A1 (en) | Nitrogen-doped porous carbon material, preparation method therefor and use thereof | |
| Mitravinda et al. | Design and development of honeycomb structured nitrogen-rich cork derived nanoporous activated carbon for high-performance supercapacitors | |
| Ratnaji et al. | Hierarchical porous carbon derived from tea waste for energy storage applications: Waste to worth | |
| Yang et al. | Electrochemically polymerized vine-like nanostructured polyaniline on activated carbon nanofibers for supercapacitor | |
| Tian et al. | Flexible cross-linked electrospun carbon nanofiber mats derived from pitch as dual-functional materials for supercapacitors | |
| Hossain et al. | In-situ O/N-heteroatom enriched activated carbon by sustainable thermal transformation of waste coffee grounds for supercapacitor material | |
| Mehra et al. | Deciphering the incredible supercapacitor performance of conducting biordered ultramicroporous graphitic carbon | |
| Li et al. | Flexible and cross-linked carbon nanofibers based on coal liquefaction residue for high rate supercapacitors | |
| Gómez-Martín et al. | Binder-free supercapacitor electrodes: Optimization of monolithic graphitized carbons by reflux acid treatment | |
| Tran Thi Dieu et al. | Preparation of activated carbon derived from oil palm empty fruit bunches and its modification by nitrogen doping for supercapacitors | |
| Feng et al. | Facile fabrication and capacitive performance of glucose-derived porous carbon | |
| CN101882479A (en) | Electrode material of polyaniline-based nitrogen-containing carbon nano-tube super-capacitor, and preparation method thereof | |
| Wu et al. | Atmosphere-free pyrolysis of harakeke fiber: A new chamber-induced activation methodology for porous carbon electrodes in supercapacitors | |
| Hossain et al. | Recovering renewable carbon materials from automotive shredder residue (ASR) for micro-supercapacitor electrodes | |
| Wang et al. | Dual template method to prepare hierarchical porous carbon nanofibers for high-power supercapacitors | |
| Kim et al. | Enhanced electrical capacitance of heteroatom-decorated nanoporous carbon nanofiber composites containing graphene |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120822 |