CN104124073A - Preparation method for phenolic resin carbon/polythiophene composite electrode - Google Patents
Preparation method for phenolic resin carbon/polythiophene composite electrode Download PDFInfo
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- CN104124073A CN104124073A CN201410314104.XA CN201410314104A CN104124073A CN 104124073 A CN104124073 A CN 104124073A CN 201410314104 A CN201410314104 A CN 201410314104A CN 104124073 A CN104124073 A CN 104124073A
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- electrode
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- 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
Abstract
The invention discloses a preparation method for a phenolic resin carbon/polythiophene composite electrode. The preparation method uses modified phenolic resin carbon, thiophene and derivative monomer of the thiophene as main ingredients, and the ingredients are directly pressed and polymerized to form the electrode under the catalytic action of FeCl3. The method can directly realize the pressing and polymerizing forming under super-capacitor production conditions and does not need to synthesize composite electrode material to prepare the electrode, and accordingly conductive agent, adhesive and other auxiliary substances are avoided. The composite electrode prepared by the method has excellent electrochemical performance.
Description
Technical field
The invention belongs to the composite electrode technology of preparing of carbonized resin and conducting polymer.Particularly phenol-formaldehyde resin modified charcoal/polythiophene electrode and preparation method thereof.
Background technology
Ultracapacitor is a kind of novel energy-storing device between capacitor and battery, safety and environmental protection, pollution-free, non-maintaining; Leakage current is little, have extended cycle life; Can fast charging and discharging, power density is high.Ultracapacitor obtains extensive use in fields such as electric automobile, mobile communication, solar energy and wind power generation, Aero-Space and science and techniques of defence.Electrode material is one of key factor determining ultracapacitor performance, and the electrode material that exploitation has excellent electrochemical performance is most crucial problem in current ultracapacitor research.Mainly contain Carbon Materials, metal oxide and conducting polymer as the material of electrode of super capacitor at present.Carbon Materials is to study the earliest and the most ripe one in electrode material for super capacitor.Its aboundresources, good conductivity, energy storage speed are fast, stable performance, but it is than the common 100F/g that is less than of electric capacity, and efficiency for charge-discharge is lower, self-discharge phenomenon is more serious, easily reunites.Ruthenic oxide (RuO
2) conductivity is better than carbon resistance rod, and can obtain higher specific energy, chemical property excellence, but expensive, be unfavorable for promoting.Other metal oxide is as manganese dioxide (MnO
2), nickel oxide (NiO) cobaltosic oxide (Co
3o
4) etc. conductivity poor, lasting cyclicity is poor, electrochemical window is narrow, usually used as the interpolation phase of other material.What in conducting polymer, be used as electrode of super capacitor mainly contains polypyrrole (polypyrrole), polyaniline (polyaniline), polythiophene (polythiophene) etc. and derivative thereof.Their advantage is that energy storage density is high, specific power is high, environmentally safe etc., can adopt organic bath and aqueous electrolyte to make electrolyte.When particularly polythiophene (polythiophene) etc. and derivative thereof are as electrode, two electrodes all can be doped, and charge storage amount is large, conductivity is higher, capacitor internal resistance is little, and power output is large, can under high working voltage, (3.0-3.2V) use.Be considered to the most promising electrode material for super capacitor.Wherein poly-3,4 ethylenedioxy thiophenes (PEDOT) are of greatest concern.But, conducting polymer and metal oxide have common disadvantage as fake capacitance material, its energy storage is slow, quick faraday's reaction in charge and discharge process can cause material phase transformation, volumetric expansion and efflorescence, has greatly weakened high rate performance and the cyclicity of electrode material.
Thereby, Carbon Materials, metal oxide and conducting polymer are combined, to maximize favourable factors and minimize unfavourable ones, the composite material that builds excellent performance becomes the main direction of current electrode material for super capacitor research.Patent ZL201010288329.4 discloses the combination electrode material preparation method of a kind of Graphene and metal oxide; Patent ZL201010209772.8 discloses a kind of preparation method of polypyrrole/graphene composite material; Patent ZL201210003652.1 discloses a kind of preparation method of graphite oxide/polypyrrole composite material; Patent ZL 200910031025.7 discloses a kind of graphene oxide/polyaniline super capacitor composite electrode material and preparation method thereof.In current disclosed patent, when preparation contains the electrode composite material of conducting polymer, generally first prepare composite material, then add binding agent, conductive agent as formation electrodes such as acetylene blacks.Manufacturing cycle is longer, and needs to add more auxiliary element, and dispersiveness, the compatibility etc. of material component all can affect the performance of composite property to a certain extent.In addition, in combined material, Graphene and other nano material are with high costs, are also unfavorable for applying.Thereby development cost is cheap, stable performance and do not need the composite electrode that adds the auxiliary elements such as binding agent to be of great significance for the preparation of ultracapacitor tool.
Summary of the invention
The object of the invention is to utilize resin carbon and conducting polymer advantage separately, overcome deficiency separately, propose a kind of method of phenolic resin carbon/polythiophene electrode of processability excellence.The present invention, taking phenol-formaldehyde resin modified as matrix, obtains its charing a kind of porous resin charcoal of remaining Anthraquinones structure, then it is mixed with thiophene and derivatives monomer, the limited electrode of super capacitor that aggregates into of direct in-situ under simulation ultracapacitor processing conditions.Simple, the prepared phenolic resin carbon/polythiophene electrode conductivity of process conditions of the present invention is high, chemical property good.
Step of preparation process order of the present invention is as follows:
(1) phenolic aldehyde oligomer is mixed to 10-60min with boron carbide under ultrasonic state or under mechanical agitation state, the formation phenol-formaldehyde resin modified that is heating and curing after mixing, curing temperature is 180 DEG C, heating rate is lower than 15 DEG C/min.The mixed proportion of phenolic aldehyde oligomer and boron carbide is controlled at 40: 60 ~ within 95: 5.
(2) phenol-formaldehyde resin modified is processed to 2h in 650-850 DEG C in the inert atmospheres such as nitrogen or under vacuum condition, obtain and remain with the resin porous charcoal of anthraquinone ring.
(3) resin porous charcoal is ground into diameter with grinder and is less than 200 object powder.
(4) porous charcoal powder is mixed with thiophene or derivatives thereof monomer, and add certain density FeCl
3solution and ethanolic solution.After mixing, simulation is pressed into electrode under ultracapacitor processing conditions.
(5) in described step (4), the mass ratio of porous charcoal powder and thiophene or derivatives thereof monomer is 15: 85 ~ 75: 25, the FeCl of interpolation
3solution and ethanolic solution account for 2 ~ 15% of carbon powder and thiophene or derivatives thereof monomer mass; FeCl
3the concentration of solution is 0.1 ~ 2mol/l; Ethanolic solution concentration is for being greater than 60%.
(6) described step (4) ultracapacitor processing conditions is temperature range: 30 ~ 95 DEG C, pressure is 0.2 ~ 15MPa, and the press time is 5s ~ 30min.
The present invention utilizes phenol-formaldehyde resin modified porous charcoal directly to mix with thiophene or derivatives thereof monomer, and under simulation ultracapacitor processing conditions, direct polymerization becomes electrode.
Compared with prior art, the present invention has following beneficial effect:
(1) porous resin charcoal is with low cost, and remaining organo-functional group anthraquinone ring is similar to thiophene monomer, is conducive to both even mixing.Advantage on cost is conducive to applying of ultracapacitor.
(2) boron in the porous resin charcoal of configuration has good doping effect to polythiophene, is conducive to improve the electrical property of electrode.
(3) directly under ultracapacitor processing conditions, aggregate into electrode after porous charcoal is mixed with thiophene or derivatives thereof monomer, be pressed into electrode without adding again adhesive, conductive agent etc. after synthetic composite material.Moulding process had both been saved in this invention, had also avoided the auxiliary elements such as interpolation adhesive, conductive agent, was conducive to the stability of electrode performance.
Brief description of the drawings
Fig. 1 is the condition of molding schematic diagram of the actual processing conditions bottom electrode of simulation ultracapacitor.
Fig. 2 is the cyclic voltammetric characteristic of the composite electrode that obtains of embodiment 1.
Embodiment
Embodiment 1
(1) 30g phenolic aldehyde oligomer is mixed to 30min with 5g boron carbide powder under ultrasonic state, after mixing from room temperature the heating rate to 180 DEG C with 2 DEG C/min, and at 180 DEG C of insulation 3h, obtain modified resin sample.
(2) phenol-formaldehyde resin modified is processed to 2h, acquisition resin porous charcoal in 680 DEG C under vacuum condition.Wherein vacuum degree is not less than 0.01MPa.
(3) resin porous charcoal is ground into and is less than 200 object powder with grinder.
(4) get 20g porous charcoal powder and 15g3,4-ethylenedioxy thiophene monomer mixes with ultrasonic wave, adds the FeCl of 4g concentration 0.5mol/l
3the ethanolic solution of solution, 3 concentration 95%.After mixing, depress to electrode in condition shown in Fig. 1.Temperature is 75 DEG C, and the time is 15min, and pressure is 0.5MPa.
(5) the cyclic voltammetric characteristic of sample is tested, its window voltage is 0.2 ~ 3.0V, illustrates that the material that this invention obtains is the good electrode material for super capacitor of a kind of electrical property.
Claims (2)
1. a preparation method for phenolic resin carbon/polythiophene composite material, is characterized in that described preparation method's key step is as follows:
(1) phenolic aldehyde oligomer and boron carbide are mixing cured, and curing temperature is 180 DEG C, and after solidifying, under inert environments, 650-850 DEG C of processing 2h obtains porous resin charcoal; (2) porous resin charcoal grinds to form diameter and is not more than after 200 object powder, mixes by a certain percentage with thiophene or derivatives thereof, mixes a certain amount of FeCl of rear interpolation
3solution and ethanolic solution; The mass ratio of carbon powder and thiophene or derivatives thereof monomer is 15: 85 ~ 75: 25, FeCl
3the concentration of solution is 0.1 ~ 2mol/l, and ethanolic solution concentration is for being greater than 60%; (3) step (2) gained mixture direct polymerization under similar ultracapacitor processing conditions is obtained to electrode, processing conditions is temperature range: 30 ~ 95 DEG C, pressure is 0.2 ~ 15MPa, and the press time is 5s ~ 30min.
2. by porous resin charcoal and the compound electrode of polythiophene, for the preparation of ultracapacitor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314104.XA CN104124073A (en) | 2014-07-03 | 2014-07-03 | Preparation method for phenolic resin carbon/polythiophene composite electrode |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410314104.XA CN104124073A (en) | 2014-07-03 | 2014-07-03 | Preparation method for phenolic resin carbon/polythiophene composite electrode |
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| CN104124073A true CN104124073A (en) | 2014-10-29 |
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| CN201410314104.XA Pending CN104124073A (en) | 2014-07-03 | 2014-07-03 | Preparation method for phenolic resin carbon/polythiophene composite electrode |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108198702A (en) * | 2018-01-12 | 2018-06-22 | 湖南工业大学 | A kind of method that polythiophene makes electrode |
| CN108257790A (en) * | 2018-01-12 | 2018-07-06 | 湖南工业大学 | A kind of method for making membranaceous polythiophene electrode |
| CN110444411A (en) * | 2019-08-26 | 2019-11-12 | 河北省科学院能源研究所 | A kind of conductive organic polymer package phenolic resin base porous carbon composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070154381A1 (en) * | 2005-12-29 | 2007-07-05 | Miller Douglas J | Carbon foam with improved graphitizability |
| CN102443167A (en) * | 2010-09-30 | 2012-05-09 | 西门子公司 | Composite material for super capacitor, super capacitor and preparation method thereof |
-
2014
- 2014-07-03 CN CN201410314104.XA patent/CN104124073A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070154381A1 (en) * | 2005-12-29 | 2007-07-05 | Miller Douglas J | Carbon foam with improved graphitizability |
| CN102443167A (en) * | 2010-09-30 | 2012-05-09 | 西门子公司 | Composite material for super capacitor, super capacitor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高峰阁,田艳红: "聚噻吩/活性炭复合材料作为超级电容器电极材料的电性能", 《高分子材料科学与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108198702A (en) * | 2018-01-12 | 2018-06-22 | 湖南工业大学 | A kind of method that polythiophene makes electrode |
| CN108257790A (en) * | 2018-01-12 | 2018-07-06 | 湖南工业大学 | A kind of method for making membranaceous polythiophene electrode |
| CN110444411A (en) * | 2019-08-26 | 2019-11-12 | 河北省科学院能源研究所 | A kind of conductive organic polymer package phenolic resin base porous carbon composite material |
| CN110444411B (en) * | 2019-08-26 | 2021-08-17 | 河北省科学院能源研究所 | Conductive organic polymer coated phenolic resin matrix porous carbon composite material |
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Application publication date: 20141029 |