CN105261485A - Method for preparing capacitor electrode material - Google Patents
Method for preparing capacitor electrode material Download PDFInfo
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- CN105261485A CN105261485A CN201510694224.1A CN201510694224A CN105261485A CN 105261485 A CN105261485 A CN 105261485A CN 201510694224 A CN201510694224 A CN 201510694224A CN 105261485 A CN105261485 A CN 105261485A
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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
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- 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 provides a method for preparing nitrogen-doped porous carbon nanofiber material with a high specific surface area. The nitrogen-doped porous carbon nanofiber material with the high specific surface area can be obtained by treating electrospun polyacrylonitrile/polyaniline composite nanofibers in an inert atmosphere at an appropriate temperature. Compared with the prior art, the invention uses the electrospun polyacrylonitrile nanofibers directly as a substrate for growing a polyaniline nanowire and synthesizing the electrospun polyacrylonitrile/polyaniline composite nanofibers. In addition to having high content of nitrogen atoms, the composite nanofibers also have an extensive pore structure on the surface. The composite nanofibers can be heat-treated to obtain the nitrogen-doped porous carbon nanofiber material with the high specific surface area. The obtained material is supercapacitor electrode material and has excellent electrochemical properties. In particular, the method for preparing the nitrogen-doped porous carbon nanofiber material with the high specific surface area is simple in preparation process, short in process flow, low in device dependence and suitable for industrial mass production.
Description
Technical field
The invention belongs to electrochemical capacitor technical field, particularly relate to a kind of preparation method of capacitor electrode material.
Background technology
Along with people are to the renewable energy utilization form of paying attention to and constantly seeking clean and effective gradually of environmental protection; ultracapacitor is owing to having had the advantage of battery and traditional capacitor concurrently; not only in the novel energy devices such as hybrid vehicle, there is huge potential using value; also play an important role in communication, space flight, national defence etc., also therefore become the object that vast researcher is paid close attention to and researched and developed.
Electrode material, as the key components of ultracapacitor, determines ultracapacitor fundamental characteristics.Material with carbon element because it is cheap and easy to get, operating temperature range is wide, proportion is little, specific area is adjustable, pore structure is flourishing, chemical stability is high, mature production technology, the advantage such as environmentally friendly be usually used to electrode material for super capacitor.This ultracapacitor based on material with carbon element, also referred to as double electric layer capacitor, possesses high power density, large current density power, excellent cyclical stability and advantages of environment protection and is studied widely.But the energy density of this double electric layer capacitor is relatively low, can not practical requirement and application.At present, research mainly concentrate on improve material with carbon element specific area, adjustment aperture distribution, add metal oxide and improve counterfeit ratio capacitance or introducing hetero-atoms (comprising nitrogen-atoms, oxygen atom, phosphorus atoms, boron atom) changes material with carbon element electron distributions state, its object is all improve the electrochemical properties of capacitor.Wherein improve material with carbon element specific area and increase electric double layer capacitance; Adjustment aperture distribution improves the large current density power of capacitor; Introducing nitrogen-atoms except improving the conductivity, wetability etc. of material to a certain extent, mainly increasing fake capacitance storage effect and obtaining high specific capacitance.The N doping porous carbon nanofiber material therefore with high-specific surface area is a kind of method of comparatively ideal raising material with carbon element electrochemical properties.
Usually the method preparing the nitrogen-doped porous carbon material of high-specific surface area has two kinds: a kind of be material with carbon element at high temperature with the common heat treatment of the nitrogenous small-molecule substances such as ammonia; A kind of is to the direct heat treatment at high temperature of nitrogenous macromolecule polyalcohol presoma.Compared to first method, second method by regulate treatment temperature can realize uniform, controlled content nitrogen element introduce and pay close attention to by everybody.The maximum presoma of current use mainly concentrates on the nitrogen containing polymer polymer such as melamine, polyaniline, polypyrrole, polyacrylonitrile and bioprotein.The nitrogen-doped porous carbon material of the relevant high-specific surface area of current acquisition, or be that microcellular structure accounts for leading material with carbon element, although have high specific area, ratio capacitance does not have raising to a great extent; Relate to complex steps, process be complicated, condition is harsh and high in cost of production problem, limit its in ultracapacitor and apply further.
Summary of the invention
The technical problem to be solved in the present invention is the preparation method of the nitrogen-doped porous carbon material providing a kind of high-specific surface area, and preparation method is simple for this electrode material.
A preparation method for electrode material for super capacitor, specifically prepares according to following steps:
Step 1: preparation concentration is the DMF solution 10ml of 0.15g/ml polyacrylonitrile;
Step 2: above-mentioned solution is carried out electrostatic spinning to obtain polyacrylonitrile nanofiber.Approximately above-mentioned for 2ml solution is poured into (note: syringe volume is 10ml in injector for medical purpose at every turn; Syringe needle is long is 2.5cm; Syringe tip external diameter is 0.7mm).Syringe tip is 15 ~ 20cm apart from the distance of collecting board, and electrode voltage is carry out spinning under the condition of 10kV, thus acquisition diameter is about the uniform polyacrylonitrile nanofiber cloth of 300 ~ 400nm.
Step 3: measure 30ml deionized water, and 0.5ml concentrated hydrochloric acid and 1.4g anhydrous ferric chloride are successively put into and stirred 30min.This solution put into by the polyacrylonitrile nanofiber cloth (note: 1cm*2cm) step 2 obtained, and make it fully to infiltrate 10min.Under temperature is 60 C water bath's conditions, in this solution, drip aniline monomer solution, the amount of aniline monomer solution is preferably 0.2ml ~ 0.8ml, is more preferably 0.4ml, and keeps 12h.
Step 4: polyacrylonitrile step 3 obtained/polyaniline product, successively uses deionized water and absolute ethanol washing 3 ~ 5 times respectively, is then placed in 80 degrees Celsius of baking oven 12h and dries, obtain the presoma preparing high-specific surface area nitrogen-doped porous carbon material thus.
Step 5: gained presoma in step 4 is placed in tube furnace, heat treatment in an inert atmosphere, the temperature of described process is preferably 800 ~ 1000 degrees Celsius, is more preferably 900 degrees Celsius, and heating rate is that 5 centigrade per minutes are from room temperature to preferable temperature.Obtain electrode material for super capacitor thus, i.e. the nitrogen-doped porous carbon material of high-specific surface area.
Utilize the preparation method of electrode material for super capacitor of the present invention, the nitrogen-doped porous carbon material of the high-specific surface area of preparation, in 1M dilute sulfuric acid aqueous solution and under the current density of 0.5A/g, its ratio capacitance value is up to 335F/g, there is extraordinary large current density power simultaneously, namely under the current density of 32A/g, its ratio capacitance still keeps 175F/g, shows good ultracapacitor performance.
The preparation method of electrode material for super capacitor of the present invention, preparation technology is simple, flow process is short, device dependence is low, be applicable to industrialization large-scale production.
The electrode material of the ultracapacitor that preparation method of the present invention obtains, can be used in the electrode of ultracapacitor, obtains the electrode of function admirable, thus improves the performance of the ultracapacitor of this electrode material.
Accompanying drawing explanation
Accompanying drawing 1 is the stereoscan photograph of polyacrylonitrile/polyaniline composite fibre presoma prepared by embodiment 1;
Accompanying drawing 2 is the stereoscan photograph of high-specific surface area N doping porous carbon nanofiber material prepared by embodiment 1;
Accompanying drawing 3 is nitrogen adsorption-desorption isothermal curve (a) of high-specific surface area nitrogen-doped porous carbon material prepared by embodiment 1 and the pore-size distribution (b) that calculated by NLDFT;
Accompanying drawing 4 is the x-ray photoelectron power spectrum of high-specific surface area nitrogen-doped porous carbon material prepared by embodiment 1.
Accompanying drawing 5 is the cyclic voltammetry curve (a) of electrode material for super capacitor under three-electrode system under different scanning rates prepared of embodiment 1 and (b); Constant current charge-discharge curve (c) under different current density and (d).
Accompanying drawing 6 is electrode material for super capacitor prepared by embodiment 1, is tested, the ratio capacitance obtained-current density plot figure by constant current charge-discharge.
Embodiment
Below in conjunction with representational embodiment, the preparation method to the electrode material of ultracapacitor of the present invention is described.And reagent used in following examples is commercially available.
Embodiment 1
(1) take 1.5g polyacrylonitrile macromolecule dissolution to 10mlN, in N-dimethylformamide solution, stir 24h to homogeneous transparent.
(2) precursor solution in step (1) is carried out electrostatic spinning to prepare polyacrylonitrile nanofiber.Approximately above-mentioned for 2ml solution is poured into (note: syringe volume is 10ml in injector for medical purpose at every turn; Syringe needle is long is 2.5cm; Syringe tip external diameter is 0.7mm).Syringe tip is 15 ~ 20cm apart from the distance of collecting board, and electrode voltage is carry out spinning under the condition of 10kV, thus acquisition diameter is about the uniform polyacrylonitrile nanofiber cloth of 300 ~ 400nm.
(3) take 1.5g anhydrous ferric chloride respectively and 0.5ml concentrated hydrochloric acid is dissolved in 30ml deionized water, stir 30min and make iron chloride and the mixed in hydrochloric acid aqueous solution.The polyacrylonitrile nanofiber cloth (note: 1cm*2cm) obtained in step (2) is put into this solution, and makes it fully to infiltrate 10min.Under temperature is 60 C water bath's conditions, drip aniline monomer solution 0.4ml in this solution, lucifuge keeps 12h.
(4) by step (3) gained polyacrylonitrile/polyaniline product, successively use deionized water and absolute ethanol washing 3 ~ 5 times respectively, then be placed in 80 degrees Celsius of baking oven 12h to dry, obtain the presoma preparing high-specific surface area N doping porous carbon nanofiber material thus.
(5) presoma that step (4) obtains is placed in tube furnace, heat treatment in an inert atmosphere, the temperature of described process is 900 degrees Celsius, heating rate be 5 centigrade per minutes from room temperature to preferable temperature, then cool to room temperature.Obtain electrode material for super capacitor thus, i.e. the N doping porous carbon nanofiber material of high-specific surface area.
Electrode material for super capacitor prepared by the present embodiment, there is high specific area, suitable pore-size distribution and nitrogen atom content, thus the ratio capacitance of electrode material for super capacitor is increased, can find out that from electrode material for super capacitor cyclic voltammetry curve prepared by the present embodiment its curve is close to rectangle and constant current charge-discharge curve linearly triangle, all illustrate that its invertibity is better, there is good super capacitor character.
Embodiment 2: the present embodiment as different from Example 1: aniline monomer amount is 0.2ml in step (3).Other are identical with specific embodiment 1.
Embodiment 3: the present embodiment as different from Example 1: aniline monomer amount is 0.8ml in step (3).Other are identical with specific embodiment 1.
Embodiment 4: this enforcement formula as different from Example 1: treatment temperature is 800 degrees Celsius in step (5).Other are identical with specific embodiment 1.
Embodiment 5: the present embodiment as different from Example 1: treatment temperature is 1000 degrees Celsius in step (5).Other are identical with specific embodiment 1.
Embodiment 6: the present embodiment as different from Example 1: aniline monomer amount is that in 0.2ml step (5), treatment temperature is 800 degrees Celsius in step (3).Other are identical with specific embodiment 1.
Embodiment 7: the present embodiment as different from Example 1: aniline monomer amount is that in 0.8ml step (5), treatment temperature is 800 degrees Celsius in step (3).Other are identical with specific embodiment 1.
Embodiment 8: the present embodiment as different from Example 1: aniline monomer amount is that in 0.2ml step (5), treatment temperature is 1000 degrees Celsius in step (3).Other are identical with specific embodiment 1.
Embodiment 9: the present embodiment as different from Example 1: aniline monomer amount is that in 0.8ml step (5), treatment temperature is 1000 degrees Celsius in step (3).Other are identical with specific embodiment 1.
Embodiment 10: the present embodiment as different from Example 1: the polyacrylonitrile fibre cloth obtained in step (2), without step (3) and step (4).Directly in step (5) through 900 celsius temperature process.Other are identical with specific embodiment 1.
Embodiment 11: the present embodiment as different from Example 1: the polyacrylonitrile fibre cloth obtained in step (2), without step (3) and step (4).Directly in step (5) through 800 celsius temperature process.Other are identical with specific embodiment 1.
Embodiment 12: the present embodiment as different from Example 1: the polyacrylonitrile fibre cloth obtained in step (2), without step (3) and step (4).Directly in step (5) through 1000 celsius temperature process.Other are identical with specific embodiment 1.
Claims (2)
1. a preparation method for capacitor electrode material, is characterized in that concrete steps are as follows:
1), the DMF solution 10ml that concentration is 0.15g/ml polyacrylonitrile is prepared;
2), above-mentioned solution is carried out electrostatic spinning to obtain polyacrylonitrile nanofiber, above-mentioned for 2ml solution is poured in injector for medical purpose at every turn, syringe tip is 15 ~ 20cm apart from the distance of collecting board, electrode voltage is carry out spinning under the condition of 10kV, thus acquisition diameter is about the uniform polyacrylonitrile nanofiber cloth of 300 ~ 400nm;
3) 30ml deionized water, is measured, and 0.5ml concentrated hydrochloric acid and 1.4g anhydrous ferric chloride are successively put into and stirred 30min, this solution put into by polyacrylonitrile nanofiber cloth step 2 obtained, and make it fully to infiltrate 10min, under temperature is 60 C water bath's conditions, in this solution, drip aniline monomer solution, the amount of aniline monomer solution is 0.2ml ~ 0.8ml;
4) polyacrylonitrile, by step 3 obtained/polyaniline product, successively uses deionized water and absolute ethanol washing 3 ~ 5 times respectively, is then placed in 80 degrees Celsius of baking oven 12h and dries, obtain the presoma preparing high-specific surface area nitrogen-doped porous carbon material thus;
5), gained presoma in step 4 is placed in tube furnace, heat treatment in an inert atmosphere, the temperature of described process is preferably 800 ~ 1000 degrees Celsius, be more preferably 900 degrees Celsius, heating rate is that 5 centigrade per minutes are from room temperature to preferable temperature, obtain the nitrogen-doped porous carbon material of high-specific surface area thus, i.e. capacitor electrode material.
2. according to the preparation method of a kind of capacitor electrode material according to claim 1, it is characterized in that in step 3, the amount of aniline monomer solution elects 0.4ml as, and in step 5, the temperature of process is 900 degrees Celsius.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995948A (en) * | 2017-04-10 | 2017-08-01 | 吉林大学 | A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications |
| CN107424847A (en) * | 2017-07-21 | 2017-12-01 | 张娟 | A kind of preparation method of nitrogen-doped carbon nano-fiber Supported Co acid nickel combination electrode material |
| CN108597912A (en) * | 2018-05-03 | 2018-09-28 | 东华大学 | Multistage nitrogen-doped carbon nano-fiber material and preparation method thereof inside and outside one kind |
| CN112517041A (en) * | 2020-12-15 | 2021-03-19 | 广州大学 | Solid-phase Fenton-like catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103255634A (en) * | 2013-05-23 | 2013-08-21 | 中原工学院 | Preparation method of polyacrylonitrile/polyaniline compound micro-nano conductive fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103255634A (en) * | 2013-05-23 | 2013-08-21 | 中原工学院 | Preparation method of polyacrylonitrile/polyaniline compound micro-nano conductive fiber |
Non-Patent Citations (2)
| Title |
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| FUJUN MIAO等: ""Flexible solid-state supercapacitors based on freestanding electrodes of electrospun polyacrylonitrile@polyaniline core-shell nanofibers"", 《ELECTROCHIMICA ACTA》 * |
| NIMALI C. ABEYKOON等: ""Supercapacitor performance of carbon nanofiber electrodes derived from immiscible PAN/PMMA polymer blends"", 《ROYAL SOCIETY OF CHEMISTRY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995948A (en) * | 2017-04-10 | 2017-08-01 | 吉林大学 | A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications |
| CN106995948B (en) * | 2017-04-10 | 2019-07-12 | 吉林大学 | A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications |
| CN107424847A (en) * | 2017-07-21 | 2017-12-01 | 张娟 | A kind of preparation method of nitrogen-doped carbon nano-fiber Supported Co acid nickel combination electrode material |
| CN108597912A (en) * | 2018-05-03 | 2018-09-28 | 东华大学 | Multistage nitrogen-doped carbon nano-fiber material and preparation method thereof inside and outside one kind |
| CN112517041A (en) * | 2020-12-15 | 2021-03-19 | 广州大学 | Solid-phase Fenton-like catalyst and preparation method and application thereof |
| CN112517041B (en) * | 2020-12-15 | 2023-03-14 | 广州大学 | Solid-phase Fenton-like catalyst and preparation method and application thereof |
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