CN102010594B - Method for preparing conductive polymer/silsesquioxane composite electrode material - Google Patents
Method for preparing conductive polymer/silsesquioxane composite electrode material Download PDFInfo
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- CN102010594B CN102010594B CN2010105204651A CN201010520465A CN102010594B CN 102010594 B CN102010594 B CN 102010594B CN 2010105204651 A CN2010105204651 A CN 2010105204651A CN 201010520465 A CN201010520465 A CN 201010520465A CN 102010594 B CN102010594 B CN 102010594B
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Abstract
The invention relates to a method for preparing a conductive polymer/silsesquioxane composite electrode material, which comprises two reactions that: silsesquioxane with end benzene ring and sulfonating agent undergo sulfonation reaction to form a phenyl sulfonic acid group, silsesquioxane with end mercapto and oxidant undergo oxidation reaction to form a sulfonic acid group, and the silsesquioxane and an intrinsic conductive polymer monomer undergo in situ polymerization to form the composite electrode material. The method has simple process and low cost; the prepared conductive polymer nano composite material has good electric conductivity (more than 5S/m) and large specific surface area; and a super capacitor prepared from the electrode material has the characteristics of high specific power, high specific energy, good recyclability and the like, and has good application prospect.
Description
Technical field
The invention belongs to the preparation field of composite electrode material for super capacitor, the preparation method of particularly a kind of conductive polymers/silsesquioxane combination electrode material.
Background technology
Along with progressively exhausting of petrochemical industry resource and becoming increasingly conspicuous of environmental problem, seeking new forms of energy becomes one of maximum challenge of 21st century.Ultracapacitor is traditional capacitor 10 on specific energy
6Doubly, specific power is tens times of battery; Have the advantage than macro-energy density of fast, the often capable of circulation and battery of the speed that discharges and recharges of traditional capacitor concurrently.Therefore, ultracapacitor is swift and violent in nearly more than ten years development, has been applied to fields such as buffered sources, photographic goods, mobile phone, toy.But will widespread use on portable type electronic product and hybrid vehicle, also need on performance, improve a lot.
Ruthenium oxide is at present than electric energy, capacitor electrode material that specific power is the highest, but with high costs because of it, is difficult to the marketization and produces; In recent years, low-valent transition metals such as manganese oxide, vanadium oxide oxide compound has partly substituted ruthenium oxide and has been used for electrical condenser.Carbon-based material also is widely used in electrical condenser because of the specific surface area of super large and controlled aperture.Conducting polymer receives ultracapacitor investigator's concern more and more because of advantage such as have little, the good electrochemical properties of mass density, fine environment stability, be easy to synthesize, and is used as electrode of super capacitor just gradually.It is raw material that Chinese invention patent ZL200510027961.2 discloses with aniline and Manganse Dioxide, adopts the polyaniline/manganese dioxide electrode materials of in-situ polymerization preparation system, but electroconductibility not high (10
-3～10
-4S/cm), the internal resistance of electrode is bigger.Chinese invention patent ZL200610105269.1 discloses at the carbon tube-surface and has coated polyaniline, has improved the electroconductibility of matrix material, but remains further to be improved than electric capacity.U.S. patent of invention US758543382 discloses with polyaniline/carbon hybrid material and has prepared double electric layers supercapacitor, and its polyaniline and aniline derivatives polymkeric substance be the adulterated polymkeric substance of right and wrong all, causes lower than electric capacity.
Traditional electrical condenser theory thinks that the transfer of electronics on electrode materials is very rapid, the determining electrode material electrochemical performance be the response of diffusion layer to discharging and recharging.But discover that recently when the dimension of electrode materials is very little, the contact surface between electrode materials and electrolytic solution increases greatly, the diffusion layer attenuation can improve the response speed that discharges and recharges greatly, even surpasses electrode material surface charge migration speed.Therefore, the introducing of advanced nano material becomes to improving the new way of ultracapacitor performance.The three-dimensional dimension of cage-type silsesquioxane is about 1～3nm, and the size that is connected with the machine group with the summit is relevant.Introduce the microtexture that cage-type silsesquioxane can improve conducting polymer, make it that better chemical property arranged.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of conductive polymers/silsesquioxane combination electrode material; Present method technology is simple; Cost is low, the conductive polymer nanometer composite material that is prepared into have good electrical conductivity (＞5S/m), bigger serface; Ultracapacitor with such electrode materials preparation has high-specific-power, high-energy-density and good characteristics such as recyclability, has a good application prospect.
The preparation method of a kind of conductive polymers of the present invention/silsesquioxane combination electrode material comprises:
(1) the 30mL vitriol oil is mixed slow Dropwise 5～15mL chlorsulfonic acid, 5～15mL, 30～50% ydrogen peroxide 50,2～3g potassium permanganate or 10～15ml, 20～30% oleums under agitation condition with 3～5g silsesquioxane; Slowly be warming up to 60～90 ℃ and keep 6～12h; Isolate the sulfonated silsesquioxane, washing, drying obtain the silsesquioxane of modification;
(2) silsesquioxane with modification is dispersed in 0.1～3molL
-1In the acidic aqueous solution, ultra-sonic dispersion is even, and silsesquioxane concentration is 0.01～1wt%;
(3) add in conductive polymers monomer to the above-mentioned acidic aqueous solution, ultrasonic 1～5h makes the silsesquioxane thorough mixing after monomer and the modification obtain mixed solution, and concentration is 0.05～0.5molL
-1
(4) above-mentioned mixed solution is cooled to 0 ℃, adds oxygenant, the concentration that oxygenant accounts for mixed solution is 0.05～0.5molL
-1Mixed solution leaves standstill the 24h after-filtration under 0 ℃, to be washed till filtrating respectively colourless for water and absolute ethyl alcohol successively, and in vacuum drying oven, dries, and obtains combination electrode material.
Silsesquioxane general formula described in the step (1) is R
xR '
y(SiO
1.5) n, wherein n is 8,10 or 12,1≤x≤n, x+y=n, and R and R ' are same to each other or different to each other; Wherein R and R ' are the reactive groups that sulfonation reaction can take place, and are specially the alkyl of phenyl, band phenyl, the alkoxyl group or the sulfydryl of band phenyl.
Acidic aqueous solution described in the step (2) is the aqueous solution of sulfuric acid, hydrochloric acid, acetate, dodecyl sodium sulfonate or hexadecyl sulfonic acid.
Conductive polymers described in the step (3) is polyaniline, polypyrrole or Polythiophene.
Oxygenant described in the step (4) is Potassium Persulphate, ammonium persulphate, hydrogen peroxide or iron trichloride.
The present invention mainly comprises two types of reactions: the silsesquioxane that has terminal phenyl ring is sent out into sulfonation reaction formation phenylbenzimidazole sulfonic acid base with sulphonating agent; The silsesquioxane and the oxygenant generation oxidizing reaction that have terminal sulfydryl form sulfonic group, silsesquioxane and intrinsically conducting polymer monomer in-situ polymerization.
Silsesquioxane can only be in a small amount of organic solvent slightly soluble; The present invention utilizes the sulfonation modifying cage-type silsesquioxane; Solve its homodisperse problem in water; And the adding conductive high polymer monomer, utilize in-situ polymerization to prepare the conductive polymer composite of the homodisperse fractal structure of silsesquioxane particles; The conducting polymer composite of fractal structure has good gap structure and high specific surface area, helps right disengaging of dopant ion and entering, has improved the ratio electric capacity of electrode materials greatly; The introducing of the silsesquioxane of cagelike structure has increased the porosity of material, makes material increase greatly than electric capacity; Silsesquioxane particles plays the effect of nucleator when the preparation conductive polymer composite, strengthened the stability of matrix material microtexture, has increased the stability that discharges and recharges of electrode materials.
Beneficial effect
Present method technology is simple, and cost is low; The conductive polymer nanometer composite material that is prepared into have good electrical conductivity (＞5S/m), bigger serface is done the electrode materials of ultracapacitor with this type of conducting polymer composite material, can reach 1810F/g than electric capacity, low internal resistance, but fast charging and discharging; Ultracapacitor with such electrode materials preparation has high-specific-power, high-energy-density and good characteristics such as recyclability, has a good application prospect.
Description of drawings
Fig. 1 is that the octaphenyl silsesquioxane is through oleum sulfonation reaction synoptic diagram;
Fig. 2 is the electromicroscopic photograph of embodiment 1 polyaniline/silsesquioxane matrix material;
Fig. 3 is that embodiment 1 pure polyaniline and polyaniline/silsesquioxane matrix material are at 100mVs
-1Cyclic voltammetry curve under the sweep velocity, wherein X-coordinate is a current potential, ordinate zou is an electric current.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) preparation of sulfonation silsesquioxane.The 30mL vitriol oil is added in the 100mL there-necked flask, add 3g octaphenyl silsesquioxane, utilize magneton to stir; Slowly drip 15mL 20% oleum; Slowly be warming up to 90 ℃ after dropwising and keep 6h.Leach the silsesquioxane after the sulfonation with No. 4 sintered filter funnels, it is neutral to be washed till filtrating with deionized water.Vacuum drying is subsequent use under the room temperature.(2) silsesquioxane after the sulfonation is dispersed in 30mL 1molL
-1In the aqueous sulfuric acid, ultra-sonic dispersion is even, and its concentration is 1.0%; (3) add aniline monomer to above-mentioned H
2SO
4In the aqueous solution, its concentration is 0.1mol L
-1, ultrasonic 1h fully acts on the silsesquioxane after aniline monomer and the chemical modification; (4) add fast ammonium persulphate 0.684g after above-mentioned mixed solution is cooled to 0 ℃, stir, mixed solution remains under 0 ℃ and leaves standstill 24h; (5) water and absolute ethyl alcohol be washed till filtrating colourless; (6) matrix material is dried in vacuum drying oven, temperature is 50 ℃.Promptly obtain conductive polymers/silsesquioxane combination electrode material.
Embodiment 2
(1) preparation of sulfonation silsesquioxane.The 30mL vitriol oil is added in the 100mL there-necked flask, add 3g octaphenyl silsesquioxane, utilize magneton to stir; Slowly drip 10mL 30% oleum; Slowly be warming up to 60 ℃ after dropwising and keep 6h.Leach the silsesquioxane after the sulfonation with No. 4 sintered filter funnels, it is neutral to be washed till filtrating with deionized water.Vacuum drying is subsequent use under the room temperature.(2) silsesquioxane after the sulfonation is dispersed in 30mL 1molL
-1In the aqueous sulfuric acid, ultra-sonic dispersion is even, and its concentration is 0.75%; (3) add aniline monomer to above-mentioned H
2SO
4In the aqueous solution, its concentration is 0.1mol L
-1, ultrasonic 1h fully acts on the silsesquioxane after aniline monomer and the chemical modification; (4) add fast ammonium persulphate 0.684g after above-mentioned mixed solution is cooled to 0 ℃, stir, mixed solution remains under 0 ℃ and leaves standstill 24h; (5) water and absolute ethyl alcohol be washed till filtrating colourless; (6) matrix material is dried in vacuum drying oven, temperature is 60 ℃.Promptly obtain conductive polymers/silsesquioxane combination electrode material.
Embodiment 3
(1) preparation of sulfonation silsesquioxane.The 30mL vitriol oil is added in the 100mL there-necked flask, add 3g ten phenylbenzene silsesquioxanes, utilize magneton to stir; Slowly drip the 8mL chlorsulfonic acid; Dropwise the back room temperature and keep 12h.Leach the silsesquioxane after the sulfonation with No. 4 sintered filter funnels, it is neutral to be washed till filtrating with deionized water.Vacuum drying is subsequent use under the room temperature.(2) silsesquioxane after the sulfonation is dispersed in 30mL 1molL
-1In the aqueous sulfuric acid, ultra-sonic dispersion is even, and its concentration is 1.0%; (3) add aniline to above-mentioned H
2SO
4In the aqueous solution, its concentration is 0.1mol L
-1, ultrasonic 1h fully acts on the silsesquioxane after aniline monomer and the chemical modification; (4) add fast ammonium persulphate 0.684g after above-mentioned mixed solution is cooled to 0 ℃, stir, mixed solution remains under 0 ℃ and leaves standstill 24h; (5) water and absolute ethyl alcohol be washed till filtrating colourless; (6) matrix material is dried in vacuum drying oven, temperature is 60 ℃.Promptly obtain conductive polymers/silsesquioxane combination electrode material.
Embodiment 4
(1) preparation of sulfonation silsesquioxane.The 30mL vitriol oil is added in the 100mL there-necked flask, add 3g iso-octyl phenyl silsesquioxane, utilize magneton to stir; Slowly drip 15mL 20% oleum; Slowly be warming up to 90 ℃ after dropwising and keep 6h.Leach the silsesquioxane after the sulfonation with No. 4 sintered filter funnels, it is neutral to be washed till filtrating with deionized water.Vacuum drying is subsequent use under the room temperature.(2) silsesquioxane after the sulfonation is dispersed in 30mL 1molL
-1In the aqueous sulfuric acid, ultra-sonic dispersion is even, and its concentration is 1.0%; (3) add pyrrole monomer to above-mentioned H
2SO
4In the aqueous solution, its concentration is 0.1mol L
-1, ultrasonic 1h fully acts on the silsesquioxane after pyrrole monomer and the chemical modification; (4) add fast iron trichloride 0.243g after above-mentioned mixed solution is cooled to 0 ℃, stir, mixed solution remains under 0 ℃ and leaves standstill 24h; (5) water and absolute ethyl alcohol be washed till filtrating colourless; (6) matrix material is dried in vacuum drying oven, temperature is 80 ℃.
Embodiment 5
(1) preparation of sulfonation silsesquioxane.The 30mL vitriol oil is added in the 100mL there-necked flask, add 3g seven isobutyl-list propyl group sulfydryl silsesquioxanes, utilize magneton to stir; Ice bath slowly drips 15mL 50% hydrogen peroxide; Slowly be warming up to 90 ℃ after dropwising and keep 6h.Leach the silsesquioxane after the sulfonation with No. 4 sintered filter funnels, it is neutral to be washed till filtrating with deionized water.Vacuum drying is subsequent use under the room temperature.(2) silsesquioxane after the sulfonation is dispersed in 30mL 1molL
-1In the aqueous sulfuric acid, ultra-sonic dispersion is even, and its concentration is 1.0%; (3) add thiophene monomer to above-mentioned H
2SO
4In the aqueous solution, its concentration is 0.1mol L
-1, ultrasonic 1h fully acts on the silsesquioxane after thiophene monomer and the chemical modification; (4) add fast iron trichloride 0.243g after above-mentioned mixed solution is cooled to 0 ℃, stir, mixed solution remains under 0 ℃ and leaves standstill 24h; (5) water and absolute ethyl alcohol be washed till filtrating colourless; (6) matrix material is dried in vacuum drying oven, temperature is 80 ℃.
Claims (5)
1. the preparation method of conductive polymers/silsesquioxane combination electrode material comprises:
(1) the 30mL vitriol oil is mixed slow Dropwise 5～15mL chlorsulfonic acid, 5～15mL30～50% ydrogen peroxide 50,2～3g potassium permanganate or 10～15ml, 20～30% oleums under agitation condition with 3～5g silsesquioxane; Slowly be warming up to 60～90 ℃ and keep 6～12h; Isolate the sulfonated silsesquioxane, washing, drying obtain the silsesquioxane of modification;
(2) silsesquioxane with modification is dispersed in 0.1～3molL
-1In the acidic aqueous solution, ultra-sonic dispersion is even, and silsesquioxane concentration is 0.01～1wt%;
(3) in above-mentioned acidic aqueous solution, add the conductive polymers monomer, ultrasonic 1～5h obtains mixed solution, and concentration is 0.05～0.5molL
-1
(4) above-mentioned mixed solution is cooled to 0 ℃, adds oxygenant, the concentration that oxygenant accounts for mixed solution is 0.05～0.5molL
-1Mixed solution leaves standstill after-filtration under 0 ℃, successively water and absolute ethyl alcohol be washed till respectively filtrating colourless, the oven dry, obtain combination electrode material.
2. the preparation method of a kind of conductive polymers according to claim 1/silsesquioxane combination electrode material is characterized in that: the silsesquioxane general formula described in the step (1) is R
xR '
y(SiO
1.5) n, wherein n is 8,10 or 12,1≤x≤n, x+y=n, and R and R ' are same to each other or different to each other; Wherein R and R ' are the reactive groups that sulfonation reaction can take place, and are specially the alkyl of phenyl, band phenyl, the alkoxyl group or the sulfydryl of band phenyl.
3. the preparation method of a kind of conductive polymers according to claim 1/silsesquioxane combination electrode material is characterized in that: the acidic aqueous solution described in the step (2) is the aqueous solution of sulfuric acid, hydrochloric acid, acetate, dodecyl sodium sulfonate or hexadecyl sulfonic acid.
4. the preparation method of a kind of conductive polymers according to claim 1/silsesquioxane combination electrode material is characterized in that: the conductive polymers described in the step (3) is polyaniline, polypyrrole or Polythiophene.
5. the preparation method of a kind of conductive polymers according to claim 1/silsesquioxane combination electrode material is characterized in that: the oxygenant described in the step (4) is Potassium Persulphate, ammonium persulphate, hydrogen peroxide or iron trichloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110408030A (en) * | 2019-08-13 | 2019-11-05 | 青岛科技大学 | The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber |
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| CN102432902B (en) * | 2011-09-05 | 2013-07-03 | 厦门华戎能源科技有限公司 | Preparation method of polyvinyl composite conducting film |
| CN104693797B (en) * | 2013-12-04 | 2018-01-12 | 东莞市天相新材料科技有限公司 | Functionalization POSS and polypyrrole composite wave-suction material a kind of preparation method |
| CN104022259B (en) * | 2014-05-09 | 2016-06-01 | 中科院广州化学有限公司 | A kind of porosity and looseness polyaniline-nanometer silicon composite material and its preparation method and application |
| CN106783221A (en) * | 2016-11-18 | 2017-05-31 | 江南大学 | A kind of organic/inorganic hybrid supercapacitor electrode material and preparation method thereof |
| CN110358090A (en) * | 2019-08-13 | 2019-10-22 | 青岛科技大学 | A kind of method of support type phosphazene catalyst catalyzed preparation of poly siloxanes |
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| CN1986605A (en) * | 2006-11-30 | 2007-06-27 | 南京大学 | Preparing method of cage anilino methyl sesquisiloxane octamer |
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| JP2006249160A (en) * | 2005-03-09 | 2006-09-21 | Konishi Kagaku Ind Co Ltd | Sulfonated polyorganosilsesquioxane and its preparation method |
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| JP特开2006-249160A 2006.09.21 |
| 武国军等.磺化POSS的合成及其与聚电解质的组装.《应用化学》.2008,第25卷(第3期),第270-275页. * |
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| CN110408030A (en) * | 2019-08-13 | 2019-11-05 | 青岛科技大学 | The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber |
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