CN101735610A - Hybrid of dedoping-state polyaniline/metallic oxide - Google Patents
Hybrid of dedoping-state polyaniline/metallic oxide Download PDFInfo
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- CN101735610A CN101735610A CN200910201263A CN200910201263A CN101735610A CN 101735610 A CN101735610 A CN 101735610A CN 200910201263 A CN200910201263 A CN 200910201263A CN 200910201263 A CN200910201263 A CN 200910201263A CN 101735610 A CN101735610 A CN 101735610A
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Abstract
The invention relates to a hybrid of a dedoping-state polyaniline/metallic oxide, which is prepared by the following steps of: carrying out oxidation polymerization on an aniline monomer for 3 hours to 12 hours at10 DEG C-30 DEG C, in the presence of an oxidant and the water-soluble inorganic strong acid salt of quadrivalent titanium or tin, and processing an obtained polymer by ammonia water and finally drying at 150 DEG C-200 DEG C. The hybrid is an electrode material and assembled as a super capacitor, 1 M of H2SO4 is uses as an electrolyte solution, and when current density is enhanced from 0.5 A g-1 to 30 A g-1, the capacity retention rate of the super capacitor exceeds 70 percent; besides, the hybrid shows good oxidation/reduction reversibility in an aqueous medium with pH value not more than 5 and can be used for preparing the electrode material of the super capacitor.
Description
Technical field
The present invention relates to a kind of hybrid that removes doped polyaniline/metal oxide, specifically, relate to a kind of hybrid that removes doped polyaniline/metal titanium (tin) oxide compound.
Background technology
Typical case as conducting polymer one of represents, electrically conductive polyaniline has raw material and is easy to get, synthesizes easy and good advantages such as environmental stability (especially simple and reversible protonic acid doping/dedoping process), makes polyaniline show huge application potential at numerous high-technology fields.
Although electrically conductive polyaniline has the physics and the chemical property of numerous excellences, processing problems is a difficult problem in its practicalization always.An important breakthrough that solves this difficult problem is to adopt organic acid as doping agent.Result of study shows, through organic acid doped electrically conductive polyaniline can be dissolved in the compatible organic solvent of these acid in (P.Ghosh, S.K.Siddhanta, S.R.Haque, A.Chakrabarit, Synth.Met.2001,123,83; A.J.Dominis, G.M.Spinks, L.A.P.Kane-Maguire, G.G.Wallace, Synth.Met.2002,129,165; S.Shreepathi, R.Holze, Chem.Mater.2005,17,4078; Y.G.Han, T.Kusunose, T.Sekino, Journal of Polymer Science:Part B:PolymerPhysics, 2009,47,1024); Yet with an organic solvent will bring serious environmental to pollute in a large number, increase difficulty and the cost of administering environment.
At present, an effective way of solution electrically conductive polyaniline processibility is the matrix material that directly prepares electrically conductive polyaniline and other material.This has not only solved the processing problems of electrically conductive polyaniline to a certain extent, and can give electrically conductive polyaniline new performance.Therefore, be that the nano composite material of main functions matrix material, especially electrically conductive polyaniline and inorganic materials receives much concern in recent years with the electrically conductive polyaniline.
Although adopt different methods to prepare the existing a lot of reports of research of electrically conductive polyaniline/titanium (tin) oxide composite, relate to the research that directly prepares the oxide hybridized thing of polyaniline/titanium (tin) at corresponding inorganic salt system and do not see open report.
Summary of the invention
The present invention carries out the oxypolymerization of aniline and the hydrolysis of inorganic salt by the control synthesis condition synchronously, and, prepared the homodisperse each other oxide hybridized thing of doped polyaniline/titanium (tin) that goes of polyaniline and titanium (tin) oxide compound by the certain post-processing means.Support based on electrically conductive polyaniline reversible protonic acid doping/dedoping characteristic and the skeleton that is dispersed in titanium (tin) oxide compound in the polyaniline, go the oxide hybridized thing of doped polyaniline/titanium (tin) in the aqueous medium of pH≤5, all to show good oxidation/reduction reversibility, be expected to be used for the electrode materials and the biological sensing material of ultracapacitor.
The hybrid that removes doped polyaniline/metal oxide of the present invention, its 10 ℃～30 ℃ and oxygenant is arranged and the water-soluble inorganic strong acid salt existence condition of titanic or tin under, through oxypolymerization 3 hours to 12 hours, resulting polymers reached through ammonia treatment and makes after 150 ℃～200 ℃ dryings by aniline monomer.
Wherein said oxygenant is the existing oxygenant (as ammonium persulphate, potassium bichromate, Potassium Iodate or hydrogen peroxide etc.) that is used for the polyaniline preparation, and the present invention recommends to use overcurrent acid ammonium.
With hybrid of the present invention is electrode materials, is assembled into ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show: when current density from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%.
In optimal technical scheme of the present invention, the mol ratio of the water-soluble inorganic strong acid salt of aniline monomer and titanium (IV) or tin (IV) is 1: (0.5～6.0);
The negatively charged ion of said water-soluble inorganic strong acid salt preferentially is selected from: Cl
-, SO
4 2-Or NO
3 -In a kind of;
Best water-soluble inorganic strong acid salt is titanium sulfate [Ti (SO
4)
2], titanium tetrachloride or tin tetrachloride.
In another optimal technical scheme of the present invention, the mol ratio of aniline monomer and oxygenant is 1: (0.5～2.0).
Description of drawings
Fig. 1 is the polyaniline/titanium oxide hybrid (content of titanium oxide: 25wt%) SEM figure of attitude of mixing.
Fig. 2 is the polyaniline/titanium oxide hybrid (content of titanium oxide: 25wt%) TEM figure of attitude of mixing.
Wherein: the calculating benchmark of the content of titanium oxide is the gross weight of polyaniline/titanium oxide hybrid of attitude of mixing
Embodiment
A kind of method for preparing the oxide hybridized thing of polyaniline/titanium (tin) of the attitude of going to mix of the present invention, it comprises the steps:
(1) titanium (IV) or the water-soluble inorganic strong acid salt of tin (IV) and the aqueous solution of aniline monomer are placed reactor, the mol ratio of the water-soluble inorganic salt of aniline monomer and titanium (IV) or tin (IV) is 1: (0.5～6.0).Under agitation condition, in this reactor, add oxygenant (as ammonium persulphate, potassium bichromate, Potassium Iodate or hydrogen peroxide etc.), the mol ratio of aniline monomer and oxygenant is 1: (0.5～2.0).Under 10 ℃～30 ℃ conditions, polyase 13 hour filtered to 12 hours, and washing gained filter cake is to neutral.
(2) will place another reactor by the filter cake that step (1) makes, adding concentration in this reactor is the ammoniacal liquor of 10wt%～20wt%, described filter cake is all soaked into, under 10 ℃～30 ℃ conditions, stirred at least 24 hours, filter, washing gained filter cake is to neutral and promptly get target compound (preferably drying conditions is: temperature is 150 ℃～200 ℃, and be 1 hour～5 hours time of drying) after the drying down at inert atmosphere (as nitrogen atmosphere etc.).
The present invention has following advantage:
(1) the present invention states the oxide hybridized thing of doped polyaniline/titanium (tin) all have good oxidation/reduction reversibility in the aqueous medium of pH≤5.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when current density from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%, has shown good multiplying power property.
In addition, the good electrochemical activity that such hybrid material shows under slightly acidic (the pH value is 4～5) condition also is better than electrically conductive polyaniline (usually electrically conductive polyaniline o'clock loses electrochemical activity in pH value＞4), therefore they also are expected in weak acidic medium biomacromolecules such as load enzyme, thereby as biological sensing material.
(2) be dispersed in the thermostability that titanium (tin) oxide compound in the polyaniline has also improved this hybrid to a certain extent.In nitrogen atmosphere, temperature rise rate is 10 ℃/minute, goes two main thermal weight loss temperature ranges of the oxide hybridized thing of doped polyaniline/titanium (tin) to be: 300 ℃～450 ℃ and 450 ℃～700 ℃; And two main thermal weight loss temperature ranges of removing doped polyaniline are: 200 ℃～250 ℃ and 450 ℃～500 ℃.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
The 1.2g titanium sulfate is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 2.28g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 6 hours under 20 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 10w% stirred 24 hours under 20 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 5 hours under 150 ℃ of conditions of inert atmosphere, obtains doped polyaniline/titanium oxide hybrid powder.
Energy spectrum analysis (EDS) proves that titanium, oxygen are present in the products therefrom; FTIR (KBr) shows, have Ti-O-Ti key (500cm in product
-1～650cm
-1).The content of titanium oxide is 15wt%～20wt% in this hybrid, and two main thermal weight loss temperature ranges are: 400 ℃～450 ℃ and 650 ℃～700 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 2
The 2.4g titanium sulfate is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 2.28g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 3 hours under 25 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 15wt% stirred 36 hours under 25 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 3 hours under 180 ℃ of conditions of inert atmosphere, obtains doped polyaniline/titanium oxide hybrid powder.
Energy spectrum analysis (EDS) proves that titanium, oxygen are present in the products therefrom; FTIR (KBr) shows, have Ti-O-Ti key (500cm in product
-1～650cm
-1).The content of titanium oxide is 15wt%～20wt% in this hybrid, and two main thermal weight loss temperature ranges are: 400 ℃～450 ℃ and 650 ℃～700 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 3
The 7.2g titanium sulfate is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 1.14g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 9 hours under 20 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 20wt% stirred 48 hours under 20 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 2 hours under 180 ℃ of conditions of inert atmosphere, obtains doped polyaniline/titanium oxide hybrid powder.
Energy spectrum analysis (EDS) proves that titanium, oxygen are present in the products therefrom; FTIR (KBr) shows, have Ti-O-Ti key (500cm in product
-1～650cm
-1).The content of titanium oxide is 15wt%～20wt% in this hybrid, and two main thermal weight loss temperature ranges are: 400 ℃～450 ℃ and 650 ℃～700 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 4
The 9.6g titanium sulfate is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 4.56g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 10 hours under 20 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 15wt% stirred 60 hours under 20 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 1 hour under 200 ℃ of conditions of inert atmosphere, obtains doped polyaniline/titanium oxide hybrid powder.
Energy spectrum analysis (EDS) proves that titanium, oxygen are present in the products therefrom; FTIR (KBr) shows, have Ti-O-Ti key (500cm in product
-1～650cm
-1).The content of titanium oxide is 20wt%～30wt% in this hybrid, and two main thermal weight loss temperature ranges are: 400 ℃～450 ℃ and 650 ℃～700 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 5
The 12.0g titanium sulfate is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 2.28g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 12 hours under 30 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 15wt% stirred 48 hours under 30 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 2 hours under 180 ℃ of conditions of inert atmosphere, obtains doped polyaniline/titanium oxide hybrid powder.
Energy spectrum analysis (EDS) proves that titanium, oxygen are present in the products therefrom; FTIR (KBr) shows, have Ti-O-Ti key (500cm in product
-1～650cm
-1).The content of titanium oxide is 20wt%～30wt% in this hybrid, and two main thermal weight loss temperature ranges are: 400 ℃～450 ℃ and 650 ℃～700 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 6
The 3.3ml titanium tetrachloride solution is dropwise joined in the reactor that contains 0 ℃ of deionized water of 80ml, and continuously stirring; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 1.14g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 12 hours under 15 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 10wt% stirred 72 hours under 15 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 2 hours under 200 ℃ of conditions of inert atmosphere, obtains doped polyaniline/titanium oxide hybrid powder.
Energy spectrum analysis (EDS) proves that titanium, oxygen are present in the products therefrom; FTIR (KBr) shows, have Ti-O-Ti key (500cm in product
-1～650cm
-1).The content of titanium oxide is 20wt%～25wt% in this hybrid, and two main thermal weight loss temperature ranges are: 400 ℃～450 ℃ and 650 ℃～700 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 7
The 5.2g tin tetrachloride is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 2.28g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 6 hours under 20 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 10wt% stirred 30 hours under 20 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 3 hours under 180 ℃ of conditions of inert atmosphere, obtains doped polyaniline/tin-oxide hybrid powder.
Energy spectrum analysis (EDS) proves that tin, oxygen are present in the products therefrom; FTIR (KBr) shows, 500cm
-1～700cm
-1There are two stronger infrared absorption peaks in the zone, belongs to the characteristic peak of Sn-O key.Tin-oxide content is 30wt%～35wt% in this hybrid, and two main thermal weight loss temperature ranges are: 300 ℃～350 ℃ and 450 ℃～550 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Embodiment 8
The 15.6g tin tetrachloride is placed the reactor that contains the 80ml deionized water, be stirred to dissolving fully; Get 0.9ml aniline, join in the above-mentioned salts solution; Under agitation condition, add ammonium persulfate aqueous solution (the 2.28g ammonium persulphate is dissolved in the 20ml deionized water); Oxypolymerization 8 hours under 30 ℃, no agitation condition is subsequently filtered, filter cake washing is to neutral.Filter cake is transferred in the reactor, and the ammoniacal liquor that adds 15wt% stirred 48 hours under 30 ℃ of conditions; Filtration, filter cake washing are to neutral.Drying is 2 hours under 200 ℃ of conditions of inert atmosphere, obtains doped polyaniline/tin-oxide hybrid powder.
Energy spectrum analysis (EDS) proves that tin, oxygen are present in the products therefrom; FTIR (KBr) shows, 500cm
-1～700cm
-1There are two stronger infrared absorption peaks in the zone, belongs to the characteristic peak of Sn-O key.Tin-oxide content is 40wt%～45wt% in this hybrid, and two main thermal weight loss temperature ranges are: 300 ℃～350 ℃ and 450 ℃～550 ℃.Electrochemical research shows that this hybrid has electrochemical activity in the aqueous solution of pH≤5, and oxidation/reduction process is reversible.As electrode materials assembling ultracapacitor, 1M H
2SO
4Be electrolyte solution, under the different current densities discharging and recharging the experiment show, when the density of charging current from 0.5Ag
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%; Has good multiplying power property.
Claims (7)
1. hybrid that removes doped polyaniline/metal oxide, it is characterized in that, described hybrid be by: 10 ℃～30 ℃ and oxygenant is arranged and the water-soluble inorganic strong acid salt existence condition of titanic or tin under, through oxypolymerization 3 hours to 12 hours, resulting polymers reached through ammonia treatment and makes after 150 ℃～200 ℃ dryings by aniline monomer.
2. hybrid as claimed in claim 1 is characterized in that, wherein the mol ratio of the water-soluble inorganic strong acid salt of aniline monomer and titanic or tin is 1: (0.5～6.0).
3. hybrid as claimed in claim 2 is characterized in that, wherein said water-soluble inorganic strong acid salt is selected from: Cl
-, SO
4 2-Or NO
3 -In a kind of.
4. hybrid as claimed in claim 3 is characterized in that, wherein said water-soluble inorganic strong acid salt is titanium sulfate (IV), titanium tetrachloride or tin tetrachloride.
5. as any described hybrid in the claim 1～4, it is characterized in that wherein the mol ratio of aniline monomer and oxygenant is 1: (0.5～2.0).
6. hybrid as claimed in claim 5 is characterized in that, wherein said oxygenant is an overcurrent acid ammonium.
7. hybrid as claimed in claim 5 is characterized in that, is electrode materials with described hybrid, is assembled into ultracapacitor, 1M H
2SO
4Be electrolyte solution, when current density from 0.5A g
-1Be increased to 30Ag
-1The time, its capability retention surpasses 70%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079873A (en) * | 2010-12-08 | 2011-06-01 | 华东理工大学 | Application of conductive polyaniline/Laponite compound |
| CN102280265A (en) * | 2011-05-25 | 2011-12-14 | 中国科学院过程工程研究所 | Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor |
| CN103265699A (en) * | 2013-05-08 | 2013-08-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Nanometer tin dioxide modified polyaniline nano-tube preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100523088C (en) * | 2007-04-21 | 2009-08-05 | 大连理工大学 | Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method |
| CN101475686B (en) * | 2009-01-14 | 2011-01-12 | 华东理工大学 | Method for preparing polyaniline derivative-metal complex |
-
2009
- 2009-12-17 CN CN2009102012638A patent/CN101735610B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079873A (en) * | 2010-12-08 | 2011-06-01 | 华东理工大学 | Application of conductive polyaniline/Laponite compound |
| CN102079873B (en) * | 2010-12-08 | 2012-09-05 | 华东理工大学 | Application of conductive polyaniline/Laponite compound |
| CN102280265A (en) * | 2011-05-25 | 2011-12-14 | 中国科学院过程工程研究所 | Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor |
| CN102280265B (en) * | 2011-05-25 | 2012-11-21 | 中国科学院过程工程研究所 | Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor |
| CN103265699A (en) * | 2013-05-08 | 2013-08-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Nanometer tin dioxide modified polyaniline nano-tube preparation method |
| CN103265699B (en) * | 2013-05-08 | 2015-11-18 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of nano-stannic oxide modifies the preparation method of polyaniline nanotube |
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|---|---|
| CN101735610B (en) | 2011-11-30 |
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