CN102568841A - Preparation method for polyaniline membrane electrode - Google Patents
Preparation method for polyaniline membrane electrode Download PDFInfo
- Publication number
- CN102568841A CN102568841A CN2012100037882A CN201210003788A CN102568841A CN 102568841 A CN102568841 A CN 102568841A CN 2012100037882 A CN2012100037882 A CN 2012100037882A CN 201210003788 A CN201210003788 A CN 201210003788A CN 102568841 A CN102568841 A CN 102568841A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polyaniline
- film electrode
- aniline
- polyaniline film
- 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.)
- Granted
Links
Images
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for a polyaniline membrane electrode, which relates to a method for preparing a membrane electrode. The invention solves the technical problem that the current preparation method for the polyaniline membrane electrode has complex process and poor battery performance. The method comprises the following steps: step one, aniline is uniformly mixed with diluted hydrochloric acid, then the mixture is placed in a water bath and stirred when ammonium persulfate is gradually dropped, the mixture is continuously stirred and filtered, the filter cake is soaked in ammonia water, the mixture is washed by deionized water after being filtered, and then the mixture is dried in vacuum, so that eigenstate polyaniline is obtained; step two, a reducing agent is added in the solvent and uniformly mixed, and when the reducing agent is stirred, the eigenstate polyaniline is added until an saturated solution is prepared; step three, foam nickel is soaked in the saturated solution, and then the foam nickel is dried in vacuum, therefore, the polyaniline membrane electrode is obtained. The electrode provided by the invention has stronger controllability, steadier electrode, better electrochemical performance and higher specific capacitance. With the advantages of simple and convenient preparation process, low cost and no pollution, the invention has wide application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of membrane electrode.
Background technology
Along with The development in society and economy; People are increasing to demands for energy; More and more pay close attention to for green energy resource and biological environment simultaneously, research environmental protection and reproducible new forms of energy are challenges that present All Countries faces, and the storage of the energy is one of them pith.Ultracapacitor (Supercapacitor) is as a kind of novel energy storage device, because its superiority that can not be substituted receives people's attention gradually.Have outstanding advantage: power density is big, have extended cycle life, efficiency for charge-discharge is high, and pollution-free, and environmental friendliness becomes one of research focus of current field of chemical power source.
The electrolyte that influence at present ultracapacitor development key factor and electrode material is arranged, mate with electrode material and the technology of preparing of electrode etc.Electrode material is the critical bottleneck of preparation ultracapacitor.Though electrode material for super capacitor mainly contains three kinds of material with carbon element, metal oxide and conducting polymers. raw material of wood-charcoal material good stability, more not high enough than electric capacity; The metal oxide electrochemical window is narrow and cost an arm and a leg and be restricted; Common conducting polymer materials has polypyrrole (PPY), polythiophene, polyaniline (PANI), gathers polymer to benzene, polyacetylene ferrocene, polyurethane and their derivatives etc.
Polyaniline (PANI) since it is nontoxic, be easy to synthetic and environmental stability better and chemical property is outstanding, the good characteristics of chemical invertibity are considered to the super capacitor material that is hopeful in reality, to be applied most, and then receive people's attention.
Although there are various good performances in polyaniline,, make its application receive very big restriction because it is insoluble not molten.Traditional method for preparing electrode has, smear method and electrodeposition process.Smear method be with polyaniline through the method for filming on a collection liquid surface, the method is difficult to the thickness of control electrode, and don't evenly, and only acts on the top layer, causes the chemical property of electrode to reduce and complex procedures.Traditional electro-deposition method causes deposition rate lower because current density is lower, thereby the heavy industrialization application is restricted.
Summary of the invention
The present invention will solve the technical problem that existing polyaniline film electrode preparation method exists complex process, battery performance difference; And the preparation method of polyaniline film electrode is provided.
The preparation method of polyaniline film electrode is undertaken by following step among the present invention: step 1, be 1 by the mol ratio of aniline and HCl: (1～5) is that the watery hydrochloric acid of 1.0～3.0mol/L mixes with aniline and molar concentration, places water-bath, temperature to be controlled at 0～25 ℃ then; Dropwise drip ammonium persulfate while stirring; The mol ratio of ammonium persulfate and aniline is 1: (0.5～2), and the dropping time is 1～3h, continues to stir 4～6 hours; Filter; It is that 6%～10% ammoniacal liquor soaks 8～24h that the filter cake that filters is placed mass concentration, filters the back and uses deionized water wash to washing lotion to be neutrality, and vacuumize gets polyaniline in eigenstate; Step 2, in the solvent of 30～50mL, add the reducing agent of 0.2～0.3g, mix, add polyaniline in eigenstate that step 1 obtains then while stirring until being made into saturated solution; Step 3, nickel foam is put into saturated solution soaked 8～24 hours or soaked repeatedly, vacuumize is 5～8 hours then; Promptly obtain the polyaniline film electrode.
The said solvent of step 2 is N, a kind of or wherein several kinds the mixing in dinethylformamide, N-methyl pyrrolidone, chloroform, the dimethyl sulfoxide (DMSO), and said reducing agent is citric acid, ascorbic acid or oxalic acid.
The present invention can make the material of collector in saturated solution; Through the method for soaking with polyaniline in eigenstate thinly attached to wherein; Regulate the addition of polyaniline and soak the thickness that number of times comes the control electrode material, make the electrode for super capacitor of a controllable thickness.The controllability of electrode is stronger among the present invention, and electrode is more stable, and chemical property is better, has higher ratio electric capacity.It is easy that the present invention prepares preparation technology, with low cost, pollution-free, has wide practical use.As work electrode, calomel electrode is a reference electrode with above-mentioned electrode, and platinum electrode is to electrode, and concentration is that the potassium hydroxide solution of 3mol/L～8mol/L is an electrolyte, carries out the cyclic voltammetric test.After 200 circulations, this electrode only decays 7.03% than electric capacity.
Description of drawings
Fig. 1 tests one being added with the N of ascorbic acid, soaks the cyclic voltammogram that records in the dinethylformamide; Fig. 2 is that test two is soaked the cyclic voltammogram that records in being added with the N-methyl pyrrolidone of citric acid.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the preparation method of polyaniline film electrode is undertaken by following step in this execution mode: step 1, be 1 by the mol ratio of aniline and HCl: (1～5) is that the watery hydrochloric acid of 1.0～3.0mol/L mixes with aniline and molar concentration; Place water-bath then; Temperature is controlled at 0～25 ℃, dropwise drips ammonium persulfate while stirring, and the mol ratio of ammonium persulfate and aniline is 1: (0.5～2); The dropping time is 1～3h; Continue to stir 4～6 hours, and filtered, it is that 6%～10% ammoniacal liquor soaks 8～24h that the filter cake that filters is placed mass concentration; Filter the back and use deionized water wash to washing lotion to be neutrality, vacuumize gets polyaniline in eigenstate; Step 2, in the solvent of 30～50mL, add the reducing agent of 0.2～0.3g, mix, add polyaniline in eigenstate that step 1 obtains then while stirring until being made into saturated solution; Step 3, nickel foam is put into saturated solution soaked 8～24 hours or soaked repeatedly, vacuumize is 5～8 hours then; Promptly obtain the polyaniline film electrode.
Embodiment two: what this execution mode and embodiment one were different is: the mol ratio of said aniline of step 1 and HCl is 1: (2～4).Other step is identical with embodiment one with parameter.
Embodiment three: what this execution mode and embodiment one were different is: the mol ratio of said aniline of step 1 and HCl is 1: 3.Other step is identical with embodiment one with parameter.
Embodiment four: what this execution mode was different with one of embodiment one to three is: the mol ratio of described ammonium persulfate of step 1 and aniline is 1: 1.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what this execution mode was different with one of embodiment one to three is: the mol ratio of described ammonium persulfate of step 1 and aniline is 1: 1.5.Other step is identical with one of embodiment one to three with parameter.
Embodiment six: this execution mode different with one of embodiment one to five be: the said reducing agent of step 2 is citric acid, ascorbic acid or oxalic acid.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what this execution mode was different with one of embodiment one to six is: the described solvent of step 2 is N, a kind of in dinethylformamide, chloroform, the dimethyl sulfoxide (DMSO) or several kinds of mixtures with the N-methyl pyrrolidone wherein.Other step is identical with one of concrete mode one to six with parameter.
Solvent is N, during the mixture of dinethylformamide, N-methyl pyrrolidone, chloroform and dimethyl sulfoxide (DMSO), and N, the mass ratio of dinethylformamide, N-methyl pyrrolidone, chloroform and dimethyl sulfoxide (DMSO) is 1: 2: 1: (1～3): 5: 2: 3;
Solvent is N, during the mixture of dinethylformamide, N-methyl pyrrolidone and chloroform, and N, the mass ratio of dinethylformamide, N-methyl pyrrolidone and chloroform is 1: 2: (1～3): 4: 2;
Solvent is N, during the mixture of dinethylformamide, N-methyl pyrrolidone and dimethyl sulfoxide (DMSO), and N, the mass ratio of dinethylformamide, N-methyl pyrrolidone and dimethyl sulfoxide (DMSO) is 1: 2: (1～3): 5: 2;
When solvent was the mixture of N-methyl pyrrolidone, chloroform and dimethyl sulfoxide (DMSO), the mass ratio of N-methyl pyrrolidone, chloroform and dimethyl sulfoxide (DMSO) was 2: 1: (1～5): 4: 2;
Solvent is N, during the mixture of dinethylformamide and N-methyl pyrrolidone, and N, the mass ratio of dinethylformamide and N-methyl pyrrolidone is 1: (1～4): 5;
When solvent was the mixture of N-methyl pyrrolidone and chloroform, the mass ratio of the mixture of N-methyl pyrrolidone and chloroform was 1: (1～6): 5;
When solvent was the mixture of N-methyl pyrrolidone and dimethyl sulfoxide (DMSO), the mass ratio of N-methyl pyrrolidone and dimethyl sulfoxide (DMSO) was 1: (1～4): 5.
Embodiment eight: what this execution mode was different with one of embodiment one to seven is: the described immersion repeatedly of step 3 is to dry after repeating to soak, and soaks repetitive operation 2～6 times 1～2 hour at every turn.Other step is identical with one of embodiment one to seven with parameter.
Adopt following verification experimental verification invention effect:
Test one: the preparation method of polyaniline film electrode is undertaken by following step:
Step 1, by the mol ratio of aniline and HCl be 1: 1 be that the watery hydrochloric acid of 2mol/L mixes with aniline and molar concentration, place water-bath, temperature to be controlled at 0 ℃ then; The limit is stirred (250r/min) limit and is dropwise dripped ammonium persulfate; The mol ratio of ammonium persulfate and aniline is 1: 2, and the dropping time is 2h, continues to stir 4 hours; Filter; It is that 8% ammoniacal liquor soaks 10h that the filter cake that filters is placed mass concentration, filters the back and uses deionized water wash to washing lotion to be neutrality, and vacuumize gets polyaniline in eigenstate;
Step 2, to 35mLN, add the ascorbic acid of 0.2g in the dinethylformamide, mix, add polyaniline in eigenstate that the 1.0g step 1 obtains then while stirring until being made into saturated solution;
Step 3, nickel foam is put into saturated solution, soak (dry after repeating to soak, soaked repetitive operation 30 times at every turn 2 hours) repeatedly, vacuumize is 8 hours then; Promptly obtain the polyaniline film electrode.
This is carried out the cyclic voltammetric test, the result is as shown in Figure 1; Can know that from Fig. 1 the ratio electric capacity of the polyaniline film electrode of this execution mode is 1248.87F/g.
Test two: the preparation method of polyaniline film electrode is undertaken by following step:
Step 1, by the mol ratio of aniline and HCl be 1: 3 be that the watery hydrochloric acid of 2mol/L mixes with aniline and molar concentration, place water-bath, temperature to be controlled at 25 ℃ then; The limit is stirred (253r/min) limit and is dropwise dripped ammonium persulfate; The mol ratio of ammonium persulfate and aniline is 1: 1, and the dropping time is 2h, continues to stir 4 hours; Filter; It is that 8% ammoniacal liquor soaks 10h that the filter cake that filters is placed mass concentration, filters the back and uses deionized water wash to washing lotion to be neutrality, and vacuumize gets polyaniline in eigenstate;
Step 2, in the 30mLN-methyl pyrrolidone, add the citric acid of 0.3g, mix, add polyaniline in eigenstate that the 3.0g step 1 obtains then while stirring until being made into saturated solution;
Step 3, the nickel foam that will be about 1～5cm are put into saturated solution and were soaked 10 hours, and vacuumize is 8 hours then; Promptly obtain the polyaniline film electrode.
This is carried out the cyclic voltammetric test, the result is as shown in Figure 2; Can know that from Fig. 2 the ratio electric capacity of the polyaniline film electrode of this execution mode is 489.45F/g.
Claims (8)
1. the preparation method of polyaniline film electrode is characterized in that the preparation method of polyaniline film electrode is undertaken by following step:
Step 1, be 1 by the mol ratio of aniline and HCl: (1～5) is that the watery hydrochloric acid of 1.0～3.0mol/L mixes with aniline and molar concentration, places water-bath, temperature to be controlled at 0～25 ℃ then; Dropwise drip ammonium persulfate while stirring; The mol ratio of ammonium persulfate and aniline is 1: (0.5～2), and the dropping time is 1～3h, continues to stir 4～6 hours; Filter; It is that 6%～10% ammoniacal liquor soaks 8～24h that the filter cake that filters is placed mass concentration, filters the back and uses deionized water wash to washing lotion to be neutrality, and vacuumize gets polyaniline in eigenstate;
Step 2, in the solvent of 30～50mL, add the reducing agent of 0.2～0.3g, mix, add polyaniline in eigenstate that step 1 obtains then while stirring until being made into saturated solution;
Step 3, nickel foam is put into saturated solution soaked 8～24 hours or soaked repeatedly, vacuumize is 5～8 hours then; Promptly obtain the polyaniline film electrode.
2. the preparation method of polyaniline film electrode according to claim 1, the mol ratio that it is characterized in that said aniline of step 1 and HCl is 1: (2～4).
3. the preparation method of polyaniline film electrode according to claim 1, the mol ratio that it is characterized in that said aniline of step 1 and HCl is 1: 3.
4. the preparation method of polyaniline film electrode according to claim 2, the mol ratio that it is characterized in that described ammonium persulfate of step 1 and aniline is 1: 1.
5. the preparation method of polyaniline film electrode according to claim 2, the mol ratio that it is characterized in that described ammonium persulfate of step 1 and aniline is 1: 1.5.
6. according to the preparation method of the described polyaniline film electrode of each claim in the claim 1～5, it is characterized in that the said reducing agent of step 2 is citric acid, ascorbic acid or oxalic acid.
7. according to the preparation method of the described polyaniline film electrode of each claim in the claim 1～5; It is characterized in that the described solvent of step 2 is N, a kind of in dinethylformamide, chloroform, the dimethyl sulfoxide (DMSO) or several kinds of mixtures with the N-methyl pyrrolidone wherein.
8. the preparation method of polyaniline film electrode according to claim 1 is characterized in that described the immersion repeatedly of step 3 is to dry after repeating to soak, and soaks repetitive operation 10～50 times 1～2 hour at every turn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210003788.2A CN102568841B (en) | 2012-01-06 | 2012-01-06 | Preparation method for polyaniline membrane electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210003788.2A CN102568841B (en) | 2012-01-06 | 2012-01-06 | Preparation method for polyaniline membrane electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102568841A true CN102568841A (en) | 2012-07-11 |
| CN102568841B CN102568841B (en) | 2014-04-23 |
Family
ID=46414010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210003788.2A Expired - Fee Related CN102568841B (en) | 2012-01-06 | 2012-01-06 | Preparation method for polyaniline membrane electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102568841B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646921A (en) * | 2016-03-18 | 2016-06-08 | 华东师范大学 | Preparation method of independent PAN (Polyaniline) conducting membrane |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1716681A (en) * | 2004-06-30 | 2006-01-04 | 三星Sdi株式会社 | Lithium secondary battery |
| CN101210158A (en) * | 2006-12-26 | 2008-07-02 | 中南大学 | Electric bonding for battery or capacitor and composition containing the same used for electrode |
| CN101662021A (en) * | 2009-09-24 | 2010-03-03 | 无锡欧力达新能源电力科技有限公司 | Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials |
| CN101892530A (en) * | 2010-07-15 | 2010-11-24 | 东华大学 | Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure |
| CN102088075A (en) * | 2009-12-07 | 2011-06-08 | 中国科学院化学研究所 | Electrode material of conductive polyaniline composite membrane and preparation method thereof |
| CN102163471A (en) * | 2010-11-29 | 2011-08-24 | 马洋 | Compound electrode paste for solar battery and preparation method of compound electrode paste |
-
2012
- 2012-01-06 CN CN201210003788.2A patent/CN102568841B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1716681A (en) * | 2004-06-30 | 2006-01-04 | 三星Sdi株式会社 | Lithium secondary battery |
| CN101210158A (en) * | 2006-12-26 | 2008-07-02 | 中南大学 | Electric bonding for battery or capacitor and composition containing the same used for electrode |
| CN101662021A (en) * | 2009-09-24 | 2010-03-03 | 无锡欧力达新能源电力科技有限公司 | Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials |
| CN102088075A (en) * | 2009-12-07 | 2011-06-08 | 中国科学院化学研究所 | Electrode material of conductive polyaniline composite membrane and preparation method thereof |
| CN101892530A (en) * | 2010-07-15 | 2010-11-24 | 东华大学 | Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure |
| CN102163471A (en) * | 2010-11-29 | 2011-08-24 | 马洋 | Compound electrode paste for solar battery and preparation method of compound electrode paste |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646921A (en) * | 2016-03-18 | 2016-06-08 | 华东师范大学 | Preparation method of independent PAN (Polyaniline) conducting membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102568841B (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108766774B (en) | Preparation method of Ni-Co-Mn layered double hydroxide with hollow nano cage structure | |
| CN104979104A (en) | Preparation method of Ni-MOF electrode material | |
| CN107768150B (en) | Copper ion doped polyaniline electrode with carbon cloth as substrate and preparation method thereof | |
| CN105931855B (en) | The synthesis of nitrogen sulphur codope carbon-polyaniline composite material and be applied to supercapacitor | |
| CN103426649A (en) | Preparation method for different carbon fibers / cobalt hydroxide electrode and solid-liquid composite electrode system | |
| CN106910643B (en) | In-situ polymerization polyaniline-application of the sulfonated graphene composite material in electrode material | |
| CN102760583A (en) | Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method | |
| CN102568848A (en) | Preparation method of polyaniline/graphene oxide composite electrode material | |
| CN102214516A (en) | Method for preparing capacitor electrode material from waste tire pyrolytic carbon | |
| CN103854875A (en) | Polyaniline/MnO2 compound modified three-dimensional graphene composite material, preparation method and application of composite material | |
| CN106024094B (en) | A kind of compliant conductive polyaniline nano fiber bumps electrode material and preparation method thereof | |
| CN105869901B (en) | A kind of carbon nano-fiber composite material of structure-controllable and its preparation method and application | |
| CN106409527A (en) | Bismuth vanadate/carbon super-capacitor battery and preparation method thereof | |
| CN102568841A (en) | Preparation method for polyaniline membrane electrode | |
| CN101979717B (en) | Method for preparing porous polyaniline/polyurethane composite material through electrochemical deposition | |
| CN108648923B (en) | MnO (MnO)2Preparation method of-PANI/foam titanium composite electrode | |
| CN114538788B (en) | Preparation method of layered double hydroxide electrochromic energy storage film | |
| CN105097302B (en) | Activated carbon fiber for ultracapacitor and preparation method thereof | |
| CN109360947A (en) | A kind of preparation method of the porous carbon positive electrode of quasi- solid-state lithium-sulfur cell | |
| CN103996843B (en) | A kind of porous LiMn2O4 nanometer sheet and preparation method thereof | |
| CN104681281B (en) | With excellent high rate performance combination electrode material and preparation method thereof | |
| CN102157266A (en) | Flexible film super capacitor and preparation method thereof | |
| CN115000402B (en) | Organic positive electrode material and preparation method and application thereof | |
| CN104616909B (en) | Electrode material, its preparation method, its application and ultracapacitor | |
| CN102779647B (en) | Method for preparing pyrrole/3-(4-tert-butyl benzene) thiophene copolymer for supercapacitor |
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 |
Granted publication date: 20140423 Termination date: 20160106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |