CN101016412A - Method of preparing lithium salt doping state polyaniline electrode material for super capacitor - Google Patents
Method of preparing lithium salt doping state polyaniline electrode material for super capacitor Download PDFInfo
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- CN101016412A CN101016412A CNA2007100344979A CN200710034497A CN101016412A CN 101016412 A CN101016412 A CN 101016412A CN A2007100344979 A CNA2007100344979 A CN A2007100344979A CN 200710034497 A CN200710034497 A CN 200710034497A CN 101016412 A CN101016412 A CN 101016412A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a preparing method of lithium salt doping state polyaniline electrode material to produce super capacitor, which comprises the following steps: adopting interfacial polymerization method; preparing acid doping state polyaniline nanometer fiber with diameter between 30 nm and 120 nm and length at 500nm to several micrometer; contra-doping with alkali liquor; getting Eigen state; doping with lithium salt solution under the protection of inert gas; getting the product. This electric pole material possesses bigger than 120 F/g ratio capacitance value in organic electrolytic solution, which can resolve the problem of low ratio capacitance value in the organic electrolytic solution.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material for super capacitor, particularly a kind of preparation method who is used for the lithium salt doping state polyaniline electrode material of ultracapacitor.
Background technology
Polyaniline is owing to have good chemical stability, electroconductibility and high characteristics such as fake capacitance energy storage characteristic, and is easy to synthesize, and the monomer cost is low, thereby is considered to one of conductive polymer electrodes material that has most actual application prospect in the ultracapacitor field.In organic electrolyte system, polyaniline needs just possess electroconductibility and electric capacity behavior through mixing, and its doping agent generally can be selected various mineral acids, organic acid and lithium salt solution for use.(Kwang Sun Ryu such as KwangSun Ryu, Kwang Man Kim, Nam-Gyu Park, et al.Symmetricredox supercapacitor with conducting polyaniline electrodes[J] .Journal of PowerSources, 2002,103 (2): 305-309) (Kwang Sun Ryu, Kwang Man Kim, Yong JoonPark, et al.Redox supercapacitor using polyaniline doped with Li salt as electrode[J] .Solid State Ionics, 2002, (152-153): 861-866) polyaniline material of ordinary chemical method preparation is handled the back with lithium salt solution and obtain the lithium salt doping state polyaniline material, make electrode of super capacitor with it, in organic electrolyte, have than the better electrochemical capacitor behavior of doped hydrochloride attitude polyaniline material.Yet it is still more on the low side than capacitance, and energy density is kind owes desirable.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with lithium salt doping state polyaniline electrode material of high specific capacitance value.
The present invention is achieved by the following technical solutions, may further comprise the steps:
(1) utilize the polyreaction that oil/water two-phase interface takes place to prepare sour doped polyaniline nano-fiber material; 1. aniline monomer is dissolved in the organic solvent, be made into the solution A that aniline monomer concentration is 0.05～0.3mol/L, the oxygenant ammonium persulphate is dissolved in wiring solution-forming B, wherein oxidant concentration in the solution B in the inorganic proton acid solution of 0.5～2mol/L: aniline monomer concentration is 0.2～1.0 in the solution A; 2. solution A and solution B are carefully moved in the reactor successively, two kinds of solution form oil/water two-phase interface at once, and interface polymerization reaction takes place, and react 5～30h under the room temperature; 3. with the washing of the product in the B solution, vacuum-drying promptly gets sour doped polyaniline nano-fiber material;
(2) the above-mentioned sour doped polyaniline nano-fiber material that makes is handled 12～48h with 0.1～1mol/L alkali lye under agitation condition, washing, vacuum-drying, the eigenstate of acquisition polyaniline nano fiber;
(3) under protection of inert gas atmosphere, the above-mentioned polyaniline in eigenstate material that makes is soaked 48～72h in lithium salt solution, washing, vacuum-drying promptly obtains the lithium salt doping state polyaniline material.
Described organic solvent is at least a in benzene, toluene, normal hexane, tetracol phenixin, dithiocarbonic anhydride, chloroform or the methylene dichloride.
Described inorganic proton acid is hydrochloric acid or perchloric acid.
Described sour doped polyaniline nano-fiber material diameter between 30～120nm, length is 500nm to several microns.
Described alkali lye is NaOH, KOH, the NH of 0.1～1mol/L
4At least a in OH, LiOH, the tetraethyl ammonium hydroxide.
Described lithium salt solution is with LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiCF
3SO
3Or at least a among the LiCl be solute, is solvent with at least a in methylcarbonate, diethyl carbonate, propylene carbonate, NSC 11801, butylene, methyl ethyl carbonate alkene ester, carbonic acid first propyl ester or the acetonitrile.
The present invention is because characteristics such as good pore texture that polyaniline nano fiber has and high-specific surface area more help the doping of lithium salt solution and the immersion of electrolytic solution, the more convenient ionic of this kind structure embeds/deviates from charge and discharge process simultaneously, the lithium salt doping state polyaniline material of the present invention's preparation is done the electrode of super capacitor active substance, in organic electrolyte, has ratio capacitance above 120F/g, the lithium salt doping state polyaniline material that is better than prior art for preparing, also be much better than common doped hydrochloride attitude polyaniline material, efficiently solve polyaniline material low problem in organic electrolyte than capacitance.
Description of drawings
Fig. 1 is the SEM figure of the lithium salt doping state polyaniline electrode material of embodiment 1 preparation;
Fig. 2 is that the lithium salt doping state polyaniline electrode material of embodiment 1 preparation is at 1mol/L LiPF
6Charging and discharging curve figure (0～1V) among the EC/DEC/DMC (EC/DEC/DMC=1 volume ratio)
Fig. 3 is that the lithium salt doping state polyaniline electrode material of embodiment 1 preparation is at 1mol/L LiPF
6Charging and discharging curve figure (0～2.5V) among the EC/DEC/DMC (EC/DEC/DMC=1 volume ratio)
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
(1) aniline with 0.93mL is dissolved in 100mL organic solvent CCl
4In wiring solution-forming A, the ammonium persulphate of 0.57g is dissolved in wiring solution-forming B ([APS]/[AN]=1: 4) in the 1mol/L hydrochloric acid of 100mL; (2) solution A and solution B are carefully moved in the reaction flask successively, react 5h under the room temperature; (3) product in the collection solution B, water, ethanol and acetone is washed product repeatedly, is colourless until washings; (4) product after will washing obtains the polyaniline nano fiber material of doped hydrochloride in 40 ℃ of vacuum-drying 48h; (5) the polyaniline nano fiber material is used 1mol/L ammonia treatment 12h under agitation condition, washing, 80 ℃ of vacuum-drying 12h, the eigenstate of acquisition polyaniline nano fiber; (6) under protection of inert gas atmosphere with the polyaniline in eigenstate material at 1mol/L LiPF
6Soak 72h in EC/DEC/DMC (EC/DEC/DMC=1 volume ratio) solution, washing, 50 ℃ of vacuum-drying 48h promptly obtain the lithium salt doping state polyaniline material.Its single electrode can reach 132F/g than capacitance.
Embodiment 2
(1) aniline with 1.86mL is dissolved in wiring solution-forming A in the 100mL organic solvent toluene, and the ammonium persulphate of 2.28g is dissolved in wiring solution-forming B ([APS]/[AN]=1: 2) in the 2mol/L hydrochloric acid of 100mL; (2) solution A and solution B are carefully moved in the reaction flask successively, react 10h under the room temperature; (3) product in the collection solution B, water, ethanol and acetone is washed product repeatedly, is colourless until washings; (4) product after will washing obtains the polyaniline nano fiber material of doped hydrochloride in 60 ℃ of vacuum-drying 24h; (5) with the polyaniline nano fiber material under agitation condition with handling 24h in the 0.5mol/L sodium hydroxide solution, washing, 60 ℃ of vacuum-drying 24h obtain the eigenstate of polyaniline nano fiber; (6) under protection of inert gas atmosphere with the polyaniline in eigenstate material at 1mol/L LiBF
4Soak 48h in EC/DEC (EC/DEC=1 volume ratio) solution, washing, 50 ℃ of vacuum-drying 48h promptly obtain the lithium salt doping state polyaniline material.Its single electrode can reach 123F/g than capacitance.
Embodiment 3
(1) aniline with 0.465mL is dissolved in 100mL organic solvent CH
2Cl
2In wiring solution-forming A, the ammonium persulphate of 0.285g is dissolved in wiring solution-forming B ([APS]/[AN]=1: 1) in the 1mol/L perchloric acid of 100mL; (2) solution A and solution B are carefully moved in the reaction flask successively, react 20h under the room temperature; (3) product in the collection solution B, water, ethanol and acetone is washed product repeatedly, is colourless until washings; (4) product after will washing obtains the adulterated polyaniline nano fiber material of perchloric acid in 80 ℃ of vacuum-drying 12h.(5) with the polyaniline nano fiber material under agitation condition with handling 48h in the 0.2mol/L potassium hydroxide solution, washing, 80 ℃ of vacuum-drying 12h obtain the eigenstate of polyaniline nano fiber; (6) under protection of inert gas atmosphere with the polyaniline in eigenstate material at 1mol/L LiClO
4After soaking 60h in EC/DEC (EC/DEC=1 volume ratio) solution, washing, 50 ℃ of vacuum-drying 48h promptly obtain lithium salt doping state polyaniline electrode material.Its single electrode can reach 130F/g than capacitance.
Claims (6)
1. preparation method who is used for the lithium salt doping state polyaniline electrode material of ultracapacitor is characterized in that may further comprise the steps:
(1) utilize oil/water two-phase interface polymerization to prepare sour doped polyaniline nanofiber: 1. aniline monomer to be dissolved in the organic solvent, be made into the solution A that concentration is 0.05～0.3mol/L, the oxygenant ammonium persulphate is dissolved in wiring solution-forming B in the inorganic proton acid solution of 0.5～2mol/L, oxidant concentration: aniline monomer concentration is 0.2～1.0; 2. solution A and solution B are carefully moved in the reactor successively, at room temperature carry out oil/water two-phase interface polyreaction 5～30h; 3. with the washing of the product in the B solution, vacuum-drying promptly gets sour doped polyaniline nano-fiber material;
(2) the above-mentioned sour doped polyaniline nano-fiber material that makes is handled 12～48h with 0.1～1mol/L alkali lye under agitation condition, washing, vacuum-drying, the eigenstate of acquisition polyaniline nano fiber;
(3) under protection of inert gas atmosphere the above-mentioned polyaniline in eigenstate material that makes is soaked 48～72h in lithium salt solution, washing, vacuum-drying obtain the lithium salt doping state polyaniline material.
2. preparation method according to claim 1 is characterized in that: described organic solvent is at least a in benzene, toluene, normal hexane, tetracol phenixin, dithiocarbonic anhydride, chloroform or the methylene dichloride.
3. preparation method according to claim 1 is characterized in that: described inorganic proton acid is hydrochloric acid or perchloric acid.
4. preparation method according to claim 1 is characterized in that: described sour doped polyaniline nano-fiber material diameter between 30～120nm, length is 500nm to several microns.
5. preparation method according to claim 1 is characterized in that: described alkali lye is NaOH, KOH, NH
4At least a in OH, LiOH, the tetraethyl ammonium hydroxide.
6. preparation method according to claim 1 is characterized in that: described lithium salt solution is with LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiCF
3SO
3Or at least a among the LiCl be solute, is solvent with at least a in methylcarbonate, diethyl carbonate, propylene carbonate, NSC 11801, butylene, methyl ethyl carbonate alkene ester, carbonic acid first propyl ester or the acetonitrile.
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| CNA2007100344979A CN101016412A (en) | 2007-03-06 | 2007-03-06 | Method of preparing lithium salt doping state polyaniline electrode material for super capacitor |
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| CNA2007100344979A CN101016412A (en) | 2007-03-06 | 2007-03-06 | Method of preparing lithium salt doping state polyaniline electrode material for super capacitor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532892A (en) * | 2012-01-20 | 2012-07-04 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN105449156A (en) * | 2015-03-27 | 2016-03-30 | 万向A一二三系统有限公司 | Preparation method of negative electrode of lithium-ion battery |
| CN105778085A (en) * | 2016-03-28 | 2016-07-20 | 重庆金固特新材料科技有限公司 | Preparation method for polyaniline |
| CN111250016A (en) * | 2020-02-06 | 2020-06-09 | 徐国栋 | Liquid plasma device for treating tumor and skin disease |
| CN112992556A (en) * | 2021-02-06 | 2021-06-18 | 威海三合永新能源科技有限公司 | Preparation method and application of lithium ion capacitor pre-embedded lithium additive |
-
2007
- 2007-03-06 CN CNA2007100344979A patent/CN101016412A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532892A (en) * | 2012-01-20 | 2012-07-04 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN102532892B (en) * | 2012-01-20 | 2013-07-24 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN105449156A (en) * | 2015-03-27 | 2016-03-30 | 万向A一二三系统有限公司 | Preparation method of negative electrode of lithium-ion battery |
| CN105778085A (en) * | 2016-03-28 | 2016-07-20 | 重庆金固特新材料科技有限公司 | Preparation method for polyaniline |
| CN111250016A (en) * | 2020-02-06 | 2020-06-09 | 徐国栋 | Liquid plasma device for treating tumor and skin disease |
| CN112992556A (en) * | 2021-02-06 | 2021-06-18 | 威海三合永新能源科技有限公司 | Preparation method and application of lithium ion capacitor pre-embedded lithium additive |
| CN112992556B (en) * | 2021-02-06 | 2022-07-19 | 威海三合永新能源科技有限公司 | Preparation method and application of lithium ion capacitor pre-intercalation additive |
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Open date: 20070815 |