CN103665376B - A kind of preparation method of polypyrrole micro/nano tube - Google Patents
A kind of preparation method of polypyrrole micro/nano tube Download PDFInfo
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- CN103665376B CN103665376B CN201310700726.1A CN201310700726A CN103665376B CN 103665376 B CN103665376 B CN 103665376B CN 201310700726 A CN201310700726 A CN 201310700726A CN 103665376 B CN103665376 B CN 103665376B
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Abstract
The present invention relates to a kind of preparation method of polypyrrole micro/nano tube, step is as follows: oxygenant dissolves in deionized water by (1), and obtained concentration is the oxidizing agent solution of 130 ~ 150mmol/L; (2) by tropeolin-D and Sodium dodecylbenzene sulfonate be 1:(0.8 ~ 1.2 in molar ratio) be dissolved in deionized water, obtained two Micellar Gel solution; (3) pyrrole monomer is joined in two Micellar Gel solution, obtain stock liquid; Droplets of feed is added in oxidizing agent solution, in 0 ~ 20 DEG C of reaction 10 ~ 30h; Filter, collect solid, washing, dry, to obtain final product.Preparation method of the present invention is simple, ratio capacitance performance and thermal stability excellence.
Description
Technical field
The present invention relates to a kind of preparation method of polypyrrole micro/nano tube, belong to conductive polymers micro/nano material preparing technical field.
Background technology
Conducting polymer has many advantageous properties such as electricity, electrochemistry, mechanics, optics, magnetics, all has potential application prospect in fields such as productive life, military affairs, aerospace.The pattern of conducting polymer composite and size are to the electrical property of polymkeric substance, gas sensing performance, catalytic performance produces important impact, therefore the controlledly synthesis of conductive polymers pattern, become study hotspot and the difficult point (YongqiangYang in conducting polymer synthesis field, RuiqingPang, XuejiaoZhou, YanZhang, HaixiaWuandShouwuGuo, Compositesofchemically-reducedgrapheneoxidesheetsandcarb onnanosphereswiththree-dimensionalnetworkstructureasanod ematerialsforlithiumionbatteries, J.Mater.Chem., 2012, 22, 23194 – 23200, S.N.Beesabathuni, J.G.Stockham, J.H.Kim, H.B.Lee, J.H.ChungandA.Q.Shen, Fabricationofconductingpolyanilinemicrospheresusingdropl etmicrofluidics, RSCAdv., 2013, 3, 24423 – 24429), be that soft template can prepare particulate state with tensio-active agent, the electric polypyrrole of threadiness and tubulose, due to the difference of its pattern and structure, these conductive polymerss are in specific conductivity, super capacitor material and lithium ion battery material show excellent performance (XuehuaZhang, ShashaWang, ShanLu, JiaSu, TaoHe, Influenceofdopinganionsonstructureandpropertiesofelectro-polymerizedpolypyrrolecounterelectrodesforuseindye-sensi tizedsolarcells, J.PowerSources, 246 (2014) 491-498, WeiyangLi, QianfanZhang, GuangyuanZheng, ZhiWeiSeh, HongbinYao, YiCui, UnderstandingtheRoleofDifferentConductivePolymersinImpro vingtheNanostructuredSulfurCathodePerformance, NanoLett.2013,13,5534-5540).Usually granular electric polypyrrole (K á tiaR.L.Castagno is obtained with Sodium dodecylbenzene sulfonate; VivianeDalmorob; DeniseS.Azambuja; Characterizationandcorrosionofpolypyrrole/sodiumdodecylb enzenesulfonateelectropolymerisedonaluminumalloy1100, MaterialsChemistryandPhysics130 (2011) 721 – 726; BaobaoZhao, ZhaodongNan, Formationofself-assemblednanofiber-likeAgPPycore/shellstructuresinducedbySDBS, MaterialsScienceandEngineeringC32 (2012) 1971 – 1975); Be that the tubulose polypyrrole micro/nano tube specific conductivity that Template preparation goes out reaches 33.0S/cm with tropeolin-D; Solubility property slightly improves (J.Upadhyay, A.Kumar, Structural, thermalanddielectricstudiesofpolypyrrolenanotubessynthes izedbyreactiveselfdegradetemplatemethod, MaterialsScienceandEngineeringB178 (2013) 982 – 989).
Chinese patent literature CN102924718A(application number: 201210463063.1) disclose a kind of preparation method with the polypyrrole of nanostructure; Comprise step: will there is the Manganse Dioxide of certain nanostructured morphologies as reaction template, react with pyrrole monomer in an acidic solution, the pH of described acidic solution is 0 ~ 6, temperature of reaction is-10 ~ 50 DEG C, molar weight ratio >=the 1:2 of pyrrole monomer and Manganse Dioxide, prepare polypyrrole, the nanostructured morphologies of described polypyrrole is identical with the nanostructured morphologies of described Manganse Dioxide.But this polypyrrole ratio capacitance with nanostructure is less; And temperature of reaction is higher, be unfavorable for energy conservation.
At present, jointly prepare electric polypyrrole as soft template using tropeolin-D and Sodium dodecylbenzene sulfonate and not yet have report.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of polypyrrole micro/nano tube.
Technical scheme of the present invention is as follows:
A preparation method for polypyrrole micro/nano tube, step is as follows:
(1) under agitation, dissolved in deionized water by oxygenant, obtained concentration is the oxidizing agent solution of 130 ~ 150mmol/L; Described oxygenant is ammonium persulphate;
(2) under agitation, be 1:(0.8 ~ 1.2 in molar ratio by tropeolin-D and Sodium dodecylbenzene sulfonate) be dissolved in deionized water, obtained two Micellar Gel solution; In described two Micellar Gel solution, the concentration of tropeolin-D is 0.5 ~ 4.0mmol/L;
(3) pyrrole monomer is joined in two Micellar Gel solution, obtain stock liquid; Droplets of feed is added in oxidizing agent solution, in 0 ~ 20 DEG C of reaction 10 ~ 30h; Filter, collect solid, washing, dry, obtain polypyrrole micro/nano tube;
Described pyrrole monomer and the mol ratio of oxygenant are 1:(0.8 ~ 1.2).
According to the present invention, preferably, the concentration of the oxidizing agent solution described in step (1) is 144mmol/L.
According to the present invention, preferably, the mol ratio of the tropeolin-D described in step (2) and Sodium dodecylbenzene sulfonate is 1:1;
Preferably, in described two Micellar Gel solution, the concentration of tropeolin-D is 2.0 ~ 3.0mmol/L.
According to the present invention, preferably, the pyrrole monomer described in step (3) is (0.3 ~ 1) with the volume ratio of two Micellar Gel solution: 150, more preferably 0.5:150;
Preferably, described pyrrole monomer and the mol ratio of oxygenant are 1:1;
Preferably, described temperature of reaction is 0 ~ 10 DEG C, and the reaction times is 24h;
Preferably, described mode of washing is alcohol wash after washing, uses washing with alcohol 2 ~ 3 times after more preferably washing 1 ~ 2 time;
Preferably, drying mode is dry 10 ~ 24h in 40 ~ 80 DEG C of air atmospheres.
According to the present invention, preferably, the speed of step (1) and the stirring described in (2) is 200 ~ 500r/min.
Tropeolin-D of the present invention and Sodium dodecylbenzene sulfonate are jointly as soft template, and the polypyrrole micro/nano tube prepared is hollow thorn-like; The diameter of polypyrrole micro/nano tube at about 400nm, wall thickness at about 60nm, at the polypyrrole of the thorn-like of the Surface Creation granulometric composition of polypyrrole micro/nano tube.
The invention has the beneficial effects as follows:
1, the present invention with the solution of tropeolin-D and Sodium dodecylbenzene sulfonate for template, use in situ chemical oxidation method, synthesize hollow thorn-like polypyrrole micro/nano tube first, this polypyrrole micro/nano tube conductivity is significantly improved, discharge and recharge under the current density of 0.2A/g, ratio capacitance reaches 380F/g, in super capacitor material field, have good application prospect.
2, temperature of reaction of the present invention is 0 ~ 20 DEG C, neither needs very low temperature, does not also need higher temperature, and reaction conditions is gentle, and energy consumption is low; Preparation process is simple, is easy to suitability for industrialized production.
3, the polypyrrole micro/nano tube Heat stability is good prepared of the present invention, significantly improves than the thermostability of the polypyrrole micro/nano tube by tropeolin-D being only Template preparation.
Accompanying drawing explanation
Scanning electron microscope (SEM) photo of the polypyrrole micro/nano tube of Fig. 1 prepared by embodiment 1.
Transmission electron microscope (TEM) photo of the polypyrrole micro/nano tube of Fig. 2 prepared by embodiment 1.
The thermogravimetric curve figure of the polypyrrole micro/nano tube of Fig. 3 prepared by embodiment 1 and comparative example.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited thereto.
Raw materials usedly in embodiment be conventional commercial products; Equipment used is conventional equipment, and testing method is ordinary method.
Wherein: tropeolin-D, Tianjin Kermel Chemical Reagent Co., Ltd. is on sale; Ammonium persulphate, the wide promise in Shanghai chemistry Science and Technology Ltd. is on sale; Sodium dodecylbenzene sulfonate, Tianjin Bo Di Chemical Co., Ltd. is on sale; Pyrrole monomer, Sa En chemical technology (Shanghai) Co., Ltd. is on sale; Dehydrated alcohol, Tianjin Bo Di Chemical Co., Ltd. is on sale.
In embodiment 1, the stereoscan photograph of prepared sample detects through Japanese HitachiS-4800 field emission scanning electron microscope to obtain; Transmission electron microscope photo detects through Japanese JEM-1011 transmission electron microscope to obtain, and charge-discharge test detects through PARSTAT2263 electrochemical workstation to obtain, and thermogravimetric curve checks through the SDTQ600 of TA company of the U.S. to obtain.
Embodiment 1
A preparation method for polypyrrole micro/nano tube, step is as follows:
(1) under 300r/min agitation condition, be dissolved in 50mL deionized water by ammonium persulphate 7.2mmol, stirring, it is for subsequent use to be placed in constant pressure funnel, obtained oxidizing agent solution;
(2) 0.3mmol tropeolin-D and 0.3mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, obtained two Micellar Gel solution;
(3) in two Micellar Gel solution, 0.5mL(7.2mmol is added) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 0 DEG C of reaction 24h, obtains black reaction liquid; Gained reaction solution is filtered, liquids recovery, for subsequent use; Solid is through water washing, absolute ethanol washing, and in 50 DEG C of air atmospheres, dry 24h, obtains polypyrrole micro/nano tube.
Fig. 1 is the stereoscan photograph of polypyrrole micro/nano tube prepared by the present embodiment, and Fig. 2 is the transmission electron microscope photo of polypyrrole micro/nano tube prepared by the present embodiment.Polypyrrole micro/nano tube prepared by the present embodiment the present embodiment be hollow tubular structures, the diameter of pipe at about 400nm, wall thickness at about 60nm, at the polypyrrole of the thorn-like of the Surface Creation granulometric composition of polypyrrole micro/nano tube.From Fig. 1,2, polypyrrole micro/nano tube prepared by the present embodiment is thorn-like.
Carry out charge-discharge test to polypyrrole micro/nano tube prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 380F/g.
Embodiment 2
A preparation method for polypyrrole micro/nano tube, step, with embodiment 1, is 10 DEG C unlike temperature of reaction in: step (3).
Carry out charge-discharge test to polypyrrole micro/nano tube prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 268F/g.
Embodiment 3
A preparation method for polypyrrole micro/nano tube, step is as follows:
(1) under 500r/min agitation condition, be dissolved in 50mL deionized water by ammonium persulphate 7.2mmol, stirring, it is for subsequent use to be placed in constant pressure funnel, obtained oxidizing agent solution;
(2) 0.1mmol tropeolin-D and 0.1mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, obtained two Micellar Gel solution;
(3) in two Micellar Gel solution, 0.5mL(7.2mmol is added) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 0 DEG C of reaction 30h, obtains black reaction liquid; Gained reaction solution is filtered, liquids recovery, for subsequent use; Solid is through water washing, absolute ethanol washing, and in 80 DEG C of air atmospheres, dry 12h, obtains polypyrrole micro/nano tube.
Carry out charge-discharge test to polypyrrole micro/nano tube prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 312F/g.
Embodiment 4
A preparation method for polypyrrole micro/nano tube, step, with embodiment 3, is 10 DEG C unlike temperature of reaction in: step (3).
Carry out charge-discharge test to polypyrrole micro/nano tube prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 285F/g.
Embodiment 5
A preparation method for polypyrrole micro/nano tube, step is as follows:
(1) under 400r/min agitation condition, be dissolved in 50mL deionized water by ammonium persulphate 6.5mmol, stirring, it is for subsequent use to be placed in constant pressure funnel, obtained oxidizing agent solution;
(2) 0.1mmol tropeolin-D and 0.08mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, obtained two Micellar Gel solution;
(3) in two Micellar Gel solution, 0.5mL(7.2mmol is added) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 5 DEG C of reaction 20h, obtains black reaction liquid; Gained reaction solution is filtered, liquids recovery, for subsequent use; Solid is through water washing, absolute ethanol washing, and in 70 DEG C of air atmospheres, dry 15h, obtains polypyrrole micro/nano tube.
Carry out charge-discharge test to polypyrrole micro/nano tube prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 254F/g.
Embodiment 6
A preparation method for polypyrrole micro/nano tube, step is as follows:
(1) under 400r/min agitation condition, be dissolved in 50mL deionized water by ammonium persulphate 7.5mmol, stirring, it is for subsequent use to be placed in constant pressure funnel, obtained oxidizing agent solution;
(2) 0.1mmol tropeolin-D and 0.12mmol Sodium dodecylbenzene sulfonate are joined in 150mL deionized water, be placed in there-necked flask, stir, obtained two Micellar Gel solution;
(3) in two Micellar Gel solution, 0.5mL(7.2mmol is added) pyrrole monomer, obtain stock liquid; Stock liquid is slowly added drop-wise in oxidizing agent solution, in 15 DEG C of reaction 12h, obtains black reaction liquid; Gained reaction solution is filtered, liquids recovery, for subsequent use; Solid is through water washing, absolute ethanol washing, and in 60 DEG C of air atmospheres, dry 20h, obtains polypyrrole micro/nano tube.
Carry out charge-discharge test to polypyrrole micro/nano tube prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 223F/g.
Comparative example
The single template solution of this comparative example prepares polypyrrole micro/nano tube, and step, with embodiment 1, does not add Sodium dodecylbenzene sulfonate unlike in step (2), only adds tropeolin-D and obtain template solution.
Charge-discharge test is carried out to polypyrrole micro/nano tube prepared by this comparative example, under 0.2A/g discharge and recharge condition, ratio capacitance is 177F/g.
To polypyrrole micro/nano tube test thermal stability prepared by embodiment 1 and comparative example, result as shown in Figure 3.As shown in Figure 3, the thermostability of the polypyrrole micro/nano tube of embodiment 1 preparation significantly improves than comparative example.
Claims (12)
1. a preparation method for polypyrrole micro/nano tube, step is as follows:
(1) under agitation, dissolved in deionized water by oxygenant, obtained concentration is the oxidizing agent solution of 130 ~ 150mmol/L; Described oxygenant is ammonium persulphate;
(2) under agitation, be 1:(0.8 ~ 1.2 in molar ratio by tropeolin-D and Sodium dodecylbenzene sulfonate) be dissolved in deionized water, obtained two Micellar Gel solution; In described two Micellar Gel solution, the concentration of tropeolin-D is 0.5 ~ 4.0mmol/L;
(3) pyrrole monomer is joined in two Micellar Gel solution, obtain stock liquid; Droplets of feed is added in oxidizing agent solution, in 0 ~ 20 DEG C of reaction 10 ~ 30h; Filter, collect solid, washing, dry, obtain polypyrrole micro/nano tube;
Described pyrrole monomer and the mol ratio of oxygenant are 1:(0.8 ~ 1.2).
2. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, the concentration of the oxidizing agent solution described in step (1) is 144mmol/L.
3. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, the mol ratio of the tropeolin-D described in step (2) and Sodium dodecylbenzene sulfonate is 1:1.
4. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, in the two Micellar Gel solution described in step (2), the concentration of tropeolin-D is 2.0 ~ 3.0mmol/L.
5. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, the pyrrole monomer described in step (3) is (0.3 ~ 1) with the volume ratio of two Micellar Gel solution: 150.
6. the preparation method of polypyrrole micro/nano tube according to claim 5, is characterized in that, the pyrrole monomer described in step (3) is 0.5:150 with the volume ratio of two Micellar Gel solution.
7. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, the mol ratio of the pyrrole monomer described in step (3) and oxygenant is 1:1.
8. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, the temperature of reaction described in step (3) is 0 ~ 10 DEG C, and the reaction times is 24h.
9. the preparation method of polypyrrole micro/nano tube according to claim 1, is characterized in that, the mode of washing described in step (3) is alcohol wash after washing.
10. the preparation method of polypyrrole micro/nano tube according to claim 9, is characterized in that, the mode of washing described in step (3) is use washing with alcohol 2 ~ 3 times after washing 1 ~ 2 time.
The preparation method of 11. polypyrrole micro/nano tube according to claim 1, is characterized in that, in step (3), drying mode is dry 10 ~ 24h in 40 ~ 80 DEG C of air atmospheres.
The preparation method of 12. polypyrrole micro/nano tube according to claim 1, is characterized in that, the speed of step (1) and the stirring described in (2) is 200 ~ 500r/min.
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| US9851267B1 (en) * | 2016-06-01 | 2017-12-26 | Microsoft Technology Licensing, Llc | Force-sensing element |
| CN107794600A (en) * | 2017-11-15 | 2018-03-13 | 惠州市永耐宝新材料有限公司 | A kind of preparation method of polyaniline/polythiophene composite nano tube |
| CN108250744A (en) * | 2017-12-19 | 2018-07-06 | 彭枭雄 | A kind of polyaniline/polypyrrole composite nano tube and preparation method thereof |
| CN108373535A (en) * | 2018-03-26 | 2018-08-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of Mn oxide load polypyrrole nanotube |
| CN109851783B (en) * | 2019-01-22 | 2021-11-26 | 齐鲁工业大学 | Preparation method of hollow quadrangular-prism-shaped conductive polypyrrole |
| CN112058187A (en) * | 2020-09-15 | 2020-12-11 | 安徽大学 | Preparation method of hollow polypyrrole microspheres |
| CN116666665A (en) * | 2023-05-29 | 2023-08-29 | 湖北文理学院 | Catalytic layer, method for producing same, and fuel cell |
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| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
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| Preparation and characterization of PPy with methyl orange as soft template;Mei Li等;《J Mater Sci: Mater Electron》;20120727;第24卷;906–910 * |
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