CN104072768B - A kind of preparation method of hollow tubular polypyrrole film - Google Patents
A kind of preparation method of hollow tubular polypyrrole film Download PDFInfo
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- CN104072768B CN104072768B CN201410325427.9A CN201410325427A CN104072768B CN 104072768 B CN104072768 B CN 104072768B CN 201410325427 A CN201410325427 A CN 201410325427A CN 104072768 B CN104072768 B CN 104072768B
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Abstract
The present invention relates to a kind of preparation method of hollow tubular electric polypyrrole film, comprise the steps: that (1) is under 300r/min agitation condition, iron(ic) chloride 3.6mmol is dissolved in 50mL deionized water; (2) in there-necked flask, 0.3mmol tropeolin-D is joined in 150mL deionized water, stir after ultrasonic dissolution; (3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min; (4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC; (5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 40oC air atmosphere, obtains hollow tubular polypyrrole film.The present invention is soft template by tropeolin-D first, has prepared the polypyrrole film be made up of polypyrrole hollow Nano pipe with the chemical oxidization method of simple possible.
Description
Technical field
The present invention relates to a kind of preparation method of conductive polymer membrane, belong to conducting polymer thin film technical field of material.
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, ByoungHoonLee, Jong-HoonLee, YungHoKahng, NaraKim, YongJaeKim, JongjinLee, TakheeLee, KwangheeLee, Graphene-ConductingPolymerHybridTransparentElectrodesfor EfficientOrganicOptoelectronicDevices, Adv.Funct.Mater.DOI:10.1002/adfm.201302928), 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, OlegYuPosudievsky, OlgaA.Kozarenko, VyacheslavS.Dyadyuna, ScottW.Jorgensen, JamesA.Spearot, VyacheslavG.Koshechko, VitalyD.Pokhodenko, Mechanochemicallypreparedternaryhybridcathodematerialfor lithiumbatteries, Electrochim.Acta.109 (2013) 866 – 873, QianLiu, ZonghuaPu, ChunTang, AbdullahM.Asiri, AbdullahH.Qusti, AbdulrahmanO.Al-Youbi, XupingSun, N-dopedcarbonnanotubesfromfunctionaltubularpolypyrrole:A highlyefficientelectrocatalystforoxygenreductionreaction, Electrochem.Commun.36 (2013) 57 – 61).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 (JuanLi, LiCui, XiaogangZhang, Preparationandelectrochemistryofone-dimensionalnanostruc turedMnO2/PPycompositeforelectrochemicalcapacitor, AppliedSurfaceScience256 (2010) 4339 – 4343, SukFunChin, SuhCemPang, Tetrapropylammonium-manganeseoxide/polypyrrolehybridnano compositethinfilmsasnovelelectrodematerialsforsupercapac itors, MaterialsChemistryandPhysics124 (2010) 29 – 32, J.Upadhyay, A.Kumar, Structural, thermalanddielectricstudiesofpolypyrrolenanotubessynthes izedbyreactiveselfdegradetemplatemethod, MaterialsScienceandEngineeringB178 (2013) 982 – 989).Better (the XiaoDu of capacitive property of film of poly pyrrole, XiaogangHao, ZhongdeWang, XuliMa, GuoqingGuan, AbudulaAbuliti, GuozhangMa, ShibinLiu, Highlystablepolypyrrolefilmpreparedbyunipolarpulseelectr o-polymerizationmethodaselectrodeforelectrochemicalsuper capacitor, SyntheticMetals175 (2013) 138 – 145, SujataS.Shinde, GirishS.Gunda, DeepakP.Dubalb, SupriyaB.Jambure, ChandrakantD.Lokhande, Morphologicalmodulationofpolypyrrolethinfilmsthroughoxid izingagentsandtheirconcurrenteffectonsupercapacitorperfo rmance, ElectrochimicaActa119 (2014) 1 – 10, B.H.Patil, R.N.Bulakhe, C.D.Lokhande, Supercapacitiveperformanceofchemicallysynthesizedpolypyr rolethinfilms:effectofmonomertooxidantratio, JMaterSci:MaterElectron (2014) 25:2188 – 2198).Prepare electric polypyrrole film using tropeolin-D as soft template and not yet have report.
Summary of the invention
The present invention utilizes tropeolin-D for Template preparation electric polypyrrole film, provides a kind of method preparing hollow tubular electric polypyrrole film, and this hollow tubular electric polypyrrole film discharge and recharge under the current density of 0.2A/g, ratio capacitance reaches 647F/g.
The present invention prepares hollow tubular polypyrrole film, and its preparation process comprises the steps:
A. under agitation, tropeolin-D be dissolved in deionized water, obtained concentration is 2 × 10
-3the methyl orange aqueous solution of mol/L;
B. under agitation, dissolved in deionized water by oxygenant, obtained concentration is 7.2 × 10
-4the aqueous oxidizing agent solution of mol/L;
C. under agitation, pyrrole monomer is added in the methyl orange solution that a prepares, stir and pyrrole monomer is mixed with methyl orange solution;
D. in 0oC ice bath, in the mixed solution in c, dropwise add the liquor ferri trichloridi that step b prepares, solution colour is deepened gradually, and pyrrole monomer and the ratio of the amount of substance of oxygenant are react 24h under 0.5:1,0oC;
E. black precipitate steps d obtained, filters, washing, dry, finally obtains hollow tubular polypyrrole film.
Stir speed (S.S.) in described step a, b is 200 ~ 400r/min;
In described step b, oxygenant is iron trichloride;
Stir speed (S.S.) in described step c is 200 ~ 400r/min;
Temperature of reaction in described steps d is about 0oC;
Drying temperature in described step e is 40 ~ 60oC.
Compare with prior art, the present invention has the following advantages:
(1) the present invention take methyl orange solution as soft template, with chemical oxidization method, be that oxygenant has synthesized hollow tubular polypyrrole film first with iron trichloride, the conductivity of this polypyrrole film is significantly improved compared with pure polypyrrole, has many potential purposes in super capacitor material field;
(2) present invention process is simple, is applicable to large-scale industrial and produces.
Accompanying drawing explanation
The photo of the polypyrrole film sample S-1 of Fig. 1 prepared by embodiment 1;
Scanning electron microscope (SEM) photo of the polypyrrole film sample S-1 of Fig. 2 prepared by embodiment 1;
Transmission electron microscope (TEM) photo of the polypyrrole film sample S-1 of Fig. 3 prepared by embodiment 1.
Embodiment
Be further elaborated technical scheme of the present invention below in conjunction with specific embodiment, these embodiments are just in order to set forth the restriction that technical scheme of the present invention can not be considered as the claims in the present invention content.
Tropeolin-D in embodiment is purchased from Tianjin Kermel Chemical Reagent Co., Ltd.;
Iron trichloride is purchased from Tianjin Bo Di Chemical Co., Ltd.;
Pyrroles is purchased from Sa En chemical technology (Shanghai) Co., Ltd.;
Dehydrated alcohol is purchased from Tianjin Bo Di Chemical Co., Ltd..
The stereoscan photograph of sample prepared by the present invention 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.
embodiment 1
(1) under 300r/min agitation condition, be dissolved in 50mL deionized water by iron(ic) chloride 3.6mmol, stirring, it is for subsequent use to be placed in constant pressure funnel;
(2) in there-necked flask, 0.3mmol tropeolin-D is joined in 150mL deionized water, stir after ultrasonic dissolution, there-necked flask is transferred in cryostat, maintain the temperature of cryostat at about 0oC;
(3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min, solution is mixed;
(4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC, obtain black reaction liquid;
(5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 40oC air atmosphere, obtains target product (sample S-1).
Fig. 1 is shown in by the photo of prepared sample S-1 polypyrrole film;
The stereoscan photograph of prepared sample S-1 is shown in Fig. 2;
The transmission electron microscope photo of prepared sample S-1 is shown in Fig. 3;
Sample is for having some strength and elastic polypyrrole film as seen from Figure 1; As seen from Figure 2, sample S-1 is mainly fibrous by polypyrrole, the diameter of fiber is at about 70 ~ 80nm, pipe range is at about 5-6 μm, product is polypyrrole fibrous inside is as seen from Figure 3 hollow structure, sample is actually the conductive polymer membrane formed by polypyrrole nanotube, and thickness of pipe is about about 20 ~ 30nm.
Carry out charge-discharge test to polypyrrole film prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 647F/g.
embodiment 2
(1) under 500r/min agitation condition, by iron(ic) chloride 1.44mmol solution in 50mL deionized water, stirring, it is for subsequent use to be placed in constant pressure funnel;
(2) 0.3mmol tropeolin-D joined in 150mL deionized water in there-necked flask, ultrasonic dissolution stirs, and is transferred to by there-necked flask in cryostat, maintains the temperature of cryostat at about 10oC;
(3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min, solution is mixed;
(4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC, obtain black reaction liquid;
(5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 60oC air atmosphere, obtains hollow tubular polypyrrole film.
Carry out charge-discharge test to polypyrrole film prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 352F/g.
embodiment 3
(1) under 500r/min agitation condition, by iron(ic) chloride 2.16mmol solution in 50mL deionized water, stirring, it is for subsequent use to be placed in constant pressure funnel;
(2) 0.3mmol tropeolin-D joined in 150mL deionized water in there-necked flask, ultrasonic dissolution stirs, and is transferred to by there-necked flask in cryostat, maintains the temperature of cryostat at about 10oC;
(3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min, solution is mixed;
(4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC, obtain black reaction liquid;
(5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 60oC air atmosphere, obtains hollow tubular polypyrrole film.
Carry out charge-discharge test to polypyrrole film prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 406F/g.
embodiment 4
(1) under 300r/min agitation condition, be dissolved in 50mL deionized water by iron trichloride 5.76mmol, stirring, it is for subsequent use to be placed in constant pressure funnel;
(2) 0.3mmol tropeolin-D joined in 150mL deionized water in there-necked flask, ultrasonic dissolution stirs, and is transferred to by there-necked flask in cryostat, maintains the temperature of cryostat at about 0oC;
(3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min, solution is mixed;
(4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC, obtain black reaction liquid;
(5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 60oC air atmosphere, obtains black film of poly pyrrole.
Carry out charge-discharge test to polypyrrole film prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 473F/g.
embodiment 5
(1) under 500r/min agitation condition, by iron(ic) chloride 7.2mmol solution in 50mL deionized water, stirring, it is for subsequent use to be placed in constant pressure funnel;
(2) 0.3mmol tropeolin-D joined in 150mL deionized water in there-necked flask, ultrasonic dissolution stirs, and is transferred to by there-necked flask in cryostat, maintains the temperature of cryostat at about 10oC;
(3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min, solution is mixed;
(4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC, obtain black reaction liquid;
(5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 60oC air atmosphere, obtains hollow tubular polypyrrole film.
Carry out charge-discharge test to polypyrrole film prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 392F/g.
embodiment 6
(1) under 300r/min agitation condition, be dissolved in 50mL deionized water by iron trichloride 10.8mmol, stirring, it is for subsequent use to be placed in constant pressure funnel;
(2) 0.3mmol tropeolin-D joined in 150mL deionized water in there-necked flask, ultrasonic dissolution stirs, and is transferred to by there-necked flask in cryostat, maintains the temperature of cryostat at about 0oC;
(3) in the methyl orange solution stirred, add 0.5mL pyrrole monomer, continue to stir 30min, solution is mixed;
(4) in mixed solution, slowly drip the solution of oxygenant under agitation, react 24h in about 0oC, obtain black reaction liquid;
(5) gained reaction solution is carried out solid-liquid separation, liquids recovery, for subsequent use; Solid is through washing, alcohol wash three times, and dry 12h in 60oC air atmosphere, obtains black film of poly pyrrole.
Carry out charge-discharge test to polypyrrole film prepared by the present embodiment, discharge and recharge under the current density condition of 0.2A/g, ratio capacitance is 284F/g.
comparative example
This comparative example, in polypyrrole preparation process, changes oxygenant into ammonium persulphate, and all the other steps are with embodiment 1, and what obtain is black polypyrrole powder.
Charge-discharge test is carried out to Platinum material prepared by this comparative example, under 0.2A/g discharge and recharge condition, ratio capacitance is 386F/g.
Claims (7)
1. a preparation method for hollow tubular electric polypyrrole film, step is as follows:
A. under agitation, tropeolin-D be dissolved in deionized water, obtained concentration is 2 × 10
-3mol/L methyl orange aqueous solution;
B. under agitation, dissolved in deionized water by oxygenant, obtained concentration is 1.44 ~ 10.8 × 10
-4the aqueous oxidizing agent solution of mol/L;
C. under agitation, pyrrole monomer is added in the methyl orange solution that a prepares, stir and pyrrole monomer is mixed with methyl orange solution;
D. in 0oC ice bath, in the mixed solution in c, dropwise add the aqueous oxidizing agent solution that step b prepares, solution colour is deepened gradually, and pyrrole monomer and the ratio of the amount of substance of oxygenant are react 24h under 0.2:1 ~ 1.5:1,0oC;
E. black precipitate steps d obtained, filters, washing, dry, finally obtains the film of poly pyrrole be made up of polypyrrole hollow Nano pipe.
2. preparation method as claimed in claim 1, it is characterized in that, the stir speed (S.S.) in described step a is 200 ~ 500r/min.
3. preparation method as claimed in claim 1, it is characterized in that, the oxygenant in described step b is iron trichloride.
4. preparation method as claimed in claim 3, it is characterized in that, the concentration of described ferric chloride aqueous solutions is 3.6 × 10
- 4mol/L.
5. preparation method as claimed in claim 1, it is characterized in that, the churning time in affiliated step c is 30min.
6. preparation method as claimed in claim 1, it is characterized in that, the pyrrole monomer in described steps d is 0.5:1 with the ratio of the amount of substance of oxygenant.
7. preparation method as claimed in claim 1, it is characterized in that, in affiliated step e, final sample water, dehydrated alcohol respectively wash three times.
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CN105845904B (en) * | 2016-04-01 | 2019-06-18 | 中南大学 | A kind of sodium-ion battery metal oxide/polypyrrole hollow nanotube anode material and preparation method thereof |
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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 |
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偶氮染料掺杂聚吡咯纳米/微米结构材料的制备;李亮等;《武汉工程大学学报》;20130415;第35卷(第4期);55-60 * |
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