CN106398207B - A kind of preparation method and its super capacitor performance of polypyrrole film - Google Patents
A kind of preparation method and its super capacitor performance of polypyrrole film Download PDFInfo
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Abstract
The present invention relates to a kind of polypyrrole film and its preparation method and application, the polypyrrole film is to have absorption peak at 320,440,463 and 540 nm in wavelength;The characteristic absorption of the infrared spectroscopy of the polypyrrole film is 1545 cm–1、1466 cm–1、1305 cm–1、1182 cm–1、1092 cm–1、1043 cm–1、915 cm–1、787 cm–1And 678 cm–1.The present invention also provides the preparation methods of the polypyrrole film.The purposes of polypyrrole film is used for working electrode and supercapacitor.Large scale synthesized by the present invention, film of poly pyrrole of controlling oneself, are not only suitable for the basic materializations properties such as mechanics, electronics and the optics of research polypyrrole film;And facilitate cutting, it is suitable for assembling flexible super capacitor or battery.
Description
Technical field
The present invention relates to a kind of preparation method of polypyrrole film and its super capacitor performance, belong to conducting polymer and super
Capacitor electrode material preparation technical field.
Background technique
As a kind of conducting polymer, polypyrrole have be readily synthesized, good conductivity, specific capacity and specific energy height etc. it is excellent
Point is applied widely in fields such as microwave absorption, gas sensing, separation of metal ions and electrochemical energy storages(CN
104072768A、CN 102898669A、CN 102817042A、Electrochimica Acta2014, 119, 1–10.).
In recent years, people significantly increase conductive, self-bearing polymer film demand, the reason is that they chemistry or biosensor, from
The fields such as proton exchange, organic electronics, polymer battery and supercapacitor have broad application prospects
(Macromolecules2011, 44, 4583–4585).
So far, people have developed a variety of methods preparing conducting polymer thin film, for example, spin-coating method, template,
Vapour deposition process, electrochemical polymerization method and interfacial polymerization(Small 2015, 11, 5498–5504; Mater. Sci. Semicond. Process. 2015, 39, 659–664; Macromol. Rapid Commun. 2016, 37, 590−
596; Thin Solid Films 2009, 517, 4156–4160; J. Mater. Chem. A 2013, 1, 1740–
1744.).Electrochemical polymerization method is the common method in electrode surface growth polypyrrole film.CN101012309A and
CN101979438A grown Porous Polypyrrole film in electrode surface using the method.Due to by electrode surface area and electrode fabrication at
This limitation, the polypyrrole film using electrochemical process synthesis large scale are at high cost;Moreover, because polypyrrole film is to be grown in electricity
Pole surface is difficult to remove from electrode surface, and which has limited electrochemical processes to synthesize the application in polypyrrole film of controlling oneself.In order not to must
Remove polypyrrole film from electrode surface, CN102779648A provides a kind of electrochemistry preparation side of polypyrrole compound fabric
Method.The method passes through magnetron sputtering first and obtains conductive gold plating fabric, is used as working electrode, then containing to toluene
In the acetonitrile solution or aqueous solution of sulfonic acid and pyrrole monomer, polypyrrole compound fabric is obtained by electrochemical polymerization.It should
Polypyrrole compound fabric had both had ventilative, flexible, the stretchable feature of fabric, but also with the electric conductivity of polypyrrole, while drawing
It stretches and still keeps good chemical property under state;But it is answered using magnetron sputtering in gold-plated undoubtedly will increase of fabric surface
The synthesis cost of object is closed, while being limited by electrode specific surface, the polypyrrole compound fabric difficulty for synthesizing large scale is larger.
Interfacial polymerization includes liquid-liquid, liquid-gas and solid-liquid interface polymerization again(Org. Electron. 2012, 13,
3032–3039; Macromolecules 2011, 44, 4583–4585; J. Colloid Interface Sci.
2011, 364, 555–560; Chem. Commun. 2012, 48, 8246–8248; J. Mater. Chem. 1997,
7, 1409–1413.).CN102516538A discloses a kind of micron order of the liquid-liquid interface polymerization preparation with network structure
Polypyrrole film.Its specific practice is that iron content ionic liquid is dissolved in deionized water, and pyrrole monomer is dissolved in n-hexane or 1- alkane
In base -3- methylimidazole hexafluorophosphate hydrophobic solvent, iron content ionic liquid plays the role of initiator and soft template simultaneously,
The interface of water and hydrophobic solvent, which generates, has network structure, the polypyrrole film with a thickness of hundreds of microns.Due in polypyrrole film
Organic hydrophobic agents of ionic liquid and more dosage have been used in synthesis process, thus prepare polypyrrole film cost using the method
Height, environment are unfriendly.
In conclusion in the synthetic method for the polypyrrole film that above-mentioned document is recorded, in the prevalence of film synthesis cost it is high,
Environment is unfriendly, is difficult to the disadvantages of scale industrial production.
Summary of the invention
In view of the deficiencies of the prior art, the present invention proposes it is a kind of synthesis large scale, control oneself polypyrrole film straightforward procedure,
And as the electrode material of soft formula supercapacitor, the assembling of drum-type supercapacitor is realized.
Term is explained:
Self-holding polypyrrole film:Independent of any backing material, it is capable of the polypyrrole film of individualism.
A kind of polypyrrole film, it is characterised in that:The polypyrrole film is the film that polypyrrole is formed, the structural unit of polypyrrole
For
Wherein n is 52~56,M w/M nIt is 1.5~2.5.
Preferably, the polypyrrole film with a thickness of 130 ~ 300 nm;It is furthermore preferred that the polypyrrole film with a thickness of
140 ± 10 nm, i.e. 130 ~ 150nm, i.e. 130 ~ 150nm.The thickness of film is not particularly limited in the present invention, art technology
Personnel can set the thickness of film according to actual needs.The thickness of film can be by changing the reaction time in 130 ~ 300 nm
Regulated and controled in range.
Preferably, the polypyrrole film, can in the UV-visible range of 200-800 nm of wavelength, respectively 320,
440, there is absorption peak at 463 and 540 nm.
Preferably, the polypyrrole film, the characteristic absorption of infrared spectroscopy are 1545 cm–1、1466 cm–1、1305 cm–1、1182 cm–1、1092 cm–1、1043 cm–1、915 cm–1、787 cm–1And 678 cm–1。
The present invention also provides the preparation methods of the polypyrrole film, it is characterised in that:
A. water is placed in container, freezes, makes to form a smooth, smooth ice face;
B. the aqueous oxidizing agent solution of pre-cooling is poured in the ice face of step a, is freezed, made to be formed one and smooth, smooth contain
The ice sheet of oxidant;
C. in organic solvent by pyrrole monomer dissolution, then pre-cooling is poured upon the ice containing oxidant in step b
Layer surface keeps 5 min to 6 h under freezing conditions, obtains the polypyrrole film of ice support;
D. melt the ice sheet below polypyrrole film, remove film and ice sheet, film water is washed, be freeze-dried, it is poly- derived from holding
Pyrroles's film.
Preferred according to the present invention, freezing described in step a refers to water at its below freezing to -20 °C or more
6 ~ 12 h are placed in temperature range.
Preferred according to the present invention, the container in step a, surface area S is 0.001 ~ 0.02 m2;Described in step a
Ice, with a thickness of 0.2 ~ 1 cm.
Preferred according to the present invention, smooth, smooth ice face described in step a is by adding a small amount of low surface into water
Energy, water-miscible organic solvent obtain;The low-surface-energy, water-miscible organic solvent include methanol, ethyl alcohol, propyl alcohol, acetone, fourth
Ketone, Ethyl formate, methyl acetate, ethyl acetate or by two or more mixture formed in them;It is described mixed
It closes in object, the ratio between two or more solvent is not particularly limited, and those skilled in the art can be according to practical feelings
Condition is adjusted.
The ratio between volume of the low-surface-energy, water-miscible organic solvent and water is (1 ~ 2): 500.
Preferred according to the present invention, oxidant described in step b is ammonium persulfate, potassium peroxydisulfate, potassium permanganate, weight chromium
Sour potassium, iron chloride, ferric nitrate, ferric sulfate or their mixture.
Preferred according to the present invention, institute states aqueous oxidizing agent solution in step b, and volume is 0.1S ~ 0.3S L;S is
The surface area of container, unit m2。
Preferred according to the present invention, aqueous oxidizing agent solution described in step b, pH value of solution is 1 ~ 4.
It is preferred according to the present invention, aqueous oxidizing agent solution described in step b, wherein the concentration of oxidant be 0.037 ~
0.83 mol/L。
It is preferred according to the present invention, freezing described in step b refer to place 2 in -2 ~ -20 °C of temperature ranges ~
6 h。
Preferred according to the present invention, pre-cooling, which refers to, described in step b is down to 0 ~ 5 ° for the temperature of aqueous oxidizing agent solution
Between C.
It is preferred according to the present invention, organic solvent described in step c, including methanol, ethyl alcohol, propyl alcohol, butanol, acetone,
Butanone, Ethyl formate, methyl acetate, ethyl acetate or by two or more mixture formed in them.
Preferred according to the present invention, organic solvent described in step c, volume is 0.02S ~ 0.06S L.S is to hold
The surface area of device, unit m2。
According to the present invention preferably, pyrroles described in step c, the amount of substance and the substance of oxidant in step b
The ratio between amount is (0.67 ~ 5): 1.
Preferred according to the present invention, pre-cooling, which refers to, described in step c is down to 0 for the temperature for dissolving the organic solvent of pyrroles
Between ~ 5 °C.
Preferred according to the present invention, freezing conditions described in step c are temperature between -2 ~ -20 °C.
Preferred according to the present invention, melting the ice sheet below polypyrrole film in step d is to be made below polypyrrole film with water
Ice sheet melt.Specifically, removing film and ice sheet with appropriate distilled water flushing polypyrrole film.
The purposes of polypyrrole film of the present invention is used for flexible working electrode.
The purposes of polypyrrole film of the present invention is used for flexible super capacitor.
Beneficial effect
1, the present invention is by chemical oxidization method, using interface confinement polymerization reaction, using ice as solid, on solid-liquid interface
The film of poly pyrrole that obtains large scale, thickness and size adjustable, can control oneself, synthetic method is simple, at low cost, is easy to scale
Industrial production.
2, the large scale synthesized by the present invention, film of poly pyrrole of controlling oneself, are not only suitable for mechanics, the electricity of research polypyrrole film
Son is learned and the basic materializations properties such as optics;And facilitate cutting, it is suitable for assemble compact or miniature flexible battery/super capacitor
Device.
3, the drum-type supercapacitor assembled using large scale synthesized by the present invention, film of poly pyrrole of controlling oneself,
Have the characteristics that energy density per unit volume and volumetric specific power are high, has a good application prospect.
Detailed description of the invention
Fig. 1 is field emission scanning electron microscope (FESEM) figure of S-1 sample.
Fig. 2 is field emission scanning electron microscope (FESEM) figure of S-2 sample.
Fig. 3 is field emission scanning electron microscope (FESEM) figure of S-3 sample.
Fig. 4 is field emission scanning electron microscope (FESEM) figure of S-4 sample.
Fig. 5 is field emission scanning electron microscope (FESEM) figure of S-5 sample.
Fig. 6 is atomic force microscope (AFM) figure of S-4 sample.
Fig. 7 is atomic force microscope (AFM) figure of S-5 sample.
Fig. 8 is S-4 sample and S-5 sample AFM analysis chart.
Fig. 9 is to swim in culture dish(Culture dish bottom spreads the A4 paper with word)The number of sample S-4 on the middle water surface
Camera photos.
Figure 10 is ultraviolet-transmission spectrum figure of sample S-4.
Figure 11 is the infrared spectrogram of sample S-4 and S-5.
Figure 12 is the super electric capacitor of polypyrrole film base in 2 mA cm–1Under stable circulation linearity curve.
Specific embodiment
Technical solution of the present invention is further elaborated below by specific embodiment and in conjunction with attached drawing, these embodiments
It is intended merely to illustrate technical solution of the present invention, and the limitation to the claims in the present invention content cannot be considered as.
Pyrroles in embodiment is purchased from Shanghai Tong Yuan Chemical Co., Ltd.;Ammonium persulfate, Iron(III) chloride hexahydrate, permanganic acid
Potassium is purchased from Tianjin great Mao chemical reagent factory;Dehydrated alcohol, acetone, ethyl acetate are purchased from the limited public affairs of Tianjin richness space fine chemistry industry
Department;Polyvinyl alcohol(The degree of polymerization 1750 ± 50)Purchased from Shanghai fuzz Chemical Co., Ltd.;The concentrated sulfuric acid is purchased from Laiyang economic technology
Development zone Fine Chemical Works;Template is purchased from Chinese medicines group Shanghai Co., Ltd;Highland barley paper is purchased from Shanghai spy Xiang electrical apparatus insulation material
Expect Co., Ltd.
The stereoscan photograph of sample prepared by the present invention is through Hitachi S-4800 field emission scanning electron microscope
(FESEM) detection obtains;Atomic force microscope (AFM) photo is detected through MFP-3D-SA atomic force microscope and is obtained;Ultraviolet-can
See spectrophotometric spectra data through Persee TU-1901 it is ultraviolet-visible spectrophotometer detection obtain;The infrared spectrogram of sample passes through
The detection of Shimadzu IRPrestige-21 infrared spectrometer obtains;The molecular weight of sample is through Agilent Technologies
The detection of 50 gel permeation chrommatograph of PL-GPC obtains;The soft formula electrode of polypyrrole film base and takeup type polypyrrole film based super capacitor
Chemical property is detected through CHI 660E electrochemical workstation and is obtained.
Embodiment 1
A kind of preparation method of polypyrrole film, steps are as follows:
(1) 258 mL water are added into the vinyl disc having a size of the cm × 6 of 43 cm × 30 cm, 1 mL is then added dropwise
Vinyl disc is placed in -2 °C of refrigerator-freezer and freezes 12 h by dehydrated alcohol, obtains a smooth, smooth ice face.
(2) 0.33 g ammonium persulfate is dissolved in the water that 39 mL pH are 1, solution is placed in 0 °C of refrigerator and is pre-chilled
Then 0.5 h is poured upon in step (1) resulting ice face, weak vibrations vinyl disc makes ammonium persulfate aqueous solution equably
It is laid in ice face, in -2 °C of 6 h of heat preservation, obtains a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL (7.2 mmol) pyrroles is added in 2.6 mL butanol, 0.5 h is pre-chilled in 0 °C of refrigerator, so
After be poured upon in step (2) resulting oxidant ice sheet surface, in -2 °C of 1 h of heat preservation, obtain the poly- pyrrole being supported in ice face
Cough up film.
(4) with appropriate distilled water flushing polypyrrole film, remove film and ice sheet, for several times, freeze-drying derives from washing film
Hold polypyrrole film sample S-1.
Embodiment 2
A kind of preparation method of polypyrrole film, steps are as follows:
(1) 500 mL water are added into the vinyl disc having a size of the cm × 6 of 43 cm × 30 cm, 1 mL is then added dropwise
Vinyl disc is placed in -20 °C of refrigerator-freezer and freezes 6 h by acetone, obtains a smooth, smooth ice face.
(2) 2.92 g Iron(III) chloride hexahydrates are dissolved in 13 mL distilled water, solution is placed in 5 °C of refrigerators in advance
Then cold 0.5 h is poured upon in step (1) resulting ice face, weak vibrations vinyl disc keeps ferric chloride aqueous solutions uniform
Ground is laid in ice face, in -20 °C of 2 h of heat preservation, obtains a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL pyrroles is added in 3 mL acetone, 0.5 h is pre-chilled in 0 °C of refrigerator, is then poured upon in step
Suddenly (2) resulting oxidant ice sheet surface obtains the polypyrrole film being supported in ice face in -20 °C of 5 min of heat preservation.
(4) with appropriate distilled water flushing polypyrrole film, remove film and ice sheet, for several times, freeze-drying derives from washing film
Hold polypyrrole film sample S-2.
Embodiment 3
A kind of preparation method of polypyrrole film, steps are as follows:
(1) 1290 mL water are added into the vinyl disc having a size of the cm × 6 of 43 cm × 30 cm, are then added dropwise
Vinyl disc is placed in -10 °C of refrigerator-freezer and freezes 6 h by 5.16 mL ethyl acetate, obtains a smooth, smooth ice face.
(2) 0.57 g potassium permanganate is dissolved in the water that 18 mL pH are 2, solution is placed in 5 °C of refrigerators and is pre-chilled 1
Then h is poured upon in step (1) resulting ice face, weak vibrations vinyl disc makes potassium permanganate solution equably tile
In ice face, in -20 °C of 2 h of heat preservation, a smooth, smooth ice sheet containing oxidant is obtained.
(3) 0.5 mL pyrroles is added in 7.7 mL ethyl acetate, 0.5 h is pre-chilled in 5 °C of refrigerators, is then inclined
It is poured on step (2) resulting oxidant ice sheet surface, in -10 °C of 1 h of heat preservation, obtains the polypyrrole film being supported in ice face.
(4) with appropriate distilled water flushing polypyrrole film, remove film and ice sheet, for several times, freeze-drying derives from washing film
Hold polypyrrole film sample S-3.
Embodiment 4
A kind of preparation method of polypyrrole film, steps are as follows:
(1) 500 mL water are added into the vinyl disc having a size of the cm × 6 of 43 cm × 30 cm, 1 mL is then added dropwise
Vinyl disc is placed in -20 °C of refrigerator-freezer and freezes 6 h by dehydrated alcohol, obtains a smooth, smooth ice face.
(2) 2.35 g Iron(III) chloride hexahydrates are dissolved in the water that 18 mL pH are 2, solution is placed in 5 °C of refrigerators
0.5 h of middle pre-cooling, is then poured upon in step (1) resulting ice face, weak vibrations vinyl disc makes ferric chloride aqueous solutions
It is equably laid in ice face, in -20 °C of 2 h of heat preservation, obtains a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL pyrroles is added in 3 mL dehydrated alcohols, 0.5 h is pre-chilled in 0 °C of refrigerator, is then poured upon
The polypyrrole film being supported in ice face is obtained in -20 °C of 40 min of heat preservation in step (2) resulting oxidant ice sheet surface.
(4) with appropriate distilled water flushing polypyrrole film, remove film and ice sheet, for several times, freeze-drying derives from washing film
Hold polypyrrole film sample S-4.
Embodiment 5
The reaction time of step (3) in embodiment 4 is extended into 6 h, remaining condition is constant, and gained is controlled oneself polypyrrole film sample
Product are labeled as S-5.
Interpretation of result
The FESEM that Fig. 1-5 is sample S-1 to S-5 schemes.From figure 1 it appears that sample S-1 is dense film, the thickness of film
For 260 ± 10 nm.Figure it is seen that the film with network structure that sample S-2 is formed for particle packing, the thickness of film
Degree is 270 ± 20 nm.From figure 3, it can be seen that sample S-3 be dense film, film with a thickness of 270 ± 15 nm.Fig. 4 and figure
5 displays, sample S-4 and S-5 are dense film, and the thickness of film is respectively 140 ± 5 and 260 ± 15 nm.This explanation, film
Thickness can be regulated and controled by changing the reaction time.Fig. 6 is atomic force microscope (AFM) figure of S-4 sample.Fig. 7 is S-5 sample
Atomic force microscope (AFM) figure of product.Fig. 8 is S-4 sample and S-5 sample AFM analysis chart.It is analyzed by AFM it is found that sample S-
The average thickness of 4 and S-5 is respectively 140 ± 5 and 260 ± 15 nm(Fig. 8), this result and using the poly- of FESEM observation
The thickness results of pyrroles's membrane sample are consistent(Fig. 4, Fig. 5).
The transparency of film can be reflected by the digital camera photo of film and ultraviolet-transmission spectrum of film.Fig. 9
For the digital camera photo of sample S-4.From fig. 9, it can be seen that not only size is big by sample S-4, decimeter grade is reached, and is had good
The transparency.Figure 10 is ultraviolet-transmission spectrum of sample S-4.From fig. 10 it can be seen that sample S-4 is 200-to wavelength
The light transmittance of 800 nm is all larger than 30%, illustrates that sample has good translucency.It is located at 320,440,463 and 540 in Figure 10
The absorption peak of nm respectively corresponds the π-π * transition of electronics in polypyrrole, the transition of valence band to conduction band, valence band to bipolaron band top
And polaron band is as low as the transition with top(Can. J. Chem. 1995, 73, 1711–1718; Sensors 2012, 12,
7965–7974.).The synthesized film of this explanation is polypyrrole film.
Synthesized film is that polypyrrole film can also be confirmed from the infrared spectroscopy of sample.Figure 11 be sample S-4 and
The infrared spectrogram of S-5.It is located at 1545 and 1466 cm in Figure 11–1Peak respectively correspond the antisymmetry of pyrrole ring and symmetrical flexible
Vibration peak corresponds to C-N stretching vibration peak in pyrrole ring positioned at the peak of 1305 wave numbers, is located at 1182,1092 and 1043 cm–1Peak
C-H in-plane bending vibration peak in corresponding pyrrole ring, is located at 915,787 and 678 cm–1Peak correspond to C-H out-of-plane bending in pyrrole ring
Vibration peak(Macromolecules 2011, 44, 4583–4585; J. Colloid Interface Sci. 2011,
364, 555–560; Chem. Commun.2012, 48, 8246–8248.).Ir data shows obtained film
For polypyrrole film.
Embodiment 6
A kind of production of polypyrrole film base flexible working electrode, steps are as follows:
Polypyrrole film sample S-4 is cut into the two panels having a size of the cm of 1 cm × 2, is pasted polypyrrole film using silver paste
To on having a size of the cm of 1 cm × 3, the graphite paper with a thickness of 0.03 mm, at room temperature dry 2 h to get.
With Hg/Hg2SO4For reference electrode, platinized platinum is to electrode, 1 mol L–1 H2SO4For electrolyte, with above-mentioned polypyrrole
Film base flexible electrode is working electrode, using the chemical property of three electrode mode test job electrodes.
Interpretation of result
Table 1 gives under different current densities, by the specific discharge capacity of the sample S-4 flexible electrode made(Area ratio
Capacity, volume and capacity ratio).As can be seen from Table 1, gained flexible electrode has very high area specific capacity and volume and capacity ratio.
Specific capacity of the flexible electrode that table 1 is made by sample S-4 under different current densities
Current density (mA cm–2) | 3 | 5 | 6 | 7 | 8 | 9 |
Area specific capacity (mF cm–2) | 598.8 | 438.0 | 345.6 | 328.4 | 230.4 | 208.8 |
Volume and capacity ratio (F cm–3) | 199.6 | 146.0 | 115.2 | 109.5 | 76.8 | 69.6 |
Embodiment 7
A kind of production of polypyrrole film based super capacitor, steps are as follows:
(1) polypyrrole film sample S-4 is cut into the two panels having a size of the cm of 3 cm × 1.5, using silver paste by polypyrrole
Film pastes on the graphite paper having a size of the cm × 0.003 of 4 cm × 1.5 cm, dries 2 h at room temperature;
(2) aqueous polyurethane for being 2 mm along edge coating width on polypyrrole film surface, places 4 h at room temperature;
(3) in polypyrrole film surface coating polyethylene alcohol/electrolyte sulfuric acid, 2 h are placed at room temperature for;
(4) the two of electrolyte will be coated with to face to fold, be placed on having a size of 3 cm × 2 cm × 0.0015cm template
On, the mode along insulating paper in outer layer crimps, and is sealed using aqueous polyurethane, obtains takeup type polypyrrole film based super capacitor
RSC-1。
Interpretation of result
Table 2 is specific discharge capacity of the polypyrrole film based super capacitor RSC-1 under different current densities(Area specific volume
Amount, volume and capacity ratio).As can be seen from Table 2, polypyrrole film based super capacitor RSC-1 has very high area specific capacity and volume
Specific capacity.
Specific capacity of the 2 supercapacitor RSC-1 of table under different current densities
Current density (mA cm–2) | 2 | 3 | 4 | 5 | 6 | 7 |
RSC-1 area specific capacity (mF cm–2) | 151.4 | 132.6 | 125.6 | 96.0 | 73.2 | 72.8 |
RSC-1 volume and capacity ratio (F cm–3) | 16.8 | 14.7 | 14.0 | 10.7 | 8.1 | 8.1 |
Figure 12 is RSC-1 in 2 mA cm–1The stable circulation linearity curve of 5000 circle of circulation under current density.It can from Figure 12
It is 59.1% although the capacity retention ratio of RSC-1 is not high to find out;But the area specific capacity after 5000 circle of circulation is kept
In 88.5 mF cm–2, volume and capacity ratio is maintained at 9.83 F cm–3, energy density per unit volume is 1.37 mW h cm–3, volume ratio function
Rate is 111.1 mW cm–3.These results indicate that the volume assembled using polypyrrole film synthesized by the present invention as active material
Wound polypyrrole film based super capacitor, energy density per unit volume still with higher and volumetric specific power after 5000 circle circulations
(Science2012, 335, 1326–1330.).Therefore, the polypyrrole film synthesized by the present invention is led in flexible super capacitor
Domain has broad application prospects.
Claims (6)
1. a kind of preparation method of polypyrrole film, which is characterized in that include the following steps:
A. water is placed in container, freezes, makes to form a smooth, smooth ice face;
B. the aqueous oxidizing agent solution of pre-cooling is poured in the ice face of step a, is freezed, it is smooth, smooth containing oxidation to make to be formed one
The ice sheet of agent;
C. in organic solvent by pyrrole monomer dissolution, then pre-cooling is poured upon the ice sheet table containing oxidant in step b
Face keeps 5min to 6h under freezing conditions, obtains the polypyrrole film that ice supports;
D. melt the ice sheet below polypyrrole film, remove film and ice sheet, film water is washed, be freeze-dried, derived from holding polypyrrole
Film;
The polypyrrole film, it is characterised in that:The structural unit of the polypyrrole film is:
Wherein n is 52~56, Mw/MnIt is 1.5~2.5;
The polypyrrole film, can be in the UV-visible range of 200-800nm of wavelength, respectively in 320,440,463 and
There is absorption peak at 540nm;
The polypyrrole film, the characteristic absorption of infrared spectroscopy are 1545cm–1、1466cm–1、1305cm–1、1182cm–1、
1092cm–1、1043cm–1、915cm–1、787cm–1And 678cm–1。
2. the preparation method of polypyrrole film as described in claim 1, which is characterized in that freezing described in step a refer to by
Water places 6~12h within the scope of its below freezing to -20 DEG C or more temperature.
3. the preparation method of polypyrrole film as claimed in claim 1 or 2, which is characterized in that the container in step a, surface
Product S is 0.001~0.02m2;Ice described in step a, with a thickness of 0.2~1cm;
Smooth, smooth ice face described in step a is by adding a small amount of low-surface-energy, water-miscible organic solvent acquisition into water
's;The low-surface-energy, water-miscible organic solvent include methanol, ethyl alcohol, propyl alcohol, acetone, butanone, Ethyl formate, methyl acetate,
Ethyl acetate or by two or more mixture formed in them;
The ratio between volume of the low-surface-energy, water-miscible organic solvent and water is (1~2):500.
4. the preparation method of polypyrrole film as described in claim 1, which is characterized in that oxidant described in step b was
Ammonium sulfate, potassium peroxydisulfate, potassium permanganate, potassium bichromate, iron chloride, ferric nitrate, ferric sulfate or their mixture;
Aqueous oxidizing agent solution described in step b, volume are 0.1S~0.3S L;S is the surface area of container, unit m2;
Aqueous oxidizing agent solution described in step b, pH value of solution are 1~4;
Aqueous oxidizing agent solution described in step b, wherein the concentration of oxidant is 0.037~0.83mol/L;
Freezing described in step b refers to 2~6h of placement in -2~-20 DEG C of temperature ranges;
Pre-cooling, which refers to, described in step b is down to the temperature of aqueous oxidizing agent solution between 0~5 DEG C.
5. the preparation method of polypyrrole film as described in claim 1, which is characterized in that organic solvent described in step c, packet
Include methanol, ethyl alcohol, propyl alcohol, butanol, acetone, butanone, Ethyl formate, methyl acetate, ethyl acetate or by two kinds in them
Or the mixture of two or more formation;
Organic solvent described in step c, volume are 0.02S~0.06S L;S is the surface area of container, unit m2;
The ratio between amount of substance of oxidant is (0.67~5) in pyrroles described in step c, the amount of substance and step b:1;
Pre-cooling, which refers to, described in step c is down to the temperature for dissolving the organic solvent of pyrroles between 0~5 DEG C;
Freezing conditions described in step c are temperature between -2~-20 DEG C.
6. the preparation method of polypyrrole film as described in claim 1, which is characterized in that make below polypyrrole film in step d
Ice sheet thawing is to melt the ice sheet below polypyrrole film with water;Specifically, making film with appropriate distilled water flushing polypyrrole film
It is removed with ice sheet.
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