CN106398207A - Preparation method of polypyrrole film and supercapacitor property thereof - Google Patents
Preparation method of polypyrrole film and supercapacitor property thereof Download PDFInfo
- Publication number
- CN106398207A CN106398207A CN201610967270.9A CN201610967270A CN106398207A CN 106398207 A CN106398207 A CN 106398207A CN 201610967270 A CN201610967270 A CN 201610967270A CN 106398207 A CN106398207 A CN 106398207A
- Authority
- CN
- China
- Prior art keywords
- polypyrrole film
- film
- polypyrrole
- water
- ice
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
Abstract
The invention relates to a polypyrrole film and a preparation method and an application thereof. The polypyrrole film has absorption peaks at the wavelengths of 320nm, 440nm, 463nm and 540nm; characteristic absorption of infrared spectrum of the polypyrrole film are 1545cm<-1>, 1466cm<-1>, 1305cm<-1>, 1182cm<-1>, 1092cm<-1>, 1043cm<-1>, 915cm<-1>, 787cm<-1> and 678cm<-1>. The invention also provides the preparation method of the polypyrrole film. The polypyrrole film is used for preparing working electrodes and supercapacitors. The synthesized large-size and self-held polypyrrole film is suitable for study on the basic physical-chemical properties of mechanics, electronics and optics of the polypyrrole film; the cutting is convenient, and the polypyrrole film is suitable for assembling flexible supercapacitors or batteries.
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 preparing technical field.
Background technology
As a kind of conducting polymer, polypyrrole have be readily synthesized, good conductivity, specific capacity and specific energy height etc. 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 to conductive, self-bearing polymer film demand, reason be them chemistry or biosensor, from
The fields such as proton exchange, organic electronics, polymer battery and ultracapacitor have broad application prospects
（Macromolecules2011, 44, 4583–4585）.
So far, people have developed multiple methods in order to prepare conducting polymer thin film, for example spin-coating method, template,
Vapour deposition process, electrochemical polymerization method and interfacial polymerization（Small2015, 11, 5498–5504;Mater. Sci. Semicond. Process.2015, 39, 659–664;Macromol. Rapid Commun.2016, 37, 590−
596;Thin Solid Films2009, 517, 4156–4160;J. Mater. Chem. A2013, 1, 1740–
1744.）.Electrochemical polymerization method is the common method growing polypyrrole film in electrode surface.CN101012309A and
CN101979438A grown Porous Polypyrrole film using this method in electrode surface.Due to being become with electrode fabrication by electrode surface area
This restriction, synthesizes the polypyrrole film high cost of large scale using electrochemical process；Being additionally, since polypyrrole film is to be grown in electricity
Pole surface, is difficult to peel off from electrode surface, which has limited the application that electrochemical process is controlled oneself in polypyrrole film in synthesis.In order to need not
Polypyrrole film is made to peel off from electrode surface, CN102779648A provides a kind of electrochemistry preparation side of polypyrrole compound fabric
Method.This method first passes through the gold plating fabric that magnetron sputtering obtains conduction, is used as working electrode, then containing to toluene
In the acetonitrile solution of sulfonic acid and pyrrole monomer or aqueous solution, polypyrrole compound fabric is obtained by electrochemical polymerization.Should
Polypyrrole compound fabric had both had ventilative, flexible, the stretchable feature of fabric, but also with the electric conductivity of polypyrrole, was drawing simultaneously
Stretch and under state, still keep good chemical property；But, answered in gold-plated undoubtedly can the increasing of fabric face using magnetron sputtering
The synthesis cost of compound, is limited by electrode specific surface simultaneously, and the polypyrrole compound fabric difficulty of synthesis large scale is larger.
Interfacial polymerization includes liquid-liquid, liquid-gas and solid-liquid interface polymerization again（Org. Electron.2012, 13,
3032–3039;Macromolecules2011, 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 the micron order that a kind of liquid-liquid interface polymerization preparation has network structure
Polypyrrole film.Its specific practice is that iron content ionic liquid is dissolved in deionized water, and pyrrole monomer is dissolved in normal hexane or 1- alkane
In base -3- Methylimidazole. hexafluorophosphate hydrophobic solvent, iron content ionic liquid simultaneously works as the effect of initiator and soft template,
The polypyrrole film that the interface generation of water and hydrophobic solvent has network structure, thickness is hundreds of microns.Due in polypyrrole film
Employ organic hydrophobic agents of ionic liquid and more consumption in building-up process, thus prepare polypyrrole film cost using this method
High, environment is unfriendly.
In sum, in the synthetic method of polypyrrole film that above-mentioned document is recorded, generally existing film synthesis high cost,
Environment is unfriendly, the shortcomings of be difficult to scale industrial production.
Content of the invention
The present invention be directed to the deficiencies in the prior art it is proposed that a kind of synthesis large scale, control oneself polypyrrole film straightforward procedure,
And the electrode material as soft formula ultracapacitor is it is achieved that the assembling of drum-type ultracapacitor.
Term is explained：
Self-holding polypyrrole film：Do not rely on any backing material, be capable of the polypyrrole film of individualism.
A kind of polypyrrole film it is characterised in that：The film that described polypyrrole film is formed for polypyrrole, the construction unit of polypyrrole
For
Wherein n is 52～56,M w/M nFor 1.5～2.5.
Preferably, the thickness of described polypyrrole film is 130 ~ 300 nm；It is furthermore preferred that the thickness of described polypyrrole film is
140 ± 10 nm, i.e. 130 ~ 150nm, i.e. 130 ~ 150nm.The present invention is not particularly limited to the thickness of film, art technology
Personnel can set the thickness of film according to actual needs.The thickness of film can be by the change response time in 130 ~ 300 nm
In the range of regulated and controled.
Preferably, described polypyrrole film, can in the UV-visible range of wavelength 200 800 nm, respectively 320,
440th, there is absworption peak at 463 and 540 nm.
Preferably, described polypyrrole film, the characteristic absorption of its infrared spectrum, is 1545 cm–1、1466 cm–1、1305 cm–1、1182 cm–1、1092 cm–1、1043 cm–1、915 cm–1、787 cm–1, and 678 cm–1.
The present invention also provide described polypyrrole film preparation method it is characterised in that：
A. water is placed in container, freezing, makes smooth, the smooth ice face of formation one；
B. the aqueous oxidizing agent solution of pre-cooling is poured in the ice face of step a, freezing, make formation one smooth, smooth containing oxidation
The ice sheet of agent；
C. pyrrole monomer is dissolved in organic solvent, pre-cooling, then it is poured upon the ice sheet table containing oxidant in step b
Face, keeps 5 min to 6 h under freezing conditions, obtain the polypyrrole film of ice support；
D. so that the ice sheet below polypyrrole film is melted, so that film is peeled off with ice sheet, film water is washed, lyophilization, obtain self-holding polypyrrole
Film.
According to currently preferred, the freezing described in step a refer to by water its below freezing to more than 20 °C
6 ~ 12 h are placed in temperature range.
According to currently preferred, in step a container, its surface area S is 0.001 ~ 0.02 m2；Described in step a
Ice, its thickness is 0.2 ~ 1 cm.
According to currently preferred, smooth described in step a, smooth ice face is by adding low surface on a small quantity toward in water
Energy, water-miscible organic solvent obtain；Described low-surface-energy, water-miscible organic solvent include methanol, ethanol, propanol, acetone, fourth
Ketone, Ethyl formate, methyl acetate, ethyl acetate or the mixture being formed by two or more in them；Described mixed
In compound, the ratio between two or more solvent is not particularly limited, and those skilled in the art can be according to actual feelings
Condition is adjusted.
The ratio of the volume of described low-surface-energy, water-miscible organic solvent and water is (1 ~ 2): 500.
According to currently preferred, the oxidant described in step b is Ammonium persulfate., potassium peroxydisulfate, potassium permanganate, weight chromium
Sour potassium, iron chloride, ferric nitrate, iron sulfate or their mixture.
According to currently preferred, in step b state aqueous oxidizing agent solution, its volume is 0.1S ~ 0.3S L；S is
The surface area of container, its unit is m2.
According to currently preferred, the aqueous oxidizing agent solution described in step b, its pH value of solution is 1 ~ 4.
According to currently preferred, the concentration of the aqueous oxidizing agent solution described in step b, wherein oxidant is 0.037 ~
0.83 mol/L.
According to currently preferred, the freezing described in step b refers to place 2 in 2 ~ 20 °C of temperature ranges ~
6 h.
According to currently preferred, the pre-cooling described in step b refers to for the temperature of aqueous oxidizing agent solution to be down to 0 ~ 5 °
Between C.
According to currently preferred, the organic solvent described in step c, including methanol, ethanol, propanol, butanol, acetone,
Butanone, Ethyl formate, methyl acetate, ethyl acetate or the mixture being formed by two or more in them.
According to currently preferred, the organic solvent described in step c, its volume is 0.02S ~ 0.06S L.S is to hold
The surface area of device, its unit is m2.
According to currently preferred, the pyrroles described in step c, the amount of its material and the material of oxidant in step b
The ratio of amount is (0.67 ~ 5): 1.
According to currently preferred, the pre-cooling described in step c refers to for the temperature of the organic solvent of dissolving pyrroles to be down to 0
Between ~ 5 °C.
According to currently preferred, the freezing conditions described in step c are temperature between 2 ~ 20 °C.
According to currently preferred, so that the ice sheet below polypyrrole film is melted in step d is to be made below polypyrrole film with water
Ice sheet melt.Specifically, with appropriate distilled water flushing polypyrrole film, making film peel off with ice sheet.
The purposes of polypyrrole film of the present invention, for flexible working electrode.
The purposes of polypyrrole film of the present invention, for flexible super capacitor.
Beneficial effect
1st, the present invention passes through chemical oxidization method, using interface confinement polyreaction, with ice as solid, obtains on solid-liquid interface
Large scale, thickness and size adjustable, the film of poly pyrrole that can control oneself, synthetic method is simple, and low cost is it is easy to large-scale industrial
Produce.
2nd, the large scale synthesized by the present invention, film of poly pyrrole of controlling oneself, are not only suitable for studying mechanics, the electricity of polypyrrole film
Son is learned and the basic materialization properties such as optics；And facilitate cutting it is adaptable to assemble compact or miniature flexible battery/super capacitor
Device.
3rd, the drum-type ultracapacitor being assembled using the 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, there is good application prospect.
Brief description
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 the sample S-4 on the middle water surface
Camera photos.
Figure 10 is the UV, visible light transmitted light spectrogram of sample S-4.
Figure 11 is the infrared spectrogram of sample S-4 and S-5.
Figure 12 is for the super electric capacitor of polypyrrole film base in 2 mA cm–1Under stable circulation linearity curve.
Specific embodiment
Below by specific embodiment and combine accompanying drawing technical scheme is further elaborated, these embodiments
It is intended merely to illustrate technical scheme, and the restriction to the claims in the present invention content can not 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 Tianjin richness limited public affairs of space fine chemistry industry
Department；Polyvinyl alcohol（The degree of polymerization 1750 ± 50）Purchased from Shanghai fuzz Chemical Co., Ltd.；Concentrated sulphuric acid is purchased from Laiyang economic technology
Development zone Fine Chemical Works；Template is purchased from Chinese medicines group Shanghai company limited；Semen avenae nudae paper is purchased from Shanghai spy's Xiang electrical apparatus insulation material
Material company limited.
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 detects through MFP-3D-SA atomic force microscope and obtains；Ultraviolet can
See that spectrophotometric spectra data detects through Persee TU-1901 ultraviolet-uisible spectrophotometer to obtain；The infrared spectrogram warp of sample
The detection of Shimadzu IRPrestige-21 infrared spectrometer obtains；The molecular weight of sample is through Agilent Technologies
The detection of PL-GPC 50 gel permeation chrommatograph obtains；Polypyrrole film base soft formula electrode and takeup type polypyrrole film based super capacitor
Chemical property detects through CHI 660E electrochemical workstation and obtains.
Embodiment 1
A kind of preparation method of polypyrrole film, step is as follows：
(1) 258 mL water are added toward in the vinyl disc of a size of 43 cm × 30 cm × 6 cm, then Deca 1 mL is anhydrous
Ethanol, vinyl disc is placed in 2 °C of refrigerator-freezer and freezes 12 h, obtains a smooth, smooth ice face.
(2) 0.33 g Ammonium persulfate. being dissolved in 39 mL pH is in 1 water, and solution is placed in pre-cooling in 0 °C of refrigerator
0.5 h, is then poured upon in the ice face of step (1) gained, weak vibrations vinyl disc, makes ammonium persulfate aqueous solution equably
It is laid in ice face, is incubated 6 h in 2 °C, obtain a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL (7.2 mmol) pyrroles is added in 2.6 mL butanol, pre-cooling 0.5 h in 0 °C of refrigerator, so
It is poured upon the oxidant ice sheet surface in step (2) gained afterwards, is incubated 1 h in 2 °C, obtain the poly- pyrrole being supported in ice face
Cough up film.
(4) with appropriate distilled water flushing polypyrrole film, so that film and ice sheet is peeled off, washing film for several times, lyophilization, derive from
Hold polypyrrole film sample S-1.
Embodiment 2
A kind of preparation method of polypyrrole film, step is as follows：
(1) 500 mL water are added toward in the vinyl disc of a size of 43 cm × 30 cm × 6 cm, then Deca 1 mL third
Ketone, vinyl disc is placed in 20 °C of refrigerator-freezer and freezes 6 h, 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
Cold 0.5 h, is then poured upon in the ice face of step (1) gained, weak vibrations vinyl disc, makes ferric chloride aqueous solutionses uniform
Be laid in ice face, in 20 °C be incubated 2 h, obtain a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL pyrroles is added in 3 mL acetone, in 0 °C of refrigerator, pre-cooling 0.5 h, is then poured upon in step
Suddenly the oxidant ice sheet surface of (2) gained, is incubated 5 min in 20 °C, obtains the polypyrrole film being supported in ice face.
(4) with appropriate distilled water flushing polypyrrole film, so that film and ice sheet is peeled off, washing film for several times, lyophilization, derive from
Hold polypyrrole film sample S-2.
Embodiment 3
A kind of preparation method of polypyrrole film, step is as follows：
(1) 1290 mL water are added toward in the vinyl disc of a size of 43 cm × 30 cm × 6 cm, then Deca 5.16 mL
Ethyl acetate, vinyl disc is placed in 10 °C of refrigerator-freezer and freezes 6 h, obtains a smooth, smooth ice face.
(2) 0.57 g potassium permanganate being dissolved in 18 mL pH is in 2 water, and solution is placed in pre-cooling 1 in 5 °C of refrigerators
H, is then poured upon in the ice face of step (1) gained, weak vibrations vinyl disc, so that potassium permanganate solution is equably tiled
In ice face, it is incubated 2 h in 20 °C, obtain a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL pyrroles is added in 7.7 mL ethyl acetate, in 5 °C of refrigerators, pre-cooling 0.5 h, is then inclined
It is poured on the oxidant ice sheet surface of step (2) gained, is incubated 1 h in 10 °C, obtain the polypyrrole film being supported in ice face.
(4) with appropriate distilled water flushing polypyrrole film, so that film and ice sheet is peeled off, washing film for several times, lyophilization, derive from
Hold polypyrrole film sample S-3.
Embodiment 4
A kind of preparation method of polypyrrole film, step is as follows：
(1) 500 mL water are added toward in the vinyl disc of a size of 43 cm × 30 cm × 6 cm, then Deca 1 mL is anhydrous
Ethanol, vinyl disc is placed in 20 °C of refrigerator-freezer and freezes 6 h, obtains a smooth, smooth ice face.
(2) 2.35 g Iron(III) chloride hexahydrates being dissolved in 18 mL pH is in 2 water, and solution is placed in 5 °C of refrigerators
Middle pre-cooling 0.5 h, is then poured upon in the ice face of step (1) gained, weak vibrations vinyl disc, makes ferric chloride aqueous solutionses
Equably it is laid in ice face, is incubated 2 h in 20 °C, obtain a smooth, smooth ice sheet containing oxidant.
(3) 0.5 mL pyrroles is added in 3 mL dehydrated alcohol, in 0 °C of refrigerator, pre-cooling 0.5 h, is then poured upon
In the oxidant ice sheet surface of step (2) gained, it is incubated 40 min in 20 °C, obtain the polypyrrole film being supported in ice face.
(4) with appropriate distilled water flushing polypyrrole film, so that film and ice sheet is peeled off, washing film for several times, lyophilization, derive from
Hold polypyrrole film sample S-4.
Embodiment 5
The response time of step (3) in embodiment 4 is extended to 6 h, remaining condition is constant, gained is controlled oneself polypyrrole film sample mark
It is designated as S-5.
Interpretation of result
The FESEM figure for sample S-1 to S-5 for the Fig. 1-5.From figure 1 it appears that sample S-1 is dense film, the thickness of film is
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
For 270 ± 20 nm.From figure 3, it can be seen that sample S-3 is dense film, the thickness of film is 270 ± 15 nm.Fig. 4 and Fig. 5
Display, sample S-4 and S-5 is 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 response 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.Analyzed by AFM, sample S-
4 and S-5 average thickness is respectively 140 ± 5 and 260 ± 15 nm（Fig. 8）, this result and poly- using 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 UV, visible light transmitted spectrum of the digital camera photo of film and film.Fig. 9
Digital camera photo for sample S-4.From fig. 9, it can be seen that sample S-4 not only size is big, reach decimeter grade, and have good
The transparency.Figure 10 is the UV, visible light transmitted spectrum of sample S-4.From fig. 10 it can be seen that sample S-4 is 200 to wavelength
The light light transmittance of 800 nm is all higher than 30%, illustrates that sample has good light transmission.It is located at 320,440,463 and 540 in Figure 10
The absworption peak of nm, corresponds to the π π * transition of electronics in polypyrrole, the transition of valence band to conduction band, valence band is to dual polarization subband top respectively
And polaron band low to top transition（Can. J. Chem.1995, 73, 1711–1718;Sensors2012, 12,
7965–7974.）.The synthesized film of this explanation is polypyrrole film.
Synthesized film can also be confirmed for polypyrrole film from the infrared spectrum 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 correspond to the antisymmetry of pyrrole ring respectively and symmetrically stretch
Vibration peak, C N stretching vibration peak in the corresponding pyrrole ring in the peak of 1305 wave numbers, positioned at 1182,1092 and 1043 cm–1Peak
C H in-plane bending vibration peak in corresponding pyrrole ring, positioned at 915,787 and 678 cm–1The corresponding pyrrole ring in peak in C H out-of-plane bending
Vibration peak（Macromolecules2011, 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 making of polypyrrole film base flexible working electrode, step is as follows：
Polypyrrole film sample S-4 is cut into the two panels of a size of 1 cm × 2 cm, using silver paste, polypyrrole film is pasted chi
Very little be 1 cm × 3 cm, thickness be on the graphite paper of 0.03 mm, 2 hs are dried under room temperature, obtain final product.
With Hg/Hg2SO4For reference electrode, platinized platinum is to electrode, 1 mol L–1H2SO4For 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 the specific discharge capacity of the flexible electrode under different electric current densities, being made by sample S-4（Area specific 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 under different electric current densities for the flexible electrode that table 1 is made by sample S-4
| Electric 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 making of polypyrrole film based super capacitor, step is as follows：
(1) polypyrrole film sample S-4 is cut into the two panels of a size of 3 cm × 1.5 cm, using silver paste, polypyrrole film is glued
It is attached on the graphite paper of a size of 4 cm × 1.5 cm × 0.003 cm, 2 hs under room temperature, are dried；
(2) aqueous polyurethane being 2 mm along edge coating width on polypyrrole film surface, places 4 h under room temperature；
(3) in polypyrrole film surface-coated polyvinyl alcohol/electrolyte sulfuric acid, room temperature places 2 h；
(4) the two of electrolyte will be scribbled in the face of folded, are placed on the template of a size of 3 cm × 2 cm × 0.0015cm,
Crimp in the mode of outer layer along insulating paper, using aqueous polyurethane sealing, obtain takeup type polypyrrole film based super capacitor RSC-
1.
Interpretation of result
Table 2 is specific discharge capacity under different electric current densities for the polypyrrole film based super capacitor RSC-1（Area specific capacity, body
Long-pending specific capacity）.From table 2, polypyrrole film based super capacitor RSC-1 has very high area specific capacity and volume specific volume
Amount.
Specific capacity under different electric current densities for the table 2 ultracapacitor RSC-1
| Electric 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 for RSC-1 in 2 mA cm–1The stable circulation linearity curve of circulation 5000 circle under electric current density.Can from Figure 12
Go out although the capability retention of RSC-1 is not high, be 59.1%；But, the area specific capacity after circulation 5000 circle is maintained at
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, volumetric specific power
For 111.1 mW cm–3.These results indicate that the winding that the polypyrrole film synthesized by with the present invention assembles for active substance
Formula polypyrrole film based super capacitor, still has higher energy density per unit volume 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 (10)
1. a kind of polypyrrole film it is characterised in that：The construction unit of described polypyrrole film is：
Wherein n is 52～56,M w/M nFor 1.5～2.5.
2. polypyrrole film as claimed in claim 1 it is characterised in that：
Described polypyrrole film, can be in the UV-visible range of wavelength 200 800 nm, respectively 320,440,463 and 540
There is absworption peak at nm；
Described polypyrrole film, the characteristic absorption of its infrared spectrum, is 1545 cm–1、1466 cm–1、1305 cm–1、1182 cm–1、
1092 cm–1、1043 cm–1、915 cm–1、787 cm–1, and 678 cm–1.
3. the preparation method of polypyrrole film as claimed in claim 1 or 2 is it is characterised in that comprise the following steps：
A. water is placed in container, freezing, makes smooth, the smooth ice face of formation one；
B. the aqueous oxidizing agent solution of pre-cooling is poured in the ice face of step a, freezing, make formation one smooth, smooth containing oxidation
The ice sheet of agent；
C. pyrrole monomer is dissolved in organic solvent, pre-cooling, then it is poured upon the ice sheet table containing oxidant in step b
Face, keeps 5 min to 6 h under freezing conditions, obtain the polypyrrole film of ice support；
D. so that the ice sheet below polypyrrole film is melted, so that film is peeled off with ice sheet, film water is washed, lyophilization, obtain self-holding polypyrrole
Film.
4. polypyrrole film as claimed in claim 3 preparation method it is characterised in that the freezing described in step a refer to by
Water its below freezing to more than 20 °C of temperature within the scope of place 6 ~ 12 h.
5. the preparation method of the polypyrrole film as described in claim 3 or 4 is it is characterised in that container in step a, its surface
Long-pending S is 0.001 ~ 0.02 m2；Ice described in step a, its thickness is 0.2 ~ 1 cm；
Smooth described in step a, smooth ice face is by adding a small amount of low-surface-energy, water-miscible organic solvent acquisition toward in water
's；Described low-surface-energy, water-miscible organic solvent include methanol, ethanol, propanol, acetone, butanone, Ethyl formate, methyl acetate,
Ethyl acetate or the mixture being formed by two or more in them；
The ratio of the volume of described low-surface-energy, water-miscible organic solvent and water is (1 ~ 2): 500.
6. the preparation method of polypyrrole film as claimed in claim 3 was it is characterised in that the oxidant described in step b was
Ammonium sulfate, potassium peroxydisulfate, potassium permanganate, potassium dichromate, iron chloride, ferric nitrate, iron sulfate or their mixture；
In step b state aqueous oxidizing agent solution, its volume be 0.1S ~ 0.3S L；S is the surface area of container, and its unit is
m2；
Aqueous oxidizing agent solution described in step b, its pH value of solution is 1 ~ 4；
The concentration of the aqueous oxidizing agent solution described in step b, wherein oxidant is 0.037 ~ 0.83 mol/L；
Freezing described in step b refers to place 2 ~ 6 h in 2 ~ 20 °C of temperature ranges；
Pre-cooling described in step b refers to the temperature of aqueous oxidizing agent solution is down between 0 ~ 5 °C.
7. the preparation method of polypyrrole film as claimed in claim 3, it is characterised in that the organic solvent described in step c, is wrapped
Include methanol, ethanol, propanol, 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, its volume is 0.02S ~ 0.06S L；S is the surface area of container, and its unit is m2；
Pyrroles described in step c, the amount of its material is (0.67 ~ 5) with the ratio of the amount of the material of oxidant in step b:
1；
Pre-cooling described in step c refers to the temperature of the organic solvent of dissolving pyrroles is down between 0 ~ 5 °C；
Freezing conditions described in step c are temperature between 2 ~ 20 °C.
8. the preparation method of polypyrrole film as claimed in claim 3 is it is characterised in that make below polypyrrole film in step d
Ice sheet melts, and so that the ice sheet below polypyrrole film is melted with water；Specifically, with appropriate distilled water flushing polypyrrole film, making film
Peel off with ice sheet.
9. the purposes of polypyrrole film as claimed in claim 1 or 2, or the method system as described in any one of claim 3 ~ 8
The purposes of standby polypyrrole film, for flexible working electrode.
10. the purposes of polypyrrole film as claimed in claim 1 or 2, or the method system as described in any one of claim 3 ~ 8
The purposes of standby polypyrrole film, for flexible super capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610967270.9A CN106398207B (en) | 2016-10-28 | 2016-10-28 | A kind of preparation method and its super capacitor performance of polypyrrole film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610967270.9A CN106398207B (en) | 2016-10-28 | 2016-10-28 | A kind of preparation method and its super capacitor performance of polypyrrole film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106398207A true CN106398207A (en) | 2017-02-15 |
| CN106398207B CN106398207B (en) | 2018-11-30 |
Family
ID=58014201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610967270.9A Active CN106398207B (en) | 2016-10-28 | 2016-10-28 | A kind of preparation method and its super capacitor performance of polypyrrole film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106398207B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474469A (en) * | 2017-08-28 | 2017-12-15 | 浙江理工大学 | A kind of preparation method of the flexible sensor electrode of molybdenum disulfide quantum dot modification |
| CN108470597A (en) * | 2018-02-27 | 2018-08-31 | 齐鲁工业大学 | A kind of pyrroles's oligomer and its application |
| CN109161529A (en) * | 2018-08-23 | 2019-01-08 | 长春理工大学 | A kind of film of poly pyrrole substrate preparation method for cell culture |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795953A (en) * | 1995-01-19 | 1998-08-18 | Korea Institute Of Science And Technology | Soluble, electroconductive polypyrrole and method for preparing the same |
| CN101979438A (en) * | 2010-11-25 | 2011-02-23 | 武汉大学 | Preparation method of conductive polypyrrole |
| CN102817042A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Preparation method for electroactive polypyrrole film |
| CN103098159A (en) * | 2010-08-12 | 2013-05-08 | 麻省理工学院 | Flexible conducting polymer energy storage device |
| CN103337381A (en) * | 2013-07-05 | 2013-10-02 | 电子科技大学 | Method for fabricating flexible electrode |
-
2016
- 2016-10-28 CN CN201610967270.9A patent/CN106398207B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795953A (en) * | 1995-01-19 | 1998-08-18 | Korea Institute Of Science And Technology | Soluble, electroconductive polypyrrole and method for preparing the same |
| CN103098159A (en) * | 2010-08-12 | 2013-05-08 | 麻省理工学院 | Flexible conducting polymer energy storage device |
| CN101979438A (en) * | 2010-11-25 | 2011-02-23 | 武汉大学 | Preparation method of conductive polypyrrole |
| CN102817042A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Preparation method for electroactive polypyrrole film |
| CN103337381A (en) * | 2013-07-05 | 2013-10-02 | 电子科技大学 | Method for fabricating flexible electrode |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474469A (en) * | 2017-08-28 | 2017-12-15 | 浙江理工大学 | A kind of preparation method of the flexible sensor electrode of molybdenum disulfide quantum dot modification |
| CN108470597A (en) * | 2018-02-27 | 2018-08-31 | 齐鲁工业大学 | A kind of pyrroles's oligomer and its application |
| CN108470597B (en) * | 2018-02-27 | 2019-06-11 | 齐鲁工业大学 | A kind of pyrroles's oligomer and its application |
| CN109161529A (en) * | 2018-08-23 | 2019-01-08 | 长春理工大学 | A kind of film of poly pyrrole substrate preparation method for cell culture |
| CN109161529B (en) * | 2018-08-23 | 2020-08-04 | 长春理工大学 | Preparation method of polypyrrole film substrate for cell culture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106398207B (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | A review of studies using graphenes in energy conversion, energy storage and heat transfer development | |
| Jiang et al. | Synthesis and performance of a graphene decorated NaTi2 (PO4) 3/C anode for aqueous lithium-ion batteries | |
| Mi et al. | Polyaniline nanofibers as the electrode material for supercapacitors | |
| Bai et al. | Electrosynthesis of polypyrrole/sulfonated polyaniline composite films and their applications for ammonia gas sensing | |
| Liu et al. | Electrochromic and chemochromic performance of mesoporous thin-film vanadium oxide | |
| CN104134788B (en) | A kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application | |
| Zhang et al. | A novel process to prepare porous membranes comprising SnO2 nanoparticles and P (MMA-AN) as polymer electrolyte | |
| Hosono et al. | The high power and high energy densities Li ion storage device by nanocrystalline and mesoporous Ni/NiO covered structure | |
| CN103903870A (en) | Super capacitor capable of changing colors and being stretched and manufacturing method thereof | |
| CN106025183B (en) | A kind of preparation method of the carbon-based fexible film electrode of lithium ion battery | |
| CN102347143A (en) | Graphene composite porous counter electrode, preparation method and application thereof | |
| CN106398207A (en) | Preparation method of polypyrrole film and supercapacitor property thereof | |
| CN105405663B (en) | A kind of MoS2The electrochemical preparation method of/graphene combined counter electrode | |
| Ling et al. | Core–shell structure γ-MnO2-PANI carbon fiber paper-based flexible electrode material for high-performance supercapacitors | |
| Zhao et al. | Activated carbon felts with exfoliated graphene nanosheets for flexible all-solid-state supercapacitors | |
| Zhao et al. | A high ion-conductive and stable porous membrane for neutral aqueous Zn-based flow batteries | |
| CN106340397B (en) | A kind of polypyrrole film base flexible electrode and its preparation method and application | |
| CN112994523A (en) | Wet gas power generation device based on electrostatic spinning nanofiber membrane and preparation and application thereof | |
| CN105719846B (en) | A kind of preparation method of cobalt sulfide/carbon composite and products thereof and application | |
| Ikeda et al. | Multivalent cation conductive solid polymer electrolytes using photo-cross-linked polymers: II. Magnesium and zinc trifluoromethanesulfonate systems | |
| CN106298254A (en) | Polyaniline/porous metal film material, anode composite pole piece, preparation method and application | |
| Lu et al. | UV-curable-based plastic crystal polymer electrolyte for high-performance all-solid-state Li-ion batteries | |
| Chen et al. | Highly ordered asymmetric cellulose-based honeycomb membrane for moisture-electricity generation and humidity sensing | |
| CN108219453B (en) | A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material | |
| Tang et al. | Research progress of the counter electrode in dye-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201230 Address after: 233000 No.10, building 32, Zone 8, Guangcai market, bengshan District, Bengbu City, Anhui Province Patentee after: Bengbu Hongjing Technology Co.,Ltd. Address before: 250353 science and Technology Park, Xincheng University, Daxue Road, Changqing District, Jinan City, Shandong Province Patentee before: Qilu University of Technology |