CN106298254A - Polyaniline/porous metal film material, anode composite pole piece, preparation method and application - Google Patents
Polyaniline/porous metal film material, anode composite pole piece, preparation method and application Download PDFInfo
- Publication number
- CN106298254A CN106298254A CN201610666012.7A CN201610666012A CN106298254A CN 106298254 A CN106298254 A CN 106298254A CN 201610666012 A CN201610666012 A CN 201610666012A CN 106298254 A CN106298254 A CN 106298254A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- film material
- thin
- pole piece
- porous metal
- 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.)
- Pending
Links
Classifications
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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 discloses a kind of polyaniline/porous metal film material, anode composite pole piece, preparation method and application, belong to supercapacitor technologies field.This thin-film material, with nano-porous gold Ag films as substrate, utilizes gold silver thin film oxidation reaction in acid solution to prepare metal-oxide, and this metal-oxide can participate in redox reaction as fake capacitance and carry out energy storage and release.This thin-film material can also utilize polyaniline electric double layer effect to carry out electric charge storage and release simultaneously, the two collaborative charging/discharging voltage improving material.In the present invention, anode composite pole piece by above-mentioned thin-film material and is compressed on the solid electrolyte of material surface and constitutes, compared with traditional ultracapacitor being made up of active substance and liquid electrolyte, liquid electrolyte and active contacts generation side reaction can be avoided, improve security performance and the cycle performance of capacitor.
Description
Technical field
The present invention relates to a kind of polyaniline/porous metal film material, also relate to use this thin-film material to prepare
Anode composite pole piece, and the preparation method and application of anode composite sheet, belong to supercapacitor technologies field.
Background technology
Ultracapacitor is a kind of model electrochemical energy storage device between traditional capacitor and battery.Compare tradition
Capacitor, ultracapacitor has higher energy density；Compare battery, have again higher power density and preferably circulation
Life-span.Therefore, it combines the advantage of traditional capacitor and battery, is a kind of electrochmical power source having a extensive future, belongs to new
Emerging power back-off and energy storage device category.
In recent years, the development of supercapacitor technologies caused the extensive concern of people, and had been successfully applied in consumption
The fields such as electronic product, energy traffic (such as electric automobile, solar energy, wind energy energy storage), power back-off, its market scale is
Rapid expansion.In order to improve the energy density of ultracapacitor, multiple electrode material includes that electric double layer and fake capacitance material are by extensively
General application.Further, in order to improve the limitation of homogenous material, electric conductivity and structural stability such as high-capacitance material are poor, high
The capacitive property of conductive material is relatively low etc., and the substantial amounts of composite of researcher developmental research, such as material with carbon element, (Graphene, carbon are received
Mitron etc.), conducting polymer etc. improve the electric conductivity of material, and the oxide material etc. of mutually doping improves material
Electric capacity stability.But, intrinsic shortcoming such as high dispersion, the easy coalescence etc. of nano material is the most to be improved.There is researcher
Attempt using nano material such as nanoporous or the large pore material etc. of continuous structure to improve capacitive property.As Cui Yi etc. (J R,
McDonough J,et al.Carbon nanofiber supercapacitors with large areal
Capacitances.AppL Phys.Lett, 2009,95,243109.) utilize the foam metal of macropore or fabric to prepare
A series of structure continuous print capacitance materials, and obtained bigger apparent capacity.And for example publication No. CN101671478A send out
Disclosed in bright patent, a kind of carbon nano tube/polyaniline netty compound material, (as the most molten in 0.5mol/L sulphuric acid at electrolyte solution
Liquid) in add the aniline solution of concentration 0.3mol/L and amidatioon CNT obtains mixed liquor, then with platinized platinum as auxiliary electrode,
Saturated calomel is reference electrode, uses cyclic voltammetry electro-deposition to prepare, and this electrode material has higher specific capacity with good
Cyclical stability.
It is known that nano porous metal thin film has uniform hole/wall size and excellent electric conductivity, as supporting knot
Structure is provided that unobstructed ion channel, is conducive to efficiently utilizing active material and preventing nanostructured from reuniting, thus improves material
Overall performance, but, cycle performance when nano porous metal thin film uses separately as pole piece is poor.Similarly for electrification
Learning material, transition metal oxide or hydroxide are (such as MnO2、Co3O4、Co(OH)2、Ni(OH)2Deng) there is higher counterfeit electricity
Hold.Nano-porous gold/the MnO developed such as Chen Mingwei etc.2Composite, it is possible to make MnO2Ratio electric capacity bring up to 1145F/g (X Y
Lang,AHirata,et al.Nanoporous metal/oxide hybrid electrodes for
electrochemical supercapacitors.Nature Nanotech.2011,6,232-236).Follow this thinking,
If can be with nano porous metal thin film as matrix, at one layer of conducting polymer materials of its surface electro-deposition, and as raw material system
Standby positive electrode, is beneficial to improve the specific capacity of electrode material, power-performance and cycle performance, improves ultracapacitor simultaneously
Energy density.
Summary of the invention
It is an object of the invention to provide a kind of polyaniline/porous metal film material.
Meanwhile, the present invention also provides for a kind of anode composite pole piece using above-mentioned thin-film material to prepare.
Finally, the present invention reoffers the preparation method and application of a kind of above-mentioned anode composite pole piece.
In order to realize object above, the technical solution adopted in the present invention is:
Polyaniline/porous metal film material, by nano porous metal thin film and polyaniline/carbon of being deposited on thin film
Nanometer tube composite materials is constituted.
Described thin film is nano-porous gold Ag films, is by thickness 100～500nm, the gold silver thin film of gold silver mass ratio 1:1
In acid solution, reaction prepares.
The preparation method of above-mentioned polyaniline/porous metal film material, comprises the following steps:
1) preparation of nano porous metal thin film
Gold silver thin film is placed in acid solution reaction, obtains nano porous metal thin film；
2) preparation of polyaniline/nano porous metal thin-film material
In lithium perchlorate solution, add aniline monomer and Carboxylation CNT obtains being electrolysed mixed liquor, with nanoporous
Metallic film is working electrode, uses electrochemical deposition method to prepare thin-film material.
Step 1) in the thickness of gold silver thin film be 100～500nm, in gold silver thin film, the mass ratio of gold, silver is 1:1.
Step 1) in acid solution such as use concentrated nitric acid, concentrated sulphuric acid etc..Gold silver thin film is 1～10g (gold with the amount ratio of concentrated nitric acid
Ag films): 100～200mL (concentrated nitric acids), react 0.1～5h under room temperature.
Step 2) in electrolysis the consisting of of mixed liquor: aniline monomer 1～10g, Carboxylation CNT 0.1～1g, 1～
1.5mol/L lithium perchlorate solution 100mL.
Step 2) in the running parameter of electrochemical deposition be: constant voltage 0.5～1.0V, be energized 10～60min.Deposit
Finish, clean, be dried, then be placed in 0.5mol/L LiPF6/ DEC+EC (volume ratio 1:1) solution soaks 30min, is dried, to obtain final product.
Anode composite pole piece, by polyaniline/nano porous metal thin-film material and the electricity that is attached to thin-film material surface
Solution composite material is constituted.
Described electrolyte composite material is by the electrolyte that mass ratio is 10～40:10～20:1～5, conductive agent and binding agent
Composition.Electrolyte is LiAlO2Or LiAlCl4, conductive agent is white carbon black (SP), and binding agent is Kynoar (PVDF).
The preparation method of above-mentioned anode composite pole piece, comprises the following steps:
1) preparation of electrolyte slurry
Electrolyte, conductive agent and binding agent are added in solvent, is uniformly mixed so as to obtain electrolyte slurry；
2) preparation of anode composite pole piece
Electrolyte slurry is coated in the surface of polyaniline/nano porous metal thin-film material, suppresses after drying, to obtain final product.
Step 1) in electrolyte be LiAlO2Or LiAlCl4, conductive agent is white carbon black, and binding agent is Kynoar, and solvent is
N-Methyl pyrrolidone, by quality ratio, electrolyte: conductive agent: binding agent: solvent=10～40:10～20:1～5:40～
80。
Step 2) in electrolyte slurry be coated at least one side of polyaniline/nano porous metal thin-film material, coating
Thickness is 1～5 μm.
Step 2) in compacting can use roll squeezer, pressing pressure 1～5MPa.
Above-mentioned polyaniline/porous metal film material or the application in preparing ultracapacitor of the anode composite pole piece.
Concrete, in ultracapacitor, cathode pole piece is made up of the activated carbon that mass ratio is 95:5 and Kynoar, electricity
Solution liquid is LiPF6/ DEC+EC (volume ratio 1:1), wherein LiPF6For solute, DEC, EC are solvent, concentration 1～1.3mol/L.
Beneficial effects of the present invention:
In the present invention, polyaniline/porous metal film material is with nano-porous gold Ag films as substrate, utilizes gold silver thin film
Oxidation reaction in acid solution prepares metal-oxide, and this metal-oxide can participate in redox reaction as fake capacitance to be carried out
Energy storage and release.This thin-film material can also utilize polyaniline electric double layer effect to carry out electric charge storage and release simultaneously, the two
The collaborative charging/discharging voltage improving material.In this thin-film material, nano-porous gold Ag films can again can as active substance
Support active substance as collector, active substance has high-specific surface area, the CNT of high conductivity promotes it simultaneously
In charge and discharge process, carry out electric charge store and release.And active substance without with conductive agent and binding agent with the use of, have
It is beneficial to improve energy density and the power density of pole piece.
In the present invention, anode composite pole piece by above-mentioned polyaniline/nano porous metal thin-film material and is compressed on material list
The solid electrolyte in face is constituted, with traditional by active substance compared with the ultracapacitor that liquid electrolyte forms, this pole piece
It is avoided that electrolyte and active contacts generation side reaction, thus improves security performance and the cycle performance of capacitor.
The present invention uses electrochemical process to prepare polyaniline/porous metal film material, compares chemical synthesis, nanoporous
Metallic film is bigger with the adhesion of polyaniline, can form the material structure of densification, is conducive to improving the specific capacity of material.
Accompanying drawing explanation
Fig. 1 is the cyclic voltammetry curve figure of ultracapacitor in test example；
Fig. 2 is the AC internal Resistance comparison diagram of ultracapacitor in test example；
Fig. 3 is the cyclic curve figure of ultracapacitor in test example.
Detailed description of the invention
The present invention is only described in further detail by following embodiment, but does not constitute any limitation of the invention.
Embodiment 1
Polyaniline/porous metal film material, by nano-porous gold Ag films and polyaniline/carbon of being deposited on thin film
Nanometer tube composite materials is constituted, and its preparation process is:
1) preparation of nano porous metal thin film
The 5g gold silver thin slice (thickness 300nm, the mass ratio of gold, silver is 1:1) weighed is put in 150mL concentrated nitric acid, often
After temperature reaction 1h, clean 3 times with redistilled water, obtain nano porous metal thin film A；
2) preparation of polyaniline/nano porous metal thin-film material
The 5g aniline monomer weighed, the Carboxylation CNT of 0.5g are joined the lithium perchlorate of 100mL concentration 1mol/L
In solution, it is uniformly mixing to obtain electrolysis mixed liquid B；Nano porous metal thin film A is connected as working electrode with copper cash, saturated
Calomel electrode is to electrode, electro-deposition 30min under the constant-pressure conditions of voltage 0.7V, is dried, then is placed in 0.5mol/L after cleaning
LiPF6/ DEC+EC (volume ratio 1:1) solution soaks 30min, natural air drying, to obtain final product.
Anode composite pole piece, by above-mentioned polyaniline/porous metal film material and the electrolyte that is attached to material surface
Composite is constituted, and its preparation process is:
1) preparation of electrolyte slurry
The 30g solid electrolyte LiAlO that will weigh2, 15g binding agent PVDF, 3g conductive agent SP add 60g solvent NMP (matter
Amount is than 30:15:3:60) in, stir with homogenizer, obtain electrolyte slurry C；
2) preparation of anode composite pole piece
Electrolyte slurry C is coated on the two sides of above-mentioned polyaniline/porous metal film material, coating by scraper plate method
Thickness is 2 μm, suppresses with roll squeezer after drying, pressing pressure 3MPa, to obtain final product.
Ultracapacitor, uses above-mentioned anode composite pole piece, and cathode pole piece is by the activated carbon that mass ratio is 95:5 and gathers partially
Fluorothene is made, and barrier film is ceramic diaphragm, uses winding method to prepare 3000F ultracapacitor afterwards.
Embodiment 2
Polyaniline/porous metal film material, by nano-porous gold Ag films and polyaniline/carbon of being deposited on thin film
Nanometer tube composite materials is constituted, and its preparation process is:
1) preparation of nano porous metal thin film
The 1g gold silver thin slice (thickness 100nm, the mass ratio of gold, silver is 1:1) weighed is put in 100mL concentrated nitric acid, often
After temperature reaction 0.1h, clean 3 times with redistilled water, obtain nano porous metal thin film A；
2) preparation of polyaniline/nano porous metal thin-film material
The 1g aniline monomer weighed, the Carboxylation CNT of 0.1g are joined the perchloric acid of 100mL concentration 1.25mol/L
In lithium solution, it is uniformly mixing to obtain electrolysis mixed liquid B；Nano porous metal thin film A is connected as working electrode with copper cash, full
It is to electrode with calomel electrode, electro-deposition 10min under the constant-pressure conditions of voltage 0.5V, it is dried after cleaning, then is placed in 0.5mol/
L LiPF6/ DEC+EC (volume ratio 1:1) solution soaks 30min, natural air drying, to obtain final product.
Anode composite pole piece, by above-mentioned polyaniline/porous metal film material and the electrolyte that is attached to material surface
Composite is constituted, and its preparation process is:
1) preparation of electrolyte slurry
The 10g solid electrolyte LiAlCl that will weigh4, 10g binding agent PVDF, 1g conductive agent SP add 40g solvent NMP
In (mass ratio 10:10:1:40), stir with homogenizer, obtain electrolyte slurry C；
2) preparation of anode composite pole piece
Electrolyte slurry C is coated on the two sides of above-mentioned polyaniline/porous metal film material, coating by scraper plate method
Thickness is 1 μm, suppresses with roll squeezer after drying, pressing pressure 1MPa, to obtain final product.
Ultracapacitor, uses above-mentioned anode composite pole piece, and cathode pole piece is by the activated carbon that mass ratio is 95:5 and gathers partially
Fluorothene is made, and barrier film is ceramic diaphragm, uses winding method to prepare 3000F ultracapacitor afterwards.
Embodiment 3
Polyaniline/porous metal film material, by nano-porous gold Ag films and polyaniline/carbon of being deposited on thin film
Nanometer tube composite materials is constituted, and its preparation process is:
1) preparation of nano porous metal thin film
The 10g gold silver thin slice (thickness 500nm, the mass ratio of gold, silver is 1:1) weighed is put in 200mL concentrated nitric acid, often
After temperature reaction 5h, clean 3 times with redistilled water, obtain nano porous metal thin film A；
2) preparation of polyaniline/nano porous metal thin-film material
The 10g aniline monomer weighed, the Carboxylation CNT of 1g are joined the lithium perchlorate of 100mL concentration 1.5mol/L
In solution, it is uniformly mixing to obtain electrolysis mixed liquid B；Nano porous metal thin film A is connected as working electrode with copper cash, saturated
Calomel electrode is to electrode, electro-deposition 60min under the constant-pressure conditions of voltage 1.0V, is dried, then is placed in 0.5mol/L after cleaning
LiPF6/ DEC+EC (volume ratio 1:1) solution soaks 30min, natural air drying, to obtain final product.
Anode composite pole piece, by above-mentioned polyaniline/porous metal film material and the electrolyte that is attached to material surface
Composite is constituted, and its preparation process is:
1) preparation of electrolyte slurry
The 40g solid electrolyte LiAlO that will weigh2, 20g binding agent PVDF, 5g conductive agent SP add 80g solvent NMP (matter
Amount is than 40:20:5:80) in, stir with homogenizer, obtain electrolyte slurry C；
2) preparation of anode composite pole piece
Electrolyte slurry C is coated on the two sides of above-mentioned polyaniline/porous metal film material, coating by scraper plate method
Thickness is 5 μm, suppresses with roll squeezer after drying, pressing pressure 5MPa, to obtain final product.
Ultracapacitor, uses above-mentioned anode composite pole piece, and cathode pole piece is by the activated carbon that mass ratio is 95:5 and gathers partially
Fluorothene is made, and barrier film is ceramic diaphragm, uses winding method to prepare 3000F ultracapacitor afterwards.
Comparative example
Polyaniline/metallic film material, its preparation process is:
10g polyaniline (purchased from Shanghai Chun Yuan phytochemistry company limited, model: 25233-30-1) is compressed on 10g gold
Belong to gold silver thin slice (thickness 500nm, the mass ratio of gold, silver is 1:1) surface, and be connected with copper cash in this, as working electrode, full
It is to electrode with calomel electrode, uses and embodiment 1 is electrolysed mixed liquid B, electro-deposition under the constant-pressure conditions of voltage 0.7V
30min, is dried after cleaning, then is placed in 0.5mol/L LiPF6/ DEC+EC (volume ratio 1:1) solution soaks 30min, natural wind
Dry, to obtain final product.
Ultracapacitor, with above-mentioned polyaniline/metallic film material as positive plate；With activated carbon as negative electrode active material,
PVDF is that negative plate prepared by binding agent (mass ratio 95:5)；With ceramic diaphragm as barrier film, the LiPF of concentration 1mol/L6/EC+DEC
(volume ratio 1:1) is electrolyte, uses winding method to prepare 3000F ultracapacitor afterwards.
Test example
1) in Example 1 and comparative example, ultracapacitor makees cyclic voltammetry curve.Method of testing is: super by assemble
Level capacitor carries out cyclic voltammetric on Shanghai Founder ZF-9 constant potential/galvanostat (Shanghai Electronics Co., Ltd of pros)
(C-V) test (two electrode systems), sweep speed is 5mV/s, and voltage range is-1.5～1.5V, and result is shown in Fig. 1.
As shown in Figure 1, in embodiment 1, thin-film material is in addition to having obvious rectangle cyclic voltammogram, also 0.02 and-
There is a pair obvious oxidoreduction peak in 0.18V (VS SCE), illustrates that an energy storage mode part for this material comes from double
Electric layer capacitance energy storage, another part comes from fake capacitance energy storage.The electromotive force that the most paired oxidoreduction is peak-to-peak is less, illustrates anti-
The reversibility answered is preferable.Further, on the curve of embodiment 1, oxidoreduction peak is significantly stronger than comparative example, illustrates that this material is more easy to produce
Raw fake capacitance.The rectangle frame area of embodiment 1 is significantly greater than comparative example simultaneously, illustrates that electrochemical process prepares double electricity of thin-film material
Hold more than chemical oxidization method.Analysis reason is: in embodiment 1, thin-film material is with nano porous metal oxide as matrix, on it
Depositing homogeneous, fine and close polyaniline, wherein loose structure can increase the contact area of material and electrolyte, and intensified response is active,
Make polyaniline fully participate in discharge and recharge reaction, improve the utilization rate of material, thus improve the response current of capacitor.
2) Example 1～3 and comparative example in ultracapacitor, use DC-5 type full-automatic battery controlled testing instrument (on
The square Electronics Co., Ltd in sea), under the conditions of electric current density 50mA/g, carry out constant current charge-discharge test, voltage range 2.5
～4.2V；Simultaneously 65 DEG C, electric current 5A, circulate 3000 times under the conditions of voltage 2.5～4.2V.
AC internal Resistance test: this test carry out on electrochemical workstation (alternating-current magnitude is 10mV, test frequency range be
100kHz～0.1Hz.
Maximum current is tested: obtain maximum current according to mullion electric current in cyclic voltammetry curve.
Test result see table 1,2 and Fig. 2.
Table 1 embodiment 1～3 and comparative example in the chemical property of ultracapacitor
As shown in Table 1, comparing comparative example, in embodiment, the specific capacity of positive electrode is higher, analyzes reason and is: nanoporous
Metallic film has bigger specific surface area, can store more ion.Nano porous metal thin film can as active substance,
Active substance can be supported as collector again, active substance make containing high-specific surface area, the CNT of high conductivity simultaneously
It carries out in charge and discharge process electric charge store with release, and without with conductive agent, binding agent with the use of, pole piece can be improved
Energy density and power density.Embodiment uses electrochemical process that polyaniline is deposited on nano porous metal film surface, can shape
Become fine and close material structure, reduce material expansion rate in charge and discharge process, thus improve its cycle performance.
Table 2 embodiment 1～3 and comparative example in the maximum current of ultracapacitor and internal resistance
From table 2 and Fig. 2, the capacitance corresponding to CV curve reduces with the reduction of scanning speed.The CV curve of ESC
All occurring in that obvious oxidoreduction peak, this is the direct reflection of redox reaction during PANI doping-dedoping.With
Time, the voltage difference between oxidation peak and reduction peak is less, and charged ion fast transferring in oxidation-reduction process is described, material
Reversibility is good.Analysis reason is: the PANI using electrochemical process to prepare has less particle diameter, the specific surface of thin film
Long-pending height, and use that the particle diameter of the polyaniline material that physical mixed suppresses is big, internal resistance is high so that its electric current is less.Meanwhile, nanometer is many
Pore structure can increase the contact area of oxide and polyaniline, reduces its internal resistance.
3) Example 1～3 and comparative example in ultracapacitor make cyclic curve.Method of testing is: in electric current density
Circulating 3000 times under the conditions of 50mA/g, voltage 2.5～4.2V, result is shown in Fig. 3.
From the figure 3, it may be seen that the cycle performance of ultracapacitor is substantially better than comparative example in embodiment 1～3.Analysis reason is:
Nano porous metal thin film and polyaniline have bigger contact area, can improve the adhesion of material, reduce internal resistance, the most
Hole on mesoporous metal thin film can accommodate more electrolyte, improves the imbibition liquid-keeping property of material, being circulated throughout for capacitor
Journey provides sufficient electrolyte, thus improves its cycle performance.
Claims (10)
1. polyaniline/porous metal film material, it is characterised in that: described thin-film material is by nano porous metal thin film and sinks
Amass the Polymerization of Polyaniline/carbon Nanotube composite on thin film to constitute.
2. the preparation method of thin-film material as claimed in claim 1, it is characterised in that: comprise the following steps:
1) gold silver thin film is placed in acid solution reaction, obtains nano porous metal thin film；
2) in lithium perchlorate solution, add aniline monomer and Carboxylation CNT obtains being electrolysed mixed liquor, with nano-porous gold
Genus thin film is working electrode, uses electrochemical deposition method to prepare thin-film material.
Preparation method the most according to claim 2, it is characterised in that: step 1) in the thickness of gold silver thin film be 100～
500nm, in gold silver thin film, the mass ratio of gold, silver is 1:1.
Preparation method the most according to claim 3, it is characterised in that: step 1) in acid solution be concentrated nitric acid, the consumption of the two
Ratio is 1～10g gold silver thin film: 100～200mL concentrated nitric acids, reacts 0.1～5h under room temperature.
5. according to the preparation method described in claim 2 or 4, it is characterised in that: step 2) in electrolysis the consisting of of mixed liquor: benzene
Amine monomers 1～10g, Carboxylation CNT 0.1～1g, 1～1.5mol/L lithium perchlorate solution 100mL.
6. anode composite pole piece, it is characterised in that described pole piece is thin by the polyaniline/nano porous metal described in claim 1
Membrane material and be attached to thin-film material surface electrolyte composite material constitute.
Pole piece the most according to claim 6, it is characterised in that described electrolyte composite material is 10～40 by mass ratio:
Electrolyte, conductive agent and the binding agent composition of 10～20:1～5.
The preparation method of pole piece the most as claimed in claims 6 or 7, it is characterised in that: comprise the following steps:
1) electrolyte, conductive agent and binding agent are added in solvent, be uniformly mixed so as to obtain electrolyte slurry；
2) electrolyte slurry is coated in the surface of polyaniline/nano porous metal thin-film material, suppresses after drying, to obtain final product.
Preparation method the most according to claim 8, it is characterised in that: by quality ratio, step 1) in electrolyte: conduction
Agent: binding agent: solvent=10～40:10～20:1～5:40～80.
10. pole piece application in preparing ultracapacitor described in thin-film material, claim 6 or 7 as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610666012.7A CN106298254A (en) | 2016-08-12 | 2016-08-12 | Polyaniline/porous metal film material, anode composite pole piece, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610666012.7A CN106298254A (en) | 2016-08-12 | 2016-08-12 | Polyaniline/porous metal film material, anode composite pole piece, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106298254A true CN106298254A (en) | 2017-01-04 |
Family
ID=57670330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610666012.7A Pending CN106298254A (en) | 2016-08-12 | 2016-08-12 | Polyaniline/porous metal film material, anode composite pole piece, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106298254A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107219285A (en) * | 2017-04-19 | 2017-09-29 | 超威电源有限公司 | A kind of lead-acid accumulator test working electrode and preparation method thereof |
| CN107275114A (en) * | 2017-05-04 | 2017-10-20 | 浙江工业大学 | A kind of preparation method of graphene composite film |
| CN111223676A (en) * | 2020-01-14 | 2020-06-02 | 益阳市万京源电子有限公司 | Supercapacitor material based on hollow nanotube and preparation method thereof |
| CN113307969A (en) * | 2021-02-05 | 2021-08-27 | 北京航空航天大学 | Conductive polymer porous membrane and preparation method thereof |
| CN114220944A (en) * | 2021-12-14 | 2022-03-22 | 天津巴莫科技有限责任公司 | Positive pole piece modified by polymer film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671478A (en) * | 2009-09-27 | 2010-03-17 | 西南交通大学 | Preparation method of carbon nano tube/polyaniline netty compound material |
| CN102810406A (en) * | 2012-09-11 | 2012-12-05 | 复旦大学 | Super capacitor taking polyaniline/aligned carbon nanotube compound film as electrode and manufacturing method thereof |
| CN102856080A (en) * | 2012-09-24 | 2013-01-02 | 山东大学 | Nanometer porous metal conducting polymer based super capacitor material and preparation method thereof |
-
2016
- 2016-08-12 CN CN201610666012.7A patent/CN106298254A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671478A (en) * | 2009-09-27 | 2010-03-17 | 西南交通大学 | Preparation method of carbon nano tube/polyaniline netty compound material |
| CN102810406A (en) * | 2012-09-11 | 2012-12-05 | 复旦大学 | Super capacitor taking polyaniline/aligned carbon nanotube compound film as electrode and manufacturing method thereof |
| CN102856080A (en) * | 2012-09-24 | 2013-01-02 | 山东大学 | Nanometer porous metal conducting polymer based super capacitor material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| AKIRA WATANABE等: "Comparative study of redox reactions of polyaniline films in aqueous and nonaqueous solutions", 《MACROMOLECULES》 * |
| 孙帆: "电解液对超级电容器电化学性能影响的研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107219285A (en) * | 2017-04-19 | 2017-09-29 | 超威电源有限公司 | A kind of lead-acid accumulator test working electrode and preparation method thereof |
| CN107275114A (en) * | 2017-05-04 | 2017-10-20 | 浙江工业大学 | A kind of preparation method of graphene composite film |
| CN107275114B (en) * | 2017-05-04 | 2019-02-01 | 浙江工业大学 | A kind of preparation method of graphene composite film |
| CN111223676A (en) * | 2020-01-14 | 2020-06-02 | 益阳市万京源电子有限公司 | Supercapacitor material based on hollow nanotube and preparation method thereof |
| CN113307969A (en) * | 2021-02-05 | 2021-08-27 | 北京航空航天大学 | Conductive polymer porous membrane and preparation method thereof |
| CN114220944A (en) * | 2021-12-14 | 2022-03-22 | 天津巴莫科技有限责任公司 | Positive pole piece modified by polymer film and preparation method thereof |
| CN114220944B (en) * | 2021-12-14 | 2024-04-26 | 天津巴莫科技有限责任公司 | High polymer film modified positive electrode plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102543464B (en) | ZnO/reduced graphene oxide/polypyrrole ternary composite material preparation method, and application of the ternary composite material | |
| CN103594254B (en) | The preparation method of a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material | |
| Staiti et al. | Investigation of polymer electrolyte hybrid supercapacitor based on manganese oxide–carbon electrodes | |
| CN104134788B (en) | A kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application | |
| CN106298254A (en) | Polyaniline/porous metal film material, anode composite pole piece, preparation method and application | |
| CN108630920A (en) | A kind of nano-metal-oxide/MXene heterojunction structure composite material and preparation methods | |
| Kazazi | High-performance electrode based on electrochemical polymerization of polypyrrole film on electrophoretically deposited CNTs conductive framework for supercapacitors | |
| CN110330016A (en) | An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole | |
| CN102013330A (en) | Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof | |
| CN103545123A (en) | Hybrid energy storage device with zinc ion battery and supercapacitor | |
| CN106981374B (en) | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application | |
| CN109192523B (en) | A kind of Ni (OH)2Preparation method of multilayer graphene composite material | |
| Fang et al. | Fabrication and supercapacitive properties of a thick electrode of carbon nanotube–RuO2 core–shell hybrid material with a high RuO2 loading | |
| CN102516764B (en) | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof | |
| CN106981371A (en) | A kind of water system electrolyte super capacitance cell | |
| CN105244180A (en) | Preparation of three-dimensional graphene manganese dioxide nano-composite modified electrode and capacitive property test method thereof | |
| CN103680995A (en) | Mesoporous carbon/RuO2 composite material for supercapacitor and preparation method thereof | |
| CN104715934A (en) | Hybrid super capacitor and manufacturing method thereof | |
| CN102915844A (en) | Method for preparing different-electrode composite materials of carbon plate/manganese dioxide nanometer sheet and application thereof | |
| CN104264267A (en) | Porous polyaniline-doped nano fiber material with three-dimensional structure as well as preparation method and application of porous polyaniline-doped nano fiber material | |
| CN105655146A (en) | Sodium intercalation manganese dioxide/graphene double-shell hollow microsphere material and preparing method and application thereof | |
| CN102093712A (en) | Preparation method of composite super capacitor electrode material | |
| CN102426925B (en) | Method for preparing cobalt and zinc doped nickel hydroxide composite electrode material through electrodeposition | |
| CN103280339A (en) | Method for preparing cerium oxide electrode of supercapacitor | |
| CN106169377A (en) | Carbon nano-tube network/Ni (OH)2/ PPY combination electrode, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |
|
| RJ01 | Rejection of invention patent application after publication |