CN105513825B - A kind of symmetry button type electrode material for super capacitor and symmetry button type ultracapacitor - Google Patents
A kind of symmetry button type electrode material for super capacitor and symmetry button type ultracapacitor Download PDFInfo
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- CN105513825B CN105513825B CN201510909523.2A CN201510909523A CN105513825B CN 105513825 B CN105513825 B CN 105513825B CN 201510909523 A CN201510909523 A CN 201510909523A CN 105513825 B CN105513825 B CN 105513825B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 73
- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 229920000767 polyaniline Polymers 0.000 claims abstract description 78
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 48
- 239000011149 active material Substances 0.000 claims abstract description 12
- -1 cerium ion Chemical class 0.000 claims description 38
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
Classifications
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of symmetry button type electrode material for super capacitor and symmetry button ultracapacitors, the electrode material includes the hollow polyaniline microspheres active material that surface doping has trivalent cerium ion, it has the characteristics that specific capacity is big, energy density is high, electro-chemical activity is high, it can be used for preparing the electrode slice material of symmetry button type ultracapacitor, obtain the high-performance symmetry button type ultracapacitor that specific capacity is big, AC impedance is small and voltage maintains ability good.
Description
Technical field
There are the hollow polyaniline microspheres of trivalent cerium ion as the symmetrical of active material using surface doping the present invention relates to a kind of
Property button type electrode material for super capacitor, and the symmetry button type ultracapacitor made of this electrode material belongs to
In chemical capacitor field.
Background technology
Energy crisis and environmental protection are increasingly becoming two hang-ups of 21 century.For alleviate increasingly serious energy crisis and
New Energy Industry is all being actively developed in resulting a series of environmental problems, countries in the world.Wind energy, solar energy and tide energy
Etc. regenerative resources by very big concern.But these energy suffer from the shadow of external condition (such as meteorology, weather, region)
It rings and unstability and discontinuity is presented.It is real to solve the problems, such as that this just needs the related mating high-efficiency energy-storage device of development
The efficient storage and release of existing energy.Therefore, it is to solve current energy crisis and environmental protection to develop efficient apparatus for storing electrical energy
The a major challenge faced in process.
Ultracapacitor (also known as electric chemical super capacitor) is a kind of novel storage between battery and traditional capacitor
It can device.Compared with battery and traditional capacitor, it not only have high power density, charge-discharge cycle long lifespan, cycle efficieny it is high,
Charging time is short, high reliability, environmentally friendly feature is also shown, in stand-by power supply, sun-generated electric power, new energy
The fields such as automobile, information technology, day electronic product, aerospace and science and techniques of defence show to be widely applied foreground.
For ultracapacitor, the technological break-through of electrode material be the key that driving ultracapacitor industry development because
Element.Carbon material is widely used in electrode material for super capacitor at present, but relatively low in carbon material specific capacity itself, energy density
Limited, the comprehensive performance for the capacitor being assembled into is influenced to a certain extent.Compared with carbon material, conducting polyaniline material synthesis
Simplicity, environmental stability are good, and specific capacity, the energy density of opposite carbon material are preferable, but individually use polyaniline material, capacitance
Specific capacity and energy density the improvement ability of device are limited, it is made to be limited in the application in ultracapacitor field.Therefore, it develops
The better novel conductive polyaniline composite electrode material of specific capacity bigger, electro-chemical activity higher, comprehensive performance has important meaning
Justice.
Invention content
For existing active carbon electrode material, that there are specific capacities is low, energy density is low and what electro-chemical activity was not high enough lacks
It falls into, has that specific capacity is big, high electrochemical activity is with trivalent cerium ion doped polyaniline the purpose of the invention is to provide one kind
Hollow microsphere is the symmetry button type electrode material for super capacitor of active material.
Another object of the present invention is to be to provide that a kind of specific capacity obtained based on the electrode material is big, exchange resistance
The symmetry button type ultracapacitor that anti-small and voltage maintains ability good.
In order to achieve the above technical purposes, the present invention provides a kind of symmetry button type electrode material for super capacitor,
The active material of the electrode material is the hollow polyaniline microspheres that surface doping has trivalent cerium ion.
Preferred embodiment, symmetry button type electrode material for super capacitor are made of following content of component：
Surface doping has 70~80 parts of the hollow polyaniline microspheres of trivalent cerium ion；
10~20 parts of acetylene black；
5~15 parts of the ptfe emulsion that solid content is 55~65%.
More preferably scheme, symmetry button type electrode material for super capacitor are made of following content of component：Surface
Doped with 75 parts of the hollow polyaniline microspheres of trivalent cerium ion；15 parts of acetylene black；Solid content is 60% ptfe emulsion 10
Part.
More preferably scheme, it is 340~420nm that surface doping, which has the outer diameter of the hollow polyaniline microspheres of trivalent cerium ion, interior
Diameter is 220~260nm, and conductivity is 8.95~47.46S/cm.
More preferably scheme, surface doping have the quality percentage of trivalent cerium ion in the hollow polyaniline microspheres of trivalent cerium ion
It is 5~30% than content.
Further preferred scheme, surface doping have the hollow polyaniline microspheres of trivalent cerium ion to be prepared via a method which
It arrives：It is hollow that aniline in the solution containing poly- (2- acrylamide-2-methylpro panesulfonic acids) is prepared into polyaniline by self-assembly method
Microballoon, hollow polyaniline microspheres are stirred in cerous nitrate (III) solution after doping has the poly- of trivalent cerium ion to get surface doping
Aniline hollow microsphere.
The area load of the present invention has the specific preparation method of the hollow polyaniline microspheres of rare-earth cerium ion：By poly- (2- third
Acrylamide base -2- methyl propane sulfonic acids) and aniline be added in ethanol/water mixed solvent, be uniformly mixed, obtain mixed solution, mix
Close solution mass percentage composition be：Poly- (2- acrylamide-2-methylpro panesulfonic acids) 0.5~4.9%, aniline 2.2~
2.5%, ethyl alcohol 7.4~7.8%, water 84.8~89.9%；After gained mixed liquor is warming up to 50~80 DEG C, temperature is rapidly joined
For 50~80 DEG C of ammonium persulfate aqueous solution, after maintaining 1~2min of thermotonus, 0~5 DEG C is adjusted the temperature to immediately further instead
Answer 4~12h；Demulsification, washing, obtained hollow polyaniline microspheres；Gained hollow polyaniline microspheres are placed in mass percent concentration
For in 0.057~2.79% cerous nitrate (III) solution, 4~12h of stirring doping at a temperature of 25~50 DEG C is filtered, washing, is done
Dry, obtaining surface doping has the hollow polyaniline microspheres of trivalent rare earth cerium ion.
The present invention also provides a kind of symmetry button type ultracapacitors, including capacitor case, positive plate, cathode
Piece, diaphragm and electrolyte, the positive plate and negative plate are made of the button type electrode material for super capacitor.
Preferred scheme, positive plate or negative plate are prepared via a method which to obtain：By symmetry button type super capacitor
Device electrode material is reconciled with organic solvent, and ultrasonic disperse obtains slurry；After gained slurry volatilization removal partial solvent, it is rolled into
Thin slice, further strikes out disk, and disk is by being dried in vacuo to get to positive plate or negative plate.
The specific preparation method of positive plate or negative plate is in the symmetry button type ultracapacitor of the present invention：By surface
It is mixed in proportion doped with the hollow polyaniline microspheres of trivalent cerium ion, acetylene black, ptfe emulsion, a small amount of nothing is added
Water-ethanol is reconciled, and 5~15min of ultrasound obtains mixed slurry；After slurry is removed unnecessary alcohol, it is 0.1 to be rolled into thickness
The thin slice of~0.3mm；The disk that slice stamping is about 10mm at diameter by mold is reused, vacuum is dry at a temperature of 60~80 DEG C
Dry 10~16h obtains positive plate or negative plate.
In preferred symmetry button type ultracapacitor, diaphragm is non-woven fibre cloth.Non-woven fibre cloth is commercially available industry
Grade product, a diameter of 19.0mm.
In preferred symmetry button type ultracapacitor, electrolyte is the H of 0.5~1M2SO4Solution.
In preferred symmetry button type ultracapacitor, capacitor case is outside 2016 type button type lithium ion batteries
Shell.
The acetylene black and ptfe emulsion that the present invention uses is conventional commercial product.
Compared with prior art, the advantageous effect that technical scheme of the present invention is brought：Technical scheme of the present invention for the first time with
It is electrode material activity substance that surface doping, which has the hollow polyaniline microspheres of trivalent cerium ion, and hollow polyaniline microspheres are nanoscale
Particle, have the characteristics that particle uniformly, large specific surface area, and there is hollow microsphere structure, it is good to volume change buffer capacity, it is special
The trivalent rare earth cerium that has been not its surface doping, can effectively improve the electro-chemical activity on polyaniline surface.This active matter will be contained
Symmetry button type ultracapacitor prepared by the positive electrode of matter can significantly improve the capacitance of capacitor, reduce exchange resistance
Anti-, improvement voltage maintains stability.
Lot of experimental data is shown：
The present invention's has the hollow polyaniline microspheres of trivalent cerium ion as the electrode assembling of active material using surface doping
At capacitor, in 1mA/cm2Charging or discharging current density under, capacitance reaches 248.2F/g, opposite with hollow polyaniline microspheres
Capacitance 201.6F/g for the electrode of active material is higher by 23.1%.
The present invention has the electrode assembling of the hollow polyaniline microspheres of trivalent cerium ion as active material using surface doping
Capacitor, charge transfer resistance are 1.215 Ω, opposite using hollow polyaniline microspheres as the capacitor of the electrode assembling of active material
6.223 Ω of charge transfer resistance reduce nearly 80.5%.
The present invention has the electrode assembling of the hollow polyaniline microspheres of trivalent cerium ion as active material using surface doping
Capacitor, the phase angle that low frequency range is shown in by Bode figures reach 73.9 °, closer to the phase angle (90 °) of ideal capacitor.
The present invention has the electrode assembling of the hollow polyaniline microspheres of trivalent cerium ion as active material using surface doping
There is capacitor preferable voltage to maintain ability, leakage current 0.1481mA opposite using hollow polyaniline microspheres as active material
Electrode assembling condenser leakage current 0.2982mA, reduce about 50.3%.
In conclusion surface doping has the hollow polyaniline microspheres of trivalent cerium ion to be more suitable for high-performance super capacitor
Electrode material has wide application market in new energy field.
Description of the drawings
【Fig. 1】The scanning electricity that surface doping there are the hollow polyaniline microspheres of rare-earth cerium ion is made for the embodiment of the present invention 1
Sub- microscope figure, energy spectrum analysis figure and transmission electron microscope figure：A is the scanning electron microscope (SEM) photograph under 20,000 multiplying powers；B is 100,000 multiplying powers
Under scanning electron microscope (SEM) photograph；C is corresponding to the energy spectrum analysis in rectangular area in a；D is transmission electron microscope picture.
【Fig. 2】There is the infrared spectrogram of the hollow polyaniline microspheres of trivalent cerium ion for surface doping prepared by embodiment 1.
【Fig. 3】The symmetry button type capacitor schematic diagram assembled for embodiment 2.
【Fig. 4】For the cyclic voltammetry curve for the symmetry capacitor that embodiment 2 assembles.
【Fig. 5】For the AC impedance curve for the symmetry capacitor that embodiment 2 assembles.
【Fig. 6】For the leakage current test curve for the symmetry capacitor that embodiment 2 assembles.
【Fig. 7】For the cyclical stability test curve for the symmetry capacitor that embodiment 2 assembles.
Specific implementation mode
Following specific examples is intended to further illustrate the content of present invention, is not intended to limit the present invention claimed
Range.
Embodiment 1
6.32g absolute ethyl alcohols, 72.00g water, 2.08g is taken to contain poly- (2- acrylamide-2-methylpro panesulfonic acids) (referred to as
PAMPS, mass fraction 20%) aqueous solution be added in 250mL beakers, stir.Then be added 1.86g aniline in
In above-mentioned mixed liquor, the above-mentioned mixture system containing aniline is warming up to 80 DEG C, and magnetic force at this temperature after ultrasonic 10min
Stir 10min.It it is 80 DEG C by temperature, the aqueous solution of the 40mL containing 4.56g ammonium persulfates is rapidly joined containing the above-mentioned of aniline
In mixed liquor, 80 DEG C of constant temperature reacts 60s under agitation.In the ice-water bath for being then 0-5 DEG C by reaction system transposition temperature
The reaction was continued 12h.It using acetone demulsification, washing, filters, obtains hollow polyaniline microspheres.The hollow polyaniline microspheres that will be obtained
It is added in the 50mL aqueous solutions containing 0.36g cerous nitrates (III), magnetic agitation 12h, filters, washes, is dried to obtain at room temperature
Surface doping has the hollow polyaniline microspheres of rare-earth cerium ion.Doping is about 20%.
Surface doping prepared by the electron scanning micrograph display of Fig. 1 has the polyaniline microsphere outer diameter of trivalent cerium ion
About 380nm, it is hollow that surface doping prepared by transmission electron microscope figure display has the polyaniline microsphere of rare-earth cerium ion to present
Structure, and wall thickness is about 67nm or so, and ball internal diameter is about 244nm or so.
Fig. 2 is the infrared spectrogram for the polyaniline microsphere that surface doping has trivalent cerium ion.1562cm-1And 1490nm-1Point
Not Wei polyaniline quinone ring and phenyl ring characteristic peak, it was demonstrated that the presence of polyaniline.1645cm-1For PAMPS characteristic peaks.1142cm-1For
C-N telescope features peak, this characteristic peak broadens after rare earth doped cerium ion, in 1105cm-1Place also occur peak position illustrate cerium ion with
Electron rich N is acted synergistically.
Embodiment 2
There is the polyaniline microsphere of trivalent cerium ion for button type ultracapacitor with surface doping made from embodiment 1
Composition：
It is 75 that cerium hollow polyaniline microspheres, acetylene black, ptfe emulsion, which will be mixed, according to mass ratio:15:10 ratio
Mixing, is added a small amount of absolute ethyl alcohol and is reconciled, ultrasonic 10min.It is rolled into after slurry after ultrasound is removed unnecessary alcohol
The thin slice that thickness is about 0.2mm.Using mold by slice stamping at the disk of a diameter of 10mm, it is dried in vacuo 12h at 70 DEG C and obtains
To pole piece.Using two pole pieces identical in quality as the positive and negative electrode of capacitor, centre press from both sides one layer of non-woven fibre cloth be used as every
Film, with 1mol/L H2SO4As electrolyte, 2016 type button capacitors are assembled into according to the form of Fig. 3.
Fig. 4 is that is be assembled into mix the cyclic voltammetry curve of cerium polyaniline capacitor.Cerium polyaniline is mixed as we can see from the figure
For hollow microsphere capacitor under the sweep speed of 5mV/s, there are symmetry redox peaks in cyclic voltammetry curve, shows farad
The characteristics of fake capacitance.By being calculated, in 1mA/cm2Charging or discharging current density under, mix the capacitance of cerium polyaniline electrode
Reach 248.2F/g, the 201.6F/g than polyaniline electrode is higher by 23.1%.
Fig. 5 is that is be assembled into mix the ac impedance measurement of cerium polyaniline capacitor, and corresponding fitting data is as shown in table 1.
The charge transfer resistance for adulterating the polyaniline capacitor of trivalent cerium ion is reduced to 1.215 Ω, the range of decrease from 6.223 Ω of polyaniline
Nearly 80.5%.Compared with mixing zinc ion polyaniline capacitor, this impedance value is still smaller.
The main fitting data of ac impedance spectroscopy of 1 polyaniline capacitor of table
Fig. 6 is the leakage current test curve for mixing cerium polyaniline capacitor, and corresponding calculating data are as shown in table 2.Data are aobvious
Show that trivalent cerium ion can promote the voltage maintenance ability of capacitor.The leakage current of cerium polyaniline capacitance is mixed from polyaniline capacitor
0.2982mA be reduced to 0.1481mA, decrease by 50.3%, will than mixing the 0.2308mA of polyaniline capacitor of zinc ion
It is low.
The leakage current test data of 2 polyaniline capacitor of table
Fig. 7 is the cyclical stability test curve for mixing cerium polyaniline capacitor.Polyaniline capacitor is in 5 mA/cm2's
1000 cycles have been carried out under constant current charge-discharge density.In first 100 times, the specific capacitance of polyaniline capacitor drastically reduces, table
Bright polyaniline electrode has poor cyclical stability.It is more slow than the specific capacitance range of decrease of other capacitors to mix cerium polyaniline capacitor
Slowly, illustrate that mixing cerium polyaniline capacitor has the more preferable ability for maintaining specific capacitance stability.After cycle 500 times, polyaniline
The specific capacitance of capacitor reduces trend and slows down.But the capacitor of cerium ion and zinc ion is adulterated still than polyaniline capacitor table
Reveal higher specific capacity.After cycle 1000 times, the specific capacitance of polyaniline capacitor is reduced to deficiency from initial 183.8F/g
60F/g；The specific capacity for mixing cerium polyaniline capacitor remains to maintain to arrive 85F/g.
Comparative example 1
By hollow polyaniline microspheres, acetylene black, ptfe emulsion according to mass ratio be 75:15:10 ratio mixing,
A small amount of absolute ethyl alcohol is added to be reconciled, ultrasonic 10min.It is rolled into thickness about after slurry after ultrasound is removed unnecessary alcohol
For the thin slice of 0.2mm.Using mold by slice stamping at the disk of a diameter of 10mm, it is dried in vacuo 12h at 70 DEG C and obtains pole piece.
Using two pole pieces identical in quality as the positive and negative electrode of capacitor, centre one layer of non-woven fibre cloth of folder as diaphragm, with
1mol/L H2SO4As electrolyte, 2016 type button capacitors are assembled into according to the form of Fig. 3.
Polyaniline capacitor is in 1mA/cm2Charging or discharging current density under, specific capacitance 201.6F/g；The exchange of capacitor hinders
Anti- data show that the charge transfer resistance of electrode is 6.233 Ω；The leakage current density of capacitor is 0.2982mA.
Comparative example 2
It is 75 that zinc ion hollow polyaniline microspheres, acetylene black, ptfe emulsion, which will be mixed, according to mass ratio:15:10
Ratio mixes, and a small amount of absolute ethyl alcohol is added and is reconciled, ultrasonic 10min.It is ground after slurry after ultrasound is removed unnecessary alcohol
It is pressed into the thin slice that thickness is about 0.2mm.Using mold by slice stamping at the disk of a diameter of 10mm, it is dried in vacuo at 70 DEG C
12h obtains pole piece.Using two pole pieces identical in quality as the positive and negative electrode of capacitor, centre presss from both sides one layer of non-woven fibre cloth
As diaphragm, with 1mol/L H2SO4As electrolyte, 2016 type button capacitors are assembled into according to the form of Fig. 3.
Zinc ion polyaniline capacitor is mixed in 1mA/cm2Charging or discharging current density under, specific capacitance 239.8F/g；Capacitor
Impedance data show that the charge transfer resistance of electrode is 1.921 Ω；The leakage current density of capacitor is 0.2308mA.
Claims (8)
1. a kind of symmetry button type electrode material for super capacitor, it is characterised in that：The super electricity of symmetry button type
Container electrode material is made of following content of component：
Surface doping has 70~80 parts of the hollow polyaniline microspheres of trivalent cerium ion；
10~20 parts of acetylene black；
5~15 parts of the ptfe emulsion that solid content is 55~65%；
Active material is the hollow polyaniline microspheres that surface doping has trivalent cerium ion；The surface doping has trivalent cerium ion
Hollow polyaniline microspheres outer diameter be 340~420nm, internal diameter be 220~260nm, conductivity be 8.95~47.46S/cm,
The mass percentage content of trivalent cerium ion is 5~30%.
2. symmetry button type electrode material for super capacitor according to claim 1, it is characterised in that：By following quality
Part group is grouped as：
Surface doping has 75 parts of the hollow polyaniline microspheres of trivalent cerium ion；
15 parts of acetylene black；
10 parts of the ptfe emulsion that solid content is 60%.
3. symmetry button type electrode material for super capacitor according to claim 1, it is characterised in that：The surface
It is prepared via a method which to obtain doped with the hollow polyaniline microspheres of trivalent cerium ion：By aniline containing poly- (2- acrylamides
Base -2- methyl propane sulfonic acids) solution in hollow polyaniline microspheres are prepared by self-assembly method, hollow polyaniline microspheres are in cerous nitrate
(III) there are the hollow polyaniline microspheres of trivalent cerium ion in solution after stirring doping to get surface doping.
4. a kind of symmetry button type ultracapacitor, including capacitor case, positive plate, negative plate, diaphragm and electrolyte,
It is characterized in that：The positive plate and negative plate is by claims 1 to 3 any one of them symmetry button type super capacitor
Device electrode material is made.
5. symmetry button type ultracapacitor according to claim 4, it is characterised in that：Symmetry button type is super
Capacitor electrode material is reconciled with organic solvent, and ultrasonic disperse obtains slurry；After gained slurry volatilization removal partial solvent, grind
It is pressed into thin slice, further strikes out disk, disk is by being dried in vacuo to get to positive plate or negative plate.
6. symmetry button type ultracapacitor according to claim 4, it is characterised in that：The diaphragm is that nonwoven is fine
Wei Bu.
7. symmetry button type ultracapacitor according to claim 4, it is characterised in that：The electrolyte is 0.5
The H of~1M2SO4Solution.
8. symmetry button type ultracapacitor according to claim 4, it is characterised in that：The capacitor case is
2016 type button type casing of lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510909523.2A CN105513825B (en) | 2015-12-09 | 2015-12-09 | A kind of symmetry button type electrode material for super capacitor and symmetry button type ultracapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510909523.2A CN105513825B (en) | 2015-12-09 | 2015-12-09 | A kind of symmetry button type electrode material for super capacitor and symmetry button type ultracapacitor |
Publications (2)
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| CN101241803A (en) * | 2008-03-11 | 2008-08-13 | 清华大学 | A poly-bile mixed super capacitor and its making method |
| CN104637699A (en) * | 2015-02-12 | 2015-05-20 | 福建师范大学 | Method for preparing super capacitor on basis of three-dimensional porous graphene composite material |
| CN104629071A (en) * | 2015-02-03 | 2015-05-20 | 中南大学 | Preparation method of polyaniline hollow microspheres with rare earth cerium ions loaded on surfaces |
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| CN101241803A (en) * | 2008-03-11 | 2008-08-13 | 清华大学 | A poly-bile mixed super capacitor and its making method |
| CN104629071A (en) * | 2015-02-03 | 2015-05-20 | 中南大学 | Preparation method of polyaniline hollow microspheres with rare earth cerium ions loaded on surfaces |
| CN104637699A (en) * | 2015-02-12 | 2015-05-20 | 福建师范大学 | Method for preparing super capacitor on basis of three-dimensional porous graphene composite material |
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