CN103198929A - Electrode plate of electric double layer capacitor (EDLC) and preparation method thereof - Google Patents
Electrode plate of electric double layer capacitor (EDLC) and preparation method thereof Download PDFInfo
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- CN103198929A CN103198929A CN2013100714967A CN201310071496A CN103198929A CN 103198929 A CN103198929 A CN 103198929A CN 2013100714967 A CN2013100714967 A CN 2013100714967A CN 201310071496 A CN201310071496 A CN 201310071496A CN 103198929 A CN103198929 A CN 103198929A
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- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- LDOAUKNENSIPAZ-UHFFFAOYSA-N tetrafluoroammonium Chemical compound F[N+](F)(F)F LDOAUKNENSIPAZ-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AJPPAKACCOFNEN-UHFFFAOYSA-K tetraethylazanium;phosphate Chemical group [O-]P([O-])([O-])=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC AJPPAKACCOFNEN-UHFFFAOYSA-K 0.000 description 1
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- 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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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the technical field of electric double layer capacitor manufacturing, and relates to an electrode plate of an electric double layer capacitor (EDLC) and a preparation method thereof. According to the electrode plate of the EDLC and the preparation method thereof, conductive carbon granules are embedded in one surface or two surfaces of a current collector, and the surface is bonded with electrode material through conductive adhesive; the electrode material is formed by electrode active substance, conductive agent and adhesive agent; the conductive adhesive is formed by conductive agent and rubber, and the rubber is capable of preventing current collector from being corroded electrochemically in electrolyte; and the current collector is made of aluminum foil as thick as 20um-30um, and the conductive carbon granules are embedded on the surface of the current collector with a high purity graphite bar by means of electrical spark discharge. The electrode active substance is active carbon like asphalt base ball, the specific surface area of the electrode active substance is larger than or equal to 2000m<2>/g, the grain size is 10um-23um, and the bore diameter is 1nm-3nm. By means of the electrode plate of the EDLC and the preparation method thereof, internal resistance of the EDLC is decreased, the electrochemical corrosion resistance of the EDLC current collector is improved, service life of the EDLC is prolonged, and working voltage is stabilized.
Description
Technical field
The invention belongs to super capacitor manufacturing technology field, particularly a kind of super capacitor electrode slice and preparation method thereof.
Background technology
Ultracapacitor, (Electric Double Layer Capacitor EDLC), is effective energy-storage travelling wave tube to be called double electric layer capacitor again.In order to increase energy density and power density, a direction that is widely known by the people is to reduce internal resistance, increases operating voltage and operating time.But, as described below, in reaching the process of above-mentioned target, met with all difficulties.
One of them difficulty is on the EDLC electrode metal collector one deck dielectric oxide film to be arranged.This dielectric oxide film has increased the carbon-coating of nano aperture and the contact resistance between the metal collector.The contact resistance that increases has caused the increase of internal resistance, and the efficient that has correspondingly reduced output power density and capacitor.
The method of a known elimination oxide-film effect is to utilize known mechanical treatment (for example pressurization, ultrasonic processing etc.) to embed carbon granule on the aluminium collector, yet these attempt not obtaining very good result.The aluminium collector can also be heated to fusing point (for example, utilizing resistance heating), carbon electrode be compressed on the collector of fusing then.But this needs lot of energy could allow aluminium 660 ℃ of fusings.In addition, this method can not be used for thinner aluminium collector, and EDLC normally used be exactly aluminum foil current collector.
The nano-carbon powder resistivity that forms the nano aperture carbon-coating on the electrode also is the important component part of EDLC internal resistance.The resistivity of nano-carbon powder self is to reduce another difficulty of EDLC internal resistance.
Another difficulty is the electrochemical corrosion of EDLC metal parts, especially the electrochemical corrosion of EDLC anode.Alarming is that the electrochemical corrosion meeting causes the reduction of operating voltage.
Therefore, reach than present on the market EDLC and have higher power density and the target of efficient, with regard to necessary reduction internal resistance and improve operating voltage.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of novel super capacitor electrode slice and preparation method thereof, the electrode plates of this method preparation can reduce the internal resistance of super capacitor and the operating voltage of stable super capacitor.
The electrode slice of super capacitor of the present invention comprises two kinds of single-side electrode sheet and double-face electrode sheets.
The single-side electrode sheet is to embed conductive carbon particle on one of collector surface, and this surface is by conducting resinl and the electrode material composition that is bonded together, and wherein, the area ratio of collection liquid surface embedding carbon is 50%～85%; Electrode material is made up of electrode active material, conductive agent (graphite, conductive carbon particles such as acetylene black) and adhesive (polytetrafluoroethylene), and three's mass fraction is respectively 85%～95%, 2%～10% and 3%～5%; Conducting resinl is made up of conductive agent (graphite, conductive carbon particles such as acetylene black) and rubber (Kynoar PVDF), and rubber can prevent the electrochemical corrosion of collector in electrolyte, and the quality of PVDF is 20%～60% of conducting resinl quality;
The double-face electrode sheet is all to embed conductive carbon particle on two surfaces of collector, and by conducting resinl and the electrode material composition that is bonded together, wherein, the area ratio that collection liquid surface embeds carbon is 50%～85% respectively for two surfaces; Electrode material is made up of electrode active material, conductive agent (graphite, conductive carbon particles such as acetylene black) and adhesive (polytetrafluoroethylene PTFE), and three's mass fraction is respectively 85%～95%, 2%～10% and 3%～5%; Conducting resinl is made up of Kynoar (PVDF) and conductive agent (graphite, conductive carbon particles such as acetylene black), and the quality of PVDF is 20%～60% of conducting resinl quality.
Collector is selected 20 μ m～thick aluminium foil of 30 μ m for use, by the method for spark discharge, embeds conductive carbon particle with the high purity graphite rod at collection liquid surface.
Electrode active material is to be that (be that raw material is produced granular active carbon with petroleum asphalt, the triumph petrochemical industry 1979-8-29), obtains through polybasic carboxylic acid pickling, filtration, heat treated the asphalt-base globular active carbon made of raw material again with pitch etc.Asphalt-base globular active carbon material specific area 〉=2000m after the processing
2/ g, particle diameter are 10 μ m～23 μ m, and the aperture is 1nm～3nm.
The preparation method of electrode slice of the present invention comprises the steps:
1) be raw material with the high purity graphite rod, embed conductive carbon particle with the method for spark discharge at collection liquid surface, the area ratio that embeds carbon is 50%～85%;
2) the preparation asphalt-base globular active carbon obtains electrode active material through polybasic carboxylic acid pickling, filtration, heating again;
3) add ptfe emulsion in deionized water and ethanol mixed solvent, the back that stirs adds conductive agent, and the back that stirs adds electrode active material, grinds with mortar, obtains electrode material; Then electrode material is pressed into the electrode slice of 80～100 μ m; In the electrode active material, the mass fraction of electrode active material, conductive agent and polytetrafluoroethylene adhesive is respectively 85%～95%, 2%～10% and 3%～5%; The concentration of polytetrafluoroethylene and conductive agent is 3～5wt% in deionized water and the ethanol mixed solvent, and the volume ratio of deionized water and ethanol is 1:1～2;
4) Kynoar is put into pyrrolidones and stir, put into conductive agent after the dissolving fully, continue to stir, obtain conducting resinl; Wherein the mass ratio of Kynoar, conductive agent and pyrrolidones is 1:0.67～4:7～15;
5) the thick conducting resinl of one or two surface-coated 4～5 μ m of the collector of handling in step 1); Then electrode slice and collector are bonded together by conducting resinl, dried 20～60 minutes for 120～150 ℃, 180～210 ℃ of vacuumize 5～8h, thus obtain single face and two-sided electrode slice.
Prepare stacked ultracapacitor then, barrier film and electrode slice are alternately placed, and barrier film is chosen three layers of pellicle of PP/PE/PP, the pole piece at the two poles of the earth is used the ultrasonic bonding machine welding with separately lug respectively, shell is selected three layers of aluminum plastic film composite membrane for use, injects organic electrolyte after the encapsulation, seals at last.
The solute of organic electrolyte is tetraethyl ammonium phosphate, tetra-allkylammonium, tetraethyl ammonium tetrafluoroborate, hexafluorophosphate or their mixture; Solvent is nitrile (acetonitrile, propionitrile, 3-methoxypropionitrile), lactone (gamma-butyrolacton, gamma-valerolactone etc.), carbonate (propylene carbonate, ethylene carbonate, methyl ethyl carbonate etc.), N, dinethylformamide, 1-Methyl-2-Pyrrolidone, butanone, glycol dimethyl ether, the perhaps mixed solvent of above-mentioned solvent composition, the concentration of organic electrolyte is 1mol/L.
Compared with prior art, the invention has the beneficial effects as follows the internal resistance that has reduced EDLC, improved the electrochemically resistant of EDLC collector and learned corrosive power, prolonged the useful life of EDLC, stablized operating voltage.
Description of drawings
Fig. 1: the collector schematic diagram that single face is handled;
The 1st, the conductive carbon particle of embedding aluminium foil surface, the 2nd, aluminium foil;
Fig. 2: be the collector schematic diagram of double treatment;
Fig. 3: be single-side electrode chip architecture schematic diagram, the 3rd, electrode material, the 4th, conducting resinl;
Fig. 4: be double-face electrode chip architecture schematic diagram;
Fig. 5: be stacked capacitor arrangement sectional view, the 5th, the single-side electrode sheet, the 6th, the double-face electrode sheet, the 7th, barrier film, the 8th, lug, the 9th, shell, 10 is electrolyte;
Fig. 6: the internal resistance change curve of collector under different voltages of different embodiment preparations, curve 1,2,3 is respectively embodiment 1, and embodiment 2, and embodiment 3.
Fig. 7: the time constant change curve of collector under different voltages of different embodiment preparations, curve 1,2,3 is respectively embodiment 1, and embodiment 2, and embodiment 3.
Fig. 8 adds the volume change curve under the different voltage ranges behind the conductive adhesive layer, after curve 2,3 is respectively circulation 200 times, and embodiment 2 and the volume change curve of embodiment 3 under different voltage ranges.
Embodiment
Embodiment 1
Asphalt-base globular active carbon may comprise the impurity of 0.5%wt, for example the compound of ferriferous oxide and other iron.Impurity forms oxygen-containing functional group at activated carbon surface, for example carbonyl, hydroxide, ether etc.Iron compound and oxygen-containing functional group impurity have increased the self discharge of EDLC and have shortened useful life.
Impurity can be removed by the following method: asphalt-base globular active carbon filters after the carboxylic acid pickling, collects filter residue, and filter residue is heated to 1200 ℃ from 600 ℃ under inert gas shielding.Heating process can be removed surface oxygen functional group and be increased the nano-carbon powder graphitization, strengthens conductivity.Obtain specific area 〉=2000m after the processing
2/ g, the aperture is at the active carbon of 1nm～3nm.With 600 orders and 800 purpose sieves screening particle diameter at the active carbon of 18～23 μ m as electrode active material.
Take by weighing deionized water and ethanol that volume ratio is 1:1, mix, add the PTFE(polytetrafluoroethylene) emulsion, the back that stirs adds acetylene black, continues to stir, and solid concentration is 4wt% in the mixed solvent.Mix the electrode active material after add to handle the back, grind with mortar, along with moisture and ethanol evaporate to dryness slowly, form argillaceous; With roll squeezer the argillaceous electrode material is pressed into the electrode slice of 80 μ m then.Electrode active material, acetylene black, PTFE three's mass fraction are 95%, 2% and 3%;
Select for use the thick aluminium foil of 23 μ m as collector, the method by spark discharge is raw material with the high purity graphite rod, embeds conductive carbon particle at collection liquid surface.With the graphite rod be working machine electrode A (electrode specification φ 2.5 * 40mm) as another electrode material B, uses small-power low-voltage electric spark working machine with aluminium foil, working power 120V, operating current 1A, frequency 50Hz, operating power is at 80W.It is 50% that collector embeds the carbon area ratio, thereby obtains the collector after the surface treatment.
PVDF is put into pyrrolidones stir, put into acetylene black after the dissolving fully, continue to stir, obtain conducting resinl.The mass ratio of PVDF, acetylene black and pyrrolidones is 1:2:7.
With conducting resinl after with surface treatment collector and the electrode material sheet that suppresses be bonded together the thickness 4 μ m of conductive adhesive layer.Dried 20 minutes for 150 ℃, after cutting out, 180 ℃ of vacuumize 8h obtain electrode slice to be assembled.Barrier film and electrode slice are alternately placed, the pole piece at the two poles of the earth is used the ultrasonic bonding machine welding with separately lug respectively.
With tetraethyl ammonium tetrafluoroborate (Et
4NBF
4) put into acetonitrile, fully stir, obtain the electrolyte that concentration is 1mol/L.Electrolyte is injected in the encapsulation back, seals and namely obtains the ultracapacitor monomer.
Asphalt-base globular active carbon is filtered after the carboxylic acid pickling, collect filter residue, filter residue is heated to 1200 ℃ from 600 ℃ under inert gas shielding.Obtain specific area 〉=2000m after the processing
2/ g, the aperture is at the active carbon of 1nm～3nm.With 1000 orders and 1340 purpose sieves screening particle diameter at the active carbon of 10～13 μ m as electrode active material.
Take by weighing deionized water and ethanol that volume ratio is 1:2, mix, add PTFE solution, the back that stirs adds acetylene black, continues to stir.Solid concentration is 4wt% in the mixed solvent.Mix the active carbon after the back adds processing, grind with mortar.Electrode material after will grinding with roll squeezer is pressed into the thin slice of 100 μ m.Electrode active material, acetylene black, PTFE three's mass fraction is 85%, 10% and 5%.
Selecting for use the thick aluminium foil of 23 μ m as collector, by the method for spark discharge, is raw material with the high purity graphite rod, embeds conductive carbon particle at collection liquid surface.Be the electrode A (electrode specification of working machine with the graphite rod
), as another electrode material B, use small-power low-voltage electric spark working machine with aluminium foil, working power 120V, operating current 1A, frequency 50Hz, operating power is at 80W.Collector embeds the carbon area ratio 80%.Obtain the collector after the surface treatment.
PVDF is put into pyrrolidones stir, put into graphite after the dissolving fully, continue to stir, obtain conducting resinl.The mass ratio of PVDF, acetylene black and pyrrolidones is 1:2:15.
With conducting resinl collector and the electrode material sheet that suppresses are bonded together the thickness 5 μ m of conductive adhesive layer.Dried 60 minutes for 120 ℃, after cutting out, 180 ℃ of vacuumize 8h obtain electrode slice to be assembled.Barrier film and pole piece are alternately placed, the pole piece at the two poles of the earth is used the ultrasonic bonding machine welding with separately lug respectively.
With tetraethyl tetrafluoro ammonium phosphate (Et
4NPF
6) put into propene carbonate, fully stir, obtain the electrolyte that concentration is 1mol/L.Electrolyte is injected in the encapsulation back, seals and namely obtains the ultracapacitor monomer.
Present embodiment adopts not surface treated collector, and electrode material directly is coated on the collector, does not use conducting resinl, and other processes and embodiment 2 are in full accord.
Asphalt-base globular active carbon is filtered after the carboxylic acid pickling, collect filter residue, filter residue is heated to 1200 ℃ from 600 ℃ under inert gas shielding.Obtain specific area 〉=2000m after the processing
2/ g, average grain diameter 10 μ m, the aperture is at the electrode active material of 1nm～3nm.
Take by weighing deionized water and ethanol that volume ratio is 1:2, mix, add PTFE solution, the back that stirs adds acetylene black, continues to stir.Solid concentration is 4wt% in the mixed solvent.Mix the active carbon after the back adds processing, electrode active material, acetylene black, PTFE three's mass fraction is 85%, 10% and 5%.
Select for use the thick aluminium foil of 23 μ m as collector, electrode material directly is coated on the collector.Dried 60 minutes for 120 ℃, after cutting out, 180 ℃ of vacuumize 8h obtain electrode slice to be assembled.Barrier film and pole piece are alternately placed, the pole piece at the two poles of the earth is used the ultrasonic bonding machine welding with separately lug respectively.
With tetraethyl tetrafluoro ammonium phosphate (Et
4NPF
6) put into propene carbonate, fully stir, obtain the electrolyte that concentration is 1mol/L.Electrolyte is injected in the encapsulation back, seals and namely obtains the ultracapacitor monomer.
Respectively at 0～0.7V, 0～1.0V, 0～1.5V carry out constant current charge-discharge test (measuring current is 0.2A) with the capacitor monomer among above-mentioned three embodiment, analyze data and obtain the internal resistance of each capacitor under different test conditions.As seen from Figure 6, under capacity situation very nearly the same, the internal resistance of the treated embodiment of collector 1 and embodiment 2 not have the embodiment 3 that handles much smaller than collector, and the contrast of Fig. 7 time constant has illustrated that more the reduction of internal resistance and amount of capacity have nothing to do.
Claims (5)
1. the electrode slice of a super capacitor, it is characterized in that: be the single-side electrode sheet, the single-side electrode sheet is to embed conductive carbon particle on a surface of collector, this surface is by conducting resinl and the electrode material composition that is bonded together, wherein, the area ratio of collection liquid surface embedding conductive carbon particle is 50%～85%; Electrode material is made up of electrode active material, conductive agent graphite or acetylene black and adhesive polytetrafluoroethylene, and three's mass fraction is 85%～95%, 2%～10% and 3%～5%; Conducting resinl is made up of conductive agent and Kynoar, and the quality of Kynoar is 20%～60% of conducting resinl quality.
2. the electrode slice of a super capacitor, it is characterized in that: be the double-face electrode sheet, the double-face electrode sheet is all to embed conductive carbon particle on two surfaces of collector, two surfaces are respectively by conducting resinl and the electrode material composition that is bonded together, wherein, the area ratio of collection liquid surface embedding conductive carbon particle is 50%～85%; Electrode material is made up of electrode active material, conductive agent graphite or acetylene black and polytetrafluoroethylene adhesive, and three's mass fraction is 85%～95%, 2%～10% and 3%～5%; Conducting resinl is made up of conductive agent and Kynoar, and the quality of Kynoar is 20%～60% of conducting resinl quality.
3. the electrode slice of a kind of super capacitor as claimed in claim 1 or 2, it is characterized in that: collector is selected 20 μ m～thick aluminium foil of 30 μ m for use.
4. the electrode slice of a kind of super capacitor as claimed in claim 1 or 2, it is characterized in that: electrode active material is asphalt-base globular active carbon, its specific area 〉=2000m
2/ g, particle diameter are 10 μ m～23 μ m, and the aperture is 1nm～3nm.
5. the preparation method of the electrode slice of claim 1 or 2 described super capacitors, its step is as follows:
1) be raw material with the high purity graphite rod, use the method for spark discharge to embed conductive carbon particles on a surface or two surfaces of collector, the area ratio that embeds conductive carbon particle is 50%～85%;
2) the preparation asphalt-base globular active carbon obtains electrode active material through polybasic carboxylic acid pickling, filtration, heating again;
3) in deionized water and ethanol mixed solvent, add ptfe emulsion, add conductive agent after stirring, the back that stirs adds electrode active material, grinds with mortar, obtain electrode material, then electrode material is pressed into the electrode slice of 80～100 μ m; In the electrode active material, the mass fraction of electrode active material, conductive agent and polytetrafluoroethylene adhesive is 85%～95%, 2%～10% and 3%～5%; The concentration of polytetrafluoroethylene and conductive agent is 3～5wt% in deionized water and the ethanol mixed solvent, and the volume ratio of deionized water and ethanol is 1:1～2;
4) Kynoar is put into pyrrolidones and stir, put into conductive agent after the dissolving fully, continue to stir, obtain conducting resinl; Wherein the mass ratio of Kynoar, conductive agent and pyrrolidones is 1:0.67～4:7～15;
5) the thick conducting resinl of one or two surface-coated 4～5 μ m of the collector of handling in step 1); Then electrode slice and collector are bonded together by conducting resinl, 120～150 ℃ of oven dry 20～60 minutes, 180～210 ℃ of vacuumize 5～8h, thus obtain the electrode slice of single or double.
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