WO2007108524A1 - 電気二重層キャパシタ用電極および電気二重層キャパシタ - Google Patents
電気二重層キャパシタ用電極および電気二重層キャパシタ Download PDFInfo
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- WO2007108524A1 WO2007108524A1 PCT/JP2007/055927 JP2007055927W WO2007108524A1 WO 2007108524 A1 WO2007108524 A1 WO 2007108524A1 JP 2007055927 W JP2007055927 W JP 2007055927W WO 2007108524 A1 WO2007108524 A1 WO 2007108524A1
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- WIPO (PCT)
- Prior art keywords
- electric double
- electrode
- double layer
- current collector
- layer capacitor
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/74—Terminals, e.g. extensions of current collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an electrode for an electric double layer capacitor and an electric double layer capacitor.
- electric double layer capacity capable of charging and discharging with a large current has been regarded as promising as a power storage device with high charging / discharging frequency, such as an auxiliary power source for electric vehicles, an auxiliary power source for solar cells, and an auxiliary power source for wind power generation. . Therefore, an electric double layer capacity with high energy density, rapid charge / discharge, and excellent durability is desired.
- the electric double layer capacitor has a structure in which a pair of polarizable electrode layers are opposed to each other through a separator and serve as a positive electrode and a negative electrode.
- Each polarizable electrode layer is impregnated with an aqueous electrolyte solution or a non-aqueous electrolyte solution, and each polarizable electrode layer is bonded to a current collector.
- a water-based electrolyte solution can increase the capacitance density and reduce the resistance value, but the working voltage must be less than the voltage at which water electrolysis occurs, so the energy density is increased.
- a non-aqueous electrolyte is used for.
- graphite-like carbon material As a polarizable electrode material used in an electric double layer capacitor, a carbon material having graphite-like microcrystalline carbon (hereinafter referred to as “graphite-like carbon material”) is known. 1 7 3 3 3, JP 2 0 0 0 — 0 7 7 2 7 3, JP 2 0 0 0 — 0 6 8 1 6 4, JP 2 0 0 0 — 0 6 No. 8 1 6 5 and JP 2 0 0 0— 1 0 0 6 No. 6 8 and Japanese Unexamined Patent Publication No. 2 0 0 4-2 8 9 1 3 0).
- This carbon material has a crystallite-like microcrystalline carbon crystallite interlayer distance (d.
- microcrystalline carbon having such a specific interlayer distance is brought into contact with the electrolyte solution and a voltage higher than the voltage normally used (rated voltage) is applied, an electrolyte ion is inserted between the carbon crystal layers to electrically Activation (electric field activation) occurs, and as a result, a high capacitance is exhibited (electric field activation type capacitance).
- a graphite-like carbon material maintains a high capacitance even after repeated use at a rated voltage once ions are inserted and pores are formed.
- Graphite-like charcoal material has a higher withstand voltage and can significantly increase energy density compared to activated carbon, which is generally used as a carbon material for electric double layer capacitors. Collecting.
- Graphite-like carbon material expands due to the insertion of electrolyte ions during charging. Therefore, the capacitance per unit volume (capacitance density) is offset by expansion even for black lead-like carbon materials that exhibit high capacitance by electric field activation.
- a cell structure capable of suppressing electrode expansion is used in the electric field activation type capacitor (Japanese Patent Laid-Open No. 2000-066). No. Gazette, JP 2 0 0 0-0 6 8 1 6 5).
- a current collector is bonded to the polarizable electrode layer used in the electric double layer capacity.
- a current collector in addition to a general non-hole current collector, a current collector having a through-hole to improve adhesion to the activated carbon electrode (Japanese Patent Laid-Open No. 2000-125).
- a porous body having a three-dimensional network structure Japanese Patent Laid-Open No. 6-2 3 6 8 2 9)
- mesh-like ones having a large number of pores Japanese Patent Application Laid-Open No.
- any current collector having such a hole is used in combination with an activated carbon electrode, and there is no example in combination with the above-described black lead-like carbon material. This is because, in the case of a graphite-like carbon material having a large expansion / contraction during charging / discharging, there is a concern that the structure of the current collector having pores may be deformed or the mesh may be broken. When a large pressure is applied to the electrode from the outside by means of suppressing expansion, it is not necessary to provide a through-hole in the current collector or to make it a porous body in order to improve adhesion and contact with the electrode Because.
- Capacitors using activated carbon electrodes have almost no deterioration in performance during cycle operation as described later, so current collectors with through-holes with high manufacturing costs and porous materials are used. There wasn't. Therefore, in an electric double layer capacitor using a graphite-like carbon material as a polarizable electrode material, an aluminum plate, an aluminum foil, or the like, generally having no holes or a foil, is used as a current collector. Disclosure of the invention
- an object of the present invention is to provide an electric double layer capacitor electrode and an electric double layer capacitor which can sufficiently bring out the electrode performance of the graphite-like carbon material by preventing the deterioration of the cycle characteristics described above.
- An electric double layer capacitor electrode comprising a polarizable electrode layer containing a carbon material having microcrystalline carbon similar to graphite and laminated on at least one surface of a sheet-like current collector,
- the carbon material has a BET specific surface area of not more than 800 m 2 by a nitrogen adsorption method
- the sheet-like current collector has a void on the surface in contact with the polarizable electrode layer.
- An electrode for an electric double layer capacitor is provided.
- the volume of the gap is 0 per unit area of the sheet-like current collector.
- an electric double layer capacitor electrode as described in (1) in the range of 0 0 0 2 to 0.0 0 8 cm 3 / cm 2 .
- the openings are a plurality of through holes arranged substantially evenly.
- An electrode for an electric double layer capacitor described in (3) or (4) is provided.
- the carbon material having microcrystalline carbon similar to graphite is obtained by X-ray diffraction method. Interlayer distance when not charged by d.
- An electric double layer capacity including the electrode according to any one of (1) to (6) and a means for suppressing expansion of the electrode during charging is provided.
- FIG. 1 is a schematic top view showing a method for punching a polarizable electrode produced in the example.
- An electrode for an electric double layer capacitor comprises a polarizable electrode layer containing a carbon material having a microcrystalline carbon similar to graphite as a sheet-like current collector having a gap on a surface in contact with the polarizable electrode layer. It is characterized by being laminated.
- the present inventors have found that the cycle characteristics of the electric double layer capacity can be improved by providing a gap on the surface of the sheet-like current collector that is in contact with the polarizable electrode layer. This is because the electrolyte stored in the voids of the sheet-shaped current collector makes it easier to supply the electrolyte to the pores of carbon formed during electroactivation, and is similar to graphite during charging even after electroactivation.
- the space containing the electrolytic solution inside the polarizable electrode layer is reduced, so that the electrolytic solution is pushed out of the polarizable electrode layer, and the electrolytic solution is stored in the gap.
- this stored electrolyte is re-supplied into the polarizable electrode layer.
- a plate-shaped or foil-shaped current collector that has not been used in the past is difficult to supply an electrolytic solution to the pores of carbon formed at the time of electrolytic activation, and is also charged after electrolytic activation.
- electrolyte ions are inserted between the carbon crystal layers of the graphite-like carbon material to cause expansion, so that the space containing the electrolyte inside the polarizable electrode layer is reduced, and as a result, is contained in the space.
- the electrolyte solution was pushed out of the polar electrode layer and oozed out from the periphery of the plate-like or foil-like current collector. During the subsequent discharge, the current collector hinders the polarizable electrode layer. Electrolyte is not sufficiently supplied to the inside, and as a result, the electrolyte is locally insufficient. Therefore, when charging and discharging are repeated as an electric double layer capacitor, the capacitance decreases and the internal resistance increases (cycle) Phenomenon). Is assumed that Tsu.
- the electrolyte is sufficiently supplied to the polarizable electrode layer. It is thought that the amount is maintained and the rise in internal resistance is suppressed.
- the sheet-like current collector according to the present invention has a gap on the surface in contact with the polarizable electrode layer that can store the electrolyte solution extruded from the polarizable electrode layer during charging of the electric double layer capacitor. Is. In light of this onset bright object, the volume of such void portions, per unit area of the sheet-like current collector, typically 0. 0 0 0 2 ⁇ 0. 0 0 8 cm 3 / cm 2, rather preferably 0.
- the void portion according to the present invention can be provided by providing a concave or convex portion on the surface of the sheet-like current collector or by forming an opening in the sheet-like current collector.
- the shape of the gap can be any shape, such as a circle, an oval, a rectangle, a polygon, a diamond, a cross, a groove, and a slit, regardless of the unevenness or opening.
- the opening ratio is 10 to 80%, preferably 15 to 70%, more preferably 1 regardless of the shape. It is in the range of 5 to 50%. If the opening ratio of the opening is less than 10%, the electrolyte pushed out from the polarizable electrode layer during charging cannot be sufficiently stored. On the other hand, if the aperture ratio is greater than 80%, the mechanical strength of the current collector becomes insufficient, the conductivity decreases, and the internal resistance increases.
- the openings formed in the sheet-shaped current collector are preferably a plurality of through-holes arranged substantially evenly.
- the diameter of the through hole is preferably in the range of 0.3 to 10 mm, more preferably 0.5 to 5 mm, and still more preferably 0.5 to 3 mm. If the diameter of the through hole is smaller than 0.3 mm, the electrolyte extruded from the polarizable electrode layer during charging cannot be sufficiently stored. On the other hand, if the through hole is larger than 10 mm, the mechanical strength of the current collector becomes insufficient, the conductivity decreases, and the internal resistance increases.
- the pitch of the plurality of through holes arranged approximately evenly is preferably 1.05 to 5 times, more preferably 1.1 to 3 times the hole diameter. Is in. If the pitch is shorter than 1.05 times, the mechanical strength of the current collector becomes insufficient, the conductivity decreases, and the internal resistance increases. On the other hand, when the pitch is longer than 5 times, the electrolyte pushed out from the polarizable electrode layer during charging cannot be sufficiently stored.
- any metal having high conductivity that does not cause dissolution / deposition in the operating voltage range can be used as appropriate.
- Various sheet materials including non-metal such as metal such as copper, conductive polymer film, and plastic film containing conductive filler can be used.
- mechanical processing such as punching press processing, embossing processing, laser one processing, expansion processing, mesh processing, etc. can be appropriately selected.
- the thickness of the sheet-like current collector is preferably in the range of 15 to 100 m, more preferably 20 to 70 m.
- the thickness is less than 15, the mechanical strength of the current collector becomes insufficient and the internal resistance increases, resulting in increased heat generation during discharge at high current. In addition, the manufacturing cost of the current collector is high, which is not practical. Opposite On the other hand, if the thickness is greater than 100, the volume of the current collector increases and the energy density of the electric double layer capacity decreases.
- the specific surface area of the graphite-like carbon material is preferably not more than 800 m 2 / g, more preferably not more than 500 m 2 / g, particularly preferably not more than 300 m 2 / g.
- this specific surface area exceeds 80 O m 2 / g, the amount of functional groups present on the surface of the graphite-like carbon material increases, and these functional groups cause an electrochemical reaction when a voltage is applied.
- the performance of multi-layer capacity is significantly reduced.
- impurities such as chemical substances used for activation and cleaning remain in the pores, leading to deterioration of durability.
- the ratio area is measured by adsorption isotherm by nitrogen adsorption method using “ASAP 20 100” manufactured by Shimadzu Corporation (Pretreatment temperature: 200, Drying time: 4 hours) It is the value analyzed by the BET method.
- the electrode is fired at about 400 ° C for about 2 hours, the current collector is peeled off, and the binder is decomposed. Isolate. Then, the obtained graphite-like carbon material is washed with ethanol and dried before measurement.
- a conductive auxiliary material is included as an electrode material, the specific surface area of the conductive auxiliary material must be subtracted from the measurement result.
- the graphite-like carbon material used as the polarizable electrode layer in the electric double layer capacitor electrode according to the present invention has microcrystalline carbon.
- Graphite-like carbon materials have a microcrystalline carbon interlayer distance d QQ 2 (according to X-ray diffraction method) in a specific range, that is, 0.35 0 to 0.385 nm, exceeding the rated voltage.
- electrolyte ions are inserted between microcrystalline carbon crystal layers, and show high capacitance as a polarizable electrode.
- the interlayer distance d Q () 2 is in the range of 0.35 5 to 0.37 0 nm, the electrostatic capacity is clearly manifested by the insertion of electrolyte ions between the crystal layers.
- This interlayer distance d Q () 2 is 0.3 5 0 Below the nm, electrolyte ions are less likely to be inserted between crystal layers, so the rate of increase in capacitance is low. Conversely, when this interlayer distance d 002 exceeds 0.385 nm, it is difficult for electrolyte ions to enter the crystal layer, and the amount of functional groups present on the surface of the graphite-like carbon material increases. It is not preferable because the performance of the electric double layer capacity is remarkably deteriorated due to the decomposition of these functional groups when a voltage is applied.
- the graphite-like carbon material can be a low-temperature calcined carbon material that has not been activated.
- Plant-based wood, coconut husk, pulp waste liquor, fossil fuel-based coal, heavy petroleum oil It can be produced using various materials such as coal, petroleum-based pitch, cox, synthetic resin such as phenol resin, furan resin, polyvinyl chloride resin, and polyvinyl chloride resin.
- synthetic resin such as phenol resin, furan resin, polyvinyl chloride resin, and polyvinyl chloride resin.
- two or more types of carbon materials with different raw materials and manufacturing methods can be mixed and used.
- heat treatment can be performed in an inert atmosphere before activation to prevent the activation from proceeding significantly, or treatment such as shortening the activation operation can be performed.
- the heat treatment temperature is preferably that which has been fired at a relatively low temperature of about 600 to 100 ° C.
- Other graphite-like carbon materials suitably used in the present invention and methods for producing the same are disclosed in Japanese Patent Application Laid-Open Nos. 11-1 3 1 7 3 3 and 2 0 0 0 — 0 7 7 2 7 3, JP 2 0 0 0 — 0 6 8 1 6 4, JP 2 0 0 0 — 0 6 8 1 6 5, JP 2 0 0 Reference should be made to Japanese Patent Application Publication Nos.
- the graphite-like carbon material is a polarizable electrode within a range of 50 to 99% by mass, preferably 65 to 95% by mass, based on the total mass of the conductive auxiliary material and the binder that will be described later. Included in the layer. If the content of graphite-like carbon material is less than 50% by mass, the energy density of the electric double layer capacitor will be low. On the other hand, if the content exceeds 99 mass%, the binder will be insufficient and it will be difficult to hold the carbon material in the electrode layer.
- the polarizable electrode layer according to the present invention generally contains a conductive auxiliary material for imparting conductivity to the graphite-like carbon material.
- a conductive auxiliary material carbon black such as ketjen black and acetylene black, gas-grown carbon fiber, fullerene, bonbon nanotube, nanocarbon such as carbon nanohorn, powdery or granular graphite, etc. should be used. Can do.
- the conductive auxiliary material may be added in an amount of preferably 1 to 40% by mass, more preferably 3 to 20% by mass, based on the total mass of the graphite-like carbon material and the binder. . When the amount of the conductive auxiliary material added is less than 1% by mass, the internal resistance of the electric double layer capacitor increases. On the other hand, when the added amount exceeds 40% by mass, the energy density of the electric double layer capacitor decreases.
- the polarizable electrode layer according to the present invention generally contains a binder for binding the graphite-like carbon material and the conductive auxiliary material. Binders include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), polypropylene (PP), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), etc. Can be used.
- the binder is preferable to the total mass of the graphite-like carbon material and the conductive auxiliary material. Preferably, an amount of 1 to 30% by mass, more preferably 3 to 20% by mass may be added.
- the amount of binder added is less than 1% by mass, it will be difficult to hold the carbonaceous material in the electrode layer. On the other hand, if the added amount exceeds 30% by mass, the energy density of the electric double layer capacitor is lowered and the internal resistance is increased.
- the polarizable electrode layer according to the present invention can be produced by the same sheet forming method and coating method (coating method) as in the case of using conventional activated carbon.
- the graphite-like carbon material obtained by the above-described method is adjusted in particle size so that the average particle size D 50 is about 5 to 200 m, and then added to the conductive auxiliary material.
- a binder can be added and mixed, and the sheet can be formed by rolling.
- liquid auxiliary agents such as water, ethanol, and acetonitrile may be used alone or in combination as appropriate.
- the thickness of the polarizable electrode layer is preferably from 50 to 100 m, and more preferably from 60 to 500 m.
- the thickness of the electrode layer is a value measured using a dial thickness gauge “SM-528” manufactured by Teclock Co., Ltd. without applying any load other than the main body spring load.
- the polarizable electrode layer and the sheet-like current collector When the polarizable electrode layer and the sheet-like current collector are integrated, they can function by simply pressing them together, but in order to reduce the contact resistance between them, a conductive paint is used as an adhesive. After joining the polar electrode layer and the sheet-like current collector, or applying a conductive paint to the polarizable electrode layer or the sheet-like current collector and drying, the polarizable electrode layer and the sheet-like current collector are bonded to each other. It may be crimped. However, when the polarizable electrode layer and the sheet-like current collector are bonded or pressure-bonded, the surface of the sheet-like current collector that contacts the polarizable electrode layer is provided. The essential voids must be formed.
- the opening of the sheet-shaped current collector must not be substantially filled with the conductive paint and / or the carbon material of the polarizable electrode layer by bonding or crimping.
- a required gap may be formed only on the surface of the sheet-like current collector that is in contact with the polarizable electrode having a large expansion and contraction.
- the negative electrode has a larger electrode expansion due to the difference in the ionic diameter of the electrolyte, so the sheet-shaped current collector in contact with the polarizable electrode of the negative electrode A required gap may be formed only on the surface.
- the electric double layer capacitor has a structure in which a pair of electrodes each formed by integrating a polarizable electrode layer and a sheet-like current collector are opposed to each other via a separator, and used as a positive electrode and a negative electrode.
- insulating materials such as microporous paper, glass, and plastic porous films such as polyethylene, polypropylene, polyimide, and polytetrafluoroethylene can be used.
- the thickness of a separate evening is generally about 10 to 100 m. Two or more sheets may be stacked for a separate evening.
- the pressure applied to the polarizable electrode layer during charging is preferably set within the range of 0.2 to 30 MPa, more preferably 0.3 to 20 MPa. Can be determined. If the set pressure is less than 0.2 MPa, expansion of the graphite-like carbon material during charging cannot be sufficiently suppressed, resulting in insufficient capacitance density and expansion / contraction width. If the electric material is deformed or the polarizable electrode layer is peeled off, the internal resistance increases and the durability may be insufficient. On the other hand, if the set pressure is greater than 30 MPa, the gap inside the electrode may be crushed and the diffusion resistance of the electrolyte may be increased, the separator may be crushed and the internal resistance may be increased, or a short circuit may occur.
- the void formed on the surface of the sheet-like current collector in contact with the polarizable electrode layer should not be substantially crushed by the pressurization for suppressing the expansion of the graphite-like carbon material.
- the expansion of the electrode is completely suppressed, the insertion of electrolyte ions between the crystal layers of the graphite-like carbon material becomes insufficient, and the effect of improving the electrostatic capacity becomes small, so the expansion of about 3 to 60% It is preferable to set the external pressure to occur.
- electrolyte of the electrolytic solution conventionally used quaternary ammonium salts, quaternary imidazolium salts, quaternary pyridinium salts, quaternary pyrrolidinium salts, quaternary phosphonium salts, etc., alone or in a mixture of two or more.
- BF 4 —, PF 6 _, A s F 6 —, C l o 4 —, CF 3 S o 3 —, from the viewpoint of electrochemical stability and molecular ion diameter (CF 3 S 0 2 ) 2 N—, A 1 C 1 4 ′′, S b F 6 — and the like are preferable, and BF 4 _ is particularly preferable.
- the electrolyte When the electrolyte is liquid at room temperature, it may be used without being diluted as it is, but in general, it is preferably used as an electrolytic solution dissolved in an organic solvent.
- an organic solvent can reduce the viscosity of the electrolyte and suppress the increase in the internal resistance of the electrode.
- electrolyte It is selected depending on the solubility of the resin and the reactivity with the electrode, but carbonates such as ethylene carbonate, propylene carbonate, jetyl carbonate, butylene carbonate, dimethyl carbonate, vinylene carbonate, and lactols such as aptilolactone.
- dialkyl ketones such as methyl ethyl ketone and methyl isoptyl ketone
- organic solvents such as N-methylpyrrolidone and nitromethane.
- the organic solvent may be used alone or as a mixed solvent in which two or more kinds are combined. Since the electrolyte ion inserted between the crystal layers of the graphite-like carbon material during electric field activation is considered to be solvated with the surrounding solvent, it is preferable to use a solvent having a small molecular volume.
- the concentration of the electrolyte in the electrolytic solution is preferably 0.5 mol ZL or more, and more preferably 1.0 mol ZL or more.
- the upper limit of the electrolyte concentration is the solubility determined by the combination of the specific electrolyte and organic solvent.
- Electric field activation can be performed by applying a voltage higher than the rated voltage with a relatively small current value.
- the method of activating the electric field refer to the conventional method (Japanese Patent Laid-Open No. 2 0 00-1 0 0 6 6 8).
- a petroleum pitch-based carbon material (500 g) was pulverized with a pulverizer to produce a powder with D 50 of 20 and calcined by carbonizing it in an inert atmosphere at a temperature of 800 ° C. Obtained.
- This carbonized material was mixed with potassium hydroxide in an amount twice as large as the mass ratio, and activated in an inert atmosphere at 700. Thereafter, it was cooled to room temperature, washed with water, alkali content was removed and dried.
- the obtained graphite-like carbon material had a BET specific surface area of 100 m 2 g, and an interlayer distance d 0 02 of microcrystalline carbon by an X-ray diffraction method of 0.365 nm.
- Ketjen black powder (“Ketjen Blackine Yuna National Co., Ltd.“ EC 600 JD ”) as a conductive auxiliary material
- polytetraflur as a binder Polyethylene powder (“Teflon (registered trademark) 6 J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 10% by mass was added to ethanol and mixed, and then extruded into a tape shape. Thereafter, the obtained tape-like product was rolled and rolled three times to form a sheet, and further dried at 1550 ° C.
- Punched aluminum foil with a width of 160 mm and a thickness of 50 Punched aluminum foil (A 1 N 3 0 H—H 1 8) manufactured by Showa Denko KK) (hole diameter: 1 mm, pitch) 2 mm, open area 23%, void volume 0.0 0 1 2 cm 3 / cm 2 , 60 ° staggered arrangement, lead part 60 mm is not punched)) on one side
- Apply the conductive adhesive liquid (“GA-3 7” manufactured by Hitachi Powdered Metals Co., Ltd.) with a brush so that the hole is not completely filled.
- the size of the carbon electrode part of this polarizable electrode is 2 cm square, and the lead part (the part where the polarizable electrode layer is not laminated on the current collector) is 1 X 5
- a square-polarized polar electrode was formed by punching to a cm shape.
- Stretched porous polytetrafluoroethylene sheet manufactured by Japan Gore-Tex Co., Ltd.
- two polarizable electrode bodies as a positive electrode and a negative electrode
- a hydrophilization treatment with a thickness of 80 m and 3 cm square between them as a separator.
- This aluminum pack cell is vacuum-dried at 160 ° C for 48 hours, then brought into a glove box with a dew point of 60 ° C or less in an argon atmosphere, and 1.5 mol / L as an electrolyte.
- a punching Arumini ⁇ beam foil (pore size 1 mm, pitch 1. 5 mm, opening ratio 4 0% void volume 0. 0 0 2 cm 3 / cm 2, 6 0. Staggered lead portion Punching A capacitor was assembled in the same manner as in Example 1 except that no processing was used.
- a capacitor assembly was assembled in the same manner as in Example 1 except that a 50 m thick etched aluminum foil (“K 5 1 2” manufactured by KD K Corporation) was used as the current collector.
- Example 1 and Example 1 were used except that a 5 Om thick etched aluminum foil (“C 5 1 2” manufactured by KD K Corporation) was used as the current collector and the applied pressure was 0.4 MPa. In the same way, Capashi Yu was assembled.
- C 5 1 2 manufactured by KD K Corporation
- a capacitor assembly was assembled in the same manner as in Example 1 except that the applied pressure was set to 0.05 MPa.
- a 30 m thick punched aluminum foil (pore diameter 0.1 mm, pitch 0.4 mm, aperture ratio 4.8%, void volume 0.0 0 0 0 1 cm 3 / cm 2 , 6 0 ° Staggered arrangement and the lead part without punching) was used in the same way as in Example 1. I made it.
- Capillaries were assembled in the same manner as in Example 1 except that steam-activated activated carbon (specific surface area 1700 m 2 / g) using coconut shell as a raw material was used as the carbon material.
- steam-activated activated carbon specific surface area 1700 m 2 / g
- Capacitors were assembled in the same manner as in Comparative Example 1 except that steam activated carbon (specific surface area 1700 m 2 / g) using coconut shell as a raw material was used as the carbon material.
- the capacitance at the 100th cycle was determined by an energy conversion method, and calculated by dividing the capacitance by the volume of the positive and negative electrode carbon electrodes not including the current collector after expansion. (Internal resistance)
- the cell was disassembled and observed for changes in the electrode / current collector interface.
- the capacitors including the electric double layer capacitor according to the present invention are high even if strong pressure is applied to suppress electrode expansion during charging.
- the capacitance density and low internal resistance were maintained, and the cycle characteristics were found to be excellent.
- Comparative Examples 1 and 2 although the expansion coefficient was the same as in Examples 1 and 2, respectively, the current collector had no voids, so the capacitance density decreased and the internal resistance increased.
- Comparative Example 3 although there was a gap in the current collector, the pressurization was insufficient and the expansion rate increased, thereby decreasing the capacitance density and increasing the expansion / contraction width. The part has peeled off.
- Comparative Example 4 although the electrode expansion was suppressed, the gap portion was insufficient, so that the capacitance density and the internal resistance were inferior to those of Examples 1 to 4.
- Comparative Example 5 is an example in which a perforated current collector is combined with an activated carbon electrode.
- the activated carbon is inherently deteriorated in cycle characteristics due to expansion / contraction during charging / discharging ( Since there is no problem of decrease in capacitance maintenance rate and increase in internal resistance, “improvement of cycle characteristics” is not recognized as the purpose of use of the perforated current collector.
- Capacitance density By comparing Examples 1 to 4 (2 3. 3. to 2 et al. 6 F / cm 3 ) with Comparative Examples 1 to 4 (1 5.3 to 20 F / cm 3 ), It can be seen that the inherently high capacitance of the material has been sufficiently extracted by the present invention.
- the cycle characteristics of the electric double layer capacity are improved.
- the electrode performance of graphite-like carbon material can be further enhanced.
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Abstract
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EP07739369A EP1998346A1 (en) | 2006-03-17 | 2007-03-15 | Electrode for electric double layer capacitor and electric double layer capacitor |
US12/225,284 US20100226069A1 (en) | 2006-03-17 | 2007-03-15 | Electrode for Electric Double Layer Capacitor and Electric Double Layer Capacitor |
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- 2007-03-15 US US12/225,284 patent/US20100226069A1/en not_active Abandoned
- 2007-03-15 EP EP07739369A patent/EP1998346A1/en not_active Withdrawn
- 2007-03-15 CN CNA200780017002XA patent/CN101443864A/zh active Pending
- 2007-03-15 WO PCT/JP2007/055927 patent/WO2007108524A1/ja active Application Filing
- 2007-03-16 TW TW096109139A patent/TW200746202A/zh unknown
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EP2098485A2 (en) * | 2008-03-07 | 2009-09-09 | Samsung Electronics Co.,Ltd. | Electrode module and deionization apparatus using the same |
EP2347999A3 (en) * | 2008-03-07 | 2013-06-26 | Samsung Electronics Co., Ltd. | Electrode module and deionization apparatus using the same |
EP2098485B1 (en) * | 2008-03-07 | 2016-08-10 | Samsung Electronics Co., Ltd. | Electrode module and deionization apparatus using the same |
Also Published As
Publication number | Publication date |
---|---|
EP1998346A1 (en) | 2008-12-03 |
CN101443864A (zh) | 2009-05-27 |
US20100226069A1 (en) | 2010-09-09 |
JP2007251025A (ja) | 2007-09-27 |
TW200746202A (en) | 2007-12-16 |
JP4878881B2 (ja) | 2012-02-15 |
KR20090009809A (ko) | 2009-01-23 |
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