WO2013146792A1 - Condensateur hybride - Google Patents

Condensateur hybride Download PDF

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Publication number
WO2013146792A1
WO2013146792A1 PCT/JP2013/058817 JP2013058817W WO2013146792A1 WO 2013146792 A1 WO2013146792 A1 WO 2013146792A1 JP 2013058817 W JP2013058817 W JP 2013058817W WO 2013146792 A1 WO2013146792 A1 WO 2013146792A1
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Prior art keywords
electrode
lithium
hybrid capacitor
positive electrode
oxide
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PCT/JP2013/058817
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English (en)
Japanese (ja)
Inventor
渉 杉本
航 清水
翔 牧野
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国立大学法人信州大学
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Priority to JP2014507921A priority Critical patent/JP6109153B2/ja
Publication of WO2013146792A1 publication Critical patent/WO2013146792A1/fr

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    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • 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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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

Definitions

  • the present invention relates to a hybrid capacitor, and more particularly to a hybrid capacitor capable of obtaining a high energy density at a high cell voltage.
  • An electrochemical capacitor is a device that uses a physical electric double layer or a pseudo double layer (a fast redox reaction on the electrode surface) with a Faraday reaction for charge accumulation.
  • the former is a charge accumulation mechanism when an activated carbon electrode is used as an active material
  • the latter is a charge accumulation mechanism when a metal oxide electrode such as RuO 2 or MnO 2 is used as an active material.
  • Electrolytic solutions used in such electrochemical capacitors can be broadly divided into two types: aqueous electrolytic solutions and nonaqueous electrolytic solutions.
  • Non-aqueous electrolytes represented by organic electrolytes are inferior in ionic conductivity compared to aqueous electrolytes.
  • the electrochemical capacitor using the non-aqueous electrolyte is advantageous in that a high cell voltage and a high energy density can be obtained because the electrolytic voltage of the electrolyte can be 3 V or higher.
  • the energy density is improved by the amount of the cell voltage being higher. Since the energy density is proportional to the square of the cell voltage, the energy density can be dramatically improved by increasing the cell voltage by 1V.
  • an ionic liquid having a wide potential window is used as the electrolyte, a cell voltage exceeding 3 V and a high energy density can be obtained.
  • the aqueous electrolyte has better ion conductivity than the non-aqueous electrolyte, and an electrochemical capacitor using the aqueous electrolyte is advantageous in terms of output density.
  • Non-Patent Document 1 proposes an asymmetric hybrid capacitor in which different types of electrodes are used for the positive electrode and the negative electrode, respectively, and the cell voltage and energy density are increased in the aqueous electrolyte.
  • a cell voltage on the positive electrode side exceeding the theoretical oxygen generation voltage can be obtained by using MnO 2 having a relatively high oxygen generation overvoltage for the positive electrode.
  • a maximum cell voltage of 2.2 V is obtained, and an energy density (19 Wh / kg) comparable to that of an electrochemical capacitor using an organic electrolyte is obtained.
  • Patent Document 1 proposes a technology that can charge and discharge at a working voltage exceeding the theoretical voltage of water electrolysis in a pseudo-capacitor capacitor using both an aqueous electrolyte and a non-aqueous electrolyte.
  • the pseudo-capacitor has a resin case disposed between a positive current collector and a negative current collector, and a capacitor structure is provided in the center hole of the case.
  • the capacitor structure includes a positive electrode disposed at the upper part of the central hole, a negative electrode disposed at the lower part of the central hole, a solid electrolyte plate disposed at the step of the central hole, and an aqueous electrolyte containing Li ions.
  • a first liquid chamber filled and a second liquid chamber filled with a non-aqueous electrolyte containing Li ions are provided.
  • the positive electrode is an electrode containing a metal oxide capable of redox change
  • the negative electrode is an electrode capable of inserting and extracting Li ions
  • the solid electrolyte plate has Li ion conductivity
  • the contact between the aqueous electrolyte and the negative electrode Plays a role in hindering.
  • Patent Document 1 can obtain a relatively high cell voltage because the second liquid chamber is filled with the nonaqueous electrolytic solution, but there is a problem in safety. Further, since the first liquid chamber is filled with an alkaline aqueous electrolyte, the durability of the solid electrolyte and the positive electrode may be reduced.
  • Electrochemical capacitors using aqueous electrolytes and non-aqueous electrolytes aim to improve cell voltage and energy density using various technologies, but the energy density will be further improved in the future compared to lithium ion batteries. is necessary.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a hybrid capacitor that is safe and durable and that can obtain a high energy density at a high cell voltage. .
  • a hybrid capacitor according to the present invention includes a positive electrode having one or both of a carbon material and a metal oxide, a negative electrode composed of a lithium composite electrode, and a gap between the positive electrode and the negative electrode.
  • the lithium composite electrode is a laminated electrode of a lithium ion conductive solid electrolyte, a polymer electrolyte, and an active material layer containing lithium.
  • a neutral aqueous electrolyte is used and a water-stable lithium composite electrode is used as the negative electrode
  • a safe and durable new aqueous hybrid capacitor can be obtained.
  • a high cell voltage can be obtained by utilizing a standard electrode potential of M / M + (M is a metal). I was able to.
  • the neutral aqueous electrolyte is pH 5 or more and pH 8.5 or less
  • the metal oxide is any one selected from manganese oxide, ruthenium oxide and lead oxide.
  • the positive electrode includes a sheet containing one or both of a carbon material and a metal oxide, and a metal oxide film provided on at least the surface of the sheet.
  • the sheet is a paper-like body having carbon fibers.
  • the active material layer containing lithium includes lithium, a lithium alloy, or a carbon material doped with lithium.
  • the hybrid capacitor according to the present invention has safety and durability, and can obtain a high energy density at a high cell voltage.
  • the hybrid capacitor 1 includes a positive electrode 11 having one or both of a carbon material and a metal oxide, a negative electrode 12 composed of a lithium composite electrode, and a positive electrode 11 and a negative electrode 12. And at least a neutral aqueous electrolyte 13 filled therebetween.
  • the lithium composite electrode which is the negative electrode 12 is a laminated electrode of the lithium ion conductive solid electrolyte 23, the polymer electrolyte 22, and the active material layer 21 containing lithium.
  • the neutral aqueous electrolyte solution 13 has a pH of 5 or more and a pH of 8.5 or less, and preferably has a pH of 5 or more and pH 8.
  • symbol 18 is a container in FIG.
  • the neutral aqueous electrolyte 13 is an electrolyte filled between the positive electrode 11 and the negative electrode 12.
  • an aqueous neutral electrolyte is used.
  • the neutral aqueous electrolyte include an aqueous electrolyte in which an alkali metal salt is dissolved.
  • the alkali metal salts include LiCl, LiNO 3 , Li 2 SO 4 , Li 2 CO 3 , Li 2 HPO 4 , LiH 2 PO 4 , LiCOOCH 3 , LiCOO (OH) CHCH 3 , Li 2 C 2 O 2 , NaCl.
  • a water-based electrolytic solution in which a plurality of alkali metal salts are mixed and adjusted to neutrality may be used, or a water-based electrolytic solution in which an alkali metal salt and an acid or base are mixed to provide a buffering action. Also good.
  • the aqueous electrolyte having a buffering action has a stable pH during the charge / discharge process, and can improve the safety and durability of the hybrid capacitor 1.
  • Examples of the neutral aqueous electrolyte solution 13 having a buffering action include lithium dihydrogen phosphate-lithium hydroxide (LiH 2 PO 4 -LiOH) solution (pH 6.87), lithium acetate-acetic acid (CH 3 COOLi-CH 3 COOH). Liquid (pH 5.41).
  • the aqueous electrolytic solution 13 is neutral, the electrolytic solution does not damage the negative electrode 12 and the positive electrode 11, and a stable hybrid capacitor can be configured.
  • the hybrid capacitor 1 does not use a non-aqueous electrolyte using a solvent other than water as described in Patent Document 1, it is easy to handle, safe, and low cost.
  • the neutrality of the neutral aqueous electrolyte solution 13 means a range of pH 5 or more and pH 8.5 or less, preferably a pH of 5 or more and pH 8 or less. Moreover, it is preferable that the salt concentration in the neutral aqueous electrolyte solution 13 is 0.01 mol / L or more and 5 mol / L or less.
  • the positive electrode 11 has one or both of a carbon material and a metal oxide, and causes a reversible redox reaction in contact with the neutral aqueous electrolyte solution 13 described above.
  • the positive electrode 11 may be composed of a single metal oxide or a metal. It may be composed of an oxide and a binder material, or may be composed of a metal oxide, a binder material, and a conductive material.
  • the positive electrode 11 may be comprised with the carbon material single-piece
  • carbon material various carbon materials can be exemplified, and preferably, activated carbon, acetylene black, carbon nanotube, graphite, conductive diamond, graphene and the like can be exemplified. These carbon materials may be used alone or in combination of two or more.
  • Various metal oxides can be used as long as they can cause a reversible redox reaction, such as manganese oxide, ruthenium oxide, lead oxide, tungsten oxide, cobalt oxide, tin oxide, and oxide. Examples thereof include nickel, molybdenum oxide, titanium oxide, iridium oxide, vanadium oxide, indium oxide, and the like, and hydrates thereof. These metal oxides may be used alone or in combination of two or more.
  • Preferable examples include manganese oxide, ruthenium oxide, lead oxide and the like.
  • binder materials and conductive materials can be applied.
  • binder material for example, a fluorine-based resin, a thermoplastic resin, ethylene-propylene-dienemer, natural butyl rubber and the like can be arbitrarily used.
  • conductive material for example, natural graphite, artificial graphite, acetylene black, carbon black, ketjen black, carbon whisker, needle coke, carbon fiber, metal powder or fiber can be used. These binder materials and conductive materials may be used alone or in combination of two or more.
  • the positive electrode 11 may have a sheet containing one or both of a carbon material and a metal oxide, and a metal oxide film provided on at least the surface of the sheet.
  • the sheet may be composed of a single metal oxide, may be composed of a metal oxide and an additive such as a binder material, or may be composed of a single carbon material. Alternatively, it may be composed of a carbon material and an additive such as a binder material.
  • the sheet may contain both a metal oxide and a carbon material.
  • seat containing a carbon material As a sheet
  • the sheet containing both the metal oxide and the carbon material include a sheet obtained by molding a material obtained by kneading the metal oxide and the carbon material into a sheet shape.
  • binder contained in the sheet examples include fluororesin materials such as Fluon (manufactured by Asahi Glass Co., Ltd., registered trademark) and Lubron (manufactured by Daikin Industries, Ltd., registered trademark), and styrene butadiene rubbers such as TRD2001 (manufactured by JSR Corporation) Examples thereof include system materials.
  • the metal oxide film may be provided on at least the surface of the sheet.
  • the metal oxide film may be provided only on the surface of the sheet, or may be provided on the surface of the sheet and enter the inside of the sheet.
  • the metal oxide film may be provided so as to cover the surface of each carbon fiber.
  • the hybrid capacitor 1 using the positive electrode 11 in which the metal oxide film is provided on the surface of each carbon fiber can obtain characteristics that greatly reflect the characteristics of the metal oxide of the positive electrode 11.
  • Examples of the method for forming the metal oxide film include thin film formation methods such as electrodeposition, electrophoresis, CVD (chemical vapor deposition), sputtering, and vacuum deposition.
  • the electrodeposition method is advantageous in increasing the production efficiency of the hybrid capacitor because the metal oxide film can be formed in a relatively short time.
  • the shape of the positive electrode 11 is not particularly limited, but is usually preferably a sheet shape or a plate shape.
  • the thickness of the positive electrode 11 is not particularly limited, but is, for example, in the range of 1 nm or more and 10 mm or less.
  • the positive electrode 11 is usually provided on the positive electrode current collector 16.
  • a conventionally known positive electrode current collector 16 can be arbitrarily applied.
  • the negative electrode 12 is composed of a lithium composite electrode (represented by reference numeral 12). Such a negative electrode 12 is in contact with the aqueous electrolyte solution 13 described above, and acts to occlude and release metal ions that cause a redox reaction. As shown in FIG. 1, the lithium composite electrode 12 is a laminated electrode having a lithium ion conductive solid electrolyte 23, a polymer electrolyte 22, and an active material layer 21 containing lithium.
  • the active material layer 21 containing lithium metallic lithium, a lithium alloy, or a carbon material doped with lithium is used.
  • the lithium alloy may be any lithium alloy or lithium compound mainly composed of lithium, and examples thereof include a lithium-aluminum alloy, a lithium-zinc alloy, a lithium-tin alloy, and a lithium-silicon alloy.
  • Examples of the carbon material doped with lithium include graphitizable carbon, non-graphitizable carbon, and graphite.
  • Examples of the graphitizable carbon include pyrolytic carbons, and cokes such as pitch coke, needle coke, and petroleum coke.
  • Examples of the non-graphitizable carbon include glassy carbon fibers, organic polymer compound fired bodies, activated carbon, and carbon blacks.
  • the organic polymer compound fired body is obtained by firing and carbonizing a phenol resin, a furan resin, or the like at an appropriate temperature.
  • the amount of lithium doped into the carbon material is suitably 1 ⁇ g / cm 2 or more and 1 g / cm 2 or less.
  • a lithium-doped carbon material releases lithium ions from the carbon material when a discharge voltage is applied to the hybrid capacitor, and stores lithium ions in the carbon material when a charge voltage is applied. It functions as a negative electrode active material.
  • the active material layer 21 made of such a carbon material is unlikely to deposit lithium dendritic crystals (dendrites) upon charging, and the polymer electrolyte 22 and the like provided on the active material layer 21 are caused by the lithium dendritic crystals. It is possible to avoid damage or short circuit. As a result, the durability and safety of the hybrid capacitor can be further increased. Moreover, since the amount of lithium used can be reduced by using a carbon material as the material of the active material layer 21 compared to the case of using metallic lithium or the like, it is possible to improve the safety of the hybrid capacitor and reduce the cost. Can be planned.
  • Examples of the shape of the active material layer 21 containing lithium include a sheet shape or a film shape.
  • the thickness of the active material layer 21 is not specifically limited, For example, it exists in the range of 0.1 mm or more and 3 mm or less.
  • the lithium ion conductive solid electrolyte 23 has lithium ion conductivity and water impermeability, and acts to isolate the aqueous electrolyte solution 13 and the negative electrode 12.
  • the polymer electrolyte 22 contains a solid polymer and a lithium salt.
  • polyethylene oxide (PEO), polypropylene oxide (PPO) or the like can be used as the solid polymer constituting the polymer electrolyte 22.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • These have polyalkylene oxide chains that are molecular chains in which alkylene groups and ether oxygens are alternately arranged, and have a large number of ether oxygens that solvate lithium ions, so that lithium salts can be dissolved.
  • lithium salt constituting the polymer electrolyte 22 examples include LiPF 6 , LiClO 4 , LiBF 4 , LiTFSI (Li (SO 2 CF 3 ) 2 N), Li (SO 2 C 2 F 5 ) 2 N, LiBOB ( Lithium bisoxalatoborate) and the like. These lithium salts may be used alone or in combination of two or more.
  • the polymer electrolyte 22 may be blended with a ceramic material such as barium titanate in consideration of mechanical characteristics and electrical characteristics, or other materials that do not hinder the function of the polymer electrolyte 22. You may mix
  • the amount of these materials constituting the polymer electrolyte 22 is set in consideration of the desired function of the polymer electrolyte 22.
  • the polymer electrolyte 22 can be produced by a conventionally known method. For example, a solution in which various constituent materials are dispersed in an organic solvent can be dried to be molded into a predetermined shape.
  • the thickness of the polymer electrolyte 22 is not particularly limited, but is usually in the range of 0.05 mm or more and 0.5 mm or less.
  • the polymer electrolyte 22 produced in this way is disposed between the lithium 21 and the lithium ion conductive solid electrolyte 23, and can prevent both from coming into direct contact and reacting. As a result, the lifetime of the hybrid capacitor 1 can be increased.
  • the lithium ion conductive solid electrolyte 23 is preferably a NASICON (sodium superionic conductor) type lithium ion conductor having water resistance and lithium ion conductivity.
  • the lithium ion conductive solid electrolyte 23 is preferably in the form of a sheet or a plate, and the thickness is usually in the range of 0.05 mm or more and 0.5 mm or less.
  • the negative electrode 12 is usually provided on the negative electrode current collector 17.
  • a conventionally known negative electrode current collector 17 can be arbitrarily applied.
  • the hybrid capacitor 1 composed of at least the positive electrode 11, the negative electrode 12, and the aqueous electrolyte solution 13 may be provided with other constituent materials and constituent members as necessary.
  • the size of the hybrid capacitor 1 is not particularly limited, and the shape thereof is not particularly limited. Examples of the shape include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type.
  • the neutral aqueous electrolyte 13 is used, and the water-stable lithium composite electrode 12 is used as the negative electrode.
  • a hybrid capacitor could be obtained.
  • a high cell voltage could be obtained by utilizing the standard electrode potential of Li / Li + .
  • the positive electrode 11 using activated carbon was produced as follows. First, 20 mg of activated carbon powder (manufactured by Kansai Thermal Chemical Co., Ltd., trade name: MSP-20, BET specific surface area 2200 m 2 / g, average particle size 8 ⁇ m) was added to 10 mL of ultrapure water, and the activated carbon powder was sonicated. An activated carbon dispersion was obtained by uniformly dispersing in ultrapure water.
  • activated carbon powder manufactured by Kansai Thermal Chemical Co., Ltd., trade name: MSP-20, BET specific surface area 2200 m 2 / g, average particle size 8 ⁇ m
  • Manganese oxide (MnO 2 ) powder was synthesized according to Non-Patent Document 1. Specifically, the positive electrode 11 using manganese oxide was produced as follows. First, 0.773 g of fumaric acid [C 2 H 2 (COOH) 2 ] is added to an aqueous potassium permanganate solution in which 3.16 g of potassium permanganate (KMnO 4 ) is dissolved in 100 mL of ultrapure water. After stirring under reduced pressure for minutes, the mixture was allowed to stand at room temperature for 1 day to obtain a slurry.
  • this slurry was washed with 0.1 M sulfuric acid (H 2 SO 4 ), ultrapure water and acetone in this order, dried, pulverized, and average pore diameter was 5 nm, BET specific surface area was A 235 m 2 / g manganese oxide (MnO 2 ) powder was obtained.
  • the obtained manganese oxide powder was mixed with acetylene black, which is a conductive material, in a mass ratio of 7: 3, and used in place of the activated carbon powder in the above-described activated carbon electrode production method, to produce a manganese oxide electrode A.
  • Manganese oxide electrode B was produced by electrodepositing manganese oxide on the surface of carbon fiber of carbon paper. Specifically, an aqueous solution of manganese sulfate hydrate (MnSO 4 .5H 2 O) and an aqueous sulfuric acid solution were mixed to prepare a sulfuric acid solution (electrolytic solution for electrodeposition) containing 0.1M MnSO 4 . Next, carbon paper (manufactured by SGL, trade name: SIGRACET GDL10) is immersed in the electrolytic solution for electrodeposition, the carbon paper is used as an anode electrode, a platinum electrode is used as a cathode electrode, and a current density is 0.
  • SGL trade name: SIGRACET GDL10
  • Electrodeposition was performed under the conditions of 0.5 mA / cm 2 , temperature: 25 ° C., and electrodeposition time: 1800 seconds, and a manganese oxide electrode B was produced.
  • the manganese oxide deposition amount of this manganese oxide electrode B was 0.4 mg / cm 2 .
  • Hydrated ruthenium oxide (RuO 2 .nH 2 O) powder was synthesized according to Non-Patent Document 2 described above. Specifically, the positive electrode 11 using ruthenium oxide hydrate was produced as follows. First, an aqueous solution obtained by dissolving 0.638 g of ruthenium chloride (RuCl 3 ) in 50 mL of ultrapure water and dropwise adding an aqueous solution of 0.6 g of sodium hydroxide in 50 mL of ultrapure water with stirring until pH 7 is reached. Thereafter, the slurry was allowed to stand at 25 ° C. for 15 hours to obtain a slurry.
  • RuCl 3 ruthenium chloride
  • this slurry was washed with ultrapure water and filtered, and this washing and filtration was repeated 5 times until the slurry became neutral.
  • the slurry was dried and then pulverized to obtain ruthenium oxide hydrate having an average particle diameter of 2 nm, a specific capacitance of 600 F / g in an H 2 SO 4 electrolyte solution at 25 ° C. and 0.5 mol / L.
  • a powder (RuO 2 ⁇ nH 2 O) was obtained.
  • the obtained ruthenium oxide hydrate powder was used in place of the activated carbon powder in the above-described method for producing an activated carbon electrode to produce a ruthenium oxide hydrate electrode.
  • Ruthenium oxide nanosheet A (Ru 4+ O 2.1 ) was synthesized according to Non-Patent Document 3 described above. Specifically, the positive electrode 11 using the ruthenium oxide nanosheet A was produced as follows. First, 0.60 g of ruthenium oxide (RuO 2 ) and 0.39 g of potassium carbonate (K 2 CO 3 ) were mixed in acetone to form pellets. Next, the pellet was fired at 800 ° C. in an argon gas atmosphere for 12 hours and then washed with ultrapure water to obtain layered potassium ruthenate. This layered potassium ruthenate was added to 100 mL of 1M HCl aqueous solution, stirred at 60 ° C.
  • RuO 2 ruthenium oxide
  • K 2 CO 3 potassium carbonate
  • layered ruthenate was added to 100 mL of an aqueous solution containing 6.88 mL of 10% by weight TBAOH (tetrabutylammonium hydroxide) and the remainder being ultrapure water, stirred at 25 ° C. for 10 days, and then centrifuged (2000 rpm, 30 minutes) to obtain a colloidal solution of ruthenium oxide nanosheet A.
  • TBAOH tetrabutylammonium hydroxide
  • Ruthenium oxide nanosheet B (Ru 3.8+ O 2 ) was synthesized according to Non-Patent Document 4 described above. Specifically, the positive electrode 11 using the ruthenium oxide nanosheet B was produced as follows. First, 0.298 g of ruthenium, 0.560 g of ruthenium oxide (RuO 2 ), and 0.142 g of sodium carbonate (Na 2 CO 3 ) were mixed in acetone to form pellets. Next, the pellet was fired at 700 ° C. for 1 hour and 900 ° C. for 12 hours in order in an argon gas atmosphere to obtain layered sodium ruthenate.
  • RuO 2 0.560 g of ruthenium oxide
  • Na 2 CO 3 sodium carbonate
  • This layered sodium ruthenate is added to a solution obtained by dissolving 1.257 g of Na 2 S 2 O 8 in 420 g of ultrapure water, then washed with ultrapure water, and further added to 200 mL of 1 M HCl aqueous solution at 60 ° C. After stirring for 72 hours, laminar ruthenic acid was obtained by washing with ultrapure water. This layered ruthenic acid was added to 183 mL of an aqueous solution containing 2.8 mL of 10% by mass TBAOH (tetrabutylammonium hydroxide) and the remainder being ultrapure water, stirred at 25 ° C.
  • TBAOH tetrabutylammonium hydroxide
  • the negative electrode 12 using the lithium composite electrode A was synthesized according to Non-Patent Document 5 described above. Specifically, the negative electrode 12 using the lithium composite electrode A was produced as follows. First, metallic lithium (manufactured by Honjo Metal Industry Co., Ltd., 0.2 ⁇ 5 ⁇ 5 mm, active material) at one end of a metallic nickel foil (manufactured by Niraco Co., Ltd., 0.1 ⁇ 5 ⁇ 150 mm, negative electrode current collector 17) Layer 21) was loaded.
  • PEO manufactured by Sigma-Aldrich Co., Ltd.
  • LiTFSI lithium bistrifluoromethanesulfonylimide, Li (CF 3 SO 2 ) 2 N, manufactured by Wako Pure Chemical Industries, Ltd.
  • LTAP lithium ion conductive glass ceramics, OHARA, Inc., thickness 0.15 mm, lithium ion conductive solid electrolyte 23
  • This laminate was sandwiched between two laminate films (produced by Nihon Co., Ltd., trade name: Rami Zip AL-15, made of aluminum) cut into 100 mm squares, and laminator (vacuum packaging machine made by Bonmac Co., Ltd.). (Trade name: BMV-281).
  • a 5 mm square hole was made in the laminate film in contact with LTAP, and a measurement window in which LTAP was in contact with the aqueous electrolyte was used.
  • a nickel foil drawn from one side of the four sides of the lithium composite electrode was used for collecting the lithium composite negative electrode.
  • the cell resistance of the produced lithium composite electrode A was 185 Wcm 2 .
  • the negative electrode 12 using the lithium composite electrode B was produced as follows. First, a laminate (hereinafter, also referred to as “lithium pre-doped graphite electrode”) of a copper foil (current collector 17 for negative electrode) and a graphite layer (active material layer 21) doped with lithium was prepared.
  • a laminate hereinafter, also referred to as “lithium pre-doped graphite electrode” of a copper foil (current collector 17 for negative electrode) and a graphite layer (active material layer 21) doped with lithium was prepared.
  • the copper foil on which the coating film was formed was punched into a 1 cm 2 circle and pressed at a pressure of 700 kg / cm 2 for 1 minute. Thereafter, the coating film was vacuum-dried at 150 ° C. for 16 hours to obtain a graphite electrode having a graphite layer formed on the surface of the copper foil.
  • lithium was doped into the graphite layer using a galvano / potentiostat (trade name: HZ3000 manufactured by Hokuto Denko Co., Ltd.) to obtain a lithium pre-doped graphite electrode.
  • a galvano / potentiostat trade name: HZ3000 manufactured by Hokuto Denko Co., Ltd.
  • Li foil manufactured by Honjo Metal Co., Ltd.
  • 1M LiPF 6 is a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (1: 1 by volume) as the electrolyte.
  • the Li foil and the graphite electrode were short-circuited for 72 hours to dope the graphite layer with lithium .
  • the natural potential of the graphite electrode was 3.0 V (vs. Li / Li + ) at the start of the short circuit and 0 V (vs. Li / Li + ) at the end of the short circuit.
  • the obtained lithium pre-doped graphite electrode was used in place of the metal nickel foil and metal lithium in the above-described method for producing the lithium composite electrode A to produce a lithium composite electrode B.
  • aqueous electrolyte Lithium chloride aqueous solution / lithium sulfate aqueous solution
  • an aqueous lithium chloride solution and an aqueous lithium sulfate solution were prepared.
  • the lithium chloride aqueous solution lithium chloride was dissolved in ultrapure water to prepare a 1M aqueous solution.
  • lithium sulfate was dissolved in ultrapure water to prepare a 1M aqueous solution.
  • Lithium acetate aqueous solution As an aqueous electrolyte, 33 g of lithium acetate (CH 3 COOLi) was dissolved in 250 mL of ultrapure water to prepare a 2M aqueous solution (pH 8.30).
  • Lithium dihydrogen phosphate-lithium hydroxide solution A lithium dihydrogen phosphate-lithium hydroxide solution was prepared as an aqueous electrolyte. First, 4.7786 g of lithium dihydrogen phosphate (LiH 2 PO 4 ) was dissolved in 500 mL of ultrapure water to prepare a 0.1 M lithium dihydrogen phosphate aqueous solution. Further, 2.098 g of lithium hydroxide (LiOH) was dissolved in 500 mL of ultrapure water to prepare a 0.1 M lithium hydroxide aqueous solution.
  • LiOH lithium hydroxide
  • Lithium acetate-acetic acid solution A lithium acetate-acetic acid solution was prepared as an aqueous electrolyte. First, 33 g of lithium acetate (CH 3 COOLi) was dissolved in 250 mL of ultrapure water to prepare a 2M lithium acetate aqueous solution. Further, 30 g of acetic acid (CH 3 COOH) was dissolved in 250 mL of ultrapure water to prepare a 2M acetic acid aqueous solution.
  • CH 3 COOLi lithium acetate
  • acetic acid CH 3 COOH
  • the prepared 2M lithium acetate aqueous solution 87.5 mL and 2M acetic acid aqueous solution 12.5 mL were mixed, and ultrapure water was added to make the total volume 200 mL, thereby preparing a lithium acetate-acetic acid solution (pH 5.41).
  • any aqueous electrolyte was subjected to nitrogen gas bubbling to remove dissolved oxygen.
  • the pH of the aqueous electrolyte was measured at 60 ° C. using a pH meter (manufactured by Toa DKK Corporation, HM-60E).
  • Example 1 Using the above-mentioned activated carbon electrode as the positive electrode 11, using the above-mentioned lithium composite electrode A as the cathode 12, and using the above-described lithium chloride aqueous solution (pH 7.64) and lithium sulfate aqueous solution (pH 5.15) as the aqueous electrolyte solution 13, Two types of hybrid capacitors 1 were constructed as shown in FIG.
  • Example 2 The above-described manganese oxide electrode is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium chloride aqueous solution (pH 6.52) and lithium sulfate aqueous solution (pH 5.50) are used as the aqueous electrolyte solution 13.
  • Two types of hybrid capacitors 1 were constructed as shown in FIG.
  • Example 3 The above-described ruthenium oxide hydrate electrode is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium chloride aqueous solution (pH 6.52) and lithium sulfate aqueous solution (pH 5.50) are used as the aqueous electrolyte solution 13.
  • Two types of hybrid capacitors 1 were constructed as shown in FIG.
  • Example 4 The above-described ruthenium oxide sheet electrode A is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium chloride aqueous solution (pH 6.54) and lithium sulfate aqueous solution (pH 5.36) are used as the aqueous electrolyte solution 13.
  • the above-described lithium chloride aqueous solution (pH 6.54) and lithium sulfate aqueous solution (pH 5.36) are used as the aqueous electrolyte solution 13.
  • two types of hybrid capacitors 1 were constructed as shown in FIG.
  • Example 5 The above-described ruthenium oxide sheet electrode B is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium chloride aqueous solution (pH 6.6) and lithium sulfate aqueous solution (pH 5.7) are used as the aqueous electrolyte solution 13.
  • two types of hybrid capacitors 1 were constructed as shown in FIG.
  • Example 6 The above-described manganese oxide electrode B is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium sulfate aqueous solution (pH 5.7) is used as the aqueous electrolyte solution 13. Configured as shown.
  • Example 7 The above-described activated carbon electrode was used as the positive electrode 11, the above-described lithium composite electrode B was used as the cathode 12, and the above-described lithium chloride aqueous solution was used as the aqueous electrolyte solution 13, so that the hybrid capacitor 1 was configured as shown in FIG.
  • Example 8 The hybrid capacitor 1 is illustrated using the above-described ruthenium oxide hydrate electrode as the positive electrode 11, the above-described lithium composite electrode A as the cathode 12, and the above-described aqueous lithium acetate solution (pH 8.30) as the aqueous electrolyte solution 13. As shown in FIG.
  • Example 9 The above-described manganese oxide electrode B is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium dihydrogen phosphate-lithium hydroxide buffer (pH 6.87) is used as the aqueous electrolyte solution 13.
  • the hybrid capacitor 1 was configured as shown in FIG.
  • Example 10 The above-described ruthenium oxide hydrate electrode is used as the positive electrode 11, the above-described lithium composite electrode A is used as the cathode 12, and the above-described lithium dihydrogen phosphate-lithium hydroxide buffer (pH 6.87) is used as the aqueous electrolyte solution 13.
  • the hybrid capacitor 1 was configured as shown in FIG.
  • Example 11 Using the above-described ruthenium oxide hydrate electrode as the positive electrode 11, using the above-described lithium composite electrode A as the cathode 12, and using the above-described lithium acetate-acetic acid buffer solution (pH 5.41) as the aqueous electrolyte solution 13, a hybrid capacitor 1 was constructed as shown in FIG.
  • Cyclic voltammetry (CV) Cyclic voltammetry (CV) Cyclic voltammetry measurement was performed using a potentiostat (HZ3000, manufactured by Hokuto Denko Co., Ltd.) and a cell (semi-micro separable cover, semi-micro separable flask, manufactured by Nihon Rikenki Co., Ltd.).
  • aqueous electrolytic solution as used in each example was used as the electrolytic solution, glassy carbon ( ⁇ 5, 19.625 mm 2 ) carrying a positive electrode material was used as the working electrode, and a silver / silver chloride electrode (HS -205C, manufactured by Toa DKK Co., Ltd.) and a Pt mesh (100 mesh, 20 ⁇ 30 mm, Niraco Co., Ltd.) was used as the counter electrode.
  • HS / silver chloride electrode HS / silver chloride electrode
  • Pt mesh 100 mesh, 20 ⁇ 30 mm, Niraco Co., Ltd.
  • carbon paper on which a manganese oxide film was electrodeposited was used as a working electrode. This cyclic voltammetry measurement was performed under the temperature condition of 60 ° C. and in the range of potential scanning speed of 2 mV / s to 500 mV / s.
  • FIG. 2 is a cyclic voltammogram using the activated carbon electrode obtained in Example 1 and an aqueous lithium chloride solution.
  • the shape of the cyclic voltammogram was rectangular, and it showed an ideal electric double layer behavior even when the scanning speed was changed.
  • the obtained specific capacitance Cp was 102 F / g (2 mV / sec).
  • Table 1 shows the specific capacitance Cp at each scanning speed. If this activated carbon electrode is used for the positive electrode of a hybrid capacitor, it is considered that the charge / discharge behavior like a capacitor is exhibited.
  • vs. RHE since a peak due to an irreversible capacity is not seen up to 1.2 V (vs. RHE), in a cell combined with a lithium composite electrode, about 4.2 V is considered in consideration of the standard electrode potential of Li / Li + . A cell voltage is considered to be obtained.
  • any cyclic voltammogram showed an electric double layer behavior. From this, it is thought that the hybrid capacitor of each Example exhibits a capacitor-like charge / discharge behavior.
  • the operating voltage on the positive electrode side is greatly limited by the oxygen generation reaction (OER). . If the OER overvoltage is high, expansion of the operating voltage on the positive electrode side can be expected. Even in the hybrid capacitor of the present invention, a manganese oxide electrode having a high OER overvoltage (stable up to 1.6 V vs. RHE), a lead oxide electrode (stable up to 2.0 V vs. RHE), a conductive diamond electrode (stable up to 2.5 V vs. RHE) Etc. can be expected to further increase the operating voltage.
  • OER oxygen generation reaction
  • FIG. 3 is a charge / discharge curve obtained in a charge / discharge test of the hybrid capacitor 1 using the activated carbon electrode obtained in Example 1 and an aqueous lithium chloride solution.
  • the cut-off potential was 3.9 V for charging and 2.9 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity.
  • Table 3 This hybrid capacitor uses a two-phase electrolyte. That is, Li + moves between the aqueous electrolyte (1M LiCl aqueous solution) between the positive electrode and the negative electrode and the polymer electrolyte (PEO-LiTFSI
  • a voltage of about 3 V can be obtained on the negative electrode side by the reaction of Li / Li + and a voltage of about 1 V can be obtained on the positive electrode side by the electric double layer.
  • the voltage between the positive and negative electrodes obtained can be expected to be about 4 V, and a cell voltage exceeding that of a conventional lithium ion capacitor can be obtained.
  • a great improvement in energy density can be expected.
  • the charge / discharge curve changes with a constant slope, and a triangular shape is obtained, which indicates that the capacitor-like behavior is exhibited. That is, it can be seen that the capacity of the activated carbon electrode is not due to the battery reaction but to the electric double layer.
  • a high cell voltage of 3.9 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the manganese oxide electrode obtained in Example 2 and each aqueous electrolyte was performed.
  • the cut-off potential was 4.3V for charging and 3.3V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 4.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 4.3 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the ruthenium oxide hydrate electrode obtained in Example 3 and each aqueous electrolyte was performed.
  • the cut-off potential was 3.8 V for charging and 2.8 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 5.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Further, a high cell voltage of 3.8 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the ruthenium oxide nanosheet electrode obtained in Example 4 and each aqueous electrolyte was performed.
  • the cut-off potential was 3.9 V for charging and 2.9 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 6.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 3.9 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the ruthenium oxide nanosheet electrode obtained in Example 5 and each aqueous electrolyte was performed.
  • the cut-off potential was 3.9 V for charging and 2.9 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 7.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 3.9 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the manganese oxide electrode B obtained in Example 6 and the aqueous electrolyte was performed.
  • the cut-off potential was set to 4.2V for charging and 3.2V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity.
  • the results are shown in Table 8.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 4.2 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the activated carbon electrode obtained in Example 7, the aqueous electrolyte, and the lithium composite electrode B was performed.
  • the cut-off potential was 3.6 V for charging and 2.6 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 9.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained.
  • a high cell voltage of 3.6 V was obtained, and a cell voltage close to that of a hybrid capacitor using the lithium composite electrode A could be obtained.
  • the charge / discharge test of the hybrid capacitor 1 using the ruthenium oxide hydrate electrode obtained in Example 8 and the aqueous electrolyte was performed.
  • the cut-off potential was set to 3.7V for charging and 2.7V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity.
  • the results are shown in Table 10.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 3.7 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the manganese oxide electrode A obtained in Example 9 and the aqueous electrolyte was performed.
  • the cut-off potential was set to 4.3V for charging and 3.3V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 11.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 4.3 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the ruthenium oxide hydrate electrode obtained in Example 10 and the aqueous electrolyte was performed.
  • the cut-off potential was 3.9 V for charging and 2.9 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 12.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 3.9 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge test of the hybrid capacitor 1 using the ruthenium oxide hydrate electrode obtained in Example 11 and the aqueous electrolyte was performed.
  • the cut-off potential was 3.9 V for charging and 2.9 V for discharging.
  • Each charge / discharge characteristic was obtained by converting the specific capacitance obtained from the discharge curve into the battery capacity. The results are shown in Table 13.
  • the charge / discharge curve changed with a constant slope, and the triangular shape was obtained. Moreover, a high cell voltage of 3.9 V was obtained, and a high cell voltage could be obtained even when compared with the current lithium ion capacitor.
  • the charge / discharge cycle test of the hybrid capacitor 1 using the ruthenium oxide hydrate electrode obtained in Example 3 and the lithium sulfate aqueous solution was performed.
  • the charge / discharge cycle test was performed for 200 cycles at a constant current density of 255 ⁇ A / cm 2 with a cut-off potential of 3.8 V for charge and 2.8 V for discharge.
  • Table 15 shows the result of converting the specific capacitance obtained from the cycle discharge curve into the battery capacity. Even after 200 cycles of charge / discharge, 95% or more of the initial capacity was maintained.
  • the charge / discharge cycle test of the hybrid capacitor 1 using the manganese oxide electrode B obtained in Example 6 and the lithium sulfate aqueous solution was performed.
  • the charge / discharge cycle test was performed 2000 cycles at a constant current density of 0.6 mA / cm 2 with a cut-off potential of 4.2 V for charge and 3.2 V for discharge.
  • Table 16 shows the results of the energy density and the capacity retention rate obtained by converting the specific capacitance obtained from the charge / discharge cycle curve into the battery capacity. Even after 2000 cycles of charge and discharge, 80% or more of the initial capacity was maintained.
  • the hybrid capacitor 1 of the present invention showed capacitor characteristics having a high cell voltage and a high energy density.
  • the hybrid capacitor 1 using the aqueous electrolyte 13 was able to achieve a dramatic improvement in energy density because of the positive electrode active material having a cell voltage of 5 V class and a very high single electrode capacity. Two were the factors.
  • the hybrid capacitor 1 of the present invention uses a neutral aqueous electrolyte, and thus has an advantage of being safe and easy to handle, and improves durability without damaging the positive electrode 11 and the lithium composite electrode 12. be able to.

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Abstract

La présente invention vise à fournir un condensateur hybride grâce auquel on obtient la sécurité et la robustesse, et grâce auquel il est possible d'obtenir une densité d'énergie élevée avec une tension de cellule élevée. A cet effet, la présente invention concerne un condensateur hybride comprenant au moins : une électrode positive (11) ayant un matériau carboné et/ou un oxyde métallique ; une électrode négative qui est constituée d'une électrode composite au lithium ; et un électrolyte aqueux neutre (13) qui remplit l'espace entre l'électrode positive (11) et l'électrode négative (12). L'électrode composite au lithium (12) est configurée pour être une électrode stratifiée d'un électrolyte à l'état solide conducteur au lithium-ion (21), d'un électrolyte polymère (22) et d'une couche de matériau actif (23) comprenant du lithium, ce qui résout le problème. Il est désirable que l'électrolyte aqueux neutre (13) ait un pH de 5 à 8,5, et que l'oxyde métallique soit choisi parmi l'oxyde de manganèse, l'oxyde de ruthénium ou l'oxyde de plomb.
PCT/JP2013/058817 2012-03-28 2013-03-26 Condensateur hybride WO2013146792A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015055351A1 (fr) * 2013-10-15 2015-04-23 Robert Bosch Gmbh Électrode au lithium pour accumulateur lithium-ions et son procédé de fabrication
WO2017122597A1 (fr) * 2016-01-14 2017-07-20 国立大学法人東京大学 Solution électrolytique aqueuse pour dispositif de stockage électrique, et dispositif de stockage électrique comprenant ladite solution électrolytique aqueuse
CN107112600A (zh) * 2015-01-14 2017-08-29 国立大学法人东京大学 蓄电装置用水系电解液和含有该水系电解液的蓄电装置
WO2018097259A1 (fr) * 2016-11-28 2018-05-31 トヨタ自動車株式会社 Solution électrolytique pour piles rechargeables au lithium-ion, son procédé de fabrication et pile rechargeable au lithium-ion
CN108780707A (zh) * 2016-03-18 2018-11-09 国立大学法人信州大学 锂复合负极及混合电容器以及它们的制造方法
JP2018181420A (ja) * 2017-04-03 2018-11-15 株式会社豊田中央研究所 水溶液系リチウム二次電池用電解液及び水溶液系リチウム二次電池
CN110945708A (zh) * 2017-09-15 2020-03-31 株式会社Lg化学 水性电解液和包括该水性电解液的储能装置
JP2020145314A (ja) * 2019-03-06 2020-09-10 株式会社ダイセル 電気化学キャパシタ用電極形成材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005223089A (ja) * 2004-02-04 2005-08-18 Japan Science & Technology Agency レドックスキャパシタ用コンポジット電極材料及びその製造方法
JP2007299801A (ja) * 2006-04-27 2007-11-15 Mitsui Mining & Smelting Co Ltd 蓄エネルギ素子
JP2011238404A (ja) * 2010-05-07 2011-11-24 Mie Univ リチウム二次電池及びリチウム二次電池用の複合負極
JP2012028366A (ja) * 2010-07-20 2012-02-09 Nec Tokin Corp 蓄電デバイス

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004342595A (ja) * 2003-04-25 2004-12-02 Nec Tokin Corp 電気化学セル用電極およびそれを用いた電気化学セル
US20070231704A1 (en) * 2006-03-30 2007-10-04 Ohara Inc. Lithium ion conductive solid electrolyte and production process thereof
JP2008066681A (ja) * 2006-09-11 2008-03-21 Osaka Prefecture Univ 電気化学キャパシタ及び電気化学キャパシタ亜鉛電極の作製方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005223089A (ja) * 2004-02-04 2005-08-18 Japan Science & Technology Agency レドックスキャパシタ用コンポジット電極材料及びその製造方法
JP2007299801A (ja) * 2006-04-27 2007-11-15 Mitsui Mining & Smelting Co Ltd 蓄エネルギ素子
JP2011238404A (ja) * 2010-05-07 2011-11-24 Mie Univ リチウム二次電池及びリチウム二次電池用の複合負極
JP2012028366A (ja) * 2010-07-20 2012-02-09 Nec Tokin Corp 蓄電デバイス

Cited By (23)

* Cited by examiner, † Cited by third party
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CN105612633B (zh) * 2013-10-15 2018-11-09 罗伯特·博世有限公司 用于锂离子蓄电池的锂电极及其制造方法
CN105612633A (zh) * 2013-10-15 2016-05-25 罗伯特·博世有限公司 用于锂离子蓄电池的锂电极及其制造方法
WO2015055351A1 (fr) * 2013-10-15 2015-04-23 Robert Bosch Gmbh Électrode au lithium pour accumulateur lithium-ions et son procédé de fabrication
US10553858B2 (en) 2013-10-15 2020-02-04 Robert Bosch Gmbh Lithium electrode for a rechargeable lithium-ion battery and method for the manufacture thereof
US10629958B2 (en) 2015-01-14 2020-04-21 The University Of Tokyo Aqueous electrolytic solution for power storage device and power storage device including said aqueous electrolytic solution
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JPWO2016114141A1 (ja) * 2015-01-14 2017-12-07 国立大学法人 東京大学 蓄電装置用水系電解液、及び当該水系電解液を含む蓄電装置
CN107112600B (zh) * 2015-01-14 2020-04-24 国立大学法人东京大学 蓄电装置用水系电解液和含有该水系电解液的蓄电装置
US10658706B2 (en) 2016-01-14 2020-05-19 The University Of Tokyo Aqueous electrolytic solution for power storage device and power storage device including said aqueous electrolytic solution
WO2017122597A1 (fr) * 2016-01-14 2017-07-20 国立大学法人東京大学 Solution électrolytique aqueuse pour dispositif de stockage électrique, et dispositif de stockage électrique comprenant ladite solution électrolytique aqueuse
JP2017126500A (ja) * 2016-01-14 2017-07-20 国立大学法人 東京大学 蓄電装置用水系電解液、及び当該水系電解液を含む蓄電装置
US20190019629A1 (en) * 2016-03-18 2019-01-17 Shinshu University Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof
EP3428941A4 (fr) * 2016-03-18 2019-03-27 Shinshu University Électrode négative composite au lithium et condensateur hybride, et leurs procédés de fabrication
US10790097B2 (en) 2016-03-18 2020-09-29 Shinshu University Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof
CN108780707A (zh) * 2016-03-18 2018-11-09 国立大学法人信州大学 锂复合负极及混合电容器以及它们的制造方法
JPWO2018097259A1 (ja) * 2016-11-28 2019-10-17 トヨタ自動車株式会社 リチウムイオン二次電池用電解液、その製造方法、及びリチウムイオン二次電池
WO2018097259A1 (fr) * 2016-11-28 2018-05-31 トヨタ自動車株式会社 Solution électrolytique pour piles rechargeables au lithium-ion, son procédé de fabrication et pile rechargeable au lithium-ion
JP2018181420A (ja) * 2017-04-03 2018-11-15 株式会社豊田中央研究所 水溶液系リチウム二次電池用電解液及び水溶液系リチウム二次電池
CN110945708A (zh) * 2017-09-15 2020-03-31 株式会社Lg化学 水性电解液和包括该水性电解液的储能装置
JP2020145314A (ja) * 2019-03-06 2020-09-10 株式会社ダイセル 電気化学キャパシタ用電極形成材料
WO2020179653A1 (fr) * 2019-03-06 2020-09-10 株式会社ダイセル Matériau de formation d'électrode pour condensateurs électrochimiques
EP3937200A4 (fr) * 2019-03-06 2022-12-28 Daicel Corporation Matériau de formation d'électrode pour condensateurs électrochimiques
US11742153B2 (en) 2019-03-06 2023-08-29 Daicel Corporation Electrode-forming material for electrochemical capacitors

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