WO2014136729A1 - Dispositif de stockage d'électricité - Google Patents

Dispositif de stockage d'électricité Download PDF

Info

Publication number
WO2014136729A1
WO2014136729A1 PCT/JP2014/055319 JP2014055319W WO2014136729A1 WO 2014136729 A1 WO2014136729 A1 WO 2014136729A1 JP 2014055319 W JP2014055319 W JP 2014055319W WO 2014136729 A1 WO2014136729 A1 WO 2014136729A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage device
carbonate
electricity storage
electrolytic solution
nitroxyl
Prior art date
Application number
PCT/JP2014/055319
Other languages
English (en)
Japanese (ja)
Inventor
基陽 安井
岩佐　繁之
教徳 西
Original Assignee
日本電気株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気株式会社 filed Critical 日本電気株式会社
Priority to JP2015504300A priority Critical patent/JPWO2014136729A1/ja
Publication of WO2014136729A1 publication Critical patent/WO2014136729A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/48—Conductive polymers
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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 electricity storage device, and in particular, includes a positive electrode including a nitroxyl compound, a negative electrode including a material capable of reversibly inserting and removing lithium ions, and an aprotic organic solvent in which a lithium salt is dissolved.
  • the present invention relates to an electricity storage device including an electrolytic solution.
  • a power storage device used in such portable electronic devices is required to have high energy density, high output characteristics, high safety, and high cycle stability.
  • a lithium ion capacitor is known as an electricity storage device having high output and high cycle stability. Since electric charges are stored by an electrostatic mechanism using an electric double layer, the energy density is small but the output is high and the cycle stability is also high. Patent Document 1 proposes storing lithium ions in advance by a chemical method for the negative electrode in order to increase the energy density. However, a sufficient energy density is still not obtained.
  • Patent Document 2 proposes a power storage device containing a nitroxyl compound in a positive electrode as a high-power power storage device (this power storage device is referred to as an “organic radical battery”).
  • This nitroxyl compound takes an oxoammonium cation partial structure in an oxidized state, takes a nitroxyl radical partial structure in a reduced state, and transfers electrons between the two states, and this reaction is used as an electrode reaction of a positive electrode. . Since this electrode reaction proceeds relatively quickly, a high output battery can be obtained, and the battery is safe without problems such as thermal runaway.
  • the power storage device described in Patent Document 2 has a high output at room temperature, but has a problem that the output decreases in a low temperature environment such as ⁇ 20 ° C.
  • a method for improving the output under a low temperature environment there is a method using an electrolytic solution having a low viscosity.
  • dimethyl carbonate (DMC) has a low viscosity of 0.59 cP at 20 ° C., but its melting point is 3 ° C. Therefore, in a low temperature environment such as ⁇ 20 ° C., the electrolytic solution is solidified and the battery does not operate.
  • An electricity storage device has a nitroxyl compound having a nitroxyl radical cation partial structure represented by the following formula (1) in an oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in a reduced state.
  • it contains 1% by volume or more and less than 25% by volume of propylene carbonate (PC).
  • FIG. 1 is a perspective view of a laminate type electricity storage device according to an embodiment of the present invention. It is sectional drawing of the lamination type electrical storage device by embodiment of this invention.
  • the electricity storage device contains propylene carbonate (PC) in the electrolytic solution.
  • PC propylene carbonate
  • PC propylene carbonate
  • the melting point of the electrolytic solution can be lowered by adding PC to the electrolytic solution, but since the viscosity is as high as 2.5 cP, the electrolytic solution to which PC is added There is a risk that the output becomes lower due to the lowering of the ionic conductivity due to the higher viscosity. Therefore, in order to operate the electricity storage device with high output in a low temperature environment, it is necessary to adjust the addition amount of PC.
  • the content rate of propylene carbonate (PC) is 1 volume% or more and less than 25 volume% with respect to the organic solvent of electrolyte solution (namely, in the total amount of the organic solvent including propylene carbonate), More preferably Is 10 volume% or more and 20 volume% or less. Further, it is preferable to adjust the composition of the electrolytic solution so that the ionic conductivity of the electrolytic solution at ⁇ 20 ° C. is 1.5 mS / cm or more and 5 mS / cm or less, more preferably 2 mS / cm or more and 5 mS / cm or less.
  • An electricity storage device includes a positive electrode including the nitroxyl compound as a positive electrode active material, a negative electrode, and an electrolytic solution including an electrolyte salt and an organic solvent.
  • the negative electrode can include a material capable of reversibly occluding and releasing lithium ions as a negative electrode active material, a lithium salt can be used as an electrolyte salt, and an aprotic solvent can be used as an organic solvent.
  • the electricity storage device can extract electrochemically stored energy in the form of electric power, and can be applied to an electric capacity device such as a primary battery, a secondary battery, a capacitor and a capacitor.
  • Electrode Material [1-1] Positive Electrode Active Material
  • the nitroxyl cation partial structure N-oxo-ammonium represented by the formula (1) in the oxidized state is used.
  • This nitroxyl compound can perform an oxidation-reduction reaction represented by the reaction formula (A) in which electrons are transferred between these two states.
  • the electricity storage device according to the present embodiment uses this oxidation-reduction reaction as the electrode reaction of the positive electrode.
  • the structure of the nitroxyl compound is not particularly limited, but is preferably a nitroxyl polymer compound from the viewpoint of solubility in an electrolytic solution.
  • the nitroxyl polymer compound is preferably a polymer containing a cyclic nitroxyl structure represented by the following formula (Ia) in the side chain in an oxidized state.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a divalent group forming a 5- to 7-membered ring, provided that X represents a side chain of the polymer.
  • X represents a side chain of the polymer.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, preferably an ethyl group or a methyl group, and particularly preferably a methyl group in terms of radical stability.
  • the hydrogen atom bonded to the atoms constituting the ring may be substituted with an alkyl group, a halogen atom, ⁇ O, an ether group, an ester group, a cyano group, an amide group, or the like.
  • Particularly preferred cyclic nitroxyl structures are 2,2,6,6-tetramethylpiperidinoxyl radical (or cation), 2,2,5,5-tetramethylpyrrolidinoxyl radical (or cation), 2,2 , 5,5-tetramethylpyrrolinoxyl radical (cation), 2,2,6,6-tetramethylpiperidinoxyl radical (or cation), 2,2,5,5-tetra A methylpyrrolidinoxyl radical (or cation) is more preferred.
  • the cyclic nitroxyl structure represented by formula (Ia) has a residue X ′ obtained by removing hydrogen from —CH 2 —, —CH ⁇ or —NH— constituting the ring member in X. Can be attached to the polymer.
  • the polymer used as the main chain of the nitroxyl polymer compound is not particularly limited as long as the cyclic nitroxyl structure represented by the formula (Ia) can be present in the side chain.
  • nitroxyl polymer compound examples include those obtained by adding a group of the formula (Ib) to a normal polymer, or those in which some atoms or groups of the polymer are substituted by the group of the formula (Ib).
  • the atoms constituting the cyclic structure of the formula (Ib) may be bonded to the polymer (main chain) via an appropriate divalent group in the middle instead of directly.
  • X ′ and atoms in the main chain of the polymer can be bonded via a divalent group such as an ester bond (—COO—) or an ether bond (—O—).
  • polyalkylene polymers such as polyethylene and polypropylene; poly (meth) acrylic acid; poly (meth) acrylamide polymers are excellent in electrochemical resistance.
  • Poly (meth) acrylate polymers and polystyrene polymers are preferred.
  • nitroxyl polymer compounds those having high stability and those represented by any of the following formulas (3) to (7) are preferable.
  • n is an integer of 1 or more.
  • the nitroxyl polymer compound represented by the formulas (3) to (5) has a 2,2,6,6-tetramethylpiperidinoxyl radical (or cation) in the side chain, and the formulas (6), (7
  • the nitroxyl polymer compound shown in (2) is a polymer compound having a 2,2,5,5-tetramethylpyrrolidinoxyl radical (or cation) in the side chain.
  • These nitroxyl polymer compounds are compounds having a sterically hindered stable radical in the side chain of the polymer.
  • the molecular weight of the nitroxyl polymer compound is preferably 1000 or more, more preferably 10,000 or more, from the viewpoint of solubility in the electrolytic solution. A higher molecular weight is preferred, but one having an average molecular weight of 5 million or less can be used.
  • the skeleton structure of the nitroxyl polymer compound may be any of a chain, a branch, and a network, and may be a structure crosslinked with a crosslinking agent.
  • nitroxyl polymer compound can be used alone, but two or more kinds may be mixed and used.
  • a conductive polymer such as polyacetylene, polyphenylene, polyaniline, polypyrrole, or a carbon material such as activated carbon, graphite, or carbon black may be added as a conductive auxiliary agent.
  • the content of the nitroxyl polymer compound in the positive electrode active material is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • Negative electrode active material As the negative electrode active material in the electricity storage device according to the present embodiment, a material capable of reversibly occluding and releasing lithium ions (a material capable of occluding and releasing lithium ions during charging and discharging during discharging) is used. Can do. As such a negative electrode active material, carbon materials such as metal oxides and graphite can be used. The shape of these materials is not particularly limited, and examples thereof include a thin film, a powdered product, a fiber, and a flake. These negative electrode active materials can be used alone or in combination.
  • Conductivity imparting agent When forming the positive electrode and the negative electrode, a conductivity imparting agent may be added for the purpose of reducing impedance.
  • the conductivity-imparting agent include carbonaceous fine particles such as graphite, carbon black, and acetylene black, carbon fibers such as carbon nanotubes, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene.
  • Binder A binder can also be used when forming the positive electrode and the negative electrode. By using the binder, the connection between the active materials, between the active material and the conductivity imparting agent, and between the active material or the conductivity imparting agent and the current collector can be strengthened.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, Examples thereof include resin binders such as polypropylene, polyethylene, polyimide, partially carboxylated cellulose, and various polyurethanes.
  • PTFE polytetrafluoroethylene
  • resin binders such as polypropylene, polyethylene, polyimide, partially carboxylated cellulose, and various polyurethanes.
  • the electrode material containing the positive electrode active material or the negative electrode active material can be provided on the current collector.
  • a foil, a sheet, a flat plate, or the like made of nickel, aluminum, copper, aluminum alloy, stainless steel, carbon, or the like can be used as the current collector.
  • FIG. 1 is a perspective view of an example of a laminate type power storage device according to the present embodiment, and FIG. As shown in these drawings, the electricity storage device 107 has a laminated structure including a positive electrode 101, a negative electrode 102 facing the positive electrode, and a separator 105 sandwiched between the positive electrode and the negative electrode.
  • the electrode lead 104 is drawn out to the outside of the exterior film 106.
  • An electrolytic solution is injected into the electricity storage device.
  • the positive electrode 101 includes a positive electrode active material, and further includes a conductivity imparting agent and a binder as necessary, and is formed on one current collector 103.
  • the negative electrode 102 includes a negative electrode active material, and further includes a conductivity imparting agent and a binder as necessary, and is formed on the other current collector 103.
  • An insulating porous separator 105 is provided between the positive electrode 101 and the negative electrode 102 to insulate and separate them.
  • a porous resin film made of polyethylene, polypropylene, or the like, a cellulose film, a non-woven cloth, or the like can be used.
  • Electrolytic Solution transports charge carriers between the positive electrode and the negative electrode, and is impregnated in the positive electrode 101, the negative electrode 102, and the separator 105.
  • a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in an organic solvent can be used.
  • an aprotic organic solvent can be used.
  • electrolyte salt examples include LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 (hereinafter “LiTFSI”), LiN (C 2 F 5 SO 2 ) 2 (hereinafter “LiBETI”). ), Li (CF 3 SO 2 ) 3 C, Li (C 2 F 5 SO 2 ) 3 C, or other ordinary electrolyte materials can be used.
  • propylene carbonate As an organic solvent, propylene carbonate (PC) is added.
  • examples of the organic solvent mixed with propylene carbonate include cyclic carbonates other than propylene carbonate such as ethylene carbonate and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; and ⁇ -lactones such as ⁇ -butyrolactone.
  • Cyclic ethers such as tetrahydrofuran and dioxolane; amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, and at least one of cyclic carbonate and chain carbonate is preferably mixed.
  • the content of cyclic carbonate other than propylene carbonate is preferably 20% by volume to 40% by volume and more preferably 25% by volume to 30% by volume in the organic solvent of the electrolytic solution.
  • the content of the chain carbonate is preferably 50% by volume to 70% by volume and more preferably 55% by volume to 65% by volume in the organic solvent of the electrolytic solution.
  • Exterior Film As the exterior film 106, an aluminum laminate film or the like can be used. Examples of the exterior body other than the exterior film include a metal case and a resin case. Examples of the outer shape of the electricity storage device include a cylindrical shape, a square shape, a coin shape, and a sheet shape.
  • the slurry was applied on a copper mesh as a current collector and then dried at 120 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 ⁇ 24 mm rectangle, and a nickel electrode lead was ultrasonically bonded. The thickness of the obtained negative electrode was 50 to 60 ⁇ m.
  • Example 1 PTMA 2.1 g as a positive electrode active material, carbon black 0.63 g as a conductivity imparting agent, carboxymethyl cellulose (CMC) 0.24 g and polytetrafluoroethylene (PTFE) 0.03 g as a binder, and 15 ml of water are mixed. The mixture was stirred with a homogenizer to prepare a uniform slurry.
  • CMC carboxymethyl cellulose
  • PTFE polytetrafluoroethylene
  • the slurry was applied on an aluminum foil as a current collector and then dried at 80 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 ⁇ 24 mm rectangle, and an aluminum electrode lead was ultrasonically bonded. The thickness of the positive electrode obtained was 140 to 150 ⁇ m.
  • a polypropylene porous film separator was sandwiched between the positive electrode and the negative electrode to obtain an electrode laminate.
  • the electrode laminate was covered with aluminum laminate and three sides including the electrode lead portion were heat-sealed.
  • a power storage device was produced in the same manner as described above.
  • PTMA 2.1 g as a positive electrode active material, carbon black 0.63 g as a conductivity imparting agent, carboxymethyl cellulose (CMC) 0.24 g and polytetrafluoroethylene (PTFE) 0.03 g as a binder, and 15 ml of water are mixed. The mixture was stirred with a homogenizer to prepare a uniform slurry.
  • the slurry was applied on an aluminum foil as a current collector and then dried at 80 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 ⁇ 24 mm rectangle, and an aluminum electrode lead was ultrasonically bonded. The thickness of the positive electrode obtained was 140 to 150 ⁇ m.
  • a polypropylene porous film separator was sandwiched between the positive electrode and the negative electrode to obtain an electrode laminate.
  • the electrode laminate was covered with aluminum laminate and three sides including the electrode lead portion were heat-sealed.
  • Table 1 shows the ionic conductivity of the electrolytic solutions used in the examples and comparative examples.
  • the content rate of propylene carbonate (PC) is represented by volume% with respect to the organic solvent of electrolyte solution. Except for Comparative Example 1 and Example 4, the ionic conductivity at 20 ° C. was generally in the range of 10 to 11 mS / cm. On the other hand, the ionic conductivity at ⁇ 20 ° C. was generally in the range of 2 to 5 mS / cm, but in Comparative Example 3 in which the content of propylene carbonate was 25% by volume, it was lower than 2 mS / cm.
  • Example 1 shows the maximum output results.
  • Example 2, Example 3, Example 4, Comparative Example 1 respectively, the maximum output of Comparative Example 2, Comparative Example 3, 32mW / cm 2, 75mW / cm 2, 70mW / cm 2, 42mW / cm 2, 20mW / cm 2, was 0mW / cm 2, 65mW / cm 2.
  • the electricity storage device of Comparative Example 2 could not be charged / discharged at ⁇ 20 ° C.
  • Example 1, Example 2, Example 3, Example 4, and Comparative Example 3 to which propylene carbonate (PC) was added were compared with Comparative Example 1 and Comparative Example 2 to which PC was not added.
  • the output characteristics were high. In particular, in Examples 2 and 3 in which the PC content was 10 to 20% by volume, high output was obtained. From this result, it was found that the output characteristics in a low temperature environment were improved by adding propylene carbonate (PC) to the electrolytic solution.
  • PC propylene carbonate
  • Table 3 shows the results. In Examples 1, 2, 3 and Comparative Example 2, the rate of increase in internal resistance (after 1 week) was almost the same, whereas in Example 3 of Comparative Example, the rate of increase in internal resistance (after 1 week) was large. From this result, it is considered that when an electrolytic solution to which 25% by volume or more of PC is added is used, the internal low efficiency of the electricity storage device increases and long-term reliability is impaired.
  • the power storage device is a power storage device for driving or auxiliary such as an electric vehicle or a hybrid electric vehicle, a power source for various portable electronic devices, a power storage device for various energy such as solar energy or wind power generation, or It can be applied to a storage power source for household appliances.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un dispositif de stockage d'électricité caractérisé en ce qu'il comprend : une cathode, qui comprend un composé de nitroxyle qui possède une structure partielle de radical nitroxyle indiquée par la formule (2) lorsqu'il est dans un état réduit et qui possède une structure partielle de cation radical nitroxyle indiqué par la formule (1) lorsqu'il est dans un état oxydé ; une anode contenant un matériau carboné de telle sorte que des ions de lithium peuvent être insérés/libérés de manière réversible ; et un électrolyte contenant un sel de lithium et un solvant organique non protique ; et le solvant organique contient au moins 1 % en volume et moins de 25 % en volume d'un carbonate de propylène (PC) par rapport au solvant organique. A l'aide de la présente invention, il est possible de fournir un dispositif de stockage d'électricité qui possède une sortie élevée dans des environnements à basse température.
PCT/JP2014/055319 2013-03-04 2014-03-03 Dispositif de stockage d'électricité WO2014136729A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015504300A JPWO2014136729A1 (ja) 2013-03-04 2014-03-03 蓄電デバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-042183 2013-03-04
JP2013042183 2013-03-04

Publications (1)

Publication Number Publication Date
WO2014136729A1 true WO2014136729A1 (fr) 2014-09-12

Family

ID=51491246

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/055319 WO2014136729A1 (fr) 2013-03-04 2014-03-03 Dispositif de stockage d'électricité

Country Status (2)

Country Link
JP (1) JPWO2014136729A1 (fr)
WO (1) WO2014136729A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020074476A (ja) * 2015-04-23 2020-05-14 株式会社ジェイテクト リチウムイオンキャパシタ

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05325972A (ja) * 1992-05-15 1993-12-10 Kanebo Ltd 有機電解質電池
JPH0883625A (ja) * 1994-09-13 1996-03-26 Toshiba Battery Co Ltd 非水電解液二次電池
JPH0973919A (ja) * 1995-09-04 1997-03-18 Fuji Elelctrochem Co Ltd 電池用電解液
JPH10284122A (ja) * 1997-04-10 1998-10-23 Kanebo Ltd 有機電解質電池
WO2010140512A1 (fr) * 2009-06-02 2010-12-09 日本電気株式会社 Dispositif accumulateur d'énergie électrique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05325972A (ja) * 1992-05-15 1993-12-10 Kanebo Ltd 有機電解質電池
JPH0883625A (ja) * 1994-09-13 1996-03-26 Toshiba Battery Co Ltd 非水電解液二次電池
JPH0973919A (ja) * 1995-09-04 1997-03-18 Fuji Elelctrochem Co Ltd 電池用電解液
JPH10284122A (ja) * 1997-04-10 1998-10-23 Kanebo Ltd 有機電解質電池
WO2010140512A1 (fr) * 2009-06-02 2010-12-09 日本電気株式会社 Dispositif accumulateur d'énergie électrique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020074476A (ja) * 2015-04-23 2020-05-14 株式会社ジェイテクト リチウムイオンキャパシタ
JP2022034033A (ja) * 2015-04-23 2022-03-02 株式会社ジェイテクト リチウムイオンキャパシタ
JP7103376B2 (ja) 2015-04-23 2022-07-20 株式会社ジェイテクト リチウムイオンキャパシタ

Also Published As

Publication number Publication date
JPWO2014136729A1 (ja) 2017-02-09

Similar Documents

Publication Publication Date Title
JP5516578B2 (ja) 蓄電デバイス
JP5329310B2 (ja) イオン液体を用いたリチウム二次電池
JP5215307B2 (ja) リチウム二次電池
JP5076560B2 (ja) 蓄電デバイス
JP5228531B2 (ja) 蓄電デバイス
JPWO2010128584A1 (ja) 非水溶媒、並びにそれを用いた非水電解液および非水系二次電池
JP2011252106A (ja) ラジカルを有する化合物、重合体、およびその重合体を用いた蓄電デバイス
WO2014092016A1 (fr) Dispositif de stockage électrique
JP5160159B2 (ja) リチウム二次電池
JP7092037B2 (ja) ラジカルポリマーを用いた電極及び二次電池
JP2013062164A (ja) 電気化学素子用非水電解液および電気化学素子
JP7115318B2 (ja) ラジカルポリマーを用いた電極及び二次電池
JP6895085B2 (ja) 蓄電デバイス
JP2008258031A (ja) ポリマー二次電池
WO2014136729A1 (fr) Dispositif de stockage d'électricité
JP6447050B2 (ja) 蓄電デバイスの製造方法
WO2020017630A1 (fr) Batterie secondaire utilisant un polymère radicalaire dans une électrode
WO2013114785A1 (fr) Dispositif de stockage d'électricité
WO2014092128A1 (fr) Dispositif de stockage électrique
JP7107395B2 (ja) ラジカルポリマーを電極に用いた二次電池
JP2023153526A (ja) 回復方法、蓄電デバイスの製造方法及び回復剤
JP2012151396A (ja) 蓄電デバイス
JP2013012331A (ja) 非水電解質二次電池およびその正極の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14759810

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015504300

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14759810

Country of ref document: EP

Kind code of ref document: A1