WO2019059053A1 - ゲル電解質、硬質ゲル電解質、および電気化学デバイス - Google Patents

ゲル電解質、硬質ゲル電解質、および電気化学デバイス Download PDF

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WO2019059053A1
WO2019059053A1 PCT/JP2018/033713 JP2018033713W WO2019059053A1 WO 2019059053 A1 WO2019059053 A1 WO 2019059053A1 JP 2018033713 W JP2018033713 W JP 2018033713W WO 2019059053 A1 WO2019059053 A1 WO 2019059053A1
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gel
electrolyte
mass
gel electrolyte
solvent
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PCT/JP2018/033713
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English (en)
French (fr)
Japanese (ja)
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恭輝 齊藤
淳史 奥原
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第一工業製薬株式会社
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Priority to CN201880058761.9A priority Critical patent/CN111095655B/zh
Priority to KR1020207005344A priority patent/KR102658513B1/ko
Publication of WO2019059053A1 publication Critical patent/WO2019059053A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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

Definitions

  • the present invention relates to a gel-like body containing a crosslinkable reactive group, which is capable of being used as an electrolyte with which an electrochemical device is provided by crosslinking reaction of the reactive group and curing the gel electrolyte;
  • the present invention relates to a cured hard gel electrolyte and an electrochemical device comprising the hard gel electrolyte.
  • an electrochemical device using an electrochemical reaction for example, various batteries, a part of a solar cell, a capacitor (capacitor) and the like are known.
  • a liquid (electrolyte solution) is used as an electrolyte used for these electrochemical devices.
  • the electrolyte is a common electrolyte, the possibility of electrolyte leakage from the electrochemical device can not be ruled out. Therefore, in recent years, for example, as in the electrochemical cell disclosed in Patent Document 1 and a method of manufacturing the same, a configuration using a gel electrolyte in which the electrolyte solution is gelled has been proposed.
  • the process which injects electrolyte solution is needed.
  • a prepolymer is generally used.
  • the prepolymer is previously dissolved in the electrolytic solution, but such an electrolytic solution (prepolymer electrolytic solution) has a viscosity higher than that of a normal electrolytic solution.
  • the electrolyte injection step since it is necessary to inject a high viscosity prepolymer electrolyte into the electrochemical device, the time required for the electrolyte injection step may be prolonged. Therefore, there is a possibility that the manufacturing process of the electrochemical device can not be made sufficiently efficient.
  • the amount of injection of the prepolymer electrolyte becomes large in the electrolyte injection step. Therefore, the injection of the prepolymer electrolyte may be insufficient. Insufficient injection of the prepolymer electrolyte may result in failure to achieve sufficient device performance in the electrochemical device.
  • the present invention has been made to solve such problems, and it is possible to improve the efficiency of the production of electrochemical devices, and to realize good device performance in the obtained electrochemical devices.
  • the gel electrolyte according to the present invention is a gel-like body constituted by at least a matrix material and an electrolytic solution, contains a crosslinkable reactive group, and crosslinks the reactive group.
  • the electrolytic solution is at least composed of an ionic substance and an electrolytic solution solvent, and the mass of the reactive group contained in the gel-like body is the electrolytic solution While it is a range which is 0.03 mass% or more and 6.5 mass% or less with respect to the mass of a solvent, it is the structure whose shear elasticity modulus of the said gel-like body in the state which the said reactive group is unreacted is 1 MPa or more.
  • the gel electrolyte in the uncured state contains an appropriate amount of reactive groups. So, even if it becomes the gel electrolyte (hard gel electrolyte) which the crosslinking reaction of the reactive group advanced fully, the said hard gel electrolyte can hold
  • the gel electrolyte since the shear modulus of elasticity of the gel electrolyte is 1 MPa or more even in the uncured state, the gel electrolyte has a good strength. Therefore, since good handleability can be realized in the gel electrolyte, it is possible to suppress the inefficiency of production of the electrochemical device. Moreover, as described above, since the crosslinking reaction may be allowed to proceed after preparing the electrochemical device using the gel electrolyte in the uncured state, the liquid injection step becomes unnecessary in the process of manufacturing the electrochemical device. Therefore, it is possible to avoid the fear that the liquid injection will be insufficient, or the fear of performance deterioration or the like due to the insufficient liquid injection.
  • the said gel-like body in addition to the said matrix material and the said electrolyte solution, may be the structure which contains the post-curing agent which has the said reactive group further.
  • the mass of the said electrolyte solution solvent may be the structure which is the range of 20 mass% or more and 80 mass% or less with respect to the total mass of the said gel-like body.
  • the mass of the said matrix material may be the structure which is the range of 1.0 mass% or more and 10 mass% or less with respect to the total mass of the said gel-like body.
  • the gel-like body contains a dilution solvent which is a component different from the electrolyte solvent and is removed before the cross-linking reaction of the reactive group
  • the mass range or the mass range of the matrix material may be defined as to the total mass of the gel-like body excluding the dilution solvent.
  • seat shape may be sufficient.
  • the thickness of the said gel-like body may be 5 micrometers or more and 100 micrometers or less.
  • the hard gel electrolyte according to the present disclosure has a configuration in which the reaction group in the gel electrolyte having the above configuration is crosslinked to increase its hardness.
  • the hard gel electrolyte having the above configuration may be configured to satisfy at least one of an ion conductivity of 0.8 mS / cm or more and a shear modulus of 6 MPa or more.
  • the electrochemical device according to the present disclosure may have a configuration provided with the hard gel electrolyte of the above configuration.
  • the gel electrolyte according to the present disclosure is a gel-like body constituted by at least a matrix material and an electrolytic solution, and contains a crosslinkable reactive group, and is cured by causing the reactive group to crosslink and cure. And an electrolyte included in an electrochemical device.
  • the electrolytic solution is composed of at least an ionic substance and an electrolytic solution solvent, but in the gel electrolyte according to the present disclosure, the mass of the reactive group contained in the gel electrolyte (gel-like body) is the mass of the electrolytic solution solvent.
  • the gel electrolyte (gel-like body) in the unreacted state of the reactive group has a strength of 1 MPa or more as well as in the range of 0.03 mass% or more and 6.5 mass% or less. There is.
  • the gel electrolyte according to the present disclosure is a gel-like body mainly composed of a matrix material and an electrolytic solution, but the gel-like body contains an unreacted reactive group.
  • the reactive group may be one possessed by the matrix material or the one possessed by the electrolytic solution, or both the matrix material and the electrolytic solution may possess reactive groups, the matrix material and the electrolysis Components other than the liquid may have a reactive group.
  • the gel-like body (gel electrolyte) may contain components other than the matrix material and the electrolytic solution. Representative other components include post-curing agents having reactive groups.
  • the matrix material constituting the gel-like material is not particularly limited as long as the gel-like material can be formed in the state containing the electrolytic solution.
  • the matrix material may be a physical gel that forms a three-dimensional structure by noncovalent bonds such as hydrogen bonds, or may be a chemical gel that forms a three-dimensional structure by covalent bonds.
  • the matrix material may have an unreacted reactive group, as long as the gel-like material has a reactive group capable of a crosslinking reaction.
  • the matrix material is a compound that forms a physical gel (for convenience, it is referred to as a physical gel compound), and an electrolyte solution is added to the matrix material to form a gel (non-covalent bond)
  • a gel electrolyte may be formed, and the gel-like body may have an unreacted reactive group.
  • the matrix material is a chemical gel-forming compound (for convenience, a chemical gel compound), and is partially cured by partially crosslinking the reactive groups of the matrix material.
  • a gel-like body (gel electrolyte) is formed, and in this semi-hardened gel-like body, it may be a configuration in which unreacted reactive groups remain.
  • the mass ratio of the reactive group possessed by (or remaining in) the gel-like substance may be in the range of 0.03 mass% or more and 6.5 mass% or less with respect to the mass of the electrolyte solvent (First condition of gel electrolyte described later).
  • the reactive group may be possessed by at least one of the matrix material and the electrolytic solution, or may be possessed by another component. Therefore, the mass ratio of the reactive group can be calculated using the ratio (molecular weight ratio) of the molecular weight of the reactive group to the molecular weight of one molecule of the component having the reactive group, as exemplified in the examples described later.
  • the gel electrolyte having an unreacted reactive group is in a state in which curing has not sufficiently progressed, this state is referred to as “uncured state” for convenience.
  • the crosslinking reaction of the reactive group proceeds to increase the hardness, and when it becomes a hard gel electrolyte, this state is referred to as “cured state” for convenience.
  • the "semi-hardened state” mentioned above means the state in which one part reacted among all the reactive groups which the said compound has.
  • the chemical gel compound does not form a gel. Further, the state in which a cross-linking reaction of a part of the reactive groups of the chemical gel compound is a “semi-hardened state”, the chemical gel compound is gelled. In this semi-hardened chemical gel compound, the reactive group remains in the range of 0.03 to 6.5% by mass with respect to the mass of the solvent of the electrolyte solution, so the gel electrolyte according to the present disclosure (gelled body It corresponds to).
  • a semi-cured chemical gel compound i.e., a gel electrolyte
  • a semi-cured chemical gel compound can be said to be "uncured.” Then, if the crosslinking reaction of the reactive group remaining in the semi-cured chemical gel compound proceeds to increase the hardness, the chemical gel compound becomes a cured hard gel electrolyte.
  • the matrix material can include a polymeric material.
  • a suitable matrix material can be appropriately selected according to the application of the gel electrolyte according to the present disclosure, that is, the type of electrochemical device produced (manufactured) using the gel electrolyte according to the present disclosure, and the like.
  • a lithium ion battery is illustrated as an example of the electrochemical device, but in this case, a polymer type, an inorganic type, or a low molecular weight type may be suitably used as the matrix material. it can.
  • fluoride polymers such as polyvinylidene fluoride (PDVF), vinylidene fluoride-hexafluoropropylene copolymer (PDVF-HFP), etc .
  • acrylic resins such as polyacrylonitrile (PAN) or methacrylic resins Etc.
  • examples of inorganic substances include, but are not particularly limited to, silica particles, alumina particles, silica / alumina mixed particles, titanium oxide particles, zinc oxide particles, zirconium oxide particles and the like.
  • Examples of the low molecular weight system include, but are not particularly limited to, fatty acid ester derivatives, cyclohexane derivatives, amino acid derivatives, cyclic peptide derivatives, alkyl hydrazide derivatives and the like.
  • matrix materials Only one type of these matrix materials may be used, or two or more types may be appropriately selected and used in combination.
  • two or more types of polymer-based matrix materials may be used in combination, or one or more types of polymer-based and inorganic-based matrix materials may be used in combination.
  • one or more types of polymer systems, inorganic systems, and low molecular systems may be selected and used in combination.
  • the gel-like body may contain a post-curing agent having a reactive group.
  • This post-curing agent can be regarded as a component different from the matrix material in a state in which the reactive group has not reacted, but if the crosslinking reaction by the reactive group proceeds sufficiently, it constitutes part of the matrix material. Become. Therefore, the post-curing agent can be handled as part of the matrix material, depending on the composition of the gel-like material and the like.
  • the specific configuration of the post-curing agent is not particularly limited, and a suitable reactive compound can be selected depending on the composition of the gel electrolyte according to the present disclosure or the type of use (electrochemical device) or the like.
  • a lithium ion battery is illustrated as an example of the electrochemical device, and the polymer system or the inorganic system described above is illustrated as the matrix material, but in this case, the post curing agent is And reactive compounds of acrylate type or oxetane type.
  • the acrylate compound include, but are not particularly limited to, for example, tetrafunctional polyether acrylate, difunctional polyether acrylate, other AO addition acrylates, polyethylene glycol diacrylate and the like.
  • tetrafunctional polyether acrylate difunctional polyether acrylate
  • other AO addition acrylates polyethylene glycol diacrylate and the like.
  • oxetane type compound although a methyl methacrylate-oxetanyl methacrylate copolymer etc. can be mentioned, it is not specifically limited.
  • These post-curing agents may be used alone or in combination of two or more.
  • the matrix material is, for example, a chemical gel compound having an unreacted reactive group as described above, a gel-like body (gel electrolyte in a semi-cured state by first crosslinking some of the reactive groups)
  • a gel-like body gel electrolyte in a semi-cured state by first crosslinking some of the reactive groups
  • the curing agent previously used to achieve the semi-cured state is referred to as a "pre-curing agent" in contrast to the post-curing agent.
  • the reactive group contained in the gel electrolyte crosslinks to increase the degree of curing of the gel electrolyte.
  • the specific type of the reactive group is not particularly limited, and a suitable reactive group can be selected according to the composition of the gel electrolyte or the type of the application (electrochemical device).
  • a lithium ion battery is illustrated as an example of the electrochemical device, and the polymer system or the inorganic system described above is illustrated as the matrix material.
  • reactive groups as exemplified below can be suitably used.
  • Specific reactive groups include double bond functional groups such as (meth) acrylic groups (acrylic and methacrylic groups) and allyl groups; oxirane based functional groups such as epoxy groups and oxetane groups; thiol groups; amino groups And combinations of functional groups of condensation reaction systems such as carboxy group (amide bond), hydroxy group and carboxy group (ester bond); isocyanates such as isocyanate group and hydroxy group (urethane bond), isocyanate group and amino group (urea bond) Combination of functional groups of the system reaction; and the like. Only one type of these functional groups (or a combination of functional groups) may be contained in the gel electrolyte (gel-like body), or two or more types may be contained. When the matrix material is a chemical gel compound having an unreacted reactive group, the compound may have at least one of these functional groups (or a combination thereof).
  • the electrolyte constituting the gel electrolyte may be any one that can exhibit an electrochemical reaction in an electrochemical device.
  • the specific configuration of the electrolytic solution is not specifically limited as in the matrix material, but the composition of the gel electrolyte or the type of application (electrochemical device), the type of the matrix material that constitutes the gel electrolyte with the electrolytic solution, etc. According to the above, an electrolytic solution having a suitable composition can be suitably used.
  • the electrolytic solution in the present disclosure may be a composition composed of at least an ionic substance and an electrolytic solution solvent as described above.
  • the electrolyte solution solvent means the solvent which comprises the electrolyte solution of an electrochemical device.
  • various salts can be used as the ionic substance.
  • a lithium ion battery is illustrated as an example of the electrochemical device, so in this embodiment, a lithium salt can be mentioned as the ionic substance.
  • lithium salt typically, lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluorophosphate (LiPF 6 ), lithium bis (fluorosulfonyl) imide (LiFSI), lithium perchlorate (LiClO 4) And lithium tetraborate (LiBF 4 ), etc., but it is not particularly limited.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • LiPF 6 lithium hexafluorophosphate
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiClO 4 lithium perchlorate
  • LiBF 4 lithium tetraborate
  • examples of the electrolyte solvent include, but are not particularly limited to, carbonate solvents, ionic liquids, nitrile solvents, ether solvents and the like.
  • cyclic carbonate typically includes ethylene carbonate (EC) or propylene carbonate (PC)
  • chain carbonate typically includes dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl Although carbonate (EMC) etc. are mentioned, it does not specifically limit.
  • an ionic liquid can be mentioned as another typical electrolyte solution solvent.
  • 1,2-ethylmethylimidazolium bis (fluorosulfonyl) imide, 1,2-ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluoro) Sulfonyl) imide abbreviation: EMImFSI
  • N-methylpropylpyrrolidinium bis (fluorosulfonyl) imide N-methylpropylpyrrolidinium bis (trifluoromethanesulfonyl) imide
  • diethylmethylmethoxyethylammonium bis (trifluoromethanesulfonyl) imide diethylmethylmethoxyethylammonium bis (trifluoromethanesulfonyl) imide
  • the gel electrolyte before the increase in the degree of curing may contain other components (other components) in addition to the matrix material and the electrolyte solution.
  • the other components include the above-described post-curing agents, but other than these, for example, various additives can be mentioned.
  • an initiator used to accelerate the crosslinking reaction of the uncrosslinked reactive group contained in the matrix material can be mentioned.
  • 2,2′-azobis (2,4-dimethylvaleronitrile) is used as an initiator.
  • the mass of the reactive group contained in the gel electrolyte may be in the range of 0.03 to 6.5% by mass with respect to the mass of the electrolyte solvent. .
  • the shear elasticity modulus should just be 1 Mpa or more. That is, in the gel electrolyte according to the present disclosure, the lower limit of the shear modulus in the unreacted state of the reactive group is set to a predetermined value under the “first condition” that the mass ratio of unreacted reactive groups is limited within a predetermined range. It meets both the "second condition" of limitation.
  • the mass ratio of the reactive group to the electrolyte solvent which is the first condition of the gel electrolyte, is calculated using the ratio (molecular weight ratio) of the molecular weight of the reactive group to the molecular weight of one molecule of the component having the reactive group. Good.
  • the post-curing agent has a reactive group in the gel electrolyte, but the ratio of the molecular weight of the reactive group to the molecular weight of the post-curing agent is calculated, and the post curing is performed based on this molecular weight ratio.
  • the mass of the reactive group is calculated from the compounding amount of the agent.
  • the mass of the reactive group may be in the range of 0.03 to 6.5 mass% with respect to the mass of the electrolyte solvent contained in the gel electrolyte.
  • the uncured gel electrolyte When the gel electrolyte satisfies the first condition, the uncured gel electrolyte contains an appropriate amount of unreacted reactive groups. Therefore, even if the crosslinking reaction of the reactive group proceeds to form a hard gel electrolyte, the hard gel electrolyte can hold a sufficient amount of electrolyte solution. In addition, it becomes possible to leak part of the electrolyte solution from the matrix material as the crosslinking reaction proceeds. Therefore, if an electrochemical device is manufactured using an uncured gel electrolyte and then the crosslinking reaction is allowed to proceed, the leaked electrolyte can be well brought into contact with the contact surface of the electrode included in the electrochemical device. it can. This enables the realization of good electrochemical reactions in electrochemical devices.
  • the shear elastic modulus of the gel electrolyte in the uncured state which is the second condition of the gel electrolyte, may be measured or evaluated by the known measurement method or evaluation method.
  • the uncured gel electrolyte obtained in each Example or Comparative Example was measured using a table-type precision universal testing machine manufactured by Shimadzu Corporation (product name: Autograph AGS-X). After mounting a pressing jig and applying a 0.05N preload, a pressing test is carried out at a speed of 0.05 mm / min, and the shear modulus is measured by the following formula (1) from the result of the pressing test. (Unit: MPa).
  • Shear modulus (G) 0.36 Fg [(D ⁇ h) / h] 3/2 / R 2 (1)
  • F in the above equation (1) is the load (test force) in the indentation test
  • g is the gravitational acceleration
  • D is the thickness (film thickness) of the gel electrolyte (gel-like body)
  • h is the load Is the change in thickness (film thickness) by R
  • R is the sphere radius of the spherical indenter in the indentation test.
  • reference 1 DJ Taylor and AM Kragh, “Determination of the rigidity moduli of thin soft coatings by indentation measurements” Journal of Physics D: Applied Physics, United Kingdom, IOP Publishing, January 1970, Volume 3, Number 1, 29 was taken as a reference.
  • the gel electrolyte When the gel electrolyte satisfies the second condition and the shear modulus of elasticity of the gel electrolyte is 1 MPa or more even in the uncured state, the gel electrolyte has good strength. Therefore, since good handleability can be realized in the gel electrolyte, it is possible to suppress the inefficiency of production of the electrochemical device. Furthermore, as described above, since it is sufficient to proceed the crosslinking reaction after preparing the electrochemical device using the gel electrolyte in the uncured state, the liquid injection step becomes unnecessary in the process of manufacturing the electrochemical device. Therefore, it is possible to avoid the fear that the liquid injection will be insufficient, or the fear of performance deterioration or the like due to the insufficient liquid injection.
  • the lower limit of the mass ratio of the reactive group which is the first condition of the gel electrolyte, may be 0.03 mass% or more with respect to the mass of the electrolyte solvent, but is 0.04 mass% or more Preferably, it is 0.05 mass% or more. If the mass of the reactive group is less than 0.03% by mass of the mass of the electrolyte solvent, the amount of the reactive group contained in the gel electrolyte becomes smaller than an appropriate amount, and good strength can be realized in the hard gel electrolyte in a cured state There is a possibility that short circuit may occur easily.
  • the amount of leakage of the electrolytic solution accompanying the progress of the crosslinking reaction decreases, and the electrolytic solution can not be well brought into contact with the contact surface of the electrode of the electrochemical device, and sufficient performance may not be realized in the electrochemical device.
  • the upper limit of the mass ratio of the reactive groups may be 6.5 mass% or less based on the mass of the electrolyte solvent, but is preferably 6.3 mass% or less, and is 6.0 mass% or less It is more preferable that If the mass of the reactive group exceeds 6.5% by mass of the mass of the electrolyte solvent, the amount of the reactive group contained in the gel electrolyte becomes excessive and the ion conductivity of the hard gel electrolyte decreases, which is sufficient in the electrochemical device Performance may not be realized. In addition, the amount of leakage of the electrolyte solution accompanying the progress of the crosslinking reaction may be increased, and a sufficient amount of electrolyte solution may not be held in the cured state (hard gel electrolyte).
  • the lower limit of the shear modulus in the uncured state which is the second condition of the gel electrolyte, may be 1 MPa or more, preferably 2 MPa or more, and more preferably 5 MPa or more. If the shear modulus is less than 1 MPa, the strength of the gel electrolyte in the uncured state is reduced, so that the handleability is also reduced, and there is a possibility that the production (production) of the electrochemical device becomes inefficient.
  • the upper limit of the shear modulus is not particularly limited, as long as the hard gel electrolyte in the cured state can hold a sufficient electrolytic solution.
  • the mass of the electrolyte solvent is 20 mass to the total mass of the gel electrolyte (gel-like body)
  • Third condition which is in the range of 80% by mass to 80% by mass, and the mass of the matrix material is in the range of 1.0% by mass to 10% by mass with respect to the total mass of the gel electrolyte (gel-like body) It is preferable to satisfy any one of the fourth conditions, and it is more preferable to satisfy both the third and fourth conditions.
  • the gel electrolyte When the gel electrolyte satisfies the third condition, a more appropriate amount of electrolyte solution is retained in both the gel electrolyte and the hard gel electrolyte. Therefore, good ionic conductivity can be realized in the electrochemical device, and the performance of the electrochemical device can be further improved. However, even when the gel electrolyte does not satisfy the third condition, a sufficiently practical electrochemical device can be manufactured by satisfying both the first condition and the second condition.
  • the gel electrolyte when the gel electrolyte satisfies the fourth condition, a more appropriate amount of matrix material is contained in both the gel electrolyte and the hard gel electrolyte. Therefore, good strength can be realized in the hard gel electrolyte, and the performance of the electrochemical device can be further improved.
  • a sufficiently practical electrochemical device can be manufactured by satisfying both the first condition and the second condition.
  • the specific shape of the gel electrolyte is not particularly limited, and a suitable shape can be formed depending on various conditions such as the type or application of the electrochemical device.
  • the gel electrolyte is gel-like, so it can be easily formed into a desired shape.
  • a sheet shape can be mentioned as the shape of the gel electrolyte.
  • the thickness is not particularly limited, but generally, a range of 5 ⁇ m or more and 100 ⁇ m or less can be mentioned. If the thickness of the sheet-like gel electrolyte is out of this range, sufficient battery performance (or other electricity) may be obtained depending on various conditions such as the type, size and specific shape of the lithium ion battery (or other electrochemical device). There is a possibility that the performance of the chemical device can not be exhibited.
  • the hard gel electrolyte is one in which the crosslinking reaction of the reactive group of the gel electrolyte is advanced to increase the hardness, but the specific configuration of the hard gel electrolyte is not particularly limited. However, in the hard gel electrolyte, it is preferable to satisfy one of the first condition that the ion conductivity is 0.8 mS / cm or more, or the second condition that the shear elastic modulus is 6 MPa or more, It is more preferable to satisfy both the one condition and the second condition.
  • the ion conductivity in the hard gel electrolyte is 0.8 mS / cm or more, preferably 1.0 mS or more, good electrochemical reaction can be realized, and sufficient performance can be exhibited in the electrochemical device. it can.
  • the ion conductivity is less than 0.8 mS / cm, although depending on the type of electrochemical device, good electrochemical reaction may not be realized, there is a possibility that sufficient performance may not be exhibited. There is.
  • the shear modulus of elasticity in the hard gel electrolyte is 6 MPa or more, the electrolyte layer in the electrochemical device can be retained well, so sufficient performance can be exhibited.
  • the shear modulus of the hard gel electrolyte is less than 6 MPa, although depending on the type of electrochemical device, there is a possibility that the electrolyte layer can not be held well, so there is a possibility that sufficient performance can not be exhibited. is there.
  • the hard gel electrolyte in the cured state is obtained.
  • the hard gel electrolyte is A shear modulus of 6 MPa of the electrolyte can be mentioned.
  • the hardness of the gel electrolyte may be measured by a known measurement method, and the cured state may be judged on the basis of the numerical value of hardness, the ratio of hardness increase, etc., but in the present disclosure, uncured gel electrolyte and Since the strength of the hard gel electrolyte is evaluated by the shear modulus, if the shear modulus of the gel electrolyte with increased hardness is 6 MPa or more, it can be determined that the hard gel electrolyte is obtained.
  • the method for producing the gel electrolyte according to the present disclosure is not particularly limited, but as a representative production method, a first method using two kinds of dilution solvents, a second method using one kind of dilution solvent, and a dilution solvent And a third method that does not use
  • This dilution solvent is a component different from the electrolyte solvent, and is a component which is removed before the cross-linking reaction of the reactive group contained in the gel-like material (gel electrolyte). Therefore, the gel electrolyte according to the present disclosure may contain a dilution solvent as another component other than the matrix material and the electrolytic solution.
  • the third and fourth conditions in the uncured gel electrolyte described above that is, the mass range of the electrolyte solvent in the gel electrolyte and the mass range of the matrix material in the gel electrolyte are the total mass of the gel electrolyte excluding the dilution solvent Is defined for This is because, as described above, the diluting solvent is removed before the cross-linking reaction of the reactive group, in other words, the hard gel electrolyte in the cured state is substantially free of the diluting solvent. It is.
  • the specific type of the dilution solvent is not particularly limited, and can be appropriately selected according to various conditions such as the type of the electrochemical device, the type of the matrix material, and the component of the electrolytic solution.
  • a solvent exemplified below can be suitably used as a dilution solvent.
  • ketone solvents such as acetone, methyl ethyl ketone (MEK), cyclohexanone and the like
  • ether solvents such as 1,2-dimethoxyethane (DME); acetonitrile (ACN) Pyrrolidone solvents such as N-methylpyrrolidone (NMP); lactone solvents such as ⁇ -butyrolactone (GBL); ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), Carbonate solvents such as diethyl carbonate (DEC) and ethyl methyl carbonate (EMC); and the like can be mentioned.
  • One of these solvents may be used as a dilution solvent in the present disclosure, or two or more thereof may be appropriately selected and used. Moreover, when using two or more types of these solvents, each solvent may be used for a different dilution objective, and you may use as a mixed solvent which mixed two or more types of solvents.
  • the first method using two types of dilution solvents among representative production methods of the gel electrolyte according to the present disclosure will be described.
  • the matrix material and the first dilution solvent are mixed to form a gel-like body (non-electrolyte gel-like body) not containing an electrolytic solution (non-electrolyte gel-like body forming step).
  • the method of mixing the matrix material and the first dilution solvent is not particularly limited, typically, the method of dissolving the matrix material in the first dilution solvent by heating the matrix material and the first dilution solvent is mentioned. Be After dissolution, for example, by cooling to room temperature, a non-electrolytic gel can be obtained.
  • this first dilution solvent can be referred to as a dilution solvent for gel, which is used to form a non-electrolyte gel-like body.
  • an electrolyte component an ionic substance such as a lithium salt
  • an electrolyte solvent and other components post curing agent, initiator, etc.
  • this diluted solution is referred to as a replacement solution (replacement solution preparation step).
  • the method of preparing the substitution solution is not particularly limited, and a known mixer or the like may be used.
  • this replacement solution is added to the non-electrolyte gel-like body (replacement solution addition step).
  • the method of adding the substitution solution is not particularly limited, and application or accumulation of the substitution solution on the non-electrolytic gel can be mentioned. Since the added replacement solution is absorbed by the non-electrolytic gel, a diluted solvent-containing gel is obtained.
  • the diluted solvent is then removed from the diluted solvent-containing gel (diluted solvent removal step).
  • the method of removing the diluted solvent is not particularly limited, for example, the diluted solvent may be evaporated and distilled off under reduced pressure conditions or high temperature conditions.
  • the gel dilution solvent and the substitution dilution solvent are removed, but if attention is paid to the non-electrolyte gel-like body formed first, the gel dilution solvent contained in the non-electrolyte gel-like body is electrolyzed. It will be replaced by liquid.
  • the gel electrolyte according to the present disclosure may be a dilution solvent-containing gel, or may be a gel from which the dilution solvent is removed. That is, the removal of the dilution solvent may be performed immediately before producing (manufacturing) the electrochemical device, or the dilution solvent may be removed in advance.
  • the matrix material and the dilution solvent are mixed to prepare a diluted solution of the matrix material.
  • this diluted solution of the matrix material is referred to as "solution A" (solution A preparation step).
  • an electrolyte component an ionic substance such as a lithium salt
  • an electrolyte solvent and other components post curing agent, initiator, etc.
  • a dilution solution such as an electrolyte Prepare.
  • a diluted solution such as this electrolytic solution is referred to as "solution B" (solution B preparation step).
  • the prepared solution A and solution B are mixed, and the obtained mixed solution is formed into a predetermined shape (mixing molding step).
  • the method of forming the mixed solution is not particularly limited, and a mold or a support may be used according to the shape of the gel electrolyte to be obtained.
  • the mixed solution is coated on the surface of the positive electrode using the positive electrode of the lithium ion battery as a support.
  • a diluted solvent-containing gel is formed.
  • the diluted solvent is removed from the diluted solvent-containing gel-like body (diluted solvent removing step).
  • a third method which does not use a dilution solvent will be described.
  • an electrolytic solution solvent is used instead of not using a dilution solvent that dissolves a matrix material or an electrolyte.
  • the matrix material and the electrolyte solvent are mixed to prepare an electrolyte solvent solution of the matrix material.
  • the solution of this matrix material is referred to as "solution A” as in the second method (solution A preparation step).
  • the electrolyte component an ionic substance such as a lithium salt
  • other components post curing agent, initiator, etc.
  • an electrolyte solvent such as an electrolyte Prepare a solution.
  • a solution such as this electrolytic solution is referred to as "solution B" as in the second method (solution B preparation step).
  • the prepared solution A and solution B are mixed, and the obtained mixed solution is molded into a predetermined shape (mixing molding process). Thereby, a gel-like body containing an electrolytic solution or the like, that is, a gel electrolyte is obtained.
  • first method, second method and third method each have their own manufacturing advantages, so it can not be concluded that either method is particularly preferred.
  • a replacement solution is prepared using a dilution solvent, and the replacement solution is used to replace the liquid component of the non-electrolyte gel-like body with the electrolyte solution. Therefore, various variations of the obtained gel electrolyte can be easily manufactured by appropriately changing the composition of the replacement solution.
  • the positive electrode or the negative electrode can be used as a support, and the mixed solution can be coated on the positive electrode or the negative electrode. Therefore, since the increase in the manufacturing process of the lithium ion battery can be avoided as compared with the first method, the manufacturing method of the lithium ion battery can be simplified.
  • an electrolyte solvent is used without using a diluting solvent. Since a gel electrolyte is obtained only by shape
  • the electrochemical device according to the present disclosure is not particularly limited as long as it utilizes an electrochemical reaction (a device capable of converting chemical energy and electrical energy), but as a typical configuration, a pair of electrodes and And an electrolyte positioned between them.
  • an electrochemical reaction a device capable of converting chemical energy and electrical energy
  • the specific configuration of the pair of electrodes included in the electrochemical device is not particularly limited, but typically, the pair of electrodes is configured as a positive electrode and a negative electrode, respectively.
  • the specific configuration of the positive electrode and the negative electrode is not particularly limited, but in order to increase the contact area with the electrolytic solution contained in the electrolyte, for example, the contact surface (surface facing the electrolyte) is porous Is preferred. Such a porous contact surface may have only the positive electrode, may have only the negative electrode, or may have both the positive electrode and the negative electrode.
  • the specific configuration of the pair of electrodes (positive electrode, negative electrode) is not particularly limited, and various materials, shapes, dimensions, etc. may be suitably used according to the type or application of the electrochemical device. it can.
  • the formation method of a porous contact surface is not specifically limited, Typically, the method of forming the powder (or particle
  • the powder of electrode material (active material) is mixed with an organic vehicle (solvent and / or binder resin, etc.) to form a paste, and this is applied to the surface of the electrode substrate And drying, curing, baking or the like.
  • the electrolyte included in the electrochemical device is interposed between a pair of electrodes, but in the present disclosure, this electrolyte increases the degree of curing of the gel electrolyte in the uncured state as described above.
  • the representative configuration of the electrochemical device according to the present disclosure is the configuration including the pair of electrodes and the hard gel electrolyte as described above, the configuration of the electrochemical device in the present disclosure is not limited thereto.
  • a pair of electrodes and components or members other than the gel electrolyte or hard gel electrolyte may be provided.
  • the specific configuration of such other components or other members is not particularly limited, and various components or parts can be used according to the specific type of electrochemical device.
  • Examples of more specific configurations of the electrochemical device according to the present disclosure include lithium ion batteries, dye-sensitized solar cells, electric double layer capacitors, gel actuators, and the like.
  • the specific configuration of a lithium ion battery which is a representative example of the electrochemical device in the present disclosure will be specifically described with reference to FIG.
  • a lithium ion battery 10 which is a type of electrochemical device, has a positive electrode 12 and a negative electrode 13 as a pair of electrodes, and a hard gel electrolyte 14 is held between the positive electrode 12 and the negative electrode 13.
  • a structure (a structure in which the hard gel electrolyte 14 is held on the positive electrode 12 and the negative electrode 13) configured by laminating the positive electrode 12, the hard gel electrolyte 14 and the negative electrode 13 is referred to as a laminated structure 11 for convenience.
  • the lithium ion battery 10 has a configuration in which the laminated structure 11 is sealed with a sealing material 15.
  • the positive electrode 12 has a configuration in which a positive electrode active material layer 22 is formed on the surface of the positive electrode base 21 (the opposite surface to the negative electrode 13 and the surface in contact with the hard gel electrolyte 14). ing.
  • the negative electrode 13 has a configuration in which the negative electrode active material layer 32 is formed on the surface of the negative electrode substrate 31 (the surface facing the positive electrode 12 and in contact with the hard gel electrolyte 14).
  • the positive electrode base 21 and the negative electrode base 31 function as current collectors that collect electrons generated by the electrochemical reaction of the positive electrode active material layer 22 and the negative electrode active material layer 32.
  • the specific configuration of the positive electrode substrate 21 and the negative electrode substrate 31 is not particularly limited, and a known metal plate or metal foil may be used. In the embodiment described later, an aluminum foil is used as the positive electrode substrate 21. In addition, copper foil is typically used as the negative electrode substrate 31.
  • the positive electrode active material used for the positive electrode active material layer 22 typically includes, but is not particularly limited to, a lithium salt of a transition metal oxide. In Examples described later, Li—Ni—Co—Mn oxide (NCM), which is a ternary lithium salt, is used as the positive electrode active material.
  • a negative electrode active material used for the negative electrode active material layer 32 typically, a lithium metal foil or a carbon material is used. In Examples to be described later, a lithium metal foil is used as the negative electrode active material.
  • the positive electrode active material layer 22 may be composed of only the positive electrode active material, and the negative electrode active material layer 32 may be composed of only the negative electrode active material, but may be composed of a layer containing other components. .
  • the positive electrode active material layer 22 and the negative electrode active material layer 32 are formed by coating with a coating solution containing an active material
  • known binder resins such as polyvinylidene fluoride (PVDF), carbon black, etc. And the like may be included.
  • the coating liquid may contain a solvent (dispersion medium) in addition to the active material, the binder resin, and the conductive additive.
  • the coating solution has a curing degree comparable to that of a gel electrolyte or hard gel electrolyte 14 before increasing the curing degree.
  • the gel electrolyte (hard gel electrolyte component) which raised C. may be included.
  • the positive electrode active material layer 22 constitutes an opposing surface facing the negative electrode 13 in the positive electrode 12 and constitutes a contact surface to the hard gel electrolyte 14.
  • the negative electrode active material layer 32 constitutes a facing surface facing the positive electrode 12 in the negative electrode 13 and constitutes a contact surface to the hard gel electrolyte 14. Therefore, as described above, it is preferable that at least one of the positive electrode active material layer 22 and the negative electrode active material layer 32 be formed in a porous state.
  • the method of forming the active material layers 22 and 32 in a porous state is not particularly limited, and various known methods can be used. Typically, as described above, a method of applying and drying a paste containing an active material can be mentioned. In addition, either one of the active material layers 22 and 32 may not be porous. In the embodiment to be described later, the positive electrode active material layer 22 is formed in a porous shape, but the negative electrode active material layer 32 is formed only of lithium foil.
  • the negative electrode 13 is comprised only with lithium foil in the Example mentioned later. Therefore, at least the positive electrode 12 and the negative electrode 13 do not have to be composed of the active material layers 22 and 32 and the substrates 21 and 31 for supporting them, as illustrated in FIG.
  • the hard gel electrolyte 14 is formed by reacting the reactive group contained in the uncured gel electrolyte to advance the crosslinking reaction to increase the degree of curing of the gel electrolyte.
  • the sealing material 15 is not particularly limited as long as it can seal the laminated structure 11 configured by the positive electrode 12, the negative electrode 13, and the hard gel electrolyte 14.
  • the sealing material 15 if the electrochemical device is a lithium ion battery 10, typically, a known laminated film, a known metal can, etc. may be mentioned.
  • a laminated film although what laminated
  • the sealing material 15 may be, for example, a known sealing agent such as a thermoplastic ionomer resin.
  • the lithium ion battery 10 shown in FIG. 1 does not have a separator. This is because the hard gel electrolyte 14 held by the positive electrode 12 and the negative electrode 13 can function in the same manner as the separator.
  • the lithium ion battery 10 may further include a separator, or may include members other than the positive electrode 12, the negative electrode 13, and the hard gel electrolyte 14.
  • an uncured gel electrolyte will contain an appropriate amount of reactive groups. So, even if it becomes the gel electrolyte (hard gel electrolyte) which the crosslinking reaction of the reactive group advanced fully, the said hard gel electrolyte can hold
  • the gel electrolyte since the shear modulus of elasticity of the gel electrolyte is 1 MPa or more even in the uncured state, the gel electrolyte has a good strength. Therefore, since good handleability can be realized in the gel electrolyte, it is possible to suppress the inefficiency of production of the electrochemical device. Moreover, as described above, since the crosslinking reaction may be allowed to proceed after preparing the electrochemical device using the gel electrolyte in the uncured state, the liquid injection step becomes unnecessary in the process of manufacturing the electrochemical device. Therefore, it is possible to avoid the fear that the liquid injection will be insufficient, or the fear of performance deterioration or the like due to the insufficient liquid injection.
  • the shear modulus of elasticity of the gel electrolyte obtained in each example or each comparative example was measured using a table-type precision universal testing machine manufactured by Shimadzu Corporation (product name: Autograph AGS-X), and a 5 mm ⁇ pressing jig was attached. After applying 0.05N preload, the indentation test is performed at a speed of 0.05 mm / min, and from the results of the indentation test, shear elasticity is obtained according to the following equation (1) with reference to the above-mentioned reference 1 The rate was measured (unit: MPa).
  • Shear modulus (G) 0.36 Fg [(D ⁇ h) / h] 3/2 / R 2 (1)
  • F load (test force) for indentation test, g: gravitational acceleration, D: thickness (film thickness) of gel electrolyte (gel-like body), h: thickness (film thickness) change due to load, R: indentation test Radius of spherical indenter) (Measurement of ion conductivity of gel electrolyte)
  • the thickness (film thickness) was measured about the gel electrolyte obtained by each Example or each comparative example. Further, the gel electrolyte sandwiched between stainless steel foils was allowed to stand in a thermostat bath at 80 ° C.
  • the gel electrolyte was used as a hard gel electrolyte.
  • This is used as a sample for measuring the ion conductivity, and using this impedance analyzer (product name: SP-150) manufactured by Biologics (Bio-Logic SAS), electrochemistry under the condition of a frequency of 1 MHz to 0.1 Hz.
  • EIS impedance
  • the ion conductivity at 30 ° C. was calculated (unit: mS / cm) by dividing the film thickness of the gel electrolyte by the bulk resistance value.
  • the capacity coercivity is 90% or more, it is evaluated as “ ⁇ ” (good), and if the capacity coercivity is 70% or more, it is evaluated as “ ⁇ ” (normal). If the capacity coercivity is less than 70% It evaluated as “x” (improper).
  • Example 1 The following work was performed under a dry air atmosphere with a dew point of -50 ° C or less. As shown in Table 1, 1.8 parts by mass of polyvinylidene fluoride (PVDF, manufactured by Kureha Co., product name: KF polymer # 7200), which is a matrix material, and acetone which is a dilution solvent for gel (Wako Pure Chemical Industries, Ltd. It heat-melted at 80 degreeC with respect to 33 mass parts, and PVDF / acetone gel (non-electrolytic gel-like body) was produced by leaving it to stand at room temperature.
  • PVDF polyvinylidene fluoride
  • KF polymer # 7200 a matrix material
  • acetone which is a dilution solvent for gel
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiBG lithium battery grade
  • EMImFSI 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide
  • tetrafunctional polyether acrylate as post-curing agent
  • Elekcel TA-210 2,2′-azobis (2,4-dimethylvaleronitrile)
  • ACN acetonitrile
  • the crosslinkable reactive group is an acrylate group contained in the post-curing agent tetrafunctional polyether acrylate (product name: Erichel TA-210).
  • the tetrafunctional polyether acrylate used has a weight average molecular weight of 11,000 and a molecular weight of 4 acrylate groups contained in one molecule is 220. Therefore, the mass of acrylate groups contained in 1 g of the tetrafunctional polyether acrylate is 0. It is .02g.
  • Example 1 the blending amount of the post-curing agent tetrafunctional polyether acrylate is 1.3 parts by mass. Therefore, the mass of the reactive group (acrylate group) contained in the gel electrolyte according to Example 1 is 0.025 parts by mass. Further, as described above, in Example 1, the blending amount of EMImFSI, which is an electrolyte solvent, is 49 parts by mass. Therefore, as shown in Table 1, in the gel electrolyte according to Example 1, the mass ratio of the reactive group to the mass of the electrolyte solvent is 0.050 mass%, and is in the range of 0.03 to 6.5 mass%. It is inside.
  • the mass ratio of the electrolyte solvent to the total mass is 78 mass%, and is in the range of 20 to 80 mass%, and the total mass
  • the mass ratio of the matrix material to B is 2.9% by mass, and is in the range of 1.0 to 10% by mass.
  • LiNi 1/3 Mn 1/3 Co 1/3 O 2 which is a positive electrode active material
  • binder resin Weigh 3.3 g of polyvinylidene fluoride (PVDF, manufactured by Kureha Co., Ltd., weight average molecular weight Mw: about 300,000), 38.4 g of N-methyl-2-pyrrolidone (NMP) as a dispersion medium, and make each of them planetary type It mixed by the mixer and prepared the coating liquid of the positive electrode active material layer of 51% of solid content.
  • This coating solution is coated on a 15 ⁇ m thick aluminum foil (positive electrode substrate) with a coating apparatus, dried at 130 ° C., and then roll pressed to obtain a positive electrode having a 2.3 mg / cm 2 positive electrode active material layer. I got
  • the positive electrode, the gel electrolyte according to Example 1, and the lithium foil as the negative electrode were stacked to form a laminate.
  • the laminate was punched into a circular shape having a diameter of 14 mm, and sealed and sealed in a coin cell jig to produce a sealed body.
  • the sealed body is allowed to stand in a constant temperature bath at 80 ° C. for 12 hours to allow the crosslinking reaction of the reactive groups contained in the gel electrolyte to sufficiently advance (the gel electrolyte is hardened to form a hard gel electrolyte). , Returned to room temperature.
  • a coin cell for evaluation lithium ion battery which is an electrochemical device according to Example 1 was produced (manufactured).
  • Example 2 A gel electrolyte according to Example 2 or a gel electrolyte according to Example 3 in the same manner as in Example 1 except that the compounding amount of the electrolyte solvent and the compounding amount of the post-curing agent are changed as shown in Table 1.
  • Table 1 A gel electrolyte according to Example 2 or a gel electrolyte according to Example 3 in the same manner as in Example 1 except that the compounding amount of the electrolyte solvent and the compounding amount of the post-curing agent are changed as shown in Table 1.
  • a coin cell for evaluation which is an electrochemical device according to Example 2 or an electrochemical device according to Example 3 was produced.
  • the mass ratio of the reactive group to the mass of the electrolyte solvent is 0.03 to 6.5 mass. %
  • the mass ratio of the electrolyte solvent to the total mass is in the range of 20 to 80 mass%
  • the mass ratio of the matrix material to the total mass is in the range of 1.0 to 10 mass% It is inside.
  • Example 4 The following operation was carried out in a dry air atmosphere having a dew point of -50 ° C. or less, as in the case of Examples 1 to 3.
  • a matrix material vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP, manufactured by Kleha Co., Ltd., product name: KF polymer # 8500, Table 2 for convenience "PVDF-HFP [1]
  • It described as "(notation)" 2.9 mass parts were heat-dissolved at 80 degreeC with respect to 29.5 mass parts of dimethyl ether (DME, Wako Pure Chemical Industries, Ltd. make) which is a dilution solvent.
  • DME dimethyl ether
  • LiFSI LiFSI
  • EMImFSI electrolytic solution solvent of an ionic liquid system
  • Parts by weight of tetrafunctional polyether acrylate (see Example 1), 0.12 parts by weight of azo initiator (see Example 1) as initiator, and 29 .5 parts by mass were mixed and mixed to prepare solution B, which is a solution for diluting DME such as an electrolytic solution.
  • a tetrafunctional polyether acrylate is blended as in Examples 1 to 3, and as in Example 1,
  • the mass ratio of reactive groups is derived.
  • the mass ratio of the reactive group to the mass of the electrolyte solvent is in the range of 0.03 to 6.5 mass% (0.063 mass%).
  • the mass ratio of the electrolyte solvent to the total mass is in the range of 20 to 80 mass% (68 mass%), and the mass ratio to the total mass
  • the mass ratio of the matrix material is in the range of 1.0 to 10% by mass (7.0% by mass).
  • this gel electrolyte / positive electrode laminate is punched into a circular shape with a diameter of 14 mm, and a lithium foil with a diameter of 14 mm, which is a negative electrode, is bonded to the gel electrolyte side of the obtained punched body. I set it.
  • a coin cell for evaluation lithium ion battery which is an electrochemical device according to Example 4 was produced (manufactured).
  • the shear elastic modulus, the film thickness, and the ion conductivity are measured or evaluated, and the obtained evaluation coin cell is obtained. Battery performance and element stability (short circuit) were evaluated. The results are shown in Table 2.
  • Examples 5 to 13 The compounding amount of the electrolyte solvent and the compounding amount of the post-curing agent are changed as shown in Table 2 (Examples 5 and 6), or bifunctional polyether acrylate as a post-curing agent (product manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • MP-150 is used to appropriately change the blending amount of the electrolyte solvent as shown in Table 2 or 3 (Examples 7 to 9) or polyethylene glycol diacrylate (Daiichi Kogyo Seiyaku Co., Ltd.) as a post-curing agent
  • the blending amount of electrolyte solvent is changed as shown in Table 3 using a product name: Enexel EG2500 (Example 10), or methyl methacrylate-oxetanyl methacrylate copolymer (No. 10) as a post curing agent
  • the blending amount of the electrolyte solvent is changed as shown in Table 3 (Examples 11 to 13) using Ichikoh Pharmaceutical Co., Ltd. product name: Eleccel ACG-127). Outside, in the same manner as in Example 4, to prepare a gel electrolyte according to Example 5-13. Further, using these gel electrolytes, coin cells for evaluation, which are the electrochemical devices according to Examples 5 to 13, were produced.
  • the crosslinkable reactive group is an acrylate group contained in the post-curing agent difunctional polyether acrylate (product name: MP-150). Since the difunctional polyether acrylate used has a weight average molecular weight of 11,000 and the molecular weight of two acrylate groups contained in one molecule is 110, the mass of the acrylate group contained in 1 g of the bifunctional polyether acrylate is 0. It is .010 g.
  • Example 7 the compounding amount of the post-curing agent difunctional polyether acrylate is 1.4 parts by mass. Therefore, the mass of the reactive group (acrylate group) contained in the gel electrolyte according to Example 7 is 0.0138 mass parts. Moreover, in Example 7, as shown in Table 2, the compounding quantity of EMImFSI which is an electrolyte solution solvent is 28 mass parts. Therefore, as shown in Table 2, in the gel electrolyte according to Example 7, the mass ratio of the reactive group to the mass of the electrolyte solvent is 0.050 mass%, and is in the range of 0.03 to 6.5 mass%. It is inside.
  • Example 7 also in the gel electrolyte according to Example 8 or Example 9, the same bifunctional polyether acrylate as in Example 7 is blended as a post-curing agent, Example 7 Similarly, the mass ratio of reactive groups is derived. As shown in Table 2, in these Examples 8 and 9, the mass ratio of the reactive group to the mass of the electrolyte solvent is 0.44 mass% (Example 8) or 2.5 mass% (Example 9). Both are in the range of 0.03 to 6.5% by mass.
  • the crosslinkable reactive group is an acrylate group contained in the post-curing agent polyethylene glycol diacrylate (product name: Eleccel EG2500).
  • the polyethylene glycol diacrylate used has a weight average molecular weight of 2,500 and the molecular weight of the acrylate group contained in one molecule is 83. Therefore, the mass of the acrylate group contained in 1 g of the polyethylene glycol diacrylate is 0.033 g.
  • Example 10 As shown in Table 3, the compounding amount of the post-curing agent polyethylene glycol diacrylate is 6.7 parts by mass. Therefore, the mass of the reactive group (acrylate group) contained in the gel electrolyte according to Example 10 is 0.221 parts by mass. Moreover, in Example 10, as shown in Table 3, the compounding quantity of EMImFSI which is an electrolyte solution solvent is 28 mass parts. Therefore, in the gel electrolyte according to Example 10, the mass ratio of the reactive group to the mass of the electrolyte solvent is 1.0 mass%, and is in the range of 0.03 to 6.5 mass%.
  • the crosslinkable reactive group is the oxetane moiety contained in the post-curing agent methyl methacrylate-oxetanyl methacrylate copolymer (product name: Elecel ACG-127). . Since the methyl methacrylate-oxetanyl methacrylate copolymer used has a weight average molecular weight of 300,000 and the molecular weight of one oxetane part is 56, the mass of the oxetane part contained in 1 g of the methyl methacrylate-oxetanyl methacrylate copolymer Is 0.13 g.
  • Example 11 the compounding amount of the post-curing agent methyl methacrylate-oxetanyl methacrylate copolymer is 0.12 parts by mass. Therefore, the mass of the reactive group (oxetane part) contained in the gel electrolyte according to Example 11 is 0.015 parts by mass. Moreover, in Example 11, as shown in Table 3, the compounding quantity of EMImFSI which is an electrolyte solution solvent is 29 mass parts. Therefore, as shown in Table 2, in the gel electrolyte according to Example 11, the mass ratio of the reactive group to the mass of the electrolyte solvent is 0.050 mass%, and is in the range of 0.03 to 6.5 mass%. It is inside.
  • Example 11 in the gel electrolyte according to Example 12 or Example 13, the same methyl methacrylate-oxetanyl methacrylate copolymer as in Example 11 is blended as a post-curing agent, Example 11 Similarly, the mass ratio of reactive groups is derived. As shown in Table 3, in these Examples 11 and 12, the mass ratio of the reactive group to the mass of the electrolyte solvent is 1.2 mass% (Example 12) or 5.6 mass% (Examples) 13), all of which are in the range of 0.03 to 6.5% by mass.
  • a tetrafunctional polyether acrylate is blended as in Examples 1 to 4, and Example 1 and Likewise, the mass ratio of reactive groups is derived. As shown in Table 2, also in these Examples 5 and 6, the mass ratio of the reactive group to the mass of the electrolyte solvent is in the range of 0.03 to 6.5 mass% (see Example 1). ).
  • the mass ratio of the electrolyte solvent to the total mass is in the range of 20 to 80% by mass
  • the mass ratio of the matrix material to the total mass is in the range of 1.0 to 10% by mass.
  • the shear modulus, the film thickness, and the ion conductivity are measured or evaluated, and the obtained coin cells for evaluation are each evaluated for cell performance and element stability.
  • the resistance (short circuit) was evaluated. The results are shown in Table 2 or Table 3.
  • Example 14 As shown in Table 4, as a matrix material, PVDF-HFP of a type different from Examples 4 to 13 (manufactured by Kureha Co., Ltd., product name: KF polymer # 9300, Table 4 for convenience "PVDF-HFP [2]" (Example 14), or silica particles (made by Nippon Aerosil Co., Ltd., product name: Aerosil 200, described as “silica” in Table 4) as a matrix material (Example 15) ), Or silica / alumina mixed particles (product name: Aerosil COK 84, manufactured by Nippon Aerosil Co., Ltd., “Silica / Alumina” in Table 4), which is an inorganic particle, as a matrix material (Example 16), electrolysis Gel electrolytes according to Examples 14 to 16 were produced in the same manner as in Example 4 except that the amounts of the liquid solvent and the post-curing agent were changed. Further, using these gel electrolytes, coin cells for
  • the mass ratio of the reactive group to the mass of the electrolyte solvent is within the range of 0.03 to 6.5 mass%.
  • the mass ratio of the electrolyte solvent to the total mass is in the range of 20 to 80 mass%, and the mass ratio of the matrix material to the total mass is in the range of 1.0 to 10 mass%.
  • Example 17 The following operations were carried out in a dry air atmosphere with a dew point of -50 ° C. or less, as in Examples 1-16.
  • 1.0 part by mass of PVDF-HFP [2] (made by Kleha Co., product name: KF polymer # 9300) same as Example 14 is a carbonate-based electrolytic solution solvent Based on 39.5 parts by mass of a mixture (mixed electrolyte solvent) of a mixture of 55 parts by mass of dimethyl carbonate (DMC, LBG, manufactured by Kishida Chemical Co., Ltd.) and 5.3 parts by mass of ethylene carbonate (EC, LBG, manufactured by Kishida Chemical Co., Ltd.) The mixture was heated and melted at 80 ° C. Thus, a solution A, which is a DMC diluted solution of PVDF-HFP, was prepared.
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • LiPF 6 lithium hexafluorophosphate lithium
  • LBG lithium hexafluorophosphate lithium
  • 39.5 mixed electrolyte solvents of the above-mentioned DMC and EC are used.
  • no dilution solvent is used in this example.
  • the mass ratio of the reactive group to the mass of the electrolyte solvent is in the range of 0.03 to 6.5 mass% (0.013
  • the mass ratio of the electrolyte solvent to the total mass is in the range of 20 to 80 mass% (79 mass%), and the mass ratio of the matrix material to the total mass is in the range of 1.0 to 10 mass% It is inside (1.0% by mass).
  • this gel electrolyte / positive electrode laminate is punched into a circular shape with a diameter of 14 mm, and a lithium foil with a diameter of 14 mm, which is a negative electrode, is bonded to the gel electrolyte side of the obtained punched body. I set it.
  • a coin cell for evaluation lithium ion battery which is an electrochemical device according to Example 17 was produced (manufactured).
  • the shear elastic modulus, the film thickness, and the ion conductivity are measured or evaluated, and the obtained evaluation coin cell is obtained. Battery performance and element stability (short circuit) were evaluated. The results are shown in Table 5.
  • Example 18 to 20 As shown in Table 5, as the carbonate-based electrolyte solvent used for preparation of solution A, ethyl methyl carbonate (EMC, manufactured by Kishida Chemical Co., Ltd., LBG, Example 18), diethyl carbonate (DEC, manufactured by Kishida Chemical Co., Ltd., LBG, Example 19) or Propylene carbonate (PC, manufactured by Kishida Chemical Co., Ltd., LBG, Example 20) was used, and when PC was used, the compounding amount of PC and EC was changed (Example 20)
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • PC Propylene carbonate
  • PC manufactured by Kishida Chemical Co., Ltd., LBG, Example 20
  • the mass ratio of the reactive group to the mass of the electrolyte solvent is within the range of 0.03 to 6.5 mass%.
  • the mass ratio of the electrolyte solvent to the total mass is in the range of 20 to 80 mass%, and the mass ratio of the matrix material to the total mass is in the range of 1.0 to 10 mass%.
  • Examples 21 to 26 As shown in Table 6, although the mass ratio of the reactive group to the electrolyte solvent in the gel electrolyte falls within the range of 0.03 to 6.5 mass%, the mass ratio of the electrolyte solvent to the total mass in the gel electrolyte is 20 Less than% by mass (Example 21), greater than 80% by mass (Example 22), or less than 0.8 mS / cm in ion conductivity (Example 23), the matrix material relative to the total mass in the gel electrolyte The mass ratio is less than 1.0% by mass (Example 24) or more than 10% by mass (Example 25), and the film thickness of the gel electrolyte is 100 ⁇ m or more, and the compounding amount of each component is changed Examples 21 to 26 are the same as Example 4 described above (Examples 21 and 23 to 26) or Example 17 (Example 22; however, only one EC solvent is used) except for the above. To The gel electrolyte was fabricated that. Using these gel electrolyte
  • the first method, the second method, or the third method is used. Even with gel electrolytes produced in any of the methods of the above, good performance electrochemical devices (lithium ion batteries) can be produced.
  • the present invention can be widely and suitably used in the field of electrochemical devices using gel electrolytes, such as lithium ion batteries, dye-sensitized solar cells, electric double layer capacitors, or gel actuators.
  • gel electrolytes such as lithium ion batteries, dye-sensitized solar cells, electric double layer capacitors, or gel actuators.
  • lithium ion battery 11 laminated structure 12: positive electrode 13: negative electrode 14: hard gel electrolyte 15: sealing material 21: positive electrode base material 22: positive electrode active material layer 31: negative electrode base material 32: negative electrode active material layer

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JP6916337B1 (ja) 2020-03-27 2021-08-11 第一工業製薬株式会社 リチウムイオン二次電池
JP7465007B1 (ja) 2022-11-04 2024-04-10 株式会社スリーダムアライアンス リチウム二次電池
WO2024207179A1 (zh) * 2023-04-04 2024-10-10 宁德时代新能源科技股份有限公司 二次电池及其制备方法、用电装置

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