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WO2018123458A1 - Procédé de production de dispositif électrochimique - Google Patents

Procédé de production de dispositif électrochimique Download PDF

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Publication number
WO2018123458A1
WO2018123458A1 PCT/JP2017/043566 JP2017043566W WO2018123458A1 WO 2018123458 A1 WO2018123458 A1 WO 2018123458A1 JP 2017043566 W JP2017043566 W JP 2017043566W WO 2018123458 A1 WO2018123458 A1 WO 2018123458A1
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WIPO (PCT)
Prior art keywords
electrolyte
electrochemical device
gel electrolyte
gel
degree
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/043566
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English (en)
Japanese (ja)
Inventor
恭輝 齊藤
淳史 奥原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DKS Co Ltd
Original Assignee
Dai Ichi Kogyo Seiyaku Co Ltd
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
Priority claimed from JP2017214100A external-priority patent/JP7004545B2/ja
Application filed by Dai Ichi Kogyo Seiyaku Co Ltd filed Critical Dai Ichi Kogyo Seiyaku Co Ltd
Priority to CN201780081003.4A priority Critical patent/CN110140252A/zh
Priority to US16/473,984 priority patent/US20210135273A1/en
Priority to KR1020197018181A priority patent/KR20190097070A/ko
Publication of WO2018123458A1 publication Critical patent/WO2018123458A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—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
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 method for producing an electrochemical device, which is a device using an electrochemical reaction, comprising a pair of electrodes and an electrolyte positioned between them, for example, a lithium ion battery, a dye-sensitized solar cell, Or it is related with the manufacturing method of the electrochemical device which can be used suitably for manufacture of an electrical double layer capacitor etc.
  • an electrochemical device using an electrochemical reaction for example, various batteries, a part of a solar battery, a capacitor (capacitor), and the like are known.
  • liquids electrolytic solutions
  • electrolytes used in these electrochemical devices.
  • the electrolyte is a common electrolyte, the possibility of electrolyte leakage from the electrochemical device cannot be denied. Therefore, in recent years, for example, a configuration using a gel electrolyte obtained by gelling an electrolytic solution, such as an electrochemical cell disclosed in Patent Document 1 and a manufacturing method thereof, or a solid electrolyte disclosed in Patent Document 2 is used. Configuration etc. have been proposed.
  • a method for manufacturing an electrochemical device is a method for manufacturing an electrochemical device including a pair of electrodes and an electrolyte positioned between the electrodes, and the electrolyte includes at least a matrix material and an electrolytic solution.
  • a gel-like body and containing a crosslinkable reactive group the degree of cure of the gel electrolyte is increased, and the reaction is performed while the gel electrolyte is held between the pair of electrodes.
  • the structure includes a step of increasing the degree of cure of the electrolyte by causing the cross-linking reaction of the group to proceed to increase the degree of cure of the gel electrolyte and causing the electrolyte to leak from the gel electrolyte as the cross-linking reaction proceeds.
  • the pair of electrodes is a positive electrode and a negative electrode, and at least one of the positive electrode and the negative electrode may have a configuration in which a contact surface with the electrolyte is porous. Good.
  • the contact surface of either one or both of the positive electrode and negative electrode which are a pair of electrodes is porous, the contact area of these positive electrodes and negative electrodes and the electrolyte solution contained in a gel electrolyte is increased. be able to.
  • At least one of the pair of electrodes includes an active material layer formed on a contact surface to the electrolyte, and the active material layer is formed of a coating liquid containing an active material.
  • coating may be sufficient.
  • the active material layer formed on the contact surface of the electrode is formed by applying the coating liquid, a thin active material layer can be easily formed.
  • the coating solution may include the gel electrolyte or a hard gel electrolyte in which the degree of cure of the gel electrolyte is increased.
  • the gel electrolyte or the hard gel electrolyte is contained in the coating solution, whereby the contact frequency between the active material layer formed on the contact surface of the electrode and the gel electrolyte can be further improved.
  • sealing is performed before the electrolyte curing degree increasing step, and the laminated structure holding the gel electrolyte between the pair of electrodes is sealed with a sealing material
  • the structure which further includes a process may be sufficient.
  • the electrolyte hardening degree increasing step is performed after sealing the laminated structure in advance, the hardening degree of the gel electrolyte is increased in a state where the gel electrolyte is well held between the pair of electrodes. Can be made.
  • the crosslinking reaction is advanced by supplying energy from the outside of the laminated structure to the gel electrolyte. Also good.
  • the degree of cure of the gel electrolyte is increased by the energy supplied from the outside, and therefore the step of increasing the degree of electrolyte cure without performing a physical operation on the gel electrolyte included in the laminated structure. It can be performed.
  • the gel electrolyte in the electrolyte curing degree increasing step, may be further pressurized while being held between the positive electrode and the negative electrode.
  • the electrochemical device may be a lithium ion battery, a dye-sensitized solar cell, or an electric double layer capacitor.
  • the electrochemical device is at least one of those described above, by applying the method for manufacturing an electrochemical device according to the present disclosure, good device performance is realized while improving the efficiency of the manufacturing process. Possible electrochemical devices can be manufactured.
  • the electrochemical device obtained by the method for manufacturing an electrochemical device according to the present disclosure may be any device that uses an electrochemical reaction (that can convert chemical energy and electrical energy). May have a configuration including a pair of electrodes and an electrolyte positioned between them.
  • 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.
  • Specific configurations of the positive electrode and the negative electrode are not particularly limited.
  • the contact surface surface facing the electrolyte
  • Such a porous contact surface may be included only in the positive electrode, only in the negative electrode, or both in the positive electrode and the negative electrode.
  • the more specific configuration of the pair of electrodes (positive electrode, negative electrode) is not particularly limited, and various materials, shapes, dimensions, and the like are preferably used depending on the type or application of the electrochemical device. it can.
  • the formation method of the porous contact surface is not particularly limited, but a typical example is a method of forming a layer of electrode material (active material) powder (or particles) on the surface of the electrode substrate.
  • the electrode material (active material) powder 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.
  • an organic vehicle solvent and / or binder resin, etc.
  • the electrolyte included in the electrochemical device is interposed between a pair of electrodes.
  • the electrolyte is a gel-like body including a matrix material having a crosslinkable reactive group and an electrolyte solution.
  • the degree of cure here refers to the degree of curing of the gel electrolyte. For example, it is evaluated by the degree of cross-linking reaction of the reactive group contained in the gel electrolyte, or evaluated by a known method for measuring the degree of curing. Can do.
  • the gel electrolyte having such an increased degree of curing is referred to as a “hard gel electrolyte”.
  • gel electrolyte it means a gel electrolyte before the degree of curing increases.
  • the matrix material constituting the gel electrolyte is not particularly limited as long as it can form a gel-like body (gel electrolyte) together with the electrolytic solution.
  • a material having a reactive group capable of crosslinking reaction can be suitably used.
  • an electrolytic solution containing a component having a reactive group capable of crosslinking with the matrix material can be used.
  • an ionic liquid having a reactive group capable of crosslinking reaction, an organic solvent, an alkali metal salt, and the like can be given. That is, in the present disclosure, it is sufficient that the gel electrolyte includes a reactive group capable of a crosslinking reaction, and the reactive group may be a matrix material or an electrolyte solution. Alternatively, both the matrix material and the electrolytic solution may be used.
  • the specific configuration of the gel-like body composed of the matrix material and the electrolytic solution is not particularly limited.
  • a chemical gel in which the cross-linked structure is constituted by a covalent bond, which has an uncrosslinked reactive group, or a physical gel in which the cross-linked structure is constituted by a bond other than a covalent bond A chemical gel or physical gel having a reactive group, or a chemical gel or physical gel having no uncrosslinked reactive group, which contains a compound or composition having an uncrosslinked reactive group (referred to as a “crosslinking reactant” for convenience) Etc.
  • the more specific configuration of the gel constituting these matrix materials is not particularly limited, and various organic polymers, inorganic polymers, organic low molecules, inorganic small molecules, etc., depending on the type or application of the electrochemical device. Can be used.
  • the gel constituting the matrix material contains a crosslinking reaction substance
  • the specific structure of the crosslinking reaction substance is not particularly limited, and various organic polymers, inorganic polymers, organic low molecules, or inorganic substances are not limited. Small molecules and the like can be used.
  • a typical crosslinking reaction substance a prepolymer having an uncrosslinked reactive group can be exemplified.
  • the matrix material may be configured as a material that can form a gel-like body (gel electrolyte solution) by impregnating the electrolyte solution, that is, a material having a matrix structure in advance.
  • the raw material of the matrix material may be semi-cured to constitute a gel-like body (gel electrolytic solution) containing the electrolytic solution.
  • the gel electrolyte is a gel-like body composed of a matrix material and an electrolyte solution, and the cross-linking reaction of the reactive group contained in the gel-like body does not proceed until the electrolyte curing degree increasing step described later is performed.
  • the hard gel electrolyte after the electrolyte hardening degree raising step becomes a gel-like body whose hardening degree has risen due to the progress of the crosslinking reaction. Therefore, in the present disclosure, the gel electrolyte before the crosslinking reaction proceeds (before the degree of curing increases) is simply referred to as “gel electrolyte” as described above, and the gel electrolyte in which the degree of curing increases due to the crosslinking reaction proceeding. Is referred to as “hard gel electrolyte” as described above.
  • the gel electrolyte before the degree of hardening increases or the hard gel electrolyte after the degree of hardening contains the electrolyte in any state.
  • the electrolyte solution may be any one that exhibits an electrochemical reaction in a state where a voltage is applied between a pair of electrodes, but typically includes a composition containing a solvent and an ionic substance or ion pair. Can do.
  • a more specific configuration of the electrolytic solution is not particularly limited, and a known solvent, salt, or the like is appropriately selected according to the type or use of the electrochemical device or the type of matrix material constituting the gel electrolyte together with the electrolytic solution. It can be selected and used.
  • components other than a solvent, an ionic substance, or an ion pair may be suitably contained in electrolyte solution.
  • the gel electrolyte before the degree of cure may include other components such as various additives.
  • the additive include a polymerization initiator in order to promote a crosslinking reaction of uncrosslinked reactive groups contained in the matrix material.
  • 2,2′-azobis (2,4-dimethylvaleronitrile) is used as an additive.
  • the electrochemical device before the electrolyte curing degree increasing step is configured such that the gel electrolyte is interposed between the pair of electrodes, and the electrochemical device after the electrolyte curing degree increasing step is a pair of electrodes. In this configuration, a hard gel electrolyte is interposed between the electrodes.
  • the electrochemical device includes both before and after the electrolyte curing degree increasing step in a broad sense, but for the convenience of explanation, the electrochemical device undergoes an electrolyte curing degree increasing step in a narrow sense.
  • the previous electrochemical device is referred to as “electrochemical device before increasing the degree of cure”, and the electrochemical device after undergoing the electrolyte curing degree increasing step is referred to as “the electrochemical device after increasing the degree of cure”.
  • the electrochemical device before increasing the degree of curing includes the pair of electrodes and the gel electrolyte described above, and the electrochemical device after increasing the degree of curing may include the pair of electrodes and the hard gel electrolyte described above.
  • the configuration of the electrochemical device in the present disclosure is not limited to this, and may include a pair of electrodes and components or members other than the gel electrolyte or the hard gel electrolyte.
  • the specific configuration of such other components or other members is not particularly limited, and various components or components depending on the specific type of electrochemical device can be used.
  • the specific configuration of the electrochemical device in the present disclosure is not particularly limited, as described above, as long as it has a configuration including a pair of electrodes and an electrolyte positioned therebetween, and uses an electrochemical reaction. Good.
  • a typical electrochemical device a lithium ion battery, a dye-sensitized solar cell, an electric double layer capacitor, or the like can be given.
  • Lithium ion battery Next, a 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 that is a type of electrochemical device includes 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 in which the positive electrode 12, the hard gel electrolyte 14 and the negative electrode 13 are laminated (a structure in which the hard gel electrolyte 14 is held on the positive electrode 12 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 a positive electrode base material 21 (a surface facing the negative electrode 13 and a surface in contact with the hard gel electrolyte 14). ing.
  • the negative electrode 13 has a configuration in which a 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 material 21 and the negative electrode base material 31 function as a current collector that collects electrons generated by the electrochemical reaction of the positive electrode active material layer 22 and the negative electrode active material layer 32.
  • the specific structure of the positive electrode base material 21 and the negative electrode base material 31 is not specifically limited, What is necessary is just to use a well-known metal plate or metal foil. In examples described later, an aluminum foil is used as the positive electrode base material 21. As the negative electrode base material 31, a copper foil is typically used.
  • a typical example of the positive electrode active material used for the positive electrode active material layer 22 is a lithium salt of a transition metal oxide, but is not particularly limited.
  • Li—Ni—Co—Mn oxide (NCM) which is a ternary lithium salt, is used as the positive electrode active material.
  • NCM Li—Ni—Co—Mn oxide
  • the negative electrode active material used for the negative electrode active material layer 32 a lithium metal foil or a carbon material is typically used. In the examples described later, 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
  • the negative electrode active material layer 32 may be composed of only the negative electrode active material, but may be configured as 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, a known binder resin such as polyvinylidene fluoride (PVDF), carbon black, and the like
  • a known binder resin such as polyvinylidene fluoride (PVDF), carbon black, and the like
  • the known conductive assistant may be included.
  • the coating liquid should just contain the solvent (dispersion medium) other than an active material, binder resin, and a conductive support agent.
  • the coating solution has a degree of cure that is the same as that of the gel electrolyte before increasing the degree of cure or the hard gel electrolyte 14. May contain a gel electrolyte (hard gel electrolyte component).
  • the positive electrode active material layer 22 constitutes a facing surface facing the negative electrode 13 in the positive electrode 12 and a contact surface with respect 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 also constitutes a contact surface with respect 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 is formed in a porous shape.
  • the method of forming the active material layers 22 and 32 in a porous shape 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 given. Further, either one of the active material layers 22 and 32 may not be porous. In the examples 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 from a lithium foil.
  • the negative electrode 13 is comprised only with lithium foil. Therefore, at least the positive electrode 12 and the negative electrode 13 do not need to be composed of the active material layers 22 and 32 and the base materials 21 and 31 that support them, as illustrated in FIG.
  • the hard gel electrolyte 14 is formed by increasing the degree of cure of the gel electrolyte as described above.
  • the electrolytic solution contained in the hard gel electrolyte 14 may be any solution in which a known lithium salt is dissolved in a known solvent.
  • the solvent include, but are not particularly limited to, carbonate solvents, nitrile solvents, ether solvents, ionic liquids, and the like.
  • Typical examples of the lithium salt include lithium hexafluorophosphate (LiPF 6 ), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), and the like. It is not limited.
  • a typical solvent includes a mixed solvent of a cyclic carbonate and a chain carbonate.
  • the cyclic carbonate typically includes ethylene carbonate (EC) or propylene carbonate (PC), and the chain carbonate typically includes dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl
  • an ionic liquid can be mentioned as another typical solvent.
  • the matrix material that constitutes the gel electrolyte together with the electrolytic solution only needs to be able to form a gel-like body in a state containing the electrolytic solution.
  • the degree of curing is increased by crosslinking reaction of reactive groups. What can be used can be used suitably.
  • a gel composition composed of a physical gel or chemical gel having no uncrosslinked reactive group and a crosslinked reactant having an uncrosslinked reactive group as a matrix material before the degree of cure is increased. Can be mentioned.
  • a known organic polymer compound can be used depending on the type of the electrolytic solution, and as a crosslinking reaction substance, a (meth) acryl group (acryl group and methacryl group), Functional groups capable of forming bonds such as double bond functional groups such as allyl groups; or oxirane compounds such as epoxy and oxetane; urethane bonds such as isocyanate groups and blocked isocyanate groups; urea bonds; ).
  • a crosslinking reaction substance for example, a prepolymer can be suitably used as described above.
  • only one type of these functional groups may be included in the cross-linking reaction material, or two or more types may be included.
  • the mixing ratio of the physical gel or chemical gel and the cross-linking reactant is not particularly limited.
  • the matrix material may contain components other than the physical gel or chemical gel and the cross-linking reactant.
  • a copolymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP) or polyvinylidene fluoride (PDVF) is used as the organic polymer compound that can be a physical gel
  • the crosslinking reaction material is , Methyl methacrylate-oxetanyl methacrylate copolymer or tetrafunctional polyether acrylate is used.
  • the cross-linking reactant may be mixed into the electrolytic solution as one component of the electrolytic solution.
  • the reactive material may be included in both the matrix material and the electrolyte solution by mixing the crosslinking reaction material in both the matrix material and the electrolyte solution.
  • the sealing material 15 is not particularly limited as long as it can seal the laminated structure 11 including the positive electrode 12, the negative electrode 13, and the hard gel electrolyte 14. If the electrochemical device is the lithium ion battery 10, the sealing material 15 typically includes a known laminated film, a known metal can, or the like. Typical examples of the laminated film include, but are not particularly limited to, a laminate of a resin film such as polypropylene (PP) on a metal foil such as an aluminum foil or a stainless steel foil. Moreover, if an electrochemical device is a dye-sensitized solar cell, as a sealing material 15, a well-known sealing agent will be mentioned, for example.
  • PP polypropylene
  • the lithium ion battery 10 shown in FIG. 1 does not include 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 include a separate separator, or may include a member other than the positive electrode 12, the negative electrode 13, and the hard gel electrolyte 14.
  • the electrochemical device manufacturing method only needs to include at least an electrolyte hardening degree increasing step as shown in FIG.
  • the electrolyte curing degree increasing step in the present disclosure is a step of increasing the curing degree of the gel electrolyte by causing the crosslinking reaction of the reactive group to proceed while the gel electrolyte is held between the pair of electrodes. As the degree of cure of the gel electrolyte increases, that is, as the cross-linking reaction of the reactive group contained in the gel electrolyte proceeds, a part of the electrolyte solution is leaked from the gel electrolyte.
  • the partial leakage of the electrolytic solution from the gel electrolyte is accompanied by an increase in the degree of curing (progress of the crosslinking reaction of the reactive group), and thus the gel electrolyte itself contains a sufficient amount of electrolytic solution.
  • the electrolytic solution gradually leaks as the curing degree increases, the electrolytic solution is discharged so that the electrolytic solution oozes out from the gel electrolyte during the electrolyte curing degree increasing step. Since the leaked electrolyte is supplied to the contact surfaces of the pair of electrodes, a sufficient contact area is maintained at the interface between the gel electrolyte and the electrodes.
  • the leaked electrolytic solution maintains a sufficient contact area at the interface with the electrode.
  • the contact surfaces of the pair of electrodes are porous, the leaked electrolyte is favorably retained on the contact surfaces of these electrodes. Therefore, a sufficient contact area can be better maintained at the interface between the hard gel electrolyte and the electrode.
  • the electrolytic solution is intentionally leaked as the degree of curing increases. Therefore, an increase in reaction resistance can be effectively suppressed in the obtained electrochemical device.
  • the method for advancing the crosslinking reaction of the reactive group is not particularly limited, but a typical example is a method of supplying energy from the outside to the gel electrolyte.
  • the energy to be supplied include thermal energy and electromagnetic wave energy, but are not particularly limited.
  • a method of supplying thermal energy for example, a method of heating or keeping the laminated structure within a predetermined temperature range may be mentioned.
  • Examples of a method for supplying electromagnetic energy include ultraviolet irradiation and radiation irradiation. Irradiation with infrared rays can be a method for supplying electromagnetic energy and a method for supplying thermal energy.
  • the hard gel electrolyte means that the degree of cure of the gel electrolyte is sufficiently increased, in other words, that the crosslinking reaction of the reactive group contained in the matrix material or the electrolyte is sufficiently advanced. Therefore, in the hard gel electrolyte, it is not necessary that substantially all the reactive groups contained in the matrix material or the electrolytic solution undergo a crosslinking reaction. According to various conditions required for the hard gel electrolyte, the degree of progress of the crosslinking reaction (the degree of increase in the degree of curing) can be adjusted as appropriate.
  • pressure may be applied to the gel electrolyte in parallel with the progress of the crosslinking reaction of the reactive group. That is, in the electrolyte hardening degree increasing step, in addition to supplying energy, the gel electrolyte may be pressurized in a state of being held between the positive electrode and the negative electrode (in a state where a laminated structure is configured).
  • the conditions for pressurization are not particularly limited, and can be appropriately set according to various conditions such as the type of electrochemical device, the type of gel electrolyte, and the thickness range required for the hard gel electrolyte. Further, the method of pressurization is not particularly limited, and a known method can be suitably used.
  • a laminated structure manufacturing process may be performed as shown in FIG. 2 before the electrolyte curing degree increasing process.
  • the gel electrolyte is held between a pair of electrodes to prepare the laminated structure, but the specific manufacturing method is not particularly limited.
  • a composition serving as a gel electrolyte may be applied to one contact surface of a pair of electrodes and the other electrode may be laminated, or a gel electrolyte formed in advance as a sheet-like gel may be used as a pair of electrodes. You may hold between.
  • the electrochemical device is the above-described lithium ion battery 10 or the like
  • a sealing step for sealing the body with a sealing material may be performed.
  • the specific sealing method is not specifically limited, What is necessary is just to employ
  • the laminated structure may be laminated and packaged, and if the encapsulant is a metal can, the laminated structure in the metal can What is necessary is just to accommodate a body and to seal a metal can. At this time, the laminated structure may be rolled and sealed in a metal can. Further, when the electrochemical device is a dye-sensitized solar cell and the sealing material is a sealing agent, the periphery of the laminated structure may be sealed with the sealing agent.
  • the degree of cure of the gel electrolyte is increased to a hard gel electrolyte through the laminated structure manufacturing process, the sealing process, and the electrolyte cure degree increasing process, so that the electrochemical device is completed.
  • the method for manufacturing an electrochemical device according to the present disclosure is not limited to the process illustrated in FIG. 2, and may include at least an electrolyte hardening degree increasing process.
  • the electrochemical device manufacturing method may include steps other than the steps shown in FIG.
  • a finishing step for completing the electrochemical device may be included after the electrolyte curing degree increasing step.
  • an electrode manufacturing process for manufacturing a pair of electrodes may be included in the previous stage of the stacked structure manufacturing process.
  • the active material layer (the positive electrode active material layer 22 and the positive electrode base material 21 and / or the negative electrode base material 31) is formed on the surface of the electrode base material (the positive electrode base material 21 and / or the negative electrode base material 31).
  • a step of forming the negative electrode active material layer 32) by applying a coating solution (active material layer forming step) may be included.
  • the coating solution may contain a gel component similar to the gel electrolyte or the hard gel electrolyte.
  • FIG. 3B shows an example of a method for manufacturing a conventional lithium ion battery 100.
  • the gel electrolyte 16 is held between the positive electrode 12 and the negative electrode 13, which are a pair of electrodes, and the laminated structure 11 is used. (Laminated structure manufacturing step). Next, as shown in the second stage of FIG. 3 (A), the produced laminated structure 11 is sealed with a sealing material 15 to produce a sealed body 40 that is an electrochemical device before the degree of cure is increased. (Sealing process).
  • the positive electrode 12 is on one surface of the positive electrode base material 21.
  • the positive electrode active material layer 22 is configured to be laminated
  • the negative electrode 13 is configured to have the negative electrode active material layer 32 laminated on one surface of the negative electrode base material 31 (see FIG. 1). Specific configurations of the positive electrode 12 and the negative electrode 13 are not limited to this.
  • hatching is performed in accordance with the schematic cross-sectional view of the lithium ion battery 10 shown in FIG. 1, but for convenience of explaining leakage of the electrolyte, FIG.
  • the gel electrolyte 16 before the degree of cure is increased only by “hatching representing liquid” which means that the electrolyte is included.
  • “lattice hatching representing liquid” means that the hard gel electrolyte 14 includes an electrolytic solution together with the lattice-like hatching similar to FIG. It is given repeatedly.
  • the degree of cure of the gel electrolyte 16 is sufficiently increased to become the hard gel electrolyte 14.
  • the lithium ion battery 10 which is an electrochemical device after the degree of curing is completed is completed.
  • a prepolymer is generally used, and the prepolymer is previously dissolved in the electrolytic solution.
  • this electrolytic solution is referred to as a “prepolymer electrolytic solution” for convenience of description
  • the prepolymer electrolytic solution is injected into the electrochemical device and then subjected to a heat treatment or the like.
  • the prepolymer is reacted to cause gelation.
  • the prepolymer electrolyte has a higher viscosity than a normal electrolyte, it takes a long time to inject the electrolyte. This may affect the production efficiency of the electrochemical device.
  • the electrochemical device is a large battery
  • the amount of the high-viscosity prepolymer electrolytic solution to be injected becomes large, so that the electrolytic solution tends to be insufficiently injected.
  • the prepolymer electrolyte is insufficiently injected, there is a possibility that sufficient device performance cannot be realized.
  • the hard gel electrolyte 14 is formed by an electrolyte hardening degree increasing step as in the above-described manufacturing example of the lithium ion battery 10. Therefore, it is not necessary to inject the electrolytic solution, which is an essential step in the conventional manufacturing method. Furthermore, for example, even when the lithium ion battery 10 is large, it is not necessary to inject the electrolyte solution, so that the possibility of insufficient injection can be avoided. As a result, it is possible to improve the efficiency of the manufacturing process and to realize good device performance.
  • the prepolymer is reacted by external energy supply (such as heat treatment) to cause gelation, and the conventional lithium ion battery 100 is completed.
  • external energy supply such as heat treatment
  • the step of causing the prepolymer to react to advance the gelation can be referred to as a conventional electrolyte curing degree increasing step.
  • the gel electrolyte 16 is configured as a gel-like body by the matrix material and the electrolytic solution, it is not necessary to inject the electrolytic solution into the separator 104, which is an essential step in the conventional method of manufacturing the lithium ion battery 100.
  • the hard gel electrolyte 14 can function as the separator 104, the separator 104 that is a constituent element of the conventional lithium ion battery 100 is not essential in the lithium ion battery 10 according to the present disclosure. Thereby, the number of members constituting the lithium ion battery 10 can be reduced.
  • a solid electrolyte may be used as an electrolyte instead of a gel electrolyte.
  • a method for forming a solid electrolyte a method of forming a solid electrolyte on an electrode is known.
  • the contact resistance between the solid electrolyte and the electrode may increase when there are few points in point contact.
  • the volume of the electrode may change during operation of the electrochemical device. In this case, due to deterioration of the contact state between the solid electrolyte and the electrode, the lifetime of the electrochemical device may be shortened early, and good long-term stability may not be realized. Therefore, even in an electrochemical device including a solid electrolyte, there is a possibility that good device performance cannot be sufficiently realized.
  • the gel electrolyte 16 is increased in the degree of curing in the electrolyte curing degree increasing step, and the gel The electrolyte 16 leaks out so as to ooze out. Therefore, even if the gel electrolyte 16 becomes the hard gel electrolyte 14, the hard gel electrolyte 14 contains a sufficient amount of the electrolyte, and the leaked electrolyte is good on the contact surface of the positive electrode 12 and the negative electrode 13. Will come into contact.
  • Example 1 [Production of positive electrode] 6. 100 g of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM), which is a positive electrode active material, and carbon black (manufactured by Timcal Graphite & Carbon Co., product name: Super-P) as a conductive additive.
  • NCM LiNi 1/3 Co 1/3 Mn 1/3 O 2
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • a 12 mm diameter lithium foil as a negative electrode was placed on the punched body to produce a laminated structure (laminated structure producing step).
  • the obtained laminated structure was fixed with a coin cell jig (manufactured by Tom Cell Co., Ltd.) and hermetically sealed in a coin cell jig to produce a sealed body that was an electrochemical device before increasing the degree of cure (sealed). Stop process).
  • the sealing body was allowed to stand in a constant temperature bath at 60 ° C. for 18 hours to advance the crosslinking reaction of the reactive group contained in the gel electrolyte, and then returned to room temperature (electrolytic hardening degree increasing step).
  • electrolytic hardening degree increasing step After, hardening of gel electrolyte progressed and it became a hard gel electrolyte, and obtained the lithium ion battery concerning Example 1 which is an electrochemical device after the degree of hardening rises.
  • a lithium ion battery according to Example 2 was obtained in the same manner as Example 1, except that .57 parts by weight was blended.
  • the capacity retention rate was evaluated in the same manner as in Example 1. As a result, the lithium ion battery according to Example 2 was able to realize a capacity retention of 86%.
  • Example 3 is the same as Example 1 except that 10 parts by weight of PVDF (manufactured by Kureha Co., Ltd., product name: # 1300) was blended instead of PVDF-HFP in the preparation of the gel electrolyte coating solution. A lithium ion battery was obtained.
  • PVDF manufactured by Kureha Co., Ltd., product name: # 1300
  • Example 3 The obtained lithium ion battery according to Example 3, the capacity retention was evaluated in the same manner as in Example 1. As a result, the lithium ion battery according to Example 3 was able to realize a capacity retention of 90%.
  • Example 2 A lithium ion battery according to a comparative example was obtained in the same manner as in Example 1 except that 5 parts by weight of methyl methacrylate-oxetanyl methacrylate copolymer was not blended in the preparation of the gel electrolyte coating solution.
  • the capacity retention was evaluated in the same manner as in Example 1.
  • a short circuit occurred during the charge / discharge test, and the lithium ion battery could not operate normally.
  • the gel electrolyte is held between the pair of electrodes, the crosslinking reaction of the reactive group included in the gel electrolyte is advanced, and the degree of cure of the gel electrolyte is increased. And an electrolyte hardening degree increasing step of leaking out the electrolytic solution from the gel electrolyte as the crosslinking reaction proceeds.
  • the degree of hardening of the gel electrolyte held between the pair of electrodes is increased, and the electrolyte solution is leaked so as to ooze out from the gel electrolyte. Therefore, even if the degree of cure of the gel electrolyte is sufficiently increased to become a hard gel electrolyte, the hard gel electrolyte contains a sufficient amount of the gel electrolyte solution, and the leaked electrolyte solution is not contained in the pair of electrodes. It will be in good contact with the contact surface. Thereby, since a favorable contact area can be realized at the interface between the electrolyte and the electrode, an increase in reaction resistance can be effectively suppressed.

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Abstract

L'invention concerne un procédé de production d'un dispositif électrochimique, permettant au processus de production d'être plus efficace, et susceptible de produire un dispositif électrochimique pouvant atteindre d'excellentes performances de dispositif et une excellente stabilité à long terme. Le procédé de production est destiné à produire un dispositif électrochimique équipé d'une paire d'électrodes et d'un électrolyte situé entre celles-ci. L'électrolyte duquel le dispositif électrochimique est pourvu est un corps sous forme de gel constitué d'au moins un matériau de matrice et d'une solution électrolytique, contient des groupes réactifs réticulables, et présente un degré élevé de durcissement d'électrolyte en gel (électrolyte en gel dure). Le procédé de production du dispositif électrochimique comprend une étape d'élévation du degré de durcissement d'électrolyte consistant à provoquer, l'électrolyte en gel étant dans un état maintenu entre les deux électrodes, une réticulation des groupes réactifs, ce qui entraîne une élévation du degré de durcissement de l'électrolyte en gel, tout en amenant la solution électrolytique à suinter hors de l'électrolyte en gel à mesure que la réticulation se poursuit.
PCT/JP2017/043566 2016-12-27 2017-12-05 Procédé de production de dispositif électrochimique Ceased WO2018123458A1 (fr)

Priority Applications (3)

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CN201780081003.4A CN110140252A (zh) 2016-12-27 2017-12-05 电化学器件的制造方法
US16/473,984 US20210135273A1 (en) 2016-12-27 2017-12-05 Production method for electrochemical device
KR1020197018181A KR20190097070A (ko) 2016-12-27 2017-12-05 전기 화학 디바이스의 제조 방법

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JP2016253193 2016-12-27
JP2017214100A JP7004545B2 (ja) 2016-12-27 2017-11-06 電気化学デバイスの製造方法
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931852A (zh) * 2019-12-18 2020-03-27 合肥工业大学 复合固态电解质、其制备方法及包含其的锂二次固态电池
US11631845B2 (en) 2020-09-17 2023-04-18 Kabushiki Kaisha Toshiba Secondary battery, battery pack, and vehicle

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030527A (ja) * 1998-07-07 2000-01-28 Nitto Denko Corp ゲル状組成物とその利用
WO2015176016A1 (fr) * 2014-05-15 2015-11-19 Amtek Research International Llc Électrolytes de gel réticulés de façon covalente

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030527A (ja) * 1998-07-07 2000-01-28 Nitto Denko Corp ゲル状組成物とその利用
WO2015176016A1 (fr) * 2014-05-15 2015-11-19 Amtek Research International Llc Électrolytes de gel réticulés de façon covalente

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931852A (zh) * 2019-12-18 2020-03-27 合肥工业大学 复合固态电解质、其制备方法及包含其的锂二次固态电池
US11631845B2 (en) 2020-09-17 2023-04-18 Kabushiki Kaisha Toshiba Secondary battery, battery pack, and vehicle

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