WO2018123458A1

WO2018123458A1 - Production method for electrochemical device

Info

Publication number: WO2018123458A1
Application number: PCT/JP2017/043566
Authority: WO
Inventors: 恭輝齊藤; 淳史奥原
Original assignee: 第一工業製薬株式会社
Priority date: 2016-12-27
Filing date: 2017-12-05
Publication date: 2018-07-05

Abstract

Provided is a production method for an electrochemical device, allowing the production process to be more efficient, and capable of producing an electrochemical device whereby excellent device performance and long-term stability may be achieved. The production method is for an electrochemical device equipped with a pair of electrodes and an electrolyte located therebetween. The electrolyte with which the electrochemical device is provided is a gel-form body constituted by at least a matrix material and an electrolytic solution, contains cross-linkable reaction groups, and has a raised gel electrolyte hardening degree (hard gel electrolyte). The production method for the electrochemical device comprises an electrolyte hardening degree raising step of causing, with the gel electrolyte in a held state between the pair of electrodes, a crosslinking of the reaction groups to proceed, thereby causing the gel electrolyte hardening degree to be raised, while causing the electrolytic solution to seep out from the gel electrolyte as crosslinking proceeds.

Description

Method for manufacturing electrochemical device

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.

As 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. Conventionally, liquids (electrolytic solutions) have been used as electrolytes used in these electrochemical devices. However, if 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.

Special table 2011-519116 gazette Japanese Patent Laid-Open No. 10-321040

However, in the configuration using a gel electrolyte as the electrolyte of the electrochemical device, a step of injecting an electrolytic solution is required. Since this process may take a relatively long time, the manufacturing process of the electrochemical device may not be sufficiently efficient.

Also, in a configuration using a solid electrolyte as the electrolyte of the electrochemical device, the solid electrolyte and the electrode are in point contact with each other. For this reason, when there are few places which do point contact, there exists a possibility that the contact resistance of a solid electrolyte and an electrode may rise.

The present invention has been made to solve such a problem, and it is possible to improve the efficiency of the manufacturing process and to manufacture an electrochemical device capable of realizing good device performance. An object of the present invention is to provide a method for manufacturing an electrochemical device.

In order to solve the above problems, a method for producing an electrochemical device according to an aspect of the present invention is a method for producing an electrochemical device comprising a pair of electrodes and an electrolyte positioned therebetween, The electrolyte is a gel-like body composed of at least a matrix material and an electrolytic solution, and includes a crosslinkable reactive group, and has an increased degree of curing of the gel electrolyte. The gel electrolyte is the pair of gel electrolytes. In a state of being held between the electrodes, the crosslinking reaction of the reactive group is advanced to increase the degree of cure of the gel electrolyte, and the electrolyte solution is leaked from the gel electrolyte as the crosslinking reaction proceeds. This is a configuration including an electrolyte hardening degree increasing step.

The present invention provides an electrochemical device manufacturing method capable of increasing the efficiency of the manufacturing process and manufacturing an electrochemical device capable of realizing good device performance with the above configuration. There is an effect that it is possible.

It is typical sectional drawing which shows an example of a structure of the lithium ion battery which is an example of the electrochemical device which concerns on embodiment of this invention. It is a schematic process drawing which shows an example of the manufacturing method of the electrochemical device which concerns on embodiment of this invention. (A) is process drawing which shows typically the manufacturing process of the lithium ion battery shown in FIG. 1, (B) is process drawing which shows the manufacturing process of the conventional lithium ion battery typically.

A method for manufacturing an electrochemical device according to the present disclosure 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.

According to the above configuration, in the electrolyte hardening degree increasing step, the degree of hardening of the gel electrolyte that is held between the pair of electrodes is increased, and the electrolyte solution is leaked out so as to ooze out from the gel electrolyte. . Therefore, even if the gel electrolyte has a sufficiently advanced degree of hardening (hard gel electrolyte), the gel electrolyte contains a sufficient amount of the gel electrolyte, and the leaked electrolyte is Good contact is made with the contact surfaces of the pair of electrodes. 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.

Moreover, since the gel electrolyte is a gel-like body composed of a matrix material and an electrolytic solution, it is not necessary to inject the electrolytic solution, which is an essential step in the conventional manufacturing method, and the electrochemical device is large in size. Even in this case, it is possible to avoid the risk of insufficient liquid injection. This makes it possible to increase the efficiency of the manufacturing process and to realize good device performance and long-term reliability. Furthermore, since the gel electrolyte whose degree of hardening has increased can function as a separator, the separator is not essential as a component of the electrochemical device. Thereby, the number of members constituting the electrochemical device can be reduced.

In the method for manufacturing an electrochemical device having the above configuration, 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.

According to the said structure, since 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.

In the method for manufacturing an electrochemical device having the above-described structure, 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. The structure formed by application | coating may be sufficient.

According to the above configuration, since 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.

In the method for manufacturing an electrochemical device having the above configuration, 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.

According to the above configuration, 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.

In the manufacturing method of the electrochemical device having the above-described configuration, 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.

According to the above configuration, since 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.

In the method for producing an electrochemical device having the above-described configuration, in the electrolyte curing degree increasing step, the crosslinking reaction is advanced by supplying energy from the outside of the laminated structure to the gel electrolyte. Also good.

According to the above configuration, 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.

In the method for manufacturing an electrochemical device having the above configuration, in the electrolyte curing degree increasing step, the gel electrolyte may be further pressurized while being held between the positive electrode and the negative electrode. .

According to the above configuration, since the pressure is applied while increasing the degree of cure of the gel electrolyte, it is possible to control the thickness of the gel electrolyte and to control the leakage of the electrolytic solution from the gel electrolyte.

In the method for manufacturing an electrochemical device having the above configuration, the electrochemical device may be a lithium ion battery, a dye-sensitized solar cell, or an electric double layer capacitor.

According to the above configuration, if 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.

Hereinafter, representative embodiments of the present disclosure will be described with reference to the drawings. In the following description, the same or corresponding elements are denoted by the same reference symbols throughout the drawings, and redundant description thereof is omitted.

[Electrochemical devices]
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. In order to increase the contact area with the electrolyte contained in the electrolyte, for example, the contact surface (surface facing the electrolyte) is porous. Is preferred. 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. Note that 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. As a method of forming such a powder material in layers, 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. And a method of drying, curing, firing, or the like.

The electrolyte included in the electrochemical device is interposed between a pair of electrodes. In the present disclosure, the electrolyte is a gel-like body including a matrix material having a crosslinkable reactive group and an electrolyte solution. As long as the degree of cure of the gel electrolyte is increased. 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. In the following description, for the sake of convenience, the gel electrolyte having such an increased degree of curing is referred to as a “hard gel electrolyte”. In addition, when simply referred to as “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. As the matrix material, for example, a material having a reactive group capable of crosslinking reaction can be suitably used. Alternatively, an electrolytic solution containing a component having a reactive group capable of crosslinking with the matrix material can be used. For example, 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. Typically, 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. In addition, when 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. As a typical crosslinking reaction substance, a prepolymer having an uncrosslinked reactive group can be exemplified.

Further, 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. Alternatively, after mixing the raw material of the matrix material and the electrolytic solution, 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. On the other hand, 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. Moreover, components other than a solvent, an ionic substance, or an ion pair may be suitably contained in electrolyte solution.

In addition to the matrix material and the electrolytic solution, the gel electrolyte before the degree of cure may include other components such as various additives. Specific examples of the additive include a polymerization initiator in order to promote a crosslinking reaction of uncrosslinked reactive groups contained in the matrix material. In Examples described later, in Example 2, 2,2′-azobis (2,4-dimethylvaleronitrile) is used as an additive.

In the present disclosure, 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. In the present disclosure, 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”.

In the present disclosure, 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. As 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.

As shown in FIG. 1, 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. have. 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.

As shown in FIG. 1, 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. Similarly, 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. In examples described later, Li—Ni—Co—Mn oxide (NCM), which is a ternary lithium salt, is used as the positive electrode active material. As 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. Further, 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 configured as a layer containing other components. .

For example, when 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 The known conductive assistant may be included. Moreover, the coating liquid should just contain the solvent (dispersion medium) other than an active material, binder resin, and a conductive support agent. Further, from the viewpoint of improving the frequency of contact with the positive electrode active material layer 22 or the negative electrode active material layer 32, 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. Similarly, 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.

In addition, since lithium foil serves as a collector (negative electrode base material 31) with a negative electrode active material, in the Example mentioned later, 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. Examples of 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. Although carbonate (EMC) etc. are mentioned, it is not specifically limited. In the examples described later, a mixed solvent in which ethylene carbonate and diethyl carbonate are mixed at a volume ratio of 3: 7 is used as a solvent for the electrolytic solution.

Moreover, an ionic liquid can be mentioned as another typical solvent. Specifically, for example, 1,2-ethylmethylimidazolium bis (fluorosulfonyl) imide, 1,2-ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide, N-methylpropylpyrrolidinium bis (fluorosulfonyl) Imide, N-methylpropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, diethylmethylmethoxyethylammonium bis (trifluoromethanesulfonyl) imide, ciethylammonium bis (fluorosulfonyl) imide, diallyldimethylammonium (trifluoromethanesulfonyl) imide, Although diallyldimethylammonium (fluorosulfonyl) imide etc. are mentioned, it is not specifically limited.

As described above, 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. For example, the degree of curing is increased by crosslinking reaction of reactive groups. What can be used can be used suitably. In the present disclosure, 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.

As a substance that can be a physical gel or a chemical gel, 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; ). As such a crosslinking reaction substance, for example, a prepolymer can be suitably used as described above. In addition, 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. In addition, the matrix material may contain components other than the physical gel or chemical gel and the cross-linking reactant. In the examples described later, 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, and the crosslinking reaction material is , Methyl methacrylate-oxetanyl methacrylate copolymer or tetrafunctional polyether acrylate is used.

As described above, since the reactive group may be included in the electrolytic solution instead of the matrix material, the cross-linking reactant may be mixed into the electrolytic solution as one component of the electrolytic solution. Of course, 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.

Note that 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. In addition, 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.

[Method of manufacturing electrochemical device]
Next, taking the above-described lithium ion battery 10 as an example, a method for manufacturing an electrochemical device according to the present disclosure will be specifically described with reference to FIGS. 2, 3 </ b> A, and 3 </ b> B.

The electrochemical device manufacturing method according to the present disclosure 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. In addition, since 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.

Even when the gel electrolyte is hardened and a hard gel electrolyte is formed, the leaked electrolytic solution maintains a sufficient contact area at the interface with the electrode. In particular, if at least one or both of 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. Usually, in an electrochemical device, it is required that the electrolytic solution be held so as not to leak out. However, in the present disclosure, 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. Examples of the energy to be supplied include thermal energy and electromagnetic wave energy, but are not particularly limited. As 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.

Here, in the electrolyte hardening degree increasing step, 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.

In addition, in the method for manufacturing an electrochemical device according to the present disclosure, a laminated structure manufacturing process may be performed as shown in FIG. 2 before the electrolyte curing degree increasing process. In the laminated structure manufacturing step, the gel electrolyte is held between a pair of electrodes to prepare the laminated structure, but the specific manufacturing method is not particularly limited. Typically, 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.

Further, if the electrochemical device is the above-described lithium ion battery 10 or the like, in the method for manufacturing an electrochemical device according to the present disclosure, the laminated structure obtained in the laminated structure manufacturing step before the electrolyte curing degree increasing step. 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 | adopt the sealing method according to various conditions, such as the structure of an electrochemical device, or the kind of sealing material. For example, if the electrochemical device is the lithium ion battery 10 and the encapsulant is a laminated film, 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.

In the example shown in FIG. 2, 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. . However, 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.

In addition, the electrochemical device manufacturing method according to the present disclosure may include steps other than the steps shown in FIG. For example, depending on the type of the electrochemical device, a finishing step for completing the electrochemical device may be included after the electrolyte curing degree increasing step. In addition, an electrode manufacturing process for manufacturing a pair of electrodes may be included in the previous stage of the stacked structure manufacturing process. In the electrode manufacturing step, as described above, 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. As described above, the coating solution may contain a gel component similar to the gel electrolyte or the hard gel electrolyte.

An example in which the method for manufacturing the electrochemical device shown in FIG. 2 is applied to the method for manufacturing the lithium ion battery 10 shown in FIG. 1 corresponds to the schematic process diagram shown in FIG. On the other hand, the schematic process diagram shown in FIG. 3B shows an example of a method for manufacturing a conventional lithium ion battery 100.

3A, in the manufacturing method of the lithium ion battery 10, first, 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).

In both of the lithium ion battery 10 in the present disclosure shown in FIG. 3A and the conventional lithium ion battery 100 shown in FIG. 3B, 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, and 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.

3A and 3B, 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. In A), the gel electrolyte 16 before the degree of cure is increased only by “hatching representing liquid” which means that the electrolyte is included. Further, in FIG. 3A, the hard gel electrolyte 14 after the degree of curing has increased, “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.

Next, as shown in the third stage of FIG. 3A, energy is supplied from the outside to the sealing body 40 as shown by the white block arrows (heating). The degree of cure of the gel electrolyte 16 included in the laminated structure 11 is increased by the treatment or the like. At this time, the crosslinking reaction proceeds in the gel electrolyte 16, and as a result, the electrolyte contained in the gel electrolyte 16 is mixed with the positive electrode active material layer 22 of the positive electrode 12 and the negative electrode active material of the negative electrode 13 as indicated by black block arrows. It leaks out toward the layer 32 (electrolyte hardening degree raising process).

Thereafter, as shown in the lowermost part of FIG. 3A, the degree of cure of the gel electrolyte 16 is sufficiently increased to become the hard gel electrolyte 14. Thereby, the lithium ion battery 10 which is an electrochemical device after the degree of curing is completed is completed.

By the way, in the conventional method of manufacturing an electrochemical device, when a gel electrolyte is used as an electrolyte, for example, the following problems occur.

In order to gel the electrolytic solution, a prepolymer is generally used, and the prepolymer is previously dissolved in the electrolytic solution. When this electrolytic solution is referred to as a “prepolymer electrolytic solution” for convenience of description, in the production of an electrochemical device, in many cases, 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. However, since 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.

Also, when 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. When such a prepolymer electrolyte is insufficiently injected, there is a possibility that sufficient device performance cannot be realized.

In the method for manufacturing an electrochemical device according to the present disclosure, 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.

For example, in the conventional manufacturing method of the lithium ion battery 100, as shown in the uppermost stage and the second stage of FIG. 3B, as in the manufacturing method of the lithium ion battery 10 in the present disclosure, A sealing step is performed. Specifically, a separator 104 (for example, a polyolefin porous film) is held between the positive electrode 12 and the negative electrode 13 instead of the gel electrolyte 16 to produce a laminated structure 101, and the laminated structure 101 is sealed. Sealing is performed with the material 15, and the sealing body 110, which is an electrochemical device before increasing the degree of curing, is produced.

Here, in the conventional manufacturing method of the lithium ion battery 100, in contrast to this, as shown in the third stage of FIG. 3B, a step of injecting an electrolytic solution into the sealing body 110 (electrolytic solution) Injection step) is required. If the electrolyte of the conventional lithium ion battery 100 is a gel electrolyte, a “prepolymer electrolyte solution” in which a prepolymer is dissolved in advance is used as the electrolyte solution. Therefore, a high-viscosity prepolymer electrolyte solution is injected into the sealing body 110. Thereafter, as shown in the lowermost stage of FIG. 3B, the prepolymer is reacted by external energy supply (such as heat treatment) to cause gelation, and the conventional lithium ion battery 100 is completed. The step of causing the prepolymer to react to advance the gelation can be referred to as a conventional electrolyte curing degree increasing step.

Here, since the prepolymer electrolyte solution has a high viscosity as described above, it takes a long time to inject the prepolymer electrolyte solution in the electrolyte solution injection step. In addition, when the electrochemical device is a large battery, the amount of the high-viscosity prepolymer electrolyte solution to be injected becomes large, so that the electrolyte solution is likely to be insufficiently injected. As described above, in the conventional method of manufacturing the lithium ion battery 100, the manufacturing process may not be sufficiently efficient, and the battery performance and long-term stability may not be sufficiently realized due to insufficient liquid injection.

In contrast, in the method for manufacturing the lithium ion battery 10 according to the present disclosure (method for manufacturing an electrochemical device), the degree of cure of the gel electrolyte 16 is increased while the gel electrolyte 16 is held between the positive electrode 12 and the negative electrode 13. When it is made to leak, it will leak out so that electrolyte solution may ooze out from the gel electrolyte 16. Therefore, even when the degree of cure of the gel electrolyte 16 is increased to become the hard gel electrolyte 14, the hard gel electrolyte 14 contains a sufficient amount of the electrolyte solution, and the leaked electrolyte solution is the positive electrode 12 and the negative electrode 13. It will be in good contact with the contact surface. As a result, a good contact area can be realized at each of the interface between the hard gel electrolyte 14 and the positive electrode 12 and the interface between the hard gel electrolyte 14 and the negative electrode 13, thereby effectively suppressing an increase in reaction resistance. it can.

In particular, if at least one of the positive electrode active material layer 22 that is the contact surface of the positive electrode 12 and the negative electrode active material layer 32 that is the contact surface of the negative electrode 13 is a porous layer, the leaked electrolyte solution (Contact surface) can be held well. Therefore, the contact area with the hard gel electrolyte 14 can be kept even better.

Moreover, since 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. In addition, it is possible to avoid the possibility of insufficient liquid injection that may occur when the lithium ion battery 100 is large. This makes it possible to increase the efficiency of the manufacturing process and to realize good device performance and long-term stability.

Furthermore, since 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.

In addition, in a conventional electrochemical device, a solid electrolyte may be used as an electrolyte instead of a gel electrolyte. As a method for forming a solid electrolyte, a method of forming a solid electrolyte on an electrode is known. However, since the solid electrolyte is in point contact with the electrode, the contact resistance between the solid electrolyte and the electrode may increase when there are few points in point contact. Further, 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.

On the other hand, in the method for manufacturing the lithium ion battery 10 (method for manufacturing an electrochemical device) according to the present disclosure, as described above, 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.

Thereby, a good contact area can be realized at the interface between the hard gel electrolyte 14 and the positive electrode 12 and the negative electrode 13, so that an increase in reaction resistance can be effectively suppressed. Further, even if the volume of the positive electrode 12 or the negative electrode 13 may change during the operation of the lithium ion battery 10, the positive electrode 12, the negative electrode 13, and the hard gel electrolyte 14 can be in good surface contact with the leaked electrolyte. . Therefore, an early decrease in battery life in the lithium ion battery 10 is suppressed, and good long-term stability can be realized.

The method for producing an electrochemical device according to the present disclosure will be described more specifically based on examples and comparative examples, but the present invention is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

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. 8 g, 3.3 g of polyvinylidene fluoride (PVDF, weight average molecular weight Mw: about 300,000, manufactured by Kureha Co., Ltd., product name: # 1300) as a binder resin, and N-methyl-2-pyrrolidone (NMP) as a dispersion medium 38.4 g was weighed and mixed with a planetary mixer to prepare a coating solution for a positive electrode active material layer having a solid content of 51%. This coating solution is coated on an aluminum foil (positive electrode base material) having a thickness of 15 μm with a coating apparatus, dried at 130 ° C., and then subjected to roll press treatment to obtain a positive electrode having a positive electrode active material layer of 2.3 mg / cm ^2. It was.

[Preparation of gel electrolyte coating solution]
The following operations were performed in a dry air atmosphere with a dew point of −50 ° C. or lower. As a solvent, 100 parts by weight of ethylene carbonate / diethyl carbonate = 3/7 (volume ratio), 18 parts by weight of lithium hexafluorophosphate (LiPF ₆ ), a copolymer of vinylidene fluoride and hexafluoropropylene (PVDF- HFP, weight average molecular weight Mw: about 380,000, manufactured by Kureha Corporation, product name: # 8500, 10 parts by weight, and methyl methacrylate-oxetanyl methacrylate copolymer (weight average molecular weight Mw = about 400,000, Daiichi Kogyo Seiyaku Co., Ltd. 5 parts by weight of a product manufactured by the company, product name: ELEXCEL ACG) was blended and mixed, and then kneaded uniformly by a rotation / revolution mixer to prepare a gel electrolyte coating solution.

[Manufacture of lithium-ion batteries]
After applying the gel electrolyte prepared as described above to the positive electrode prepared as described above with an applicator so that the film thickness is about 40 μm, it is punched into a circular shape with a diameter of 14 mm, and the positive electrode and the gel electrolyte are used. A punched body composed was obtained.

A polyimide film (film thickness: 25 μm) formed in a ring shape having an inner diameter of 12 mm and an outer diameter of 20 mm was prepared as a spacer for preventing contact between the positive electrode and the negative electrode, and this was placed on the punched body. In order not to overlap this ring-shaped polyimide film, 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).

Thereafter, 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). Thereby, 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.

[Battery power generation characteristics evaluation]
About the obtained lithium ion battery which concerns on Example 1, it charges with a 0.2C time rate on 25 degreeC conditions using a charging / discharging test device (Toyo System Co., Ltd. product name: TOSCAT3100). At the same time, discharge was performed under the conditions of 0.2C to 1C time rate, and the capacity retention rate (Q1C / Q0.1C) of the 1C discharge capacity relative to the 0.1C discharge capacity was evaluated. As a result, the lithium ion battery according to Example 1 was able to realize a capacity retention of 90%.

(Example 2)
In the preparation of the gel electrolyte coating solution, tetrafunctional polyether acrylate (weight average molecular weight Mw = about 11,000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name) was used instead of 5 parts by weight of methyl methacrylate-oxetanyl methacrylate copolymer. : ELEXCEL TA-210) 10 parts by weight and 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-65) 0 as an additive 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.

For the obtained lithium ion battery according to Example 2, 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)
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.

About 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%.

(Comparative example)
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.

For the obtained lithium ion battery according to the comparative example, the capacity retention was evaluated in the same manner as in Example 1. As a result, in the lithium ion battery according to the comparative example, a short circuit occurred during the charge / discharge test, and the lithium ion battery could not operate normally.

As described above, in the method for producing an electrochemical device according to the present disclosure, 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.

In the electrolyte hardening degree increasing step, 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.

Moreover, since the gel electrolyte is configured as a gel-like body by the matrix material and the electrolytic solution, it is not necessary to inject the electrolytic solution, which is an essential step in the conventional manufacturing method, and the electrochemical device is large-sized. Even in this case, it is possible to avoid the risk of insufficient liquid injection. This makes it possible to increase the efficiency of the manufacturing process and to realize good device performance and long-term reliability. Furthermore, since the hard gel electrolyte can function as a separator, the separator is not essential as a component of the electrochemical device. Thereby, the number of members constituting the electrochemical device can be reduced.

It should be noted that the present invention is not limited to the description of the above-described embodiment, and various modifications are possible within the scope shown in the scope of the claims, and are disclosed in different embodiments and a plurality of modifications. Embodiments obtained by appropriately combining the technical means are also included in the technical scope of the present invention.

The present invention can be widely used in the field of producing electrochemical devices such as lithium ion batteries, dye-sensitized solar cells, and electric double layer capacitors.

DESCRIPTION OF SYMBOLS 10 Lithium ion battery 11 Laminated structure 12 Positive electrode 13 Negative electrode 14 Hard gel electrolyte 15 Sealing material 16 Gel electrolyte 21 Positive electrode base material 22 Positive electrode active material layer 31 Negative electrode base material 32 Negative electrode active material layer 40 Sealing body

Claims

A method for producing an electrochemical device comprising a pair of electrodes and an electrolyte positioned between the electrodes,
The electrolyte is a gel-like body composed of at least a matrix material and an electrolytic solution, and includes a reactive group capable of crosslinking, and the degree of cure of the gel electrolyte is increased.
In a state where the gel electrolyte is held between the pair of electrodes, the crosslinking reaction of the reactive group is advanced to increase the degree of cure of the gel electrolyte, and from the gel electrolyte as the crosslinking reaction proceeds. The manufacturing method of the electrochemical device characterized by including the electrolyte hardening degree raise process which leaks out the said electrolyte solution.
The pair of electrodes is a positive electrode and a negative electrode,
The method for producing an electrochemical device according to claim 1, wherein at least one of the positive electrode and the negative electrode has a porous contact surface with the electrolyte.
At least one of the pair of electrodes includes an active material layer formed on a contact surface to the electrolyte,
The method for manufacturing an electrochemical device according to claim 1, wherein the active material layer is formed by applying a coating liquid containing an active material.
The method for producing an electrochemical device according to claim 3, wherein the coating liquid contains the gel electrolyte or a hard gel electrolyte in which the degree of cure of the gel electrolyte is increased.
The method further includes a sealing step performed before the electrolyte curing degree increasing step and sealing the laminated structure holding the gel electrolyte between the pair of electrodes with a sealing material. Item 5. The method for producing an electrochemical device according to any one of Items 1 to 4.
6. The electrochemical device according to claim 5, wherein in the electrolyte curing degree increasing step, the crosslinking reaction is advanced by supplying energy to the gel electrolyte from the outside of the laminated structure. Production method.
The said electrolyte hardening degree raise process WHEREIN: Furthermore, the said gel electrolyte is pressurized in the state hold | maintained between the said positive electrode and the said negative electrode, The any one of Claim 1 to 6 characterized by the above-mentioned. Manufacturing method of electrochemical device.
The electrochemical device is a lithium ion battery, a dye-sensitized solar cell, or an electric double layer capacitor,
The manufacturing method of the electrochemical device of any one of Claim 1 to 7.