Laminate for all solid-state electrochemical element, all solid-state electrochemical element, electrical apparatus, and mobile object

Abstract

To provide a laminate for an all solid-state electrochemical element excellent in curl suppression effect during film formation and deterioration suppression effect of a sulfide solid-state electrolyte containing layer.SOLUTION: A laminate for an all solid-state electrochemical element includes a sulfide solid-state electrolyte containing layer and an insulating resin layer disposed so as to be in contact with at least part of the sulfide solid-state electrolyte containing layer. The insulating resin layer includes a structural unit represented by the following general formula (1), and has a porous structure. (In general formula (1), R1 indicates hydrogen or a methyl group, and R2 indicates either a polyester chain or an acrylic multimeric ester derivative.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a laminate for an all-solid-state electrochemical device, an all-solid-state electrochemical device, an electric device, and a mobile body.

Background Art

[0002] Compared with conventional lithium-ion secondary batteries, all-solid-state secondary batteries are less affected by temperature changes and have a lower risk of ignition, so they are excellent in terms of safety. Also, they can be rapidly charged, so they are excellent in terms of performance. For this reason, it is expected that the demand for mounting on electric vehicles and the like will increase. In addition, the need for thin batteries for various wearable devices and medical patches is increasing, and the requirements for all-solid-state secondary batteries are diversifying.

[0003] As an all-solid-state secondary battery, for example, for the purpose of providing a solid battery that can suppress cracks generated during lamination pressing during manufacturing and suppress short circuits due to tab contact, a positive electrode for a solid electrochemical device including a positive electrode current collector and a positive electrode active material layer containing a positive electrode active material formed on the positive electrode current collector has been reported in which active material layer guides are arranged on two sides of the outer peripheral portion of the positive electrode active material layer (see, for example, Patent Document 1).

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a laminate for an all-solid-state electrochemical device that is excellent in the curl suppression effect during film formation and the deterioration suppression effect of a sulfide solid electrolyte-containing layer.

Means for Solving the Problems

[0005] The laminate for an all-solid-state electrochemical device of the present invention as means for solving the problems is a sulfide solid electrolyte-containing layer; an insulating resin layer arranged so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer, and is a laminate for an all-solid-state electrochemical device. The insulating resin layer contains a structural unit represented by General Formula (1) or General Formula (2), The insulating resin layer is a laminate for an all-solid-state electrochemical device, characterized by having a porous structure.

Chemical formula

Chemical formula

Advantages of the Invention

[0006] According to the present invention, it is possible to provide a laminate for an all-solid-state electrochemical device that is excellent in the curl suppression effect during film formation and the deterioration suppression effect of the sulfide solid electrolyte-containing layer.

Brief Description of the Drawings

[0007]

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Figure 17

MODE FOR CARRYING OUT THE INVENTION

[0008] Conventionally, when manufacturing an all-solid-state battery, for the purpose of improving the performance of the all-solid-state battery, that is, for the purpose of obtaining an all-solid-state battery having a high density, a laminate including a positive electrode, a solid electrolyte layer, and a negative electrode may be pressed at a very high pressure. At this time, there has been a concern that a short circuit may occur between the electrode and the negative electrode during use of the all-solid-state battery due to damage such as cracks in the solid electrolyte layer or displacement of the ends due to pressing.

[0009] In order to prevent such damage to all-solid-state batteries, a positive electrode for a solid electrochemical element in which a active material layer guide is arranged has been proposed as in the invention described in Patent Document 1. Since the active material layer guide is provided for preventing short circuits, it is required to have insulation and to have a thickness comparable to that of the electrode binder layer. Further, since the active material layer guide is required to have a certain degree of viscoelasticity so as to withstand high-pressure pressing, it is preferably made of a resin. When forming the active material layer guide by applying and curing a liquid composition in which a resin is dissolved, it is necessary to apply it with a liquid film thickness thicker than the desired thickness of the active material layer guide. At this time, since dripping at the edge end is a concern, it is common to use a photocurable liquid composition for producing the active material layer guide.

[0010] The photocurable liquid composition often consists of a photoinitiator and an acrylic polyfunctional polymerizable compound. In the case of photocuring using such a photocurable liquid composition containing a polyfunctional polymerizable compound, in the process of the liquid composition changing from a liquid to a solid, a large number of polymerizable compounds polymerize into one molecule, so volume shrinkage occurs due to the gap between the van der Waals distance and the covalent bond distance. Further, when curing is carried out in a state where a diluting solvent is contained, since polymerization occurs in a state greatly swollen by impregnation with the diluting solvent, volume shrinkage occurs in the solvent removal step. These volume shrinkages have a concern that peeling of the active material layer guide from the substrate, curling phenomenon in which the substrate warps up, and damage to the adjacent electrode binder layer may occur due to this.

[0011] As a result of intensive studies by the inventors, it has been found that when a porous film is formed by controlling the compatibility balance between a bifunctional or trifunctional acrylate having a flexible polyalkylene oxide structure and a solvent, volume shrinkage is suppressed (for example, see Patent Document 2). However, there is a concern that a resin layer made of polyethylene glycol diacrylate, which is a typical example of alkylene oxide-based acrylate, may cause deterioration of a sulfide solid electrolyte layer generally used as a solid electrolyte, and there is room for improvement.

[0012] The laminate for an all-solid-state electrochemical device of the present invention is a laminate for an all-solid-state electrochemical device including a sulfide solid electrolyte-containing layer and an insulating resin layer disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer. The insulating resin layer contains a specific structural unit and has a porous structure. Such a configuration can sufficiently eliminate various concerns in the prior art. More specifically, it is possible to realize a laminate for an all-solid-state electrochemical device excellent in the curl suppression effect during film formation and the deterioration suppression effect of the sulfide solid electrolyte-containing layer.

[0013] The details of the present invention will be described below.

[0014] (Laminate for all-solid-state electrochemical device) The laminate for an all-solid-state electrochemical device of the present invention includes a sulfide solid electrolyte-containing layer and an insulating resin layer disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer, and may include a substrate and other members as necessary.

[0015] The all-solid-state electrochemical device in the present specification is not particularly limited and can be appropriately selected according to the purpose. Examples include all-solid-state batteries and all-solid-state capacitors.

[0016] In the laminate for an all-solid-state electrochemical device of the present invention, the insulating resin layer is disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer. Here, "in contact" means that the sulfide solid electrolyte-containing layer and the insulating resin layer are physically in contact. When the substrate in the laminate for an all-solid-state electrochemical device is used as a reference plane, the positional relationship between the sulfide solid electrolyte-containing layer and the insulating resin layer is not particularly limited as long as they are in contact. For example, a positional relationship in which the insulating resin layer is adjacent to the periphery of the sulfide solid electrolyte-containing layer (for example, an electrode composite layer) formed on the substrate, or a positional relationship in which the sulfide solid electrolyte-containing layer is laminated on the upper surface of the insulating resin layer formed on the substrate can be mentioned.

[0017] <Substrate> As the substrate in the present invention, there is no particular limitation as long as it has electronic conductivity and is stable with respect to the applied potential, and it can be appropriately selected according to the purpose. For example, aluminum foil, copper foil, stainless steel foil, titanium foil, etched foil obtained by etching them to form fine holes, carbon-coated foil with a surface layer coated with a carbon-containing resin layer, a perforated substrate used in a lithium-ion capacitor, and the like can be mentioned.

[0018] <Sulfide solid electrolyte-containing layer> As the sulfide solid electrolyte in the sulfide solid electrolyte-containing layer in the present invention, there is no particular limitation as long as it is a solid substance having electron insulation and exhibiting ionic conductivity, and it can be appropriately selected according to the purpose. For example, Li 10 GeP 2 S 12 , Li having an argyrodite-type crystal structure 6 PS 5 X (X = F, Cl, Br, I), and the like can be mentioned. These may be used alone or in combination of two or more.

[0019] <Insulating resin layer> The insulating resin layer in the present specification contains a structural unit represented by the general formula (1) or the general formula (2) and has a porous structure.

[0020] [Chemical formula] (In the general formula (1), R1 represents hydrogen or a methyl group, and R2 represents any one selected from a polyester chain and an acrylic multimer ester derivative.)

[0021] [Chemical formula] (In the general formula (2), R3 and R4 represent hydrogen or a methyl group.) In addition, R5 in the general formula (2) is a structure derived from neopentyl glycol hydroxypivalate.

[0022] In the present invention, since the insulating resin layer contains a structural unit represented by General Formula (1) or General Formula (2), it is possible to suppress the deterioration of the sulfide solid electrolyte-containing layer disposed in contact with the insulating resin layer.

[0023] As R1 in the structural unit represented by General Formula (1) and R3 and R4 in the structural unit represented by General Formula (2), from the viewpoint of being able to lower the glass transition temperature, improve flexibility, and suppress curling, a hydrogen atom is preferable.

[0024] From the viewpoint of being able to more suppress the deterioration of the sulfide solid electrolyte-containing layer, the insulating resin layer in the present invention preferably contains a structural unit in which R2 in General Formula (1) is a polyester chain or a structural unit represented by General Formula (2). More preferably, R2 in General Formula (1) contains a structural unit that is a polyester chain, and even more preferably, R2 in General Formula (1) contains a structural unit that is a polycaprolactone chain.

[0025] There is no particular limitation on n in the structural unit represented by General Formula (1), and it can be appropriately selected within a range that does not impair the effects of the present invention. For example, an integer of 2 to 1000 can be mentioned. There is no particular limitation on m in the structural unit represented by General Formula (1), and it can be appropriately selected within a range that does not impair the effects of the present invention. For example, an integer of 1 to 4 can be mentioned. There is no particular limitation on p and q in the structural unit represented by General Formula (2), and they can be appropriately selected within a range that does not impair the effects of the present invention. For example, an integer of 2 to 1000 can be mentioned.

[0026] The insulating resin layer in the present invention may contain at least one structural unit represented by General Formula (1) or General Formula (2). That is, the insulating resin layer may contain only the structural unit represented by General Formula (1) or General Formula (2), or may contain two or more different structural units represented by General Formula (1) or General Formula (2). In any case, in addition to the structural unit represented by General Formula (1) or General Formula (2), a structural unit that does not satisfy General Formula (1) or General Formula (2) may be contained. Here, from the viewpoint of being able to suppress the deterioration of the sulfide solid electrolyte-containing layer, it is preferable that the insulating resin layer in the present invention does not contain a structural unit that does not satisfy General Formula (1) or General Formula (2). Further, from the viewpoint that the range in which the physical properties (for example, elastic modulus) of the insulating resin layer can be controlled can be expanded, it is preferable that the insulating resin layer in the present invention contains two or more different structural units represented by General Formula (1) or General Formula (2).

[0027] The insulating resin layer in the present invention has a porous structure. When the insulating resin layer has a porous structure, it becomes difficult for residual stress due to volume shrinkage to occur, so curling can be suppressed. In particular, it is more effective when forming an insulating resin layer having an average thickness of 100 μm or more.

[0028] The porous structure is preferably a co-continuous structure having a resin as a skeleton. Here, the "co-continuous structure" means a structure in which two or more substances or phases each have a continuous structure and do not form an interface. In the present embodiment, it means a structure in which a resin phase and a pore phase are both three-dimensional branched network continuous phases. These structures can be formed, for example, by polymerization-induced phase separation with a polymerizable compound that is a precursor of the insulating resin layer in the present invention (see, for example, JP-A-2003-1911628, WO 97 / 044363, JP-A-2005-298757, JP-T-2010-513589, JP-A-2001-163907, and JP-A-2001-138504, etc.).

[0029] Coincidence-induced phase separation means that, before the start of polymerization, the polymerizable compound and the solvent are compatible, and after the start of polymerization, the polymer (resin) generated during the polymerization process of the polymerizable compound and the solvent are incompatible, resulting in a phase separation state. Although there are other methods to obtain a porous structure by phase separation, the porous structure with a co-continuous structure obtained by the polymerization-induced phase separation method has the advantage of high resistance to chemicals and heat. Also, compared with other methods, it has the advantages of a short process time and easy surface modification. Next, the formation process of a porous structure using the polymerization-induced phase separation method with a liquid composition containing a polymerizable compound will be described. The polymerizable compound undergoes a polymerization reaction by light irradiation or the like to form a resin. During this process, the solubility of the growing resin in the solvent decreases, and phase separation occurs between the resin and the solvent. Finally, the resin forms a porous structure in which the solvent and the like fill the pores and has a co-continuous structure by the resin skeleton. When this is dried, the solvent and the like are removed, leaving a porous resin having a co-continuous structure of a three-dimensional network structure.

[0030] Therefore, as a preferable form of the ink, the liquid composition containing a polymerizable compound preferably has a polymerizable compound (monomer) and a solvent mixed therein, and the resin after polymerization is insoluble in the solvent or does not form a gel or a sol.

[0031] As a method for confirming that the insulating resin layer has a co-continuous structure and the pores are connected, for example, there is a method of observing an image of the cross-section of the insulating resin layer with a scanning electron microscope (SEM) or the like to confirm that the connection between the pores is continuous. [An example of the image observation method using a scanning electron microscope (SEM)] After subjecting the insulating resin layer to osmium staining, impregnating it with an epoxy resin under vacuum, cutting out the internal cross-sectional structure with a focused ion beam (FIB), and observing it using a scanning electron microscope (SEM).

[0032] The porosity of the insulating resin layer in the present invention is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 30% or more, more preferably 50% or more. Also, it is preferably 90% or less, more preferably 85% or less. When the porosity of the insulating resin layer is 30% or more, it is possible to relieve the pressure applied from the insulating resin layer to the sulfide solid electrolyte-containing layer in the pressing step after the formation of the sulfide solid electrolyte-containing layer, which is preferable. When the porosity of the insulating resin layer is 90% or less, the strength of the insulating resin layer is improved, and when passing through the pressing step, the shape of the insulating resin layer can be sufficiently maintained, which is preferable. As a method for measuring the porosity of the insulating resin layer, it can be measured by the same method as described in the item of [An example of the image observation method using a scanning electron microscope (SEM)].

[0033] The air permeability of the insulating resin layer in the present invention is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 1,000 seconds / 100 mL or less, more preferably 500 seconds / 100 mL or less, and even more preferably 300 seconds / 100 mL or less. The air permeability is measured in accordance with JIS P8117, and can be measured using, for example, a Gurley densitometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.). As an example, it may be determined that the pores communicate when the air permeability is 1,000 seconds / 100 mL or less.

[0034] The cross-sectional shape of the pores in the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. Examples include a substantially circular shape, a substantially elliptical shape, and a substantially polygonal shape. Here, the size of the pores refers to the length of the longest part in the cross-sectional shape of the insulating resin layer. The size of the pores in the insulating resin layer can be obtained, for example, from a cross-sectional photograph taken with a scanning electron microscope (SEM).

[0035] The size of the pores in the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, the ratio of the pore size to the median diameter of the sulfide solid electrolyte contained in the liquid composition (liquid composition for sulfide solid electrolyte-containing layer) for forming the sulfide solid electrolyte-containing layer provided on the insulating resin layer is preferably smaller than 1, and more preferably 0.8 or less. When the size of the pores in the insulating resin layer is larger than the median diameter of the sulfide solid electrolyte, the sulfide solid electrolyte is likely to be contained in the pores of the insulating resin layer. By making the size of the pores in the insulating resin layer smaller than the median diameter of the sulfide solid electrolyte, it is possible to form a structure in which the sulfide solid electrolyte is less likely to be contained in the insulating resin layer, which is advantageous in terms of pressure dispersion during pressing and pressure relaxation from the insulating resin layer to the sulfide solid electrolyte-containing layer.

[0036] The method for controlling the pore size and porosity of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. For example, methods such as adjusting the content of the polymerizable compound in the liquid composition, adjusting the content of the solvent in the liquid composition, and adjusting the irradiation conditions of active energy rays can be mentioned.

[0037] The volume resistivity of the insulating resin layer in the present invention is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 10 12 Ω·cm or more. Further, it is preferable to add a conductive filler or the like to obtain a resin layer having no conductive path.

[0038] <<Liquid Composition>> From the viewpoint of obtaining a more excellent curl suppression effect, the insulating resin layer in the present invention is preferably a cured product of a liquid composition containing a polymerizable compound represented by the general formula (3) or the general formula (4) and a solvent.

[0039]

Chemical Formula

[0040]

Chemical formula

[0041] - Polymerizable compound -

[0042] The polymerizable compound in this specification is represented by the general formula (3) or the general formula (4).

[0043]

Chemical formula

[0044]

Chemical formula

[0045] As r in the general formula (3), from the viewpoint of suppressing curl of the insulating resin layer, 2 or 3 is preferable, and 2 is more preferable.

[0046] The polymerizable compound in this specification means a compound having a plurality of vinyl groups capable of radical polymerization, and is preferably a compound having an acrylic group from the viewpoint of high-speed polymerizability by electron beam, that is, R6 in the general formula (3) and R8 and R9 in the general formula (4) are preferably hydrogen atoms. Generally, since an acrylic group has high radical polymerizability, a cured product can be obtained in a short time by using a photopolymerization initiator or a thermal polymerization initiator in combination. Although a cured product can also be obtained without using a polymerization initiator in combination, when a polymerizable compound having an acrylic group is used, that is, when R6 in the general formula (3) and R8 and R9 in the general formula (4) are hydrogen atoms, from the viewpoints of polymerization rate and equipment cost, it is preferable to use the polymerizable compound in combination with a thermal polymerization initiator or a photopolymerization initiator, and it is more preferable to use the polymerizable compound in combination with a photopolymerization initiator.

[0047] From the viewpoint of further suppressing the deterioration of the sulfide solid electrolyte-containing layer, the liquid composition in the present invention preferably contains a polymerizable compound in which R7 in the general formula (3) is a polyester chain, or a polymerizable compound represented by the general formula (4). More preferably, R7 in the general formula (3) contains a polymerizable compound that is a polyester chain, and even more preferably, R7 in the general formula (3) contains a polymerizable compound that is a polycaprolactone chain.

[0048] Examples of the polymerizable compound represented by the general formula (3) or the general formula (4) include hydroxypivalic acid neopentyl glycol acrylate adduct, bifunctional acrylic acid multimer ester acrylate, bifunctional caprolactam-modified acrylate, polyester acrylate, and the like.

[0049] Specific examples of the hydroxypivalic acid neopentyl glycol acrylate adduct include, by trade name, Light Acrylate HPP-A (manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat #195 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Biscoat #230 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Biscoat #260 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Miramer M210 (manufactured by Miwow), Miramer M216 (manufactured by Miwow), KAYARAD FM-400 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0050] Specific examples of the bifunctional acrylic acid polyol acrylate include, under the trade name, Biscoat #230D (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0051] Specific examples of the bifunctional caprolactam-modified acrylate include, under the trade name, KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD HX-620 (manufactured by Nippon Kayaku Co., Ltd.).

[0052] Specific examples of the polyester acrylate include, under the trade name, CN2273 (manufactured by B A Industries Co., Ltd.), CN2283 (manufactured by B A Industries Co., Ltd.).

[0053] As the polymerizable compound in the present invention, at least one polymerizable compound represented by the general formula (3) or the general formula (4) may be included. That is, the polymerizable compound in the present invention may contain only the polymerizable compound represented by the general formula (3) or the general formula (4), or may contain two or more different polymerizable compounds represented by the general formula (3) or the general formula (4). In any case, in addition to the polymerizable compound represented by the general formula (3) or the general formula (4), a polymerizable compound that does not satisfy the general formula (3) or the general formula (4) may be included. Here, from the viewpoint of being able to suppress the deterioration of the sulfide solid electrolyte-containing layer, it is preferable that the polymerizable compound in the present invention does not contain a polymerizable compound that does not satisfy the general formula (3) or the general formula (4). Further, from the viewpoint that the range in which the physical properties (for example, elastic modulus) of the insulating resin layer can be controlled can be expanded, it is preferable that the polymerizable compound in the present invention contains two or more different polymerizable compounds represented by the general formula (3) or the general formula (4).

[0054] The photoinitiator is not particularly limited and can be appropriately selected according to the purpose. For example, alkylphenone-based photoinitiators, acylphosphine sulfite-based photoinitiators, oxime ester-based photoinitiators, etc. can be mentioned. Specific examples of the alkylphenone-based polymerization initiators include, by trade name, Omnirad 651 (manufactured by IGM Resins B.V.), Omnirad 184 (manufactured by IGM Resins B.V.), Omnirad 1173 (manufactured by IGM Resins B.V.), Omnirad 2959 (manufactured by IGM Resins B.V.), Omnirad 127 (manufactured by IGM Resins B.V.), Omnirad 907 (manufactured by IGM Resins B.V.), Omnirad 369 (manufactured by IGM Resins B.V.), Omnirad 369E (manufactured by IGM Resins B.V.), Omnirad 379EG (manufactured by IGM Resins B.V.), and the like. Specific examples of the acylphosphine sulfite-based polymerization initiators include, by trade name, Omnirad TPO (manufactured by IGM Resins B.V.), Omnirad 819 (manufactured by IGM Resins B.V.), and the like. Specific examples of the oxime ester-based polymerization initiators include, by trade name, Irgacure OXE01 (manufactured by BASF Japan), Irgacure OXE02 (manufactured by BASF Japan), Irgacure OXE03 (manufactured by BASF Japan), Irgacure OXE04 (manufactured by BASF Japan), and the like.

[0055] The content of the polymerization initiator is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of obtaining a sufficient curing rate, when the total amount of the polymerizable compound is 100.0% by mass, it is preferably 0.05% by mass or more and 10.0% by mass or less, and more preferably 0.1% by mass or more and 5.0% by mass or less.

[0056] - Solvent - When forming the insulating resin layer in the present invention by the polymerization-induced phase separation method, it is preferable to add a solvent to the polymerizable compound from the viewpoint of suppressing volume shrinkage during polymerization. The solvent in the liquid composition is expected to act as a buffer for curing shrinkage because there is no variation in the intermolecular distance between solvents or between the resin and the solvent during polymerization.

[0057] As used herein, the solvent means an organic solvent having a water content of 1 w% or less, and a low-polarity hydrophobic solvent with low reactivity with the sulfide solid electrolyte-containing layer is preferred. Specific examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, anisole, and phenetole; hydrocarbon solvents such as hexane, heptane, nonane, octane, decane, menthane, cyclohexane, cyclooctane, and p-menthane; ester solvents such as ethyl butyrate, ethyl valerate, ethyl hexanoate, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl undecanoate, ethyl laurate, methyl butyrate, methyl valerate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl laurate, ethyl isovalerate, isoamyl acetate, isobutyl isobutyrate, methyl 3-methoxyisobutyrate, butyl isobutyrate, isobutyl isovalerate, butyl 2-methylbutyrate, isobutyl isovalerate, heptyl acetate, isoamyl isovalerate, 2-ethylhexyl acetate, hexyl butyrate, ethyl benzoate, hexyl hexanoate, amyl n-octanoate, and hexyl acetate; petroleum-based mixed solvents, and the like.

[0058] Examples of the petroleum-based mixed solvent include, for example, those with trade names such as ISOPAR E, ISOPAR G, ISOPAR H, ISOPAR H BHT, ISOPAR L, ISOPAR M, EXXSOL D40, EXXSOL D80, EXXSOL D110, EXXSOL D130, EXXSOL DSP80 / 100, and EXXSOL DSP145 / 60 (all manufactured by Ando Balakemi Co., Ltd.).

[0059] The content of the solvent is not particularly limited and can be appropriately selected according to the purpose. From the perspective of the curl suppression effect, it is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more based on the total amount of the liquid composition. Also, from the perspective of film thickness control, it is preferably 70% by mass or less.

[0060] In the present invention, from the perspective of the diversity of the selection of polymerizable compounds, a plurality of solvents can be used in combination.

[0061] [First Aspect of Liquid Composition] As the first aspect of the liquid composition in the present invention, the solvent in the liquid composition is a mixed solvent containing a good solvent and a poor solvent, and preferably satisfies the formula (1), from the perspective of the curl suppression effect due to volume shrinkage.

[0062] [Number]

[0063] As used herein, "good solvent" refers to a solvent in which the polymerizable compound is soluble. "Poor solvent" as used herein refers to a solvent in which the polymerizable compound is insoluble. When the term "mixed solvent" is used in this specification, it refers to a solvent containing a good solvent and a poor solvent. As used herein, "mixing ratio X" refers to the content ratio based on the mass of the good solvent in the mixed solvent, expressed as a percentage. As used herein, "polymerizable compound solubility point" refers to the minimum content ratio based on the mass of the good solvent in a mixed solvent in which the polymerizable compound is soluble, expressed as a percentage.

[0064] Here, the "soluble" in the first aspect will be described. "Soluble" means that after mixing the solvent and the polymerizable compound and ultrasonically stirring with an ultrasonic stirrer (USS-1) for 15 minutes, no cloudiness or phase separation occurs after standing at a predetermined temperature for 10 minutes. The predetermined temperature is not particularly limited as long as it is the environmental temperature during actual use, and examples include 25°C. It should be noted that the determination of soluble / insoluble is made according to the composition of the liquid composition in the first aspect. For example, the following patterns 1 to 2 can be mentioned.

[0065] [Pattern 1] In the case of a liquid composition containing one polymerizable compound represented by the general formula (3) or (4) and two solvents (mixed solvent), the solubility / insolubility is determined based on the solvent ratio (mass ratio) in the liquid composition containing 10 g of the mixed solvent and 1 g of the polymerizable compound represented by the general formula (3) or (4).

[0066] [Pattern 2] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (3) or (4) and two solvents (mixed solvent), the solubility / insolubility is determined based on the solvent ratio (mass ratio) in the liquid composition containing 10 g of the mixed solvent and 1 g of the mixed compound.

[0067] Formula (1) can also be transformed into formula (1)'.

[0068]

Number

[0069] Since the liquid composition can form a resin layer having a high porosity based on the phase separation rate by satisfying formula (1) or formula (1)', the volume shrinkage during the curing of the liquid composition can be suppressed, and a high-quality resin layer can be formed. As the "mixing ratio X - polymerizable compound solubility point" in formula (1)' approaches 0, curling due to volume shrinkage can be more effectively suppressed.

[0070] [Second aspect of the liquid composition] As a second aspect of the liquid composition in the present invention, the polymerizable compound in the liquid composition is a mixed compound containing a soluble polymerizable compound and an insoluble polymerizable compound, and preferably satisfies formula (2) from the viewpoint of the curling suppression effect due to volume shrinkage.

[0071]

Number

[0072] As used herein, the "soluble polymerizable compound" refers to a polymerizable compound that is soluble in a solvent. The "insoluble polymerizable compound" as used herein refers to a polymerizable compound that is insoluble in a solvent. When referred to as a "mixed compound" in this specification, it refers to a polymerizable compound containing a soluble polymerizable compound and an insoluble polymerizable compound. The "mixing ratio Y" as used herein refers to the content ratio based on the mass of the insoluble polymerizable compound in the mixed compound, expressed as a percentage. The "solvent solubility point" as used herein refers to the minimum content ratio based on the mass of the insoluble polymerizable compound in a mixed compound that is soluble in a solvent, expressed as a percentage.

[0073] Here, the "soluble" in the second aspect will be described. "Soluble" means that when a polymerizable compound and a solvent are mixed and ultrasonically stirred with an ultrasonic stirrer (USS-1) for 15 minutes and then allowed to stand at a predetermined temperature for 10 minutes, no cloudiness or phase separation occurs. The predetermined temperature is not particularly limited as long as it is the environmental temperature during actual use, and examples include 25°C. Note that the determination of soluble / insoluble is made according to the composition of the liquid composition in the second aspect. For example, the following patterns 3 to 4 can be cited.

[0074] [Pattern 3] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (3) or the general formula (4) and two solvents (mixed solvent), the determination of soluble / insoluble is made based on the solvent ratio (mass ratio) in the liquid composition containing 10 g of the mixed compound and 1 g of the mixed solvent.

[0075] [Pattern 4] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (3) or the general formula (4) and one solvent, the determination of soluble / insoluble is made based on the monomer ratio (mass ratio) in the liquid composition containing 10 g of the mixed compound and 1 g of the mixed solvent.

[0076] Formula (2) can also be transformed into formula (2)'.

[0077] [Number]

[0078] Since the liquid composition can form a resin layer having a high porosity based on the phase separation rate by satisfying formula (2) or formula (2)’, it is possible to suppress the volume shrinkage during the curing of the liquid composition and to form a high-quality resin layer. As the “mixing ratio Y - solvent solubility point” in formula (2)’ approaches 0, curling due to volume shrinkage can be more suppressed.

[0079] The method for producing the liquid composition is not particularly limited and can be appropriately selected according to the purpose. For example, it can be produced through steps such as a step of mixing a polymerizable compound, a step of mixing the polymerizable compound with a solvent, a step of dissolving a polymerization initiator in the solvent, a step of dissolving an insulating resin in the liquid composition, and a step of stirring.

[0080] (Method for manufacturing a laminate for an all - solid - state electrochemical device, and manufacturing apparatus for a laminate for an all - solid - state electrochemical device) The method for manufacturing a laminate for an all - solid - state electrochemical device according to the present invention may have an insulating resin layer forming step and a sulfide solid electrolyte - containing layer forming step, and may have other steps as necessary. The manufacturing apparatus for a laminate for an all - solid - state electrochemical device according to the present invention may have a storage container, an insulating resin layer forming means, and a sulfide solid electrolyte - containing layer forming means, and may have other means as necessary.

[0081] <Storage container> The storage container includes a liquid composition and a container, and is a storage container in which the liquid composition is stored in the container. Examples of the container include a glass bottle, a plastic container, a plastic bottle, a stainless - steel bottle, a one - shaku can, a drum can, etc. Since the liquid composition is the same as that described in the item (Laminate for an all - solid - state electrochemical device), duplicate descriptions are omitted.

[0082] <Insulating resin layer forming step, and insulating resin layer forming means> The insulating resin layer forming step is a step of forming an insulating resin layer on a substrate. The insulating resin layer forming step preferably includes a liquid composition applying step and a liquid composition curing step. The insulating resin layer forming means is means for forming an insulating resin layer on a substrate. The insulating resin layer forming means preferably includes a liquid composition applying means and a liquid composition curing means. The insulating resin layer forming step can be preferably carried out by the insulating resin layer forming means, the liquid composition applying step can be preferably carried out by the liquid composition applying means, and the liquid composition curing step can be preferably carried out by the liquid composition curing means.

[0083] <<Liquid composition applying step, and liquid composition applying means>> The liquid composition applying step is a step of applying a liquid composition onto a substrate. The liquid composition applying means is means for applying a liquid composition onto a substrate. There are no particular limitations on the liquid composition applying step and the liquid composition applying means, and they can be appropriately selected according to the purpose. For example, any printing apparatus corresponding to various printing methods such as spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. can be used. Among these, from the viewpoint of being able to form an insulating resin layer with high precision, the inkjet printing method is preferable.

[0084] <<Liquid composition curing step, and liquid composition curing means>> The liquid composition curing step is a step of curing by applying heat or light to the liquid composition. The liquid composition curing means is means for curing by applying heat or light to the liquid composition. By applying heat or light to the liquid composition, the polymerizable compound in the liquid composition polymerizes and polymerization-induced phase separation occurs, resulting in an insulating resin layer having a porous structure.

[0085] In the liquid composition curing step and as the light in the liquid composition curing means, it is preferably an active energy ray. As the active energy ray, any ray can be used as long as it can impart the energy necessary for promoting the polymerization reaction of the polymerizable compound in the liquid composition, and it is not particularly limited. For example, ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, X-rays, etc. can be mentioned. Among these, ultraviolet rays are preferred. In addition, when using a particularly high-energy light source, the polymerization reaction can proceed without using a polymerization initiator.

[0086] There is no particular limitation on the irradiation intensity of the active energy ray, and it can be appropriately selected according to the purpose. However, it is preferably 1 W / cm 2 or less, more preferably 300 mW / cm 2 or less, and even more preferably 100 mW / cm 2 or less. In addition, if the irradiation intensity of the active energy ray is too low, the polymerization-induced phase separation will proceed excessively, resulting in easy occurrence of variations and coarsening of the porous structure, and the productivity will decrease due to the increase in the irradiation time. Therefore, it is preferably 10 mW / cm 2 or more, and more preferably 30 mW / cm 2 or more.

[0087] <Sulfide solid electrolyte-containing layer forming step, and sulfide solid electrolyte-containing layer forming means> In the sulfide solid electrolyte-containing layer forming step in the manufacturing method of the laminate for all-solid-state electrochemical elements, it is a step of forming a sulfide solid electrolyte-containing layer so as to be in contact with at least a part of the insulating resin layer. In the sulfide solid electrolyte-containing layer forming means in the manufacturing apparatus of the laminate for all-solid-state electrochemical elements, it is a means of forming a sulfide solid electrolyte-containing layer so as to be in contact with at least a part of the insulating resin layer.

[0088] As a method for forming the sulfide solid electrolyte-containing layer, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, there can be mentioned a method of applying a liquid composition for a sulfide solid electrolyte-containing layer, which contains a sulfide solid electrolyte and, if necessary, a binder, followed by solidification and drying. The coating method at this time is not particularly limited and can be appropriately selected according to the purpose. For example, liquid ejection methods such as the inkjet method, spray coating method, and dispenser method, and spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, etc. can be mentioned.

[0089] As the binder, a polymer compound can be used. Examples of the polymer compound include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, etc., polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), isoprene rubber, polyisobutene, polyethylene glycol (PEO), polymethyl methacrylic acid (PMMA), polyethylene vinyl acetate (PEVA), etc.

[0090] <Other processes, other means> As other processes in the method for manufacturing a laminate for an all-solid-state electrochemical device, there is no particular limitation as long as the effects of the present invention are not impaired, and it can be appropriately selected according to the purpose. For example, a solvent removal process etc. can be mentioned. As other means in the manufacturing apparatus for a laminate for an all-solid-state electrochemical device, there is no particular limitation as long as the effects of the present invention are not impaired, and it can be appropriately selected according to the purpose. For example, a solvent removal means etc. can be mentioned.

[0091] <<Solvent Removal Step, Solvent Removal Means>> The solvent removal step is a step of removing the solvent from the insulating resin layer. The solvent removal means is a means of removing the solvent from the insulating resin layer. There are no particular restrictions on the solvent removal step and the solvent removal means, and they can be appropriately selected according to the purpose. For example, a method of removing the solvent from the insulating resin layer by heating can be mentioned. At this time, heating under reduced pressure promotes the removal of the solvent and can reduce the amount of residual solvent in the insulating resin layer, so it is preferable. When heating, it may be heated by a stage or by a heating mechanism other than the stage. The heating mechanism may be installed on either the upper or lower side of the substrate, or a plurality of heating mechanisms may be installed. There are no particular restrictions on the heating mechanism, and examples include a resistance heating heater, an infrared heater, a fan heater, etc. The heating temperature at this time is not particularly limited, but from the viewpoint of energy consumption, 70°C to 150°C is preferable.

[0092] The laminate for an all-solid-state electrochemical element of the present invention preferably includes a substrate and, as a sulfide solid electrolyte-containing layer, an electrode mixture layer containing an active material. In other words, the laminate for an all-solid-state electrochemical element of the present invention is a laminate for an electrochemical element including a substrate, a sulfide solid electrolyte-containing layer disposed on the substrate, and an insulating resin layer disposed on the outer peripheral portion of the sulfide solid electrolyte-containing layer, wherein the sulfide solid electrolyte-containing layer is an electrode mixture layer containing an active material, the insulating resin layer contains a structural unit represented by the general formula (1) or the general formula (2), and the insulating resin layer preferably has a porous structure. Further, the laminate for an all-solid-state electrochemical element of the present invention preferably includes a substrate, an electrode mixture layer disposed on the substrate, a sulfide solid electrolyte-containing layer disposed on the electrode mixture layer, and an insulating resin layer disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer.

[0093] (Electrode for Electrochemical Element) The laminate for all-solid-state electrochemical devices of the present invention can be suitably applied to electrodes for electrochemical devices. The electrode for an electrochemical device preferably has a substrate, an electrode composite layer containing a sulfide solid electrolyte disposed on the substrate, and an insulating resin layer disposed on the outer peripheral portion of the electrode composite layer. Note that since the substrate, the sulfide solid electrolyte, and the insulating resin layer are the same as those described in the section (Laminate for All-Solid-State Electrochemical Devices), duplicate descriptions are omitted. In this specification, the negative electrode and the positive electrode may be referred to as "electrodes", the substrate for the negative electrode and the substrate for the positive electrode may be referred to as "substrates", and the negative electrode composite layer and the positive electrode composite layer may be referred to as "electrode composite layers". Further, when the first electrode is the negative electrode, the second electrode refers to the positive electrode, and when the first electrode is the positive electrode, the second electrode refers to the negative electrode.

[0094] (Electrode laminate) The electrode for an electrochemical device according to the present invention can be suitably applied to an electrode laminate. The electrode laminate preferably has an electrode for an electrochemical device and a sulfide solid electrolyte-containing layer disposed on the electrode for an electrochemical device. In other words, the electrode laminate preferably has a substrate, an electrode composite layer containing a sulfide solid electrolyte disposed on the substrate, an insulating resin layer disposed on the outer peripheral portion of the electrode composite layer, and a sulfide solid electrolyte-containing layer disposed on the electrode composite layer and the insulating resin layer. Note that since the substrate, the sulfide solid electrolyte, the sulfide solid electrolyte-containing layer, and the insulating resin layer are the same as those described in the section (Laminate for All-Solid-State Electrochemical Devices), duplicate descriptions are omitted.

[0095] Here, an embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all. In each drawing, the same reference numerals are given to the same components, and duplicate descriptions may be omitted. Further, the number, position, shape, etc. of the constituent members are not limited to this embodiment, and can be set to preferable numbers, positions, shapes, etc. for carrying out the present invention.

[0096] FIG. 1 is a schematic cross-sectional view showing an electrode for an electrochemical element according to an embodiment of the present invention. The electrode 25 for an electrochemical element includes a first substrate 21, a first electrode composite layer 20 disposed on the first substrate 21, and an insulating resin layer 10 disposed on the outer peripheral portion of the first electrode composite layer 20. In FIG. 1, a configuration in which the electrode composite layer 20 and the insulating resin layer 10 are provided on one side of the first substrate 21 is illustrated. However, the electrode composite layer 20 and the insulating resin layer 10 may be provided on both opposite sides of the first substrate 21.

[0097] FIG. 2A is a schematic cross-sectional view showing an electrode laminate according to an embodiment of the present invention. FIG. 2B is a schematic cross-sectional view showing an electrode laminate according to another embodiment of the present invention. FIG. 2C is a schematic cross-sectional view showing an electrode laminate according to still another embodiment of the present invention. The electrode laminate 35 includes a first substrate 21, a first electrode composite layer 20 disposed on the first substrate 21, an insulating resin layer 10 disposed on the outer peripheral portion of the first electrode composite layer 20, and a sulfide solid electrolyte-containing layer 30 disposed on the first electrode composite layer 20 and the insulating resin layer 10. In FIGS. 2A to 2C, a configuration in which the electrode composite layer 20, the insulating resin layer 10, and the sulfide solid electrolyte-containing layer 30 are provided on one side of the first substrate 21 is illustrated. However, the electrode composite layer 20, the insulating resin layer 10, and the sulfide solid electrolyte-containing layer 30 may be provided on both opposite sides of the first substrate 21. Also, as shown in FIG. 2B, an adhesive layer 22 containing a metal that alloys with lithium may be provided between the substrate 21 and the electrode composite layer 20.

[0098] <Electrode composite layer> The electrode composite layer (hereinafter, may be referred to as the "active material layer") is not particularly limited and can be appropriately selected according to the purpose. For example, it may contain an active material (negative electrode active material or positive electrode active material) and a sulfide solid electrolyte, and further, if necessary, a conductive auxiliary agent, a binder, a dispersant, and other components may be included. From the perspective that the electrode for an electrochemical element or the electrode laminate has an insulating resin layer that can suppress a decrease in ionic conductivity in the sulfide solid electrolyte-containing layer, the electrode composite layer preferably contains an active material and a sulfide solid electrolyte.

[0099] The electrode composite layer may have an opening 23 as shown in Fig. 2C. The number of the openings 23 is preferably one or more, and more preferably a plurality. The opening 23 may penetrate the electrode composite layer from the surface of the electrode composite layer to the surface of the substrate, or may not penetrate to the surface of the substrate. The opening 23 may be a cavity or may be filled with a material 24. When the opening 23 is filled with the material 24, the material 24 may be a single species or a mixture of two or more species. However, in any case, the material (compound or composition) is different from the material constituting the electrode composite layer. From the perspective of improving ionic conductivity, the material 24 is preferably a material having a solid electrolyte contained in the sulfide solid electrolyte-containing layer, and more preferably a material having the same composition as the sulfide solid electrolyte contained in the sulfide solid electrolyte-containing layer. Since the electrode composite layer having the opening 23 is easy to control coating, it can be suitably manufactured by using an inkjet as a means for forming the electrode composite layer.

[0100] <<Active material>> As the active material, a positive electrode active material or a negative electrode active material can be used. The positive electrode active material or the negative electrode active material may be used alone or in combination of two or more.

[0101] ―Positive electrode active material― The positive electrode active material is not particularly limited as long as it is a material that can reversibly occlude and release alkali metal ions, but an alkali metal-containing transition metal compound can be used. Examples of the alkali metal-containing transition metal compound include lithium-containing transition metal compounds such as composite oxides containing one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium, and lithium. Examples of the lithium-containing transition metal compound include lithium cobaltate, lithium nickelate, lithium manganate, and the like.

[0102] As the alkali metal-containing transition metal compound, a polyanion compound having XO 4 tetrahedrons (X = P, S, As, Mo, W, Si, etc.) can be used. Among these, from the viewpoint of cycle characteristics, lithium-containing transition metal phosphate compounds such as lithium iron phosphate and lithium vanadium phosphate are preferable, and from the viewpoints of lithium diffusion coefficient and output characteristics, lithium vanadium phosphate is preferable. When using a polyanion compound, in terms of electronic conductivity, it is preferably surface-coated and complexed with a conductive aid such as a carbon material.

[0103] It is preferable that at least a part of the surface of the alkali metal-containing transition metal compound is coated with an ion-conductive oxide. As the ion-conductive oxide, a lithium ion-conductive oxide is preferable. The lithium ion-conductive oxide is not particularly limited and can be appropriately selected according to the purpose. For example, oxides represented by the general formula LixAOy (A is B, C, Al, Si, P, S, Ti, Zr, Nb, Mo, Ta, Sc, V, Y, Ca, Sr, Ba, Hf, Ta, Cr, or W, and x and y are positive numbers) can be mentioned. Specific examples of the lithium ion-conductive oxide include Li 3 BO 3 、LiBO 2 、Li 2 CO 3 、LiAlO 2 、Li 4 SiO 4 、Li 2 SiO 3 、Li 3PO 4 、 Li 2 SO 4 、 Li 2 TiO 3 、 Li 4 Ti 5 O 12 、 Li 2 Ti 2 O 5 、 Li 2 ZrO 3 、 LiNbO 3 、 LiTaO 3 、 Li 2 MoO 4 、 and Li 2 WO 4 etc. may be mentioned. Among these, Li 4 Ti 5 O 12 、 Li 2 ZrO 3 、 or LiNbO 3 is preferred. In addition, the lithium ion conductive oxide may be a composite oxide. As the composite oxide, any combination of lithium ion conductive oxides can be adopted. For example, Li 4 SiO 4 -Li 3 BO 3 、 and Li 4 SiO 4 -Li 3 PO 4 etc. may be mentioned.

[0104] - Anode active material - The anode active material is not particularly limited as long as it can reversibly occlude and release alkali metal ions, and can be appropriately selected according to the purpose. For example, a carbon material containing graphite having a graphite-type crystal structure can be used. Examples of the carbon material include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), etc. Examples of materials other than the carbon material include lithium titanate, titanium oxide, etc. From the perspective of increasing the energy density of lithium-ion batteries, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as negative electrode active materials.

[0105] <<Conductive aid>> There are no particular restrictions on the conductive aid, and it can be appropriately selected according to the purpose. For example, carbon black produced by the furnace method, acetylene method, gasification method, etc., and carbon materials such as carbon nanofibers, carbon nanotubes, graphene, and graphite particles can be used. As conductive aids other than carbon materials, for example, metal particles such as aluminum and metal fibers can be used. Note that the conductive aid may be pre-compounded with the active material.

[0106] The content of the conductive aid with respect to the active material is not particularly limited and can be appropriately set according to the purpose, but it is preferably 10% by mass or less, and more preferably 8% by mass or less. When the content of the conductive aid with respect to the active material is 10% by mass or less, it is suitable because the stability of the liquid composition for the electrode composite layer is improved. When the content of the conductive aid with respect to the active material is 8% by mass or less, it is suitable because the stability of the liquid composition for the electrode composite layer is further improved.

[0107] <<Binder>> The binder is not particularly limited as long as it can bind negative electrode materials to each other, positive electrode materials to each other, negative electrode materials to the negative electrode substrate, and positive electrode materials to the positive electrode substrate, and can be appropriately selected according to the purpose. When the liquid composition for forming the electrode composite layer is used for inkjet ejection, from the perspective of suppressing nozzle clogging of the liquid ejection head, the binder preferably has a low tendency to increase the viscosity of the liquid composition for forming the electrode composite layer.

[0108] As the binder, a polymer compound can be used. Examples of the polymer compound include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, etc., polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), isoprene rubber, polyisobutene, polyethylene glycol (PEO), polymethyl methacrylic acid (PMMA), polyethylene vinyl acetate (PEVA), and the like.

[0109] The content of the binder with respect to the active material is not particularly limited and can be appropriately set according to the purpose, but it is preferably 1% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 10% by mass or less. When the content of the binder with respect to the active material is 1% by mass or more, it is possible to firmly bind the active material to the substrate, which is suitable.

[0110] <<Dispersant>> The dispersant is not particularly limited as long as it can improve the dispersibility of the active material in the liquid composition for the electrode composite layer. For example, polymer dispersants such as polyethylene oxide-based, polypropylene oxide-based, polycarboxylic acid-based, naphthalenesulfonic acid formalin condensation-based, polyethylene glycol-based, polycarboxylic acid partial alkyl ester-based, polyether-based, polyalkylene polyamine-based; low molecular weight dispersants such as alkyl sulfonic acid-based, quaternary ammonium-based, higher alcohol alkylene oxide-based, polyhydric alcohol ester-based, alkyl polyamine-based; inorganic dispersants such as polyphosphate-based dispersants, and the like can be mentioned.

[0111] <Insulating resin layer> In the electrode for an electrochemical element and the electrode laminate according to the present invention, the insulating resin layer is disposed on the outer peripheral portion of the electrode composite layer provided on the substrate, and may also be disposed on the substrate and on the outer peripheral portion of the substrate.

[0112] Here, an embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all.

[0113] FIG. 3 is a schematic top view showing an electrode for an electrochemical element according to an embodiment of the present invention. FIG. 4 is a schematic top view showing an electrode for an electrochemical element according to another embodiment of the present invention. FIG. 5 is a schematic top view showing an electrode for an electrochemical element according to still another embodiment of the present invention. In FIG. 3, the insulating resin layer 10 is provided so as to be adjacent to two sides at the outer peripheral portion of the electrode composite layer 20. In FIG. 4, the insulating resin layer 10 is provided adjacent to two long sides and two corners of the two long sides at the outer peripheral portion of the electrode composite layer 20. In FIG. 5, the insulating resin layer 10 is provided continuously adjacent to all four sides at the outer peripheral portion of the electrode composite layer 20. Note that the insulating resin layer may be provided adjacent intermittently.

[0114] In this specification, "arranged at the outer peripheral portion of the electrode composite layer" means that the insulating resin layer may be arranged on at least two sides of the outer peripheral portion of the electrode composite layer, or on three sides of the outer peripheral portion of the electrode composite layer, or on all four sides of the outer peripheral portion of the electrode composite layer. Further, the insulating resin layer may have a recess or a notch for protruding the electrode tab on any side.

[0115] In this specification, "arranged at the outer peripheral portion of the substrate" means that the insulating resin layer may be arranged so as to include the end portion of the substrate, or the insulating resin layer may be arranged so that the substrate is exposed as shown in FIGS. 3 to 5.

[0116] FIG. 6A is a schematic cross-sectional view (part 1) showing the positional relationship between the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 6B is a schematic cross-sectional view (part 2) showing the positional relationship between the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 6C is a schematic cross-sectional view (part 3) showing the positional relationship between the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 6D is a schematic cross-sectional view (part 4) showing the positional relationship between the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. The insulating resin layer 10 may be separated from the electrode mixture layer 20 as shown in FIG. 6A, or may be in contact with the electrode mixture layer 20 as shown in FIGS. 6B to 6D. Among these, it is preferable that the insulating resin layer 10 is in contact with the electrode mixture layer 20. When the insulating resin layer 10 is in contact with the electrode mixture layer 20, the opposing surfaces of the insulating resin layer 10 and the electrode mixture layer 20 may be in contact with each other in a partial region as shown in FIG. 6B, or the opposing surfaces of the insulating resin layer 10 and the electrode mixture layer 20 may be in full contact as shown in FIGS. 6C to 6D. Here, when the electrode mixture layer 20 is provided after the insulating resin layer 10 is formed, the electrode mixture layer 20 overlaps the insulating resin layer 10 side as shown in FIG. 6C. Similarly, when the insulating resin layer 10 is provided after the electrode mixture layer 10 is formed, the insulating resin layer 10 overlaps the electrode mixture layer 20 side as shown in FIG. 6D.

[0117] FIG. 7 is a schematic top view showing the positional relationship between the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. Here, when the insulating resin layer 10 and the electrode mixture layer 20 are separated, the distance d between the insulating resin layer 10 and the electrode mixture layer 20 (the distance between the outer peripheral portion of the electrode mixture layer 20 and the insulating resin layer) is defined as shown in FIG. 7. That is, the state where the insulating resin layer 10 and the electrode mixture layer 20 are adjacent is set as d = 0, and the distance d between the electrode mixture layer and the insulating resin layer is the distance between the arrows shown in FIG. 7. In addition, as shown in FIGS. 6C to D, when the insulating resin layer overlaps the electrode mixture layer side, and when the electrode mixture layer overlaps the insulating resin layer side, it is indicated by a negative value.

[0118] The distance d between the insulating resin layer 10 and the electrode mixture layer 20 (the distance between the outer peripheral portion of the electrode mixture layer 20 and the insulating resin layer) is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 1 mm or less. When the distance d between the insulating resin layer 10 and the electrode mixture layer 20 is 10 mm or less, the insulating resin layer and the electrode mixture layer are likely to come into contact with each other after passing through the pressing process. Therefore, it is possible to uniformly form the solid electrolyte layer on the insulating resin layer and the electrode mixture layer, which is preferable. Further, when the solid electrolyte layer is pressed, pressure can be uniformly applied to the solid electrolyte layer, which is preferable.

[0119] FIG. 8A is a schematic cross-sectional view (part 1) showing the relationship between the average thicknesses of the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 8B is a schematic cross-sectional view (part 2) showing the relationship between the average thicknesses of the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 8C is a schematic cross-sectional view (part 3) showing the relationship between the average thicknesses of the insulating resin layer and the electrode mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. Regarding the relationship between the average thickness A of the electrode mixture layer and the average thickness B of the insulating resin layer in the electrode laminate according to the present invention, there is no particular limitation and it can be appropriately selected according to the purpose. For example, as shown in FIGS. 8A to 8C, A < B, A = B, or A > B may be possible. Among these, it is preferable that A = B or A < B.

[0120] The average thickness of the insulating resin layer is not particularly limited and can be appropriately selected according to various conditions such as the average thickness of the electrode mixture layer. However, it is preferably 1.0 μm or more and 150.0 μm or less, and more preferably 10.0 μm or more and 100.0 μm or less. When the average thickness of the insulating resin layer is 10.0 μm or more, the pressure load during pressing can be dispersed, and a short circuit between the positive electrode and the negative electrode can be prevented, which is preferable. When the average thickness of the insulating resin layer is 100.0 μm or less, an electrochemical element with high density and excellent battery characteristics can be manufactured.

[0121] In the electrode laminate according to the present invention, the ratio (B / A) of the average thickness B of the insulating resin layer to the average thickness A of the electrode binder layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 0.97 or more and 1.03 or less, and more preferably 0.98 or more and 1.02 or less.

[0122] The method for measuring the average thickness A of the electrode binder layer and the average thickness B of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. For example, it can be obtained by measuring the thicknesses at any three or more points and calculating the average value.

[0123] Since the insulating resin layer in the electrode laminate according to the present invention has a porous structure, the thickness of the electrode binder layer and the thickness of the insulating resin layer can be easily and highly accurately controlled by pressing. In addition, since the insulating resin layer can be formed by a coating and polymerization-induced phase separation method, the thickness can be easily controlled. If the insulating resin layer has a co-continuous structure, the pressure generated during pressing can be efficiently dispersed, suppressing the occurrence of problems such as breakage of the insulating resin layer and unevenness in height difference, and obtaining a high-quality insulating resin layer.

[0124] The compression ratio (after pressing at 500 MPa for 5 minutes) of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 1% or more and 50% or less, and more preferably 5% or more and 20% or less. When the compression ratio of the insulating resin layer is 50% or less, the strength of the insulating resin layer is improved, and when passing through the pressing process, the shape of the insulating resin layer can be sufficiently maintained. When the compression ratio of the insulating resin layer is 1% or more, in the pressing process after forming the sulfide solid electrolyte-containing layer, the pressure applied from the insulating resin layer to the sulfide solid electrolyte-containing layer can be relaxed.

[0125] (Method for manufacturing an electrode for an electrochemical device, and manufacturing apparatus for an electrode for an electrochemical device) The method for manufacturing an electrode for an electrochemical device according to the present invention may have an insulating resin layer forming step and an electrode mixture layer forming step, and may have other steps as necessary. The manufacturing apparatus for an electrode for an electrochemical device according to the present invention may have a storage container, an insulating resin layer forming means, and an electrode mixture layer forming means, and may have other means as necessary. Note that the storage container, the insulating resin layer forming step, the insulating resin layer forming means, the other steps, and the other means are the same as those described in the item of (method for manufacturing a laminate for an all-solid-state electrochemical device, and manufacturing apparatus for a laminate for an all-solid-state electrochemical device), and thus redundant descriptions are omitted.

[0126] <Electrode mixture layer forming step, and electrode mixture layer forming means> The electrode mixture layer forming step is a step of forming an electrode mixture layer on a substrate. The electrode mixture layer forming means is a means for forming an electrode mixture layer on a substrate. There are no particular limitations on the electrode mixture layer forming step and the electrode mixture layer forming means, and they can be appropriately selected according to the purpose. For example, a method of applying, fixing, and drying a dispersion obtained by dispersing a powdery active material, a binder, a conductive material, etc. in a liquid on a substrate can be mentioned. At this time, coating methods such as spraying, dispenser, die coater, and dip coating can be preferably used.

[0127] In the method for manufacturing an electrode for an electrochemical device, the order of the insulating resin layer forming step and the electrode mixture layer forming step is not particularly limited. That is, the electrode mixture layer forming step may be performed before the insulating resin layer forming step, and after forming the electrode mixture layer, an insulating resin layer may be formed on the outer peripheral portion of the electrode mixture layer. In that case, the method for manufacturing an electrode for an electrochemical device is performed in the order of the electrode mixture layer forming step, the insulating resin layer forming step, and the solvent removing step. Similarly, the electrode composite layer forming step may be performed after the insulating resin layer forming step. After forming the insulating resin layer on the outer peripheral portion of the substrate, the electrode composite layer may be formed inside the insulating resin layer. In that case, the method for manufacturing an electrode for an electrochemical element is performed in the order of the insulating resin layer forming step, the electrode composite layer forming step, and the solvent removing step.

[0128] (Method for manufacturing an electrode laminate, and manufacturing apparatus for an electrode laminate) The method for manufacturing an electrode laminate according to the present invention preferably includes an insulating resin layer forming step, an electrode composite layer forming step, a pressing step, and a sulfide solid electrolyte-containing layer forming step, and may have other steps as necessary. The manufacturing apparatus for an electrode laminate according to the present invention preferably includes a storage container, an insulating resin layer forming means, an electrode composite layer forming means, a pressing means, and a sulfide solid electrolyte-containing layer forming means, and may have other means as necessary. Note that the storage container, the insulating resin layer forming step, the insulating resin layer forming means, the electrode composite layer forming step, the electrode composite layer forming means, other steps, and other means are the same as those described in the items of (Method for manufacturing a laminate for an all-solid-state electrochemical element, and manufacturing apparatus for a laminate for an all-solid-state electrochemical element) and (Method for manufacturing an electrode for an electrochemical element, and manufacturing apparatus for an electrode for an electrochemical element), so duplicate descriptions are omitted.

[0129] <Pressing step, pressing means> The pressing step is a step of pressing the electrode composite layer and the insulating resin layer. The pressing means is a means for pressing the electrode composite layer and the insulating resin layer. The pressing step can be preferably performed by the pressing means.

[0130] There are no particular restrictions on the pressing process and pressing means, and it can be carried out using a commercially available pressure molding device. The electrode composite layer and the insulating resin layer may be pressed in the direction of the substrate. For example, uniaxial pressing, roll pressing, cold isostatic pressing (CIP), hot pressing, etc. can be mentioned. Among these, cold isostatic pressing (CIP) that can apply isotropic pressure is preferable.

[0131] There are no particular restrictions on the timing of performing the pressing process, and it can be appropriately selected according to the purpose. For example, after forming the electrode composite layer and the insulating resin layer on the substrate, the electrode composite layer and the insulating resin layer may be pressed, or after providing the sulfide solid electrolyte-containing layer, it may be pressed, or it may be performed at both timings. By performing the pressing process after forming the electrode composite layer and the insulating resin layer on the substrate and before forming the sulfide solid electrolyte-containing layer, the average thickness of the electrode composite layer and the average thickness of the insulating resin layer can be made substantially equal. Even when a high pressure is applied when pressing the sulfide solid electrolyte-containing layer provided on the electrode, the pressure load can be dispersed.

[0132] There are no particular restrictions on the pressing pressure, and it can be appropriately selected according to the purpose. However, it is preferably carried out at a pressure that can crimp the substrate and the electrode composite layer while densifying the electrode composite layer. More specifically, 1 MPa or more and 900 MPa or less are preferable, and 250 MPa or more and 700 MPa or less are more preferable.

[0133] <Sulfide solid electrolyte-containing layer forming step, and sulfide solid electrolyte-containing layer forming means> The sulfide solid electrolyte-containing layer forming step in the method for manufacturing an electrode laminate is a step of forming a sulfide solid electrolyte-containing layer on the electrode composite layer and the insulating resin layer. The sulfide solid electrolyte-containing layer forming means in the manufacturing apparatus for an electrode laminate is means for forming a sulfide solid electrolyte-containing layer on the electrode composite layer and the insulating resin layer.

[0134] In the method for manufacturing an electrode laminate, the order of the insulating resin layer forming step and the electrode mixture layer forming step is not particularly limited. That is, the electrode mixture layer forming step may be carried out before the insulating resin layer forming step, and after forming the electrode mixture layer, an insulating resin layer may be formed on the outer peripheral portion of the electrode mixture layer. In that case, the method for manufacturing the electrode laminate is carried out in the order of the electrode mixture layer forming step, the insulating resin layer forming step, the solvent removing step, the pressing step, and the sulfide solid electrolyte-containing layer forming step. Similarly, the electrode mixture layer forming step may be carried out after the insulating resin layer forming step, and after forming the insulating resin layer on the outer peripheral portion on the substrate, the electrode mixture layer may be formed inside the insulating resin layer. In that case, the method for manufacturing the electrode laminate is carried out in the order of the insulating resin layer forming step, the solvent removing step, the electrode mixture layer forming step, the pressing step, and the sulfide solid electrolyte-containing layer forming step.

[0135] [Embodiment of forming an insulating resin layer or an electrode laminate by directly applying a liquid composition to a substrate] FIG. 9 is a schematic view showing an example of an apparatus (liquid ejection apparatus) for manufacturing an insulating resin layer for carrying out the method for manufacturing an electrode laminate according to an embodiment of the present invention. The apparatus 500 for manufacturing the insulating resin layer includes a conveying unit 5, a printing unit 100, a polymerization unit 200, a heating unit 300, and a roller 7.

[0136] The conveying unit 5 conveys the printing substrate at a preset speed in the order of the printing unit 100, the polymerization unit 200, and the heating unit 300. The printing substrate may be a substrate provided with an electrode mixture layer on the substrate, or a substrate having no electrode mixture layer. When it is a substrate having no electrode mixture layer, the electrode mixture layer is provided after forming the insulating resin layer.

[0137] -Printing unit 100- The printing unit 100 includes a printing apparatus 1a which is an example of a liquid composition applying means, a storage container 1b for storing the liquid composition 6, and a supply tube 1c for supplying the liquid composition stored in the storage container 1b to the printing apparatus 1a.

[0138] The printing unit 100 discharges the liquid composition 6 onto the printing substrate from the printing apparatus 1a to form the liquid composition into a thin film. Note that the storage container 1b may be configured to be integrated with the manufacturing apparatus for the insulating resin layer, or may be configured to be removable from the manufacturing apparatus for the insulating resin layer. Further, it may be a container used for adding to the storage container integrated with the manufacturing apparatus for the insulating resin layer or the storage container removable from the manufacturing apparatus for the insulating resin layer.

[0139] The storage container 1b and the supply tube 1c are not particularly limited as long as they can stably store and supply the liquid composition 6, and can be appropriately selected according to the purpose. The materials constituting the storage container 1b and the supply tube 1c preferably have light-shielding properties in the relatively short wavelength regions of ultraviolet rays and visible light. This is preferable because it prevents the liquid composition 6 from starting polymerization due to external light.

[0140] -Polymerization unit 200- As shown in FIG. 9, the polymerization unit 200 includes, in the case of photopolymerization, a light irradiation device 2a which is an example of a liquid composition curing means for performing a liquid composition curing step, and a polymerization inert gas circulation device 2b for circulating a polymerization inert gas.

[0141] The light irradiation device 2a irradiates light onto the thin-film liquid composition formed by the printing unit 100 in the presence of a polymerization inert gas to perform photopolymerization and obtain a precursor of the insulating resin layer. The light irradiation device 2a is not particularly limited as long as it can initiate and proceed with the polymerization of the compound in the liquid composition, and can be appropriately selected according to the absorption wavelength of the photoinitiator contained in the liquid composition. Examples thereof include ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs. However, since the shorter the wavelength of the irradiated light, the more likely it is to reach deep parts, it is preferable to select a light source according to the thickness of the insulating resin layer to be formed.

[0142] The polymerization inert gas circulation device 2b serves to prevent the polymerization reaction of the polymerizable compound present near the surface of the liquid composition from being inhibited by reducing the concentration of oxygen having polymerization activity contained in the atmosphere. Here, examples of the polymerization inert gas include nitrogen, carbon dioxide, argon, and the like. O in the polymerization inert gas 2 As the concentration, considering that a more effective inhibition reduction effect can be obtained, it is preferably less than 20% (an environment with a lower oxygen concentration than the atmosphere), more preferably 0% or more and 15% or less, and even more preferably 0% or more and 5% or less. In addition, the polymerization inert gas circulation device 2b preferably has temperature control means capable of adjusting the temperature in order to realize stable polymerization progress conditions.

[0143] In the case of thermal polymerization, the polymerization part 200 may be a heating device. There is no particular limitation on the heating device, and it can be appropriately selected according to the purpose. For example, substrate heating (e.g., hot plate), IR heater, hot air heater, etc. can be mentioned, and these may be used in combination. Regarding the heating temperature, time, or light irradiation conditions, they can be appropriately selected according to the polymerizable compound contained in the liquid composition and the formed film thickness.

[0144] There is no particular limitation on the polymerization part 200, and it can be appropriately selected according to the purpose such as the polymerization initiator used and the polymerization mode. For example, in the case of photopolymerization, a light irradiation device that irradiates ultraviolet light with a wavelength of 365 nm for 3 seconds, and in the case of thermal polymerization, a heating device that heats at 150 °C under vacuum drying for 12 hours can be mentioned.

[0145] -Heating part 300- The heating part 300 has a heating device 3a which is an example of solvent removal means for performing a solvent removal step. As shown in FIG. 9, the heating device 3a heats the insulating resin layer precursor formed by the polymerization part 200 to dry and remove the remaining solvent. At this time, the solvent removal may be carried out under reduced pressure.

[0146] In the heating unit 300, a polymerization acceleration step of heating the precursor of the insulating resin layer with the heating device 3a to further accelerate the curing (polymerization) reaction carried out in the polymerization unit 200, and an initiator removal step of heating and drying the photoinitiator remaining in the precursor of the insulating resin layer with the heating device 3a to remove it are also performed. Note that these polymerization acceleration step and initiator removal step do not have to be simultaneous with the solvent removal step, and may be carried out before or after the solvent removal step. After the solvent removal step, the heating unit 300 performs a polymerization completion step of heating the insulating resin layer under reduced pressure.

[0147] FIG. 10 is a schematic view showing another example in a manufacturing apparatus (liquid discharge apparatus) of an insulating resin layer for carrying out a method for manufacturing an electrode laminate according to an embodiment of the present invention. The liquid discharge apparatus 300' enables the liquid composition to circulate through the liquid discharge head 306, the liquid discharge head tank 307, and the tube 308 by controlling the pump 310, the valve 311, and the valve 312. An external tank 313 is provided in the liquid discharge apparatus 300'. When the liquid composition in the liquid discharge head tank 307 decreases, it is also possible to supply the liquid composition from the external tank 313 to the tank 307 by controlling the pump 310, the valve 311, the valve 312, and the valve 314.

[0148] When using the manufacturing apparatus of the insulating resin layer, the liquid composition can be discharged to the target portion of the application object.

[0149] The manufacturing apparatus 500 of the insulating resin layer may be provided with a mechanism for capping the nozzle in order to prevent drying when the liquid composition 6 is not being discharged from the liquid discharge head.

[0150] FIG. 11 is a schematic view (part 1) for explaining a method for manufacturing an electrode for an electrochemical element according to an embodiment of the present invention. The method for manufacturing the electrode 210 for an electrochemical element, on which an insulating resin layer is provided on a substrate, includes a step of sequentially discharging the liquid composition 12A onto the substrate 211 using the liquid discharge apparatus 300'. First, prepare an elongated substrate 211. Then, wind the substrate 211 around a cylindrical core and set it on the feeding roller 304 and the winding roller 305 so that the side where the insulating resin layer 212 is to be formed is the upper side in FIG. 11. Here, the feeding roller 304 and the winding roller 305 rotate counterclockwise and convey the substrate 211 in the direction from right to left in FIG. 11. Then, in the same manner as in FIG. 10, droplets of the liquid composition 12A are ejected from the liquid ejection head 306 installed above the substrate 211 between the feeding roller 304 and the winding roller 305 onto the sequentially conveyed substrate 211. Note that a plurality of liquid ejection heads 306 may be installed in a direction substantially parallel or substantially perpendicular to the conveyance direction of the substrate 211. Next, the substrate 211 onto which the droplets of the liquid composition 12A have been ejected is conveyed to the polymerization part 309 by the feeding roller 304 and the winding roller 305. As a result, the liquid composition 12A is polymerized to form the insulating resin layer 212, and an electrode 210 for an electrochemical element provided with the insulating resin layer on the substrate is obtained. Thereafter, the electrode 210 for an electrochemical element is cut into a desired size by punching or the like.

[0151] The polymerization part 309 may be installed on either the upper or lower side of the substrate 211, or a plurality of polymerization parts 309 may be installed. The polymerization part 309 is not particularly limited as long as it does not directly contact the liquid composition 12A and can be appropriately selected according to the purpose. For example, in the case of thermal polymerization, a resistance heating heater, an infrared heater, a fan heater, etc. can be mentioned, and in the case of photopolymerization, an ultraviolet irradiation device, etc. can be mentioned. Note that a plurality of polymerization parts 309 may be installed. The conditions for heating or light irradiation are not particularly limited and can be appropriately selected according to the purpose.

[0152] FIG. 12 is a schematic diagram showing still another example in a manufacturing apparatus (liquid ejection apparatus) for an insulating resin layer for carrying out the manufacturing method of an electrode laminate according to an embodiment of the present invention. The liquid ejection devices 300A' and 300B' may be used in combination. That is, the tank may supply the liquid composition from the external tanks 313A and 313B connected to the tanks 307A and 307B, and the liquid ejection head may have a plurality of heads 306A and 306B. Accordingly, it may have the tubes 308A and 308B, the valves 311A, 311B, 312A, 312B, 314A, and 314B, and the pumps 310A and 310B.

[0153] [Embodiment of forming an insulating resin layer or an electrode laminate by indirectly applying a liquid composition to a substrate] FIG. 13 is a configuration diagram (part 1) showing an example of a printing unit that employs an inkjet method and a transfer method as liquid composition applying means in a manufacturing apparatus for an insulating resin layer according to an embodiment of the present invention. A drum-shaped intermediate transfer body is used in the printing unit of FIG. 13. The printing unit 400' is an inkjet printer that forms an insulating resin layer on a substrate by transferring a liquid composition or an insulating resin layer to the substrate via an intermediate transfer body 4001. The printing unit 400' includes an inkjet unit 420, a transfer drum 4000, a pretreatment unit 4002, an absorption unit 4003, a heating unit 4004, and a cleaning unit 4005.

[0154] The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The head 101 ejects a liquid composition onto the intermediate transfer body 4001 supported by the transfer drum 4000 to form a liquid composition film on the intermediate transfer body 4001. Each head 101 is a line head, and nozzles are arranged in a range that covers the width of the recording area of the substrate of the maximum size that can be used. The head 101 has a nozzle surface on which nozzles are formed on its lower surface, and the nozzle surface faces the surface of the intermediate transfer body 4001 with a minute gap therebetween. In the case of the present embodiment, since the intermediate transfer body 4001 is configured to circulate and move on a circular orbit, the plurality of heads 101 are arranged radially.

[0155] The transfer drum 4000 faces the impression cylinder 621 and forms a transfer nip portion. The pretreatment unit 4002 applies a reaction liquid for increasing the viscosity of the liquid composition onto, for example, the intermediate transfer member 4001 before the liquid composition is ejected by the head 101.

[0156] The absorption unit 4003 absorbs the liquid component from the liquid composition on the intermediate transfer member 4001 before transfer.

[0157] The heating unit 4004 heats the liquid composition on the intermediate transfer member 4001 before transfer. By heating the liquid composition, the liquid composition is thermally polymerized to form an insulating resin layer. Also, the solvent is removed and the transferability to the substrate is improved.

[0158] The cleaning unit 4005 cleans the intermediate transfer member 4001 after transfer and removes foreign matters such as ink and dust remaining on the intermediate transfer member 4001.

[0159] The outer peripheral surface of the impression cylinder 621 is in pressure contact with the intermediate transfer member 4001. When the substrate passes through the transfer nip portion between the impression cylinder 621 and the intermediate transfer member 4001, the insulating resin layer on the intermediate transfer member 4001 is transferred to the substrate. Note that the impression cylinder 621 may be configured to include at least one grip mechanism for holding the leading end portion of the substrate on its outer peripheral surface.

[0160] FIG. 14 is a configuration diagram (part 2) showing an example of a printing unit that employs an inkjet method and a transfer method as liquid composition applying means in an apparatus for manufacturing an insulating resin layer according to an embodiment of the present invention. An endless belt-shaped intermediate transfer member is used in the printing unit of FIG. 14. The printing unit 400´´ is an inkjet printer that forms an insulating resin layer by transferring a liquid composition or an insulating resin layer onto a substrate via the intermediate transfer belt 4006. The printing unit 400'' includes an inkjet unit 420, a transfer roller 622, an intermediate transfer belt 4006, a heating unit 4007, a cleaning roller 4008, a driving roller 4009a, a counter roller 4009b, a shape-maintaining roller 4009c, a shape-maintaining roller 4009d, a shape-maintaining roller 4009e, and a shape-maintaining roller 4009f.

[0161] The printing unit 400'' discharges droplets of the liquid composition onto the outer peripheral surface of the intermediate transfer belt 4006 from a plurality of heads 101 provided in the inkjet unit 420. The liquid composition on the intermediate transfer belt 4006 is heated by the heating unit 4007 and thermally polymerized to form an insulating resin layer. In the transfer nip portion where the intermediate transfer belt 4006 faces the transfer roller 622, the insulating resin layer on the intermediate transfer belt 4006 is transferred to the substrate. The surface of the intermediate transfer belt 4006 after transfer is cleaned by the cleaning roller 4008.

[0162] The intermediate transfer belt 4006 is spanned by a driving roller 4009a, a counter roller 4009b, a plurality of shape-maintaining rollers 4009c, a shape-maintaining roller 4009d, a shape-maintaining roller 4009e, a shape-maintaining roller 4009f, and a plurality of support rollers 4009g and moves in the direction of the arrow in FIG. 14. The support roller 4009g provided opposite to the head 101 maintains the tensile state of the intermediate transfer belt 4006 when ink droplets are discharged from the head 101.

[0163] (Electrochemical element) The electrochemical element according to the present invention preferably has an electrode laminate, and may further have an exterior as needed. Note that since the electrode laminate is the same as that described in the item of (electrode laminate), duplicate descriptions are omitted.

[0164] Here, an embodiment of the electrochemical element according to the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all.

[0165] FIG. 15 is a schematic cross-sectional view showing an electrochemical element according to an embodiment of the present invention. The electrochemical element 45 includes a first substrate 21, a first electrode composite layer 20 disposed on the first substrate 21, an insulating resin layer 10 disposed on the outer peripheral portion of the first electrode composite layer 20, a sulfide solid electrolyte-containing layer 30 disposed on the first electrode composite layer 20 and the insulating resin layer 10, a second electrode composite layer 40 disposed on the sulfide solid electrolyte-containing layer 30, and a second substrate 41 disposed on the second electrode composite layer. The electrochemical element 45 is a single cell layer, and these can be stacked to form a stacked battery. In FIG. 15, a configuration in which the electrode composite layer 20, the insulating resin layer 10, and the sulfide solid electrolyte-containing layer 30 are provided on one side of the first substrate 21 is illustrated. However, the electrode composite layer 20, the insulating resin layer 10, and the sulfide solid electrolyte-containing layer 30 may be provided on both opposite sides of the first substrate 21, and this configuration may also be a stacked battery in which these are stacked.

[0166] FIG. 16 is a schematic cross-sectional view showing an example of an all-solid-state battery which is an electrochemical element according to an embodiment of the present invention. The all-solid-state battery shown in FIG. 16 includes a positive electrode (electrode composite layer) 20, a negative electrode (electrode composite layer) 40, a sulfide solid electrolyte-containing layer 30, lead-out wires 50, lead-out wires 51, and an exterior 60. The positive electrode (electrode composite layer) 20 includes a positive electrode substrate 21 and an insulating resin layer 10 disposed on the positive electrode substrate 21. A lead-out wire 50 is connected to the positive electrode substrate 21, and a lead-out wire 51 is connected to the negative electrode substrate 41. The lead-out wires 50 and 51 are led out to the outside of the exterior 60. Here, in the all-solid-state battery, the positive electrode (electrode composite layer) 20 and the negative electrode (electrode composite layer) 40 are stacked via the sulfide solid electrolyte-containing layer 30, and the positive electrode (electrode composite layer) 20 is disposed on both sides of the negative electrode (electrode composite layer) 40. Note that the number of stacked layers of the positive electrode (electrode composite layer) 20 and the negative electrode (electrode composite layer) 40 is not particularly limited. Also, the number of positive electrodes (electrode composite layers) 20 and the number of negative electrodes (electrode composite layers) 40 may be the same or different.

[0167] As the exterior packaging, as long as it can seal the electrode laminate, there are no particular restrictions, and known exterior packaging can be appropriately selected according to the purpose.

[0168] The shape of the electrochemical element is not particularly limited and can be appropriately selected according to the purpose. Examples include a laminate type, a cylinder type, a coin type, etc.

[0169] In an electrochemical element in which a short circuit due to dendrite deposition can occur, usually, a configuration in which the negative electrode composite layer is larger than the positive electrode composite layer is common. At this time, when the positive electrode current collector and the negative electrode current collector are substantially the same size, on the positive electrode current collector, in the region where the negative electrode composite layer of the negative electrode faces, an excess portion where the positive electrode composite layer is not formed occurs. From the viewpoint of the characteristics of the electrochemical element, the insulating resin layer is preferably provided on the excess portion of the positive electrode, that is, the outer peripheral portion of the positive electrode composite layer. In addition, if the configuration is such that the negative electrode composite layer is smaller than the positive electrode composite layer when the electrochemical element is formed, the insulating resin layer is preferably provided on the excess portion of the negative electrode, that is, the outer peripheral portion of the negative electrode composite layer.

[0170] (Manufacturing method of electrochemical element, and manufacturing apparatus of electrochemical element) The manufacturing method of the electrochemical element according to the present invention preferably includes an insulating resin layer forming step, an electrode composite layer forming step, a pressing step, a sulfide solid electrolyte-containing layer forming step, an element forming step, and an electrode processing step, and may have other steps as necessary. The manufacturing apparatus of the electrochemical element according to the present invention preferably includes an insulating resin layer forming means, an electrode composite layer forming means, a pressing means, a sulfide solid electrolyte-containing layer forming means, an element forming means, and an electrode processing means, and may have other means as necessary. The insulating resin layer forming step, the insulating resin layer forming means, the electrode composite layer forming step, the electrode composite layer forming means, the pressing step, the pressing means, the sulfide solid electrolyte-containing layer forming step, the sulfide solid electrolyte-containing layer forming means, other steps, and other means are the same as those described in the items of (the method for manufacturing a laminate for an all-solid-state electrochemical device and the manufacturing apparatus for a laminate for an all-solid-state electrochemical device), (the method for manufacturing an electrode for an electrochemical device and the manufacturing apparatus for an electrode for an electrochemical device), and (the method for manufacturing an electrode laminate and the manufacturing apparatus for an electrode laminate). Therefore, duplicate descriptions are omitted.

[0171] <Element formation step and element formation means> The element formation step is a step of manufacturing an electrochemical device using an electrode laminate. The element formation means is a means of manufacturing an electrochemical device using an electrode laminate. As a method of manufacturing an electrochemical device using an electrode laminate, there is no particular limitation, and a known method for manufacturing an electrochemical device can be appropriately selected according to the purpose. For example, a method of forming a counter electrode, winding or laminating, and housing in a container to form a power storage device can be mentioned. Note that the element formation step does not necessarily need to include all the steps of element formation, and may include some of the steps of element formation.

[0172] <Electrode processing step and electrode processing means> The electrode processing step is a step of processing an electrode on which an insulating resin layer is formed, which is performed after the liquid composition application step in the insulating resin layer forming step. The electrode processing step may include at least one of a cutting step, a folding step, and a bonding step. The electrode processing means is a means of processing an electrode on which an insulating resin layer is formed. The electrode processing means may include at least one of a cutting means, a folding means, and a bonding means. The electrode processing means can, for example, cut an electrode formed with an insulating resin layer to produce a laminate of electrodes. The electrode processing means can, for example, wind or laminate a laminate of electrodes formed with an insulating resin layer. The electrode processing means has, for example, an electrode processing apparatus, and performs cutting, zigzag folding, lamination, and winding of a laminate of electrodes formed with an insulating resin layer according to the target battery form.

[0173] The use of the electrochemical element is not particularly limited and can be appropriately selected according to the purpose. For example, mobile bodies such as vehicles; electrical devices such as smartphones, notebook computers, pen input computers, mobile computers, e-book players, mobile phones, mobile faxes, mobile copiers, mobile printers, headphone stereos, video movies, liquid crystal TVs, handy cleaners, portable CDs, mini-discs, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting fixtures, toys, game devices, watches, strobes, cameras, etc. Among these, vehicles and electrical devices are preferred. Examples of vehicles include ordinary automobiles, large special automobiles, small special automobiles, trucks, large motorcycles, and ordinary motorcycles.

[0174] Here, an embodiment of a mobile body which is an electrochemical element according to the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all.

[0175] [Mobile body] FIG. 17 is a schematic diagram showing an example of a mobile body which is an electrochemical element according to an embodiment of the present invention. The mobile body 70 is, for example, an electric vehicle. The mobile body 70 includes a motor 71, an electrochemical element 72, and wheels 73.

[0176] The electrochemical element 72 is an electrochemical element according to the present invention. The electrochemical element 72 drives the motor 71 by supplying power to the motor 71. The driven motor 71 can drive the wheels 73, and as a result, the moving body 70 can move. Since the moving body 70 includes the electrochemical element 72, it can prevent a short circuit between the positive electrode and the negative electrode, and can be driven by the power from the electrochemical element having excellent battery characteristics, and can move the moving body safely and efficiently.

[0177] The moving body 70 is not limited to an electric vehicle, and may be a PHEV, an HEV, or a locomotive or a motorcycle capable of traveling by using a diesel engine and an electrochemical element in combination. Further, the moving body 70 may be a transport robot used in a factory or the like that can travel using only the electrochemical element or using an engine and an electrochemical element in combination. Further, the moving body 70 is not a moving body as a whole, but only a part thereof moves. For example, it may be an assembly robot arranged on a manufacturing line in a factory, in which only an electrochemical element or an arm or the like can operate using an engine and an electrochemical element in combination.

Examples

[0178] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples at all. In the following Examples and Comparative Examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0179] <Preparation of Liquid Composition> As shown in Tables 1 to 3, a polymerizable compound, a solvent, and a photopolymerization initiator (1-Benzoylcyclohexanol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to obtain Liquid Compositions 1 to 42 and Comparative Liquid Compositions 1 to 6. The addition amount of the photopolymerizable compound was 1% by mass based on the total amount of the polymerizable compounds.

[0180]

Table 1

[0181]

Table 2

[0182]

Table 3

[0183] The details of each material described in Tables 1 to 3 are as follows. · Biscote #230D (1,6 - hexanediol acrylate polymer ester, manufactured by Osaka Organic Chemical Industry Co., Ltd.) · KAYARAD HX220 (6 - (propenoyloxy)hexanoic acid 3 - [2,2 - dimethyl - 3 - [[1 - oxo - 6 - (propenoyloxy)hexyl]oxy]propoxy] - 2,2 - dimethyl - 3 - oxopropyl, manufactured by Nippon Kayaku Co., Ltd.) · KAYARAD HX620 (Poly[oxy(1 - oxo - 1,6 - hexanediyl)], a - hydro - w - [(1 - oxo - 2 - propenyl)oxy] -, diester with 3 - hydroxy - 2,2 - dimethylpropyl 3 - hydroxy - 2,2 - dimethylpropanoate (9CI), manufactured by Nippon Kayaku Co., Ltd.) · CN2283NS (Polyester acrylate, manufactured by Sartomer) · Light Acrylate HPP - A (Hydroxypivalic acid neopentyl glycol acrylate adduct, manufactured by Kyoeisha Chemical Co., Ltd.) · PEG200DA (PEG200 diacrylate, manufactured by Daicel - Ornex Co., Ltd.)

[0184] (Example 1) <Fabrication of Insulating Resin Layer> After applying Liquid Composition 1 onto an aluminum foil (5 cm × 5 cm, thickness: 20 μm) using a bar coater, ultraviolet irradiation was performed on the coated area (light source: UV - LED (product name: FJ800, manufactured by Phoseon), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2It was cured by irradiating for 20 s. Next, using a hot plate, the cured product was heated at 120°C for 1 minute to remove the solvent, and then dried at 120°C for 10 minutes to obtain the insulating resin layer 1 of Example 1 with an average thickness of 100 μm.

[0185] [Evaluation of curl suppression effect] The maximum distance (maximum warpage height) between the horizontal plane and the lower surface of the insulating resin layer of Example 1 placed on the horizontal plane as viewed from the horizontal plane direction was measured. The lower surface of the insulating resin layer refers to the surface facing the water side surface. Based on the measured value of the maximum warpage height, the curl suppression effect was evaluated. The number of measurement samples was 3, and the measured value was the average value of those samples. Note that those with a value of "△" or more have no problems in use. The results are shown in Tables 4 to 5. ―Evaluation criteria for curl suppression effect― ○: The maximum warpage height is 3 mm or less △: The maximum warpage height exceeds 3 mm and is less than 5 mm ×: The maximum warpage height is 5 mm or more

[0186] [Synthesis of sulfide solid electrolyte] As the sulfide solid electrolyte, based on the synthesis method described in J.Power Sources.2018,396,33 - 40, the argyrodite - type sulfide solid electrolyte Li 6 PS 5 Cl (LPSC) was synthesized. Specifically, it is as follows. 0.5 g of Li 2 S (99.9%, manufactured by Mitsuwa Chemical Co., Ltd.), 0.5 g of P 2 S 5 (99%, manufactured by Sigma - Aldrich), and 0.5 g of LiCl (99%, manufactured by Sigma - Aldrich) were pulverized for 40 hours using a planetary ball mill (PULVERISETTE, manufactured by Fritsch, Germany) to obtain a sulfide solid electrolyte. The pulverization was carried out in a zirconia pot (45 mL) using 15 zirconia balls (diameter: 10 mm) under the condition of 600 RPM.

[0187] <Preparation of Liquid Composition for Sulfide Solid Electrolyte-Containing Layer> For the preparation of the liquid composition for the sulfide solid electrolyte-containing layer, octane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the solvent. At this time, for the octane as the solvent, 10 g of molecular sieve 4A 1 / 16 (manufactured by Kanto Chemical Co., Inc.) was added per 100 ml, and then dehydration was carried out by standing for 12 hours. The one with a water content of 100 ppm or less confirmed by a Karl Fischer moisture concentration meter was used. To 100 parts by mass of this solvent, 100 parts by mass of the synthesized sulfide solid electrolyte and 1 part by mass of a dispersant (manufactured by Lubrizol, Solspersetm (registered trademark) 21000) were added and mixed to obtain a liquid composition for the sulfide solid electrolyte-containing layer.

[0188] [Evaluation of Deterioration Inhibition Effect of Sulfide Solid Electrolyte-Containing Layer] The obtained liquid composition 1 for the sulfide solid electrolyte-containing layer was applied onto the insulating resin layer 1 obtained in the item of <Fabrication of Insulating Resin Layer> so as to have an average thickness of 50 μm, and then heated and dried at 150 °C for 1 hour to form a sulfide solid electrolyte-containing layer. Then, only the sulfide solid electrolyte-containing layer remaining on the insulating resin layer was recovered. 60 mg of the obtained sulfide solid electrolyte was put into a pelletizer with a diameter of 5 mm, and pellets were fabricated under a pressure of 364 MPa to measure the ionic conductivity. When the ionic conductivity of the sulfide solid electrolyte not in contact with the insulating resin layer was taken as 100%, the ionic conductivity of the sulfide solid electrolyte was calculated, and the deterioration inhibition effect of the sulfide solid electrolyte layer was evaluated. The number of measurement samples was 3, and the measured values were the average values of those samples. Note that those with "△" or more have no problems in use. The results are shown in Tables 4 to 5. ―Evaluation Criteria for Deterioration Inhibition Effect of Sulfide Solid Electrolyte Layer― ◎: Ionic conductivity is 95% or more ○: Ionic conductivity is 90% or more and less than 95% △: Ionic conductivity is 80% or more and less than 90% ×: Ionic conductivity is less than 80%

[0189] (Examples 2 to 42, and Comparative Examples 1 to 6) Each evaluation was performed in the same manner as in Example 1, except that the liquid composition was changed to the composition described in Tables 1 to 3. The results are shown in Tables 4 to 5.

[0190]

Table 4

[0191]

Table 5

[0192] From the results of Examples 1 to 42, it can be seen that in the laminate for all-solid-state electrochemical elements having the configuration of the present invention, the curl suppression effect due to volume shrinkage and the deterioration suppression effect of the sulfide solid electrolyte-containing layer are both achieved.

[0193] From the results of Examples 24 to 28 and Examples 33 to 42, when the polymerizable compound represented by the general formula (3) or the general formula (4) contained in the insulating resin layer contains hydroxypivalic acid neopentyl glycol or a polyester chain, it is excellent in suppressing the deterioration of the sulfide solid electrolyte-containing layer, and when it contains a polycaprolactone chain, it is shown to be even more excellent in suppressing the deterioration of the sulfide solid electrolyte-containing layer.

[0194] From the results of Examples 12 to 13, 17 to 18, and Examples 31 to 32, when the relationship between the solvent (good solvent and poor solvent) or polymerizable compound (soluble polymerizable compound and insoluble polymerizable compound) contained in the liquid composition and their respective solubility points satisfies Formula 1 or Formula 2, it is shown that the curl suppression effect is more excellent.

[0195] In the composition of the liquid composition in Comparative Examples 1 to 4, an insulating resin layer having a porous structure is not formed. Then, the residual stress due to volume shrinkage cannot be dispersed, and curl occurs in the insulating resin layer. The insulating resin layer composed of the liquid compositions of Comparative Examples 5 to 6 containing PEG200DA (PEG200 diacrylate) does not have the structural unit represented by the general formula (1). Therefore, the sulfide solid electrolyte-containing layer in contact with the insulating resin layer deteriorates.

[0196] (Example 43) <Fabrication of All-Solid-State Battery> <<Fabrication of Active Material>> As the positive electrode active material, a nickel-based positive electrode active material (NCM, manufactured by Toyoshima Seisakusho Co., Ltd.) was used. As the ion conductive oxide for surface coating of the NCM particles, LiNbO 3 was used. The LiNbO 3 coating layer was formed by hydrolyzing an alkoxide solution containing lithium and niobium on the surface of the NCM powder particles based on J. Mater. Chem. A. 2021, 9, 4117 - 4125. Specifically, it is as follows. First, metallic lithium (manufactured by Honjo Metal Co., Ltd.) was dissolved in absolute ethanol (manufactured by Kanto Chemical Co., Inc.) to prepare an ethanol solution of lithium ethoxide. To this solution, niobium pentaethoxide (Nb(OC 2 H 5 )) 5 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was added to obtain an alkoxide solution containing lithium and niobium. Using a rolling fluidization device, NCM1 powder was used as a fluidized bed, and the alkoxide solution was sprayed to obtain precursor powder in which the surface of the NCM powder particles was coated with the alkoxide. By heating this precursor powder at 350 °C in a dry air atmosphere, LNO / NCM in which a LiNbO 3 layer was formed on the surface of NCM1 was synthesized.

[0197] <<Fabrication of Positive Electrode>> As the positive electrode active material, 45.3% by mass of LN0 / NMC, 2.2% by mass of acetylene black (manufactured by DENKA) as a conductive material, 1.4% by mass of polybutyl methacrylate (PBMA, manufactured by Aldrich) as a binder, and 14.7% by mass of a sulfide solid electrolyte were dispersed in 36.4% by mass of anisole (manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a positive electrode coating material. After applying this positive electrode coating on both sides of an aluminum foil substrate and drying it, a positive electrode with dimensions of 20 mm × 20 mm was obtained. The average thickness was 95 μm, and the battery capacity per unit area was 2.91 mAh / cm 2 It was.

[0198] <<Fabrication of Negative Electrode>> After attaching lithium metal with an average thickness of 50 μm (manufactured by Honjo Metal Co., Ltd.) onto a stainless steel foil, an indium foil with a further thickness of 50 μm (manufactured by Nilaco Corporation) was attached on top of it to obtain a negative electrode with dimensions of 25 mm × 25 mm.

[0199] <<Fabrication of All-Solid-State Battery>> The liquid composition of Example 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The positive electrode was placed on the stage, and the liquid composition was applied such that the distance between the outer peripheral portion of the positive electrode and the insulating resin layer was 0.5 mm. Then, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (product name: FJ800, manufactured by Phoseon), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed for curing. Next, using a hot plate, the cured product was heated at 120 °C for 1 minute to remove the solvent, resulting in a positive electrode-insulating resin layer.

[0200] At this time, the average thickness of the insulating resin layer was 124 μm, and the curl of the insulating resin layer was 2.3 mm.

[0201] After sealing the positive electrode-insulating resin layer with an aluminum laminate, it was pressurized at 500 MPa for 5 minutes using cold isostatic pressing (CIP). After pressurization, the positive electrode-insulating resin layer was taken out from the aluminum laminate. The liquid composition for the sulfide solid electrolyte-containing layer was applied onto the positive electrode by the bar coating method. After application, it was sealed again with an aluminum laminate and pressurized at 500 MPa for 5 minutes using CIP. The positive electrode-insulating resin layer and the negative electrode were opposed to each other, and after attaching lead wires respectively, they were vacuum-sealed by lamination to fabricate an all-solid-state battery. When measuring the battery voltage of the fabricated all-solid-state battery, it was 2.05 V. The capacity per unit area could be charged at a constant current up to 3.6 V at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material without any problems, and no short circuit was observed.

[0202] [Measurement method of capacity per unit area] The capacity per unit area of the electrode was measured using a charge-discharge measurement device TOSCAT3001 (manufactured by Toyo System Co., Ltd.).

[0203] First, the fabricated electrode was punched into a circular shape with a diameter of 10 mm. Next, for the electrode containing a solid electrolyte in the positive electrode, capacity evaluation was carried out by the following method. Under an argon atmosphere, the positive electrode was punched into the capacity per unit area of a circular electrode with a diameter of 10 mm. After putting 80 g of a sulfide solid electrolyte into a polyethylene terephthalate (PET) tube of a two-electrode cell (manufactured by Hokusen Co., Ltd.), a press pin was placed on it, and it was molded for 1 minute at a display pressure of 10 MPa using a uniaxial press machine (P-6, manufactured by Riken Seiki Co., Ltd.). Next, the positive electrode punched into a diameter of 10 mm was placed so as to be in contact with the active material surface and the sulfide solid electrolyte surface in the PET tube, the press pin was set, and it was molded for 1 minute at a display pressure of 30 MPa using a uniaxial press machine. A stack of lithium (manufactured by Honjo Metal Co., Ltd.) with an average thickness of 50 μm and indium (manufactured by Nilaco Corporation) with an average thickness of 50 μm in this order on a SUS foil with an average thickness of 10 μm was arranged on the surface opposite to the positive electrode composite layer, and it was molded for 3 seconds at a display pressure of 12 MPa using a uniaxial press machine. With the press pin placed, the PET tube was put into the two-electrode cell and sealed at a display pressure of 25 N·m with a digital torque wrench (KTC tool) to fabricate an electrochemical element. This electrochemical element was charged at a constant current up to 3.6 V at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material at room temperature (25 °C), and then discharged at a constant current to 2.4 V to perform initial charge and discharge. Furthermore, the same charge and discharge were carried out twice, and the discharge capacity of the second time was measured as the capacity per unit area of the initial positive electrode.

[0204] Examples of the aspects of the present invention include, for example, the following. <1> A laminate for an all-solid-state electrochemical device comprising a sulfide solid electrolyte-containing layer and an insulating resin layer disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer, wherein the insulating resin layer contains a structural unit represented by the following general formula (1) or general formula (2), and the insulating resin layer has a porous structure.

Chem.

Chem.

Chem.

Chemical formula

Mathematical formula

Chemical formula

Chemical formula

[0205] The laminate for an all-solid-state electrochemical device according to any one of <1> to <14>, the all-solid-state electrochemical device according to <15> or <16>, the electrical device according to <17>, and the moving body according to <18> or <19> can solve various conventional problems and achieve the object of the present invention.

Explanation of Reference Numerals

[0206] 10 Insulating resin layer 20 First electrode composite layer 21 First substrate 22 Adhesive layer 23 Opening 24 Material 25 Electrode for electrochemical device 30 Sulfide solid electrolyte-containing layer 31 Second substrate 35 Electrode laminate 40 Second electrode composite layer 41 Second electrode 45 Electrochemical device 500 Manufacturing apparatus for insulating resin layer 100 Printing section 1a Printing device 1b Storage container 1c Supply tube 200 Polymerization section 2a Light irradiation device 2b Polymerization inert gas circulation device 300 Heating section 3a Heating device 5 Conveying section 6 Liquid composition 7 Roller

Prior art documents

Patent documents

[0207]

Patent Document 1

Patent Document 2

Claims

1. A laminate for an all-solid-state electrochemical device, comprising a sulfide solid electrolyte-containing layer and an insulating resin layer disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer, wherein the insulating resin layer contains a structural unit represented by the following general formula (1) or general formula (2), and the insulating resin layer has a porous structure. (In the general formula (1), R1 represents hydrogen or a methyl group, and R2 represents any one selected from a polyester chain and an acrylic polymer ester derivative.) 【Chemical 1】 (In the general formula (2), R3 and R4 represent hydrogen or a methyl group.) 【Chemical 2】

2. The laminate for an all-solid-state electrochemical device according to claim 1, wherein the insulating resin layer contains a structural unit in which R2 in the general formula (1) is a polyester chain or a structural unit represented by the general formula (2).

3. The laminate for an all-solid-state electrochemical device according to claim 1, wherein the insulating resin layer contains a structural unit in which R2 in the general formula (1) is a polyester chain.

4. The laminate for an all-solid-state electrochemical device according to claim 1 or 2, wherein the insulating resin layer contains a structural unit in which R2 in the general formula (1) is a polycaprolactone chain.

5. The insulating resin layer is a cured product of a liquid composition, wherein the liquid composition contains a polymerizable compound represented by the following general formula (3) or general formula (4) and a solvent, (In the general formula (3), R6 represents a hydrogen atom or a methyl group, and R7 represents any one selected from a polyester chain and an acrylic polymer ester derivative.) 【Number】 (In the general formula (4), R8 and R9 represent a hydrogen atom or a methyl group.) 【Number】 the solvent is a mixed solvent containing a good solvent in which the polymerizable compound is soluble and a poor solvent in which the polymerizable compound is insoluble, and the solvent satisfies the following formula (1). (In the formula (1), the mixing ratio X represents the content ratio based on the mass of the good solvent in the mixed solvent, expressed as a percentage, and the polymerizable compound solubility point represents the minimum content ratio based on the mass of the good solvent in the mixed solvent in which the polymerizable compound is soluble, expressed as a percentage.) 【Number 1】

6. The insulating resin layer is a cured product of a liquid composition, wherein the liquid composition contains a polymerizable compound represented by the following general formula (3) or general formula (4) and a solvent, ​ 【Number】 (In the general formula (3), R6 represents a hydrogen atom or a methyl group, and R7 represents any one selected from a polyester chain and an acrylic polymer ester derivative.) 【Number】 (In the general formula (4), R8 and R9 represent a hydrogen atom or a methyl group.) The polymerizable compound is a mixed compound containing a soluble polymerizable compound soluble in the solvent and an insoluble polymerizable compound insoluble in the solvent, The polymerizable compound satisfies the following formula (2), and the laminate for an all-solid-state electrochemical device according to claim 1 or 2. 【Number 2】 (The mixing ratio Y in the formula (2) represents the content ratio based on the mass of the insoluble polymerizable compound in the mixed compound as a percentage, and the solvent solubility point represents the minimum content ratio based on the mass of the insoluble polymerizable compound in the mixed compound soluble in the solvent as a percentage.)

7. The insulating resin layer has a co-continuous structure, and the laminate for an all-solid-state electrochemical device according to claim 1 or 2.

8. The average thickness of the insulating resin layer is 1.0 μm or more and 150.0 μm or less, and the laminate for an all-solid-state electrochemical device according to claim 1 or 2.

9. The porosity of the insulating resin layer is 30% or more, and the laminate for an all-solid-state electrochemical device according to claim 1 or 2.

10. A substrate, A sulfide solid electrolyte-containing layer disposed on the substrate, An insulating resin layer disposed on the outer peripheral portion of the sulfide solid electrolyte-containing layer, and a laminate for an all-solid-state electrochemical device comprising: The sulfide solid electrolyte-containing layer is an electrode mixture layer containing an active material, and the laminate for an all-solid-state electrochemical device according to claim 1 or 2.

11. A substrate, An electrode mixture layer disposed on the substrate, A sulfide solid electrolyte-containing layer disposed on the electrode mixture layer, An insulating resin layer disposed so as to be in contact with at least a part of the sulfide solid electrolyte-containing layer, and the laminate for an all-solid-state electrochemical device according to claim 1 or 2.

12. An adhesive layer containing a metal that alloys with lithium is disposed between the substrate and the electrode mixture layer, and the laminate for an all-solid-state electrochemical device according to claim 11.

13. The electrode mixture layer has an opening, and the laminate for an all-solid-state electrochemical device according to claim 12.

14. The opening is filled with a sulfide solid electrolyte, and the laminate for an all-solid-state electrochemical device according to claim 13.

15. An all-solid-state electrochemical device comprising the laminate for an all-solid-state electrochemical device according to claim 1 or 2.

16. The all-solid-state electrochemical device according to claim 15, which is an all-solid-state battery.

17. An electric device comprising the all-solid-state electrochemical device according to claim 16.

18. A moving body comprising the all-solid-state electrochemical device according to claim 16.

19. The moving body according to claim 18, which is a vehicle.

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