JP2024105144A - Liquid composition, storage container, resin insulating layer, electrode, electrode laminate, electrochemical device, method for manufacturing electrode, method for manufacturing electrode laminate, device for manufacturing electrode laminate, method for manufacturing electrochemical device, and device for manufacturing electrochemical device - Google Patents

Abstract

To provide a liquid composition that can inhibit a reduction in ionic conductivity of a sulfide solid electrolyte and can form a resin insulation layer with little curling.SOLUTION: A liquid composition comprises a polymerizable compound represented by the general formula (1) in the figure and a non-aqueous solvent of a specific structure having a functional group A (A is a hydroxy group or an amino group represented by -NRH). In the case where the A is a hydroxy group, the difference in the Millikan charge between a hydrogen atom and an oxygen atom in the hydroxyl group is 0.520 or greater. In the case where the A is an amino group, the difference in the Millikan charge between a hydrogen atom and a nitrogen atom in the amino group is 0.470 or greater.SELECTED DRAWING: None

Description

The present invention relates to a liquid composition, a storage container, a resin insulating layer, an electrode, an electrode laminate, an electrochemical element, a method for manufacturing an electrode, a method for manufacturing an electrode laminate, an apparatus for manufacturing an electrode laminate, a method for manufacturing an electrochemical element, and an apparatus for manufacturing an electrochemical element.

Compared to conventional lithium-ion secondary batteries, all-solid-state secondary batteries are more resistant to temperature changes and have a lower risk of fire, making them safer. They also have high expectations for performance, such as being able to be charged quickly, and demand is expected to grow for their use in electric vehicles and other applications. In addition, there is a growing need for thin batteries to be installed in various wearable devices and medical patches, and the demand for all-solid-state secondary batteries is diversifying.

In all-solid-state batteries, which are composed of a positive electrode, a negative electrode, and a solid electrolyte layer, the laminate including the positive electrode, solid electrolyte layer, and negative electrode may be pressed under very high pressure to achieve high density and improve the performance of the all-solid-state battery. However, this pressing process can cause damage such as cracks in the solid electrolyte, which can result in a short circuit between the positive electrode and the negative electrode when the all-solid-state battery is in use.

In order to prevent damage such as cracks in the solid electrolyte in such all-solid-state batteries, a positive electrode for a solid battery has been reported that includes 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, in which positive electrode guides are disposed on at least two adjacent sides of the outer periphery of the positive electrode active material layer on the surface having the positive electrode active material layer (see, for example, Patent Document 1).

The present invention aims to provide a liquid composition that can suppress the decrease in ionic conductivity of a sulfide solid electrolyte and form a resin insulating layer with less warping.

The liquid composition of the present invention as a means for solving the above problems is a liquid composition containing a polymerizable compound represented by the following general formula (1) and a non-aqueous solvent represented by the following general formula (2), in which when A in the general formula (2) is a hydroxyl group, the difference in Millikan charge between the hydrogen atom and the oxygen atom in the hydroxyl group is 0.520 or more, and when A in the general formula (2) is an amino group, the difference in Millikan charge between the hydrogen atom and the nitrogen atom in the amino group is 0.470 or more.

(In the general formula (1), R ¹ represents an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and n represents an integer of 2 to 6.)

(In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, A represents a hydroxyl group or an amino group represented by -NR ⁵ H, and R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.)

The present invention provides a liquid composition that can suppress the decrease in ionic conductivity of the sulfide solid electrolyte and form a resin insulating layer with less warping.

FIG. 1 is a cross-sectional view showing an example of an electrode according to the present embodiment. FIG. 2 is a cross-sectional view showing an example of the electrode laminate of the present embodiment. FIG. 3 is a cross-sectional view showing an example of the electrochemical element of this embodiment. FIG. 4 is a top view showing an example of an electrode according to the present embodiment. FIG. 5 is a top view showing another example of the electrode of the present embodiment. FIG. 6 is a top view showing another example of the electrode of the present embodiment. FIG. 7 is a schematic diagram showing an example of a liquid ejection device which is a manufacturing device for the resin insulation layer of this embodiment. FIG. 8 is a schematic diagram showing another example of a liquid ejection apparatus which is a manufacturing apparatus for a resin insulation layer according to the present embodiment. FIG. 9 is a schematic diagram showing another example of a liquid ejection apparatus which is a manufacturing apparatus for a resin insulation layer according to the present embodiment. FIG. 10 is a schematic diagram showing a modification of the liquid ejection device of FIG. FIG. 11 is a configuration diagram showing an example of a printing unit using a drum-shaped intermediate transfer body as a manufacturing apparatus for a resin insulation layer according to this embodiment. FIG. 12 is a configuration diagram showing an example of a printing unit using an intermediate transfer body in the form of an endless belt as a manufacturing apparatus for a resin insulation layer according to this embodiment. FIG. 13 is a diagram showing a schematic positional relationship between the resin insulating layer and the electrode mixture layer. FIG. 14 is a diagram showing a schematic diagram of the thickness relationship between the resin insulating layer and the electrode mixture layer. FIG. 15 is a cross-sectional view showing an example of an all-solid-state battery which is an electrochemical element of this embodiment. FIG. 16 is a diagram showing a schematic diagram of the distance between the resin insulating layer and the electrode mixture layer. FIG. 17 is a diagram showing a schematic diagram of the distance between the resin insulating layer and the electrode mixture layer. FIG. 18 is a graph showing the dynamic viscosity when the mixing ratio of the alcohol to the monomer is changed. FIG. 19 is a schematic diagram showing an example of a mobile object equipped with an all-solid-state battery that is an electrochemical device of the present invention.

(Liquid Composition)
The liquid composition of the present invention is a liquid composition containing a polymerizable compound represented by the following general formula (1) and a non-aqueous solvent represented by the following general formula (2), and further contains other components as necessary.
When A in the general formula (2) is a hydroxyl group, the difference in Millikan charge between the hydrogen atom and the oxygen atom in the hydroxyl group is 0.520 or more, and when A in the general formula (2) is an amino group, the difference in Millikan charge between the hydrogen atom and the nitrogen atom in the amino group is 0.470 or more.

(In the general formula (1), R ¹ represents an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and n represents an integer of 2 to 6.)

(In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, A represents a hydroxyl group or an amino group represented by -NR ⁵ H, and R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.)

The liquid composition of the present invention is an invention based on the fact that the present inventors have found the following problems in the prior art.
That is, in a conventional method for producing an all-solid-state battery using a positive electrode for a solid-state battery, in order to prevent a short circuit between the positive electrode and the negative electrode in the all-solid-state battery, a positive electrode guide is arranged on the outer periphery of the surface of the positive electrode active material layer that faces the solid electrolyte layer, and stacking and pressing are performed. However, since extremely high pressure is applied during the production of an all-solid-state battery, cracks in the positive electrode guide and pressure load are applied to the electrode, and there is still a problem that damage due to the pressure load occurs to the electrode and the solid electrolyte layer.
In addition, the positive electrode guide is preferably made of resin because it needs to have a certain degree of viscoelasticity so that it can withstand pressing, and in consideration of productivity and the diversity of shapes of the active material layer, it is considered preferable to form a coating film by applying a liquid composition using a coater. However, Patent Document 1 (International Publication No. 2020-022111) discloses insulating materials such as insulating resins and inorganic oxides as materials for the positive electrode guide, and laminated sheets as one form of such materials, but does not disclose that the resin insulating layer is produced from a liquid composition.

In recent years, the inkjet method has been attracting attention as an industrial coater because it can handle minute to precise pattern coating, minimize material loss, and can coat precise patterns from CAD data without plate making (masks). Furthermore, inkjet printing has high film thickness uniformity, high-precision landing and separate coating, and is capable of irregular coating, fine wiring, and wiring drawing of minute pieces, so it is expected that a resin active material layer guide will be formed using a photocurable liquid composition.

In general, photocurable liquid compositions are often composed of a photoinitiator and an acrylic polyfunctional monomer. In the case of photocuring using such a polyfunctional monomer, many monomers are polymerized to become one molecule, which often leads to shrinkage during curing due to the gap from the van der Waals distance to the covalent bond distance, resulting in peeling from the substrate and curling of the resin layer. In order to suppress shrinkage during curing, it is common to add a filler or an additive liquid to the liquid composition (see, for example, Network Polymer, Vol. 36 No. 6 (2015)).

In addition, in inkjet printing using a polymerizable liquid composition consisting of a monomer and a solvent, a liquid composition with a relatively low viscosity (generally about 5 mPa·s to 20 mPa·s) is used in consideration of the ejection characteristics. When forming a positive electrode guide, adverse effects such as leakage of the solvent from the polymerized guide into the active material layer, penetration of the solvent into the active material layer, and curling due to solvent leakage may occur. In order to suppress these adverse effects, a solvent that becomes more viscous than before polymerization due to a change in intermolecular interaction is preferably used, and specifically, an alcohol-based solvent or an amine-based solvent that can form a hydrogen bond network may be mentioned. That is, this uses the phenomenon that a liquid composition that was relatively low in viscosity before polymerization because the hydrogen bond network was broken by the monomer becomes highly viscous after polymerization due to the hydrogen bond network between the solvents.
As an example, the mixing ratio of a mixed solution of tetrahydrolinalool (THL) as an alcohol and light acrylate 4EG-A (PEG200DA, manufactured by Kyoeisha Chemical Co., Ltd.) as a monomer was changed, and the dynamic viscosity was measured at a rotation speed of 100 rpm using a TV25 type viscometer (cone-plate type viscometer, manufactured by Toki Sangyo Co., Ltd.) and the results are shown in Figure 18. As a result, a decrease in viscosity was observed when the mass ratio of monomer to solvent was approximately 1:1, which suggests that the hydrogen bond network had collapsed.

On the other hand, sulfide solid electrolytes are widely used as solid electrolytes in all-solid-state batteries. Because sulfide solid electrolytes are highly reactive with proton-donor compounds such as water (see, for example, Solid State Ionics, 182(1), 3, 116-119), it is generally considered difficult to use proton-donor solvents such as alcohols and amines in the manufacture of all-solid-state batteries.

As a result of intensive research conducted by the inventors in order to achieve the above object, they discovered that the liquid composition of the present invention can suppress the decrease in the ionic conductivity of the sulfide solid electrolyte and can form a resin insulating layer with less warping, which led to the completion of the present invention.

<Polymerizable Compound>
The polymerizable compound is a polymerizable compound represented by the following general formula (1), and is a polyfunctional acrylate having 2 to 6 acrylic groups.
(In the general formula (1), R ¹ represents an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and n represents an integer of 2 to 6.)

The ^R1 is an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and examples thereof include hydrocarbon groups such as linear hydrocarbon groups, branched hydrocarbon groups, and cyclic hydrocarbon groups, polyalkylene glycol groups, hydroxypivalate groups, groups in which H has been removed from the three OH groups of _{trimethylolpropane, -CH2CH2COO- groups} (acrylic acid esters), and combinations thereof. The hydrocarbon group may be a saturated or unsaturated hydrocarbon group.
Among these, from the viewpoint of improving abrasion resistance by imparting flexibility to the film, preferred are hydrocarbon groups having 3 or more carbon atoms and functional groups having 3 or more carbon atoms and a polyalkylene glycol group, and more preferred are linear saturated hydrocarbon groups having 3 or more carbon atoms, branched saturated hydrocarbon groups having 3 or more carbon atoms, a benzene ring, a polyethylene glycol group having 3 or more carbon atoms, a polypropylene glycol group, and combinations thereof.

The polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polymerizable compound include bifunctional acrylates such as bifunctional alkyl acrylates, hydroxypivalic acid neopentyl glycol acrylic acid adducts, bifunctional polyethylene glycol acrylates, bifunctional polypropylene glycol acrylates, bifunctional polytetramethylene glycol acrylates, bifunctional cyclic acrylates, and bifunctional alkoxylated aromatic acrylates; trifunctional acrylates such as trifunctional trimethylolpropane acrylates, trifunctional alkoxylated glycerin acrylates, and trifunctional isocyanate acrylates; and tetrafunctional to hexafunctional acrylates such as tetrafunctional pentaerythritol acrylate, tetrafunctional ditrimethylolpropane acrylate, tetrafunctional diglycerin tetraacrylate, and hexafunctional dipentaerythritol hexaacrylate.
These may be used alone or in combination of two or more kinds.
Among these, in terms of cure shrinkage, bifunctional alkyl acrylates, bifunctional polyethylene glycol acrylates, and bifunctional alkoxylated aromatic acrylates are preferred, and bifunctional polyethylene glycol acrylates and bifunctional acrylic acid polymer ester acrylates are more preferred.

Examples of bifunctional alkyl acrylates include NK ester series A-HD-N, A-NON-N, A-DOD-N, and A-NPG (all manufactured by Shin-Nakamura Chemical Co., Ltd.); light acrylate series NP-A, MPD-A, 1,6HX-A, and 1,9ND-A (all manufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD NPGDA (manufactured by Nippon Kayaku Co., Ltd.); 1,4-bis(acryloyloxy)butane, 1,6-bis(acryloyloxy)hexane, and neopentyl glycol diacrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.).
Examples of hydroxypivalic acid neopentyl glycol acrylic acid adducts include Light Acrylate HPP-A (manufactured by Kyoeisha Chemical Co., Ltd.), Miramer Series M210 (manufactured by Miwow Co., Ltd.), and KAYARAD FM-400 (manufactured by Nippon Kayaku Co., Ltd.).

Examples of bifunctional polyethylene glycol acrylates include NK Ester series A-200, A-400, A-600, and A-1000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Light Acrylate series 3EG-A, 4EG-A, 9EG-A, and 14EG-A (all manufactured by Kyoeisha Chemical Co., Ltd.); Blenmer series ADE-200, ADE-300, and ADE-400A (all manufactured by NOF Corporation); and Miramer M202 (manufactured by Miwow).
Examples of bifunctional polypropylene glycol acrylates include NK Ester Series APG-200, APG-400, and APG-700 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Viscoat #310HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Blenmer ADP-400 (manufactured by NOF Corporation), and Miramer Series M216 and M220 (all manufactured by Miwow Corporation).

Examples of bifunctional polytetramethylene glycol acrylates include NK Ester A-PTMG65 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PTMGA-250 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar ADT-250 (manufactured by NOF Corporation).
Examples of bifunctional cyclic acrylates include NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), and KAYARAD Series R-604 and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of bifunctional alkoxylated aromatic acrylates include the NK Ester series ABE-300, A-BPE-4, A-BPE-10, and A-BPE-20 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); the Light Acrylate series BP-4EAL, BA-134, and BP-10EA (all manufactured by Kyoeisha Chemical Co., Ltd.); the Viscoat series #540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the KAYARAD series R-551 and R-712 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of trifunctional trimethylolpropane acrylates include NK Ester Series A-TMPT, A-TMPT-3EO, A-TMPT-9EO, and AT-20E (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Light Acrylate Series TMP-3EO-A and TMP-6EO-3A (all manufactured by Kyoeisha Chemical Co., Ltd.); and Viscoat #295 (manufactured by Osaka Organic Chemical Industry Ltd.).
Examples of trifunctional alkoxylated glycerin acrylates include NK ester series A-GLY-3E, A-GLY-9E, and A-GLY-20E (all manufactured by Shin-Nakamura Chemical Co., Ltd.).
Examples of trifunctional isocyanate acrylates include NK Ester Series A-9300 and A-9200YN (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of tetrafunctional pentaerythritol acrylates include NK Ester Series A-TMMT and ATM-35E (both manufactured by Shin-Nakamura Chemical Co., Ltd.); Light Acrylate Series PE-3A and PE-4A (both manufactured by Kyoeisha Chemical Co., Ltd.).
Examples of tetrafunctional ditrimethylolpropane acrylate include NK ester series AD-TMP and AD-TMP-4E (both manufactured by Shin-Nakamura Chemical Co., Ltd.).
An example of the tetrafunctional diglycerin tetraacrylate is Light Acrylate DGE-4E (manufactured by Kyoeisha Chemical Co., Ltd.).
An example of the hexafunctional dipentaerythritol hexaacrylate is Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.).

<Non-aqueous solvent>
The non-aqueous solvent is a non-aqueous solvent represented by the following general formula (2), and refers to an organic solvent having a water content of 1 mass % or less.
These may be used alone or in combination of two or more.
(In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, A represents a hydroxyl group or an amino group represented by -NR ⁵ H, and R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.)
The R ² , R ³ and R ⁴ each independently represent a hydrocarbon group.
From the viewpoint of suppressing reaction with the sulfide solid electrolyte, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, in other words, at least one of the groups of R ² , R ³ and R ⁴ is a hydrocarbon group having 2 or more carbon atoms.

The hydrocarbon group is not particularly limited and can be appropriately selected depending on the purpose. Examples of the hydrocarbon group include acyclic hydrocarbon groups such as a linear alkyl group, a branched alkyl group, a linear alkenyl group, a branched alkenyl group, a linear alkynyl group, and a branched alkynyl group; cyclic hydrocarbon groups such as a cycloalkyl group and a cycloalkenyl group; and combinations thereof.
It is preferable that ^R2 and ^R3 each independently represent a non-cyclic hydrocarbon group from the viewpoint of suppressing cure shrinkage.

<<Tertiary alcohol solvent>>
When A in the general formula (2) is a hydroxyl group, the non-aqueous solvent is a tertiary alcohol solvent represented by the following general formula (2a).
(In the general formula (2a), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, and the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more.)

The alcohol is not particularly limited and can be appropriately selected depending on the purpose. For example, tert-amyl alcohol (0.5206), 2,3-dimethyl-2-hexanol (0.5247), 2,5-dimethyl-2,5-hexanediol (0.5238), 2-methyl-1-phenyl-2-propanol (0.5222), linalool (0.5270), α-terpineol (0.5251), tetrahydrolinalool (0.5251), 2-methyl-4-phenyl-2-butanol (0.5235), and the like.
The numerical value in parentheses indicates the difference in Millikan charge between the hydrogen atom and the oxygen atom in the hydroxyl group of the general formula (2a).

<<Amine-based solvents>>
When A in the general formula (2) is an amino group represented by -NR ⁵ H, the non-aqueous solvent is an amine-based solvent having a primary or secondary amine represented by the following general formula (2b), which has three hydrocarbon groups on the carbon atom adjacent to the nitrogen.
(In the general formula (2b), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, and R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.)

Examples of the primary or secondary amine include 1,1,3,3-tetramethylbutylamine (0.5001) and tert-amylamine (0.4716).
The numerical value in parentheses indicates the difference in Millikan charge between the hydrogen atom and the nitrogen atom in the amino group of the general formula (2b).

[Millikan charge difference]
Mulliken charge or Millikan charge amount means the charge amount of an atom according to Millikan density analysis.
Specifically, the Millikan charge can be the amount of charge on an atom calculated using the semi-empirical quantum chemistry calculation code MOPAC7 (Hamiltonian is AM1) using Winmostar v11.1.2 (manufactured by CrossAbility Co., Ltd.), which is atomic/molecular scale structure modeling/visualization software compatible with quantum chemistry, molecular dynamics, and first-principles calculations.
The Millikan charge difference is a scalar difference between the amounts of Millikan charges of two adjacent atoms.
The difference in Millikan charge between the hydrogen atom and the oxygen atom in the hydroxyl group of the general formula (2a) (also referred to as ΔMulliken (OH)) is 0.520 or more, and preferably 0.5206 or more.
The difference in Millikan charge between the hydrogen atom and the nitrogen atom in the amino group of the general formula (2b) (also referred to as ΔMulliken (N—H)) is 0.470 or more, and preferably 0.500 or more.
When the non-aqueous solvent represented by the general formula (2b) is a primary amine and has two hydrogen atoms adjacent to the nitrogen atom, the difference between the average value of the Millikan charges of the two hydrogen atoms and the Millikan charge of the nitrogen atom is defined as the Millikan charge difference (ΔMulliken(N-H)).
The difference in Millikan charges between adjacent atoms is thought to represent the strength of the ionic bond, and it can be inferred that a larger charge difference indicates a strong bond strength, and a smaller charge difference indicates a weak bond strength.

The content of the non-aqueous solvent is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of suppressing warping of the obtained insulating resin layer, the liquid composition contains a non-aqueous solvent, and from the viewpoint of warping suppression effect, the content is preferably 30 mass % or more, more preferably 40 mass % or more, and even more preferably 50 mass % or more relative to the total amount of the liquid composition. Also, from the viewpoint of controlling the film thickness, the content of the non-aqueous solvent is preferably 70 mass % or less.
The non-aqueous solvent is expected to act as a buffer against cure shrinkage since there is no change in the intermolecular distance between the solvent and the resin or between the resin and the solvent during polymerization.

<Other ingredients>
<<Other solvents>>
Solvents other than the non-aqueous solvents mentioned above can also be used in combination.
The other solvent to be mixed with the non-aqueous solvent is not particularly limited and can be appropriately selected depending on the purpose. However, a low-polarity hydrophobic solvent that has low reactivity with the sulfide solid electrolyte is preferable. Examples of the other solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, anisole, and phenetole; hydrocarbon solvents such as hexane, heptane, nonane, octane, decane, menthane, cyclohexane, and cyclooctane; ethyl butyrate, ethyl valerate, ethyl hexanoate, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl undecanoate, laurate, and the like. and the like. Ester-based solvents such as ethyl phosphate, 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, butyl isovalerate, heptyl acetate, isoamyl isovalerate, 2-ethylhexyl acetate, hexyl butyrate, ethyl benzoate, hexyl hexanoate, amyl n-octanoate, and hexyl acetate.
The content of the solvent other than the non-aqueous solvent is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of shortening the drying time, the content of the solvent other than the non-aqueous solvent is preferably 30 mass % or less, more preferably 50 mass % or less, and even more preferably 55 mass % or less, relative to the total amount of the liquid composition.

<<Polymerization initiator>>
In general, acrylic groups have high polymerizability and high radical polymerizability, so that a resin composition can be quickly obtained by using a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator.
For example, a resin composition can be obtained without an initiator by using an electron beam, but it is preferable to use a photopolymerization initiator in terms of curing speed and equipment costs.

The photopolymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples of the photopolymerization initiator include alkylphenone-based polymerization initiators, acylphosphine oxide-based polymerization initiators, and oxime ester-based polymerization initiators.
Examples of the alkylphenone polymerization initiator include Omnirad series 651, 184, 1173, 2959, 127, 907, 369, 369E, and 379EG (all manufactured by IGM Resins B.V.).
Examples of the acylphosphine oxide polymerization initiator include Omnirad series TPO and 819 (all manufactured by IGM Resins B.V.).
Examples of the oxime ester polymerization initiator include Irgacure series OXE01, OXE02, OXE03, and OXE04 (all manufactured by BASF Japan).

The content of the polymerization initiator is preferably 0.05% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more and 5.0% by mass or less, when the total mass of the polymerizable compounds is taken as 100.0% by mass, in order to obtain a sufficient curing speed.

[Method of producing liquid composition]
The method for producing the liquid composition is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferable to produce the liquid composition through a process including a step of dissolving a polymerization initiator in a polymerizable compound, a step of further dissolving other components such as a non-aqueous solvent and other solvents, and a step of stirring to obtain a homogeneous solution.

<Containment container>
The storage vessel includes a liquid composition for forming the resin insulating layer and a container, and the liquid composition is stored in the container.
Examples of containers include glass bottles, plastic containers, plastic bottles, stainless steel bottles, one-gallon cans, drums, and the like.

(Resin insulation layer)
The resin insulating layer of the present invention is a resin insulating layer obtained by polymerizing the above-mentioned liquid composition of the present invention.
The resin insulating layer has a volume resistivity of 10 ¹² Ω·cm or more.
If a conductive path is formed by adding a conductive filler or the like, there is a possibility of a short circuit occurring between the positive electrode and the negative electrode. Therefore, a resin insulating layer that does not have a conductive path is preferred.

The resin insulating layer is preferably a porous resin, and more preferably has a bicontinuous structure with the resin as the skeleton.
The specific volume resistivity of the resin insulating layer is preferably 1×10 ¹² (Ω·cm) or more.
Here, the term "co-continuous structure" refers to a structure in which two or more substances or phases each have a continuous structure and do not form an interface, and in this embodiment, refers to a structure in which both the resin phase and the pore phase are three-dimensional branched network continuous phases. Such a structure can be formed, for example, by polymerizing the liquid composition by a polymerization induced phase separation method.

Polymerization-induced phase separation
Porous resins, or porous resins having a co-continuous structure with a resin as a skeleton, are preferably formed by polymerization-induced phase separation. Polymerization-induced phase separation refers to a state in which a polymerizable compound and a solvent are compatible with each other, but the polymerized product (resin) and the solvent produced during the polymerization of the polymerizable compound are not compatible with each other (phase separation occurs). There are other methods for obtaining porous resins by phase separation, but by using the polymerization-induced phase separation method, a porous resin having a network structure can be formed, so that a porous resin with high resistance to chemicals and heat can be expected. In addition, compared to other methods, there are also advantages such as a short process time and easy surface modification.

Next, a process for forming a porous resin using polymerization-induced phase separation with a liquid composition containing a polymerizable compound will be described. The polymerizable compound undergoes a polymerization reaction by irradiation with light 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 with a co-continuous structure due to the resin skeleton, with the solvent filling the pores. When this is dried, the solvent is removed, leaving a porous resin with a co-continuous structure of a three-dimensional network structure. Therefore, in order to form a porous resin with an appropriate porosity, the compatibility of the solvent with the polymerizable compound and the compatibility of the solvent with the resin formed by polymerization of the polymerizable compound are examined.

One method for confirming that the resin insulating layer has a bicontinuous structure and that the pores are interconnected is, for example, to observe the cross section of the porous resin using a scanning electron microscope (SEM) or the like to confirm that the pores are interconnected. In addition, air permeability is one of the physical properties that can be obtained by interconnecting the pores.

[Image Observation Using a Scanning Electron Microscope (SEM) and Measurement of Porosity]
The porosity of the porous resin is preferably 30% or more, more preferably 50% or more, and is preferably 90% or less, more preferably 85% or less.
A porosity of 30% or more can reduce the pressure applied from the resin insulating layer to the solid electrolyte layer in the pressing step after the formation of the solid electrolyte layer, while a porosity of 90% or less can adequately maintain the shape of the resin insulating layer after the pressing step from the viewpoint of the strength of the resin insulating layer.
The method for evaluating the porosity of the porous resin is not particularly limited and can be appropriately selected depending on the purpose. For example, a method can be used in which a porous resin is stained with osmium, then vacuum-impregnated with an epoxy resin, the internal cross-sectional structure is cut out with a focused ion beam (FIB), and the porosity is measured using a scanning electron microscope (SEM).

[Air permeability]
The air permeability of the porous resin is preferably 1,000 sec/100 mL or less, more preferably 500 sec/100 mL or less, and even more preferably 300 sec/100 mL or less.
The air permeability is the air permeability measured in accordance with JIS P8117, and can be measured, for example, by using a Gurley densometer (manufactured by Toyo Seiki Seisakusho, Ltd.).
As an example, it may be determined that the pores are interconnected when the air permeability is 1,000 sec/100 mL or less.

The cross-sectional shape of the pores of the porous resin may be various shapes and sizes, such as a substantially circular shape, a substantially elliptical shape, a substantially polygonal shape, etc. Here, the size of the pores refers to the length of the longest part in the cross-sectional shape. The size of the pores can be obtained from a cross-sectional photograph taken with a scanning electron microscope (SEM).
The size of the pores of the porous resin is not particularly limited and can be appropriately selected depending on the purpose, but the ratio of the size of the pores to the median diameter of the solid electrolyte contained in the liquid composition for forming the solid electrolyte layer provided on the resin insulation layer is preferably smaller than 1, more preferably 0.8 or less. If the size of the pores is larger than the median diameter of the solid electrolyte, the solid electrolyte is easily contained in the pores of the resin insulation layer. By setting the size in the above range, a configuration in which the solid electrolyte is not easily contained in the resin insulation layer can be obtained, which is advantageous in terms of pressure dispersion during pressing and relaxation of pressure applied from the resin insulation layer to the solid electrolyte.
The method for adjusting the pore size and porosity of the porous resin to fall within these ranges is not particularly limited, and examples thereof include a method of adjusting the content of the polymerizable compound in the liquid composition to fall within the above-mentioned range, a method of adjusting the content of the porogen in the liquid composition to fall within the above-mentioned range, and a method of adjusting the irradiation conditions of active energy rays.

(electrode)
The electrode of the present invention comprises an electrode substrate, an electrode mixture layer on the electrode substrate, and the above-described resin insulating layer of the present invention on the outer periphery of the electrode mixture layer.

(Electrode laminate)
The electrode laminate of the present invention comprises the electrode of the present invention described above and a solid electrolyte layer on the electrode.
In other words, the electrode laminate of the present invention has an electrode substrate, an electrode mixture layer on the electrode substrate, the resin insulating layer of the present invention described above on the outer periphery of the electrode mixture layer, and a solid electrolyte layer on the electrode mixture layer and the resin insulating layer.

An example of an electrode of the present invention is shown in Fig. 1. Fig. 1 is a cross-sectional view of an electrode 25, which has a first electrode having a first electrode substrate 21 and an electrode mixture layer 20 on the first electrode substrate 21, and a resin insulating layer 10 on the outer periphery of the first electrode mixture layer 20.
In addition, while Figure 1 illustrates a configuration in which an electrode mixture layer 20 and a resin insulation layer 10 are provided on one side of the first electrode substrate 21, an electrode mixture layer 20 and a resin insulation layer 10 may be provided on both opposing sides of the first electrode substrate 21.
An example of an electrode laminate of the present invention is shown in Fig. 2. Fig. 2 is a cross-sectional view of an electrode laminate 35, which has a first electrode substrate 21, a first electrode mixture layer 20 on the first electrode substrate 21, a resin insulating layer 10 on the outer periphery of the first electrode mixture layer 20, and a solid electrolyte layer 30 on the first electrode mixture layer 20 and the resin insulating layer 10.
In addition, FIG. 2 illustrates a configuration in which the electrode mixture layer 20, the resin insulating layer 10, and the solid electrolyte layer 30 are provided on one side of the first electrode substrate 21, but the electrode mixture layer 20, the resin insulating layer 10, and the solid electrolyte layer 30 may be provided on both opposing sides of the first electrode substrate 21.
An example of an electrochemical element of the present invention, which will be described later, is shown in Fig. 3. Fig. 3 is a cross-sectional view of an electrochemical element 45, which has a second electrode on an electrode laminate 35, the second electrode having a second electrode substrate 41 and an electrode mixture layer 40 on the second electrode substrate 41, and the solid electrolyte layer 30 and the electrode mixture layer 40 face each other. The electrochemical element 45 is a single cell layer, which can be stacked to form a stacked battery.
In addition, FIG. 3 illustrates a configuration in which the electrode mixture layer 20, the resin insulating layer 10, and the solid electrolyte layer 30 are provided on one side of the first electrode substrate 21, but the electrode mixture layer 20, the resin insulating layer 10, and the solid electrolyte layer 30 may be provided on both opposing sides of the first electrode substrate 21, and this configuration may be stacked to form a stacked battery.

<Electrodes (First Electrode, Second Electrode)>
The electrode includes an electrode substrate, an electrode mixture layer, and a resin insulating layer.
The negative electrode and positive electrode are collectively referred to as "electrodes", the negative electrode substrate and positive electrode substrate are collectively referred to as "electrode substrate", and the negative electrode mixture layer and positive electrode mixture layer are collectively referred to as "electrode mixture layer".
Moreover, when the first electrode is a negative electrode, the second electrode refers to a positive electrode, and when the first electrode is a positive electrode, the second electrode refers to a negative electrode.

<Electrode Substrate>
The electrode substrate is not particularly limited as long as it is a conductive substrate that is stable against an applied potential. Examples of the electrode substrate include aluminum foil, copper foil, stainless steel foil, titanium foil, etched foils obtained by etching these foils to form fine holes, and perforated electrode substrates used in lithium ion capacitors.

<Electrode mixture layer>
The electrode mixture layer (hereinafter, sometimes referred to as "active material layer") is not particularly limited and can be appropriately selected depending on the purpose. For example, it contains an active material (negative electrode active material or positive electrode active material) and may further contain a conductive assistant, a binder, a dispersant, a solid electrolyte, and other components as necessary.
Because the electrode or the electrode laminate has an advantage of having a resin insulating layer that can suppress a decrease in ionic conductivity of the sulfide solid electrolyte, it is preferable that the electrode mixture layer contains an active material and a sulfide solid electrolyte.

<<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 kinds.
The positive electrode active material is not particularly limited as long as it is a material capable of reversibly absorbing and releasing alkali metal ions, and 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 lithium and one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium.
Examples of the lithium-containing transition metal compound include lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide.
As the alkali metal-containing transition metal compound, a polyanion-based compound having an XO4 tetrahedron (X=P, S, As, Mo, W, Si, etc.) in the crystal structure can also be used. Among these, lithium-containing transition metal phosphate compounds such as lithium iron phosphate and lithium vanadium phosphate are preferred in terms of cycle characteristics, and lithium vanadium phosphate is particularly preferred in terms of lithium diffusion coefficient and output characteristics.
From the viewpoint of electronic conductivity, the polyanion-based compound is preferably composited by coating the surface with a conductive assistant such as a carbon material.

The negative electrode active material is not particularly limited as long as it is a material that can reversibly absorb and release alkali metal ions, and 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), and easily graphitizable carbon (soft carbon).
Examples of materials other than carbon materials include lithium titanate and titanium oxide.
In addition, from the viewpoint of increasing the energy density of a lithium ion battery, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as the negative electrode active material.

<<Conductive assistant>>
As the conductive assistant, for example, carbon black produced by a furnace method, an acetylene method, a gasification method, or the like, or a carbon material such as carbon nanofiber, carbon nanotube, graphene, or graphite particles can be used. As a conductive assistant other than a carbon material, for example, metal particles such as aluminum, or metal fibers can be used. The conductive assistant may be previously compounded with the active material.
The mass ratio of the conductive assistant to the active material is preferably 10% by mass or less, more preferably 8% by mass or less. When the mass ratio of the conductive assistant to the active material is 10% by mass or less, the stability of the liquid composition is improved. Furthermore, when the mass ratio of the conductive assistant to the active material is 8% by mass or less, the stability of the liquid composition is further improved.

<< Binder >>
The binder is not particularly limited as long as it can bind negative electrode materials together, positive electrode materials together, a negative electrode material and a negative electrode substrate, and a positive electrode material and a positive electrode substrate. However, when the liquid composition is used for inkjet ejection, it is preferable that the binder does not easily increase the viscosity of the liquid composition from the viewpoint of suppressing clogging of the nozzle of the liquid ejection head.

The content of the binder relative to the active material 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 relative to the active material is 1% by mass or more, it is possible to firmly bind the active material to the electrode substrate.

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

<<Dispersant>>
The dispersant is not particularly limited as long as it is capable of improving the dispersibility of the active material in the liquid composition, and examples thereof include 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, and polyalkylene polyamine-based; low molecular weight dispersants such as alkylsulfonic acid-based, quaternary ammonium-based, higher alcohol alkylene oxide-based, polyhydric alcohol ester-based, and alkyl polyamine-based; and inorganic dispersants such as polyphosphate-based dispersants.

<<Solid electrolyte>>
The material constituting the solid electrolyte layer contained in the electrode mixture layer is not particularly limited as long as it is a solid substance having electronic insulation and ionic conductivity. However, a sulfide solid electrolyte or an oxide solid electrolyte is preferred from the viewpoint of having high ionic conductivity.
Examples of the sulfide solid electrolyte include Li ₁₀ GeP ₂ S ₁₂ and Li ₆ PS ₅ X (X=F, Cl, Br, I) having an argyrodite crystal structure.
Examples of the oxide-based solid electrolyte include LLZ ( _Li7La3Zr2O12 ) having _a garnet-type crystal structure, LATP ( _Li1 + _xAlxTi20x ( _PO4 ) ₃ ) (0.1≦x≦ _0.4 ) having a NASICON-type crystal structure, LLT ( _{Li0.33La0.55TiO3} ) having _{a perovskite} -type _crystal structure, and _amorphous LIPON ( _{Li2.9PO3.3N0.4} ).

In addition to the above, there is no particular limitation as long as it does not deviate from the spirit of the present invention. In addition, these solid electrolytes may be used alone or in combination of two or more.
Examples of electrolyte materials that are dissolved or dispersed in liquid to form these solid electrolyte layers include solid electrolyte precursor materials such as Li ₂ S, P ₂ S ₅ , LiCl, and solid electrolyte materials such as Li ₂ S-P ₂ S ₅ based glass and Li ₇ P ₃ S ₁₁ glass ceramics.

<<Other ingredients>>
The other components include, for example, a dispersant.

<Resin insulation layer>
The resin insulating layer is provided on the outer periphery of the electrode mixture layer provided on the electrode base, and is also provided on the electrode base on the outer periphery of the electrode base.

The shape of the resin insulating layer and the region in which it is provided will be described with reference to the drawings. Figures 4 to 6 are top views of the electrode laminate 25 shown in Figure 1 and top views of other embodiments.
In Fig. 4, the resin insulating layer 10 is provided adjacent to two sides of the electrode mixture layer 20. In Fig. 5, each of the resin insulating layers 10 in two regions is provided adjacent to one long side of the electrode mixture layer 20 and two corners of the long side.
As shown in FIG. 6, the resin insulating layer 10 may be provided continuously adjacent to all four sides of the electrode mixture layer 20, or may be provided discontinuously adjacent thereto (not shown).

Here, "provided on the outer periphery of the electrode mixture layer" means that the resin insulation layer is provided on at least two sides of the outer periphery of the electrode mixture layer, and the resin insulation layer may be provided on three sides or four sides (all sides) of the outer periphery of the electrode mixture layer. Also, the resin insulation layer may have a recess or a notch on any side for allowing an electrode tab to protrude.
In addition, being provided on the "periphery of the electrode substrate" may mean that the resin insulation layer is provided so as to include the end of the electrode substrate, or that the resin insulation layer is provided around the resin insulation layer with a margin of the electrode substrate as shown in Figures 4 to 6.
The resin insulation layer may be separated from the electrode mixture layer (upper left figure in Figure 13) or adjacent to the electrode mixture layer (upper right figure, lower left figure, and lower right figure in Figure 13), but it is preferable that it is adjacent to the electrode mixture layer.
In the case where they are adjacent to each other, as shown in Fig. 13, the resin insulation layer and the electrode mixture layer may be in contact with each other in a partial region on the facing surface (upper right diagram of Fig. 13), or the resin insulation layer and the electrode mixture layer may be in contact with each other over the entire facing surface (lower left diagram and lower right diagram of Fig. 13). Here, if the resin insulation layer is provided later, the resin insulation layer overlaps the electrode mixture layer side (lower left diagram of Fig. 13), and if the electrode mixture layer side is provided later, the electrode mixture layer side overlaps the resin insulation layer (lower right diagram of Fig. 13).
When they are spaced apart, the distance d between the resin insulating layer and the electrode mixture layer 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 resin insulating layer and the electrode mixture layer is 10 mm or less, the resin insulating layer and the electrode mixture layer are likely to come into contact with each other after the pressing step, so that the solid electrolyte layer can be uniformly formed on the resin insulating layer and the electrode mixture layer, and pressure can be uniformly applied to the solid electrolyte layer when the solid electrolyte layer is pressed.
The distance d between the electrode mixture layer and the resin insulation layer (the width between the outer periphery of the electrode mixture layer and the resin insulation layer) is defined as shown in Figures 16 and 17. The state in which the electrode mixture layer and the resin insulation layer are adjacent to each other as shown in Figure 16 is defined as 0, and the distance between the arrows in Figure 17 is defined as the distance d between the electrode mixture layer and the resin insulation layer.
When the resin insulating layer overlaps the electrode mixture layer (for example, the lower left and lower right diagrams in FIG. 13), a negative value is indicated.

In the electrode laminate, the ratio (B/A) of the average thickness B of the resin insulating layer to the average thickness A of the electrode composite layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.97 or more and 1.03 or less, and more preferably 0.98 or more and 1.02 or less.
The average thickness A of the electrode mixture layer and the average thickness B of the resin insulating layer can be determined by measuring the thickness at any three or more points and calculating the average.
The relationship between the average thickness A of the electrode mixture layer and the average thickness B of the resin insulating layer before and after pressing may be A<B, A=B, or A<B, as shown diagrammatically in FIG. 14 , and any of these may be appropriately selected, but it is preferable that A=B or A<B.

The compression ratio of the resin insulating layer after pressing at 500 MPa for 5 minutes is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1% or more and 50% or less, and more preferably 5% or more and 20% or less.
When the compression ratio is 50% or less, the shape of the resin insulation layer can be sufficiently maintained when the pressing step is performed from the viewpoint of the strength of the resin insulation layer, and when the compression ratio is 1% or more, the pressure applied from the resin insulation layer to the solid electrolyte layer can be mitigated in the pressing step after the formation of the solid electrolyte layer.

When the resin insulation layer is a porous resin or has a co-continuous structure, the thickness of the resin insulation layer can be easily and precisely controlled by pressing when the thickness of the electrode mixture layer and the thickness of the resin insulation layer are to be approximately equal. In addition, the thickness of the resin insulation layer can be easily controlled by forming the resin insulation layer by coating and polymerization induced phase separation, as described later. If the resin insulation layer is a porous resin layer having a co-continuous structure, it is possible to efficiently release the pressure generated during pressing, thereby suppressing the occurrence of defects such as destruction of the resin layer and unevenness in height, and a high-quality resin layer can be obtained.
In electrochemical elements where a short circuit due to dendrite precipitation may occur, the negative electrode composite layer is generally larger than the positive electrode composite layer. In this case, if the positive electrode current collector and the negative electrode current collector are approximately the same size, a surplus portion where the positive electrode composite layer is not formed is generated in the region where the negative electrode composite layer of the negative electrode faces on the positive electrode current collector. From the viewpoint of electrical element characteristics, the resin insulating layer is preferably provided on the surplus portion of the positive electrode, that is, on the outer periphery of the positive electrode composite layer. Note that, if the negative electrode composite layer is configured to be smaller than the positive electrode composite layer when the electrochemical element is formed, the resin insulating layer is preferably provided on the surplus portion of the negative electrode, that is, on the outer periphery of the negative electrode composite layer.

The average thickness of the resin insulating layer is not particularly limited and can be appropriately selected depending on various conditions such as the average thickness of the electrode mixture layer, but is preferably 1.0 μm to 150.0 μm, more preferably 10.0 μm to 100.0 μm. By setting the average thickness to 10.0 μm or more, it is possible to distribute the pressure load and prevent short-circuiting between the positive electrode and the negative electrode, and by setting the average thickness to 100.0 μm or less, it is possible to manufacture an electrochemical element with high density and excellent battery characteristics.
The average thickness can be determined by measuring the thickness at any three or more points and calculating the average.

<Solid electrolyte layer>
As the solid electrolyte of the solid electrolyte layer, any of the materials described as the solid electrolyte of the electrode mixture layer can be appropriately selected and used.
Due to the advantage that the electrode or the electrode laminate has a resin insulating layer that can suppress a decrease in ionic conductivity of the sulfide solid electrolyte, the solid electrolyte layer is preferably a sulfide solid electrolyte layer containing a sulfide solid electrolyte.
The solid electrolyte layer may contain a binder. Examples of the binder include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, styrene butadiene rubber, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, and polybutylene terephthalate, polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), isoprene rubber, polyisobutene, polyethylene glycol (PEO), and polyethylene vinyl acetate (PEVA).

(Electrode manufacturing method and electrode manufacturing device)
The method for producing an electrode of the present invention includes an application step, a polymerization step, and an electrode mixture layer forming step, and further includes other steps as necessary.
The electrode manufacturing apparatus of the present invention comprises a container, an application means, a polymerization means, and an electrode mixture layer forming means, and further comprises other means as necessary.

(Method of manufacturing electrode laminate and device of manufacturing electrode laminate)
The method for producing an electrode laminate of the present invention includes an application step, a polymerization step, an electrode mixture layer forming step, a pressing step, and a solid electrolyte layer forming step, and further includes other steps as necessary.
The electrode laminate manufacturing apparatus of the present invention has a container, an application means, a polymerization means, an electrode mixture layer forming means, a pressing means, and a solid electrolyte layer forming means, and further has other means as necessary.

[Resin insulation layer forming step and resin insulation layer forming means]
Here, the method for forming the resin insulating layer in the electrode laminate includes at least an application step and a polymerization step.
That is, the method for forming the resin insulation layer includes an application step of applying a liquid composition containing a polymerizable compound and a liquid to the outer periphery of an electrode substrate, and a polymerization step of applying heat or light to the liquid composition to polymerize it to form a resin insulation layer, and further includes other steps as necessary.
The means for forming the resin insulation layer includes a container that contains a liquid composition containing a polymerizable compound and a liquid, an application means for applying the liquid composition to the outer periphery of the electrode substrate, and a polymerization means for applying heat or light to the liquid composition to polymerize it to form a resin insulation layer, and further includes other means as necessary.

[Order of forming resin insulating layer and electrode mixture layer]
The order of forming the resin insulating layer and the electrode mixture layer is not particularly limited and may be appropriately selected depending on the purpose.
The electrode mixture layer forming step may be performed before the applying step, and the resin insulating layer may be formed on the outer periphery of the electrode mixture layer after the electrode mixture layer is formed. In this case, the method for producing the electrode laminate is performed in the order of the resin insulating layer forming step (applying step, polymerization step), the electrode mixture layer forming step, the pressing step, and the solid electrolyte layer forming step.
Alternatively, the electrode mixture layer forming step may be performed after the polymerization step, and after the resin insulating layer is formed on the outer periphery of the electrode substrate, the electrode mixture layer may be formed on the inside of the outer periphery of the electrode substrate. In that case, the manufacturing method of the electrode laminate is performed in the order of the electrode mixture layer forming step, the resin insulating layer forming step (application step, polymerization step), the pressing step, and the solid electrolyte layer forming step.

<Application step and application means>
The applying step is a step of applying the liquid composition to the outer periphery of the electrode substrate, and can be suitably carried out by an applying means.
The applying means is a means for applying the liquid composition contained in the container to the outer periphery of the electrode substrate.

The application step and application means are not particularly limited as long as they can apply the liquid composition, and can be appropriately selected depending on the purpose. For example, any printing device can be used according to various printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing. Among these, inkjet printing is preferred. This allows a resin layer to be formed with high precision in the required areas.

<Polymerization process, polymerization means>
The polymerization step is a step in which the liquid composition is polymerized by applying heat or light to form a resin insulating layer, and can be suitably carried out by a polymerization means.
The polymerization means is a means for polymerizing the liquid composition by applying heat or light to the liquid composition to form a resin insulating layer.
The polymerization causes the polymer compound in the liquid composition to polymerize, and a porous resin is formed by polymerization-induced phase separation, making it possible to produce a resin insulating layer on the outer periphery of the electrode substrate.
The polymerization treatment and polymerization section are not particularly limited and can be appropriately selected depending on the purpose, such as the polymerization initiator and polymerization mode to be used. For example, in the case of photopolymerization, ultraviolet light having a wavelength of 365 nm is irradiated for 3 seconds. Examples of the light irradiation treatment and method include a light irradiation treatment and a heating method in the case of thermal polymerization, in which the material is heated in a vacuum at 150° C. for 12 hours.

<Other steps and other means>
Other processes in the laminate manufacturing apparatus are not particularly limited as long as they do not impair the effects of the present invention, and may be appropriately selected depending on the purpose. For example, a removal process may be included.
The other means in the method for producing the laminate are not particularly limited as long as they do not impair the effects of the present invention and can be appropriately selected depending on the purpose. For example, a removal means may be used.

<<Solvent Removal Step, Solvent Removal Means>>
The removing step is a step of removing the solvent from the porous resin obtained by polymerizing the liquid composition through the polymerization treatment, and can be suitably performed by a solvent removing unit.
The solvent removing means is a means for removing the solvent from the porous resin formed by polymerizing the liquid composition in the polymerization section.
The method for removing the solvent is not particularly limited, and examples thereof include a method for removing the solvent from the porous resin by heating. In this case, heating under reduced pressure is preferable because it can further promote the removal of the solvent and suppress the solvent from remaining in the insulating layer to be formed.
The heating may be performed by a stage or by a heating mechanism other than the stage. The heating mechanism may be installed either above or below the substrate, or multiple heating mechanisms may be installed. The heating mechanism is not particularly limited, and examples thereof include a resistance heater, an infrared heater, and a fan heater.
The heating temperature is not particularly limited, but is preferably 70° C. to 150° C. from the viewpoint of energy usage.

<Electrode composite material layer forming process, electrode composite material layer forming means>
The electrode mixture layer forming step is a step of forming an electrode mixture layer on the electrode substrate, and can be suitably carried out by an electrode mixture layer forming means.
The electrode mixture layer forming means is a means for forming an electrode mixture layer on the electrode substrate.
As for the order of carrying out the electrode mixture layer forming step, as described above, it may be carried out before the application step or after the polymerization step.
That is, after forming the electrode mixture layer, the resin insulating layer may be formed on the outer periphery of the electrode mixture layer, or after forming the resin insulating layer on the outer periphery of the electrode base, The electrode mixture layer may be formed on the electrode substrate on the inside of the outer periphery.

The method for forming the electrode mixture layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a method may be used in which a powdered active material, a binder, a conductive material, etc. are dispersed in a liquid, and the resulting dispersion is applied onto an electrode substrate, fixed, and dried.
Examples of the application method include spraying, dispenser, die coater, and pull-up coating.

<Pressing process, pressing means>
The pressing step is a step of pressing the electrode mixture layer and the resin insulating layer, and can be suitably carried out by a pressing means.
The pressing means is a means for pressing the electrode mixture layer and the resin insulating layer.
By performing the pressing, the average thickness of the electrode mixture layer and the average thickness of the resin insulating layer can be made substantially equal. Therefore, even if high pressure is applied when pressing the solid electrolyte layer provided on the electrode, the pressure load can be distributed excellently.
The timing of performing the pressing step is not particularly limited and can be appropriately selected depending on the purpose. For example, the electrode mixture layer and the resin insulating layer may be formed on the electrode base, and then the electrode mixture layer and the resin insulating layer may be pressed. Alternatively, if the thickness of the resin insulating layer before pressing and the thickness of the electrode mixture layer are approximately equal, a solid electrolyte layer may be further provided and then pressing may be performed. Alternatively, both may be performed.

The pressing method is not particularly limited and can be performed using a commercially available pressure molding device, as long as the electrode mixture layer and the resin insulating layer are pressed in the direction of the electrode substrate, and examples of the pressing method include uniaxial pressing, roll pressing, cold isostatic pressing (CIP), hot pressing, etc. Among these, cold isostatic pressing (CIP), which can apply isostatic pressure, is preferred.
The pressing pressure is preferably a pressure capable of compressing the electrode mixture layer while bonding the electrode substrate and the electrode mixture layer together, and is preferably 1 MPa to 900 MPa, more preferably 250 MPa to 700 MPa.

<Solid electrolyte layer forming step, solid electrolyte layer forming means>
The solid electrolyte layer forming step is a step of forming a solid electrolyte layer on the electrode mixture layer and the resin insulating layer, and can be suitably performed by a solid electrolyte layer forming means.
The solid electrolyte layer forming means is a means for forming a solid electrolyte layer on the electrode mixture layer and the resin insulating layer.
The method for forming the solid electrolyte layer is not particularly limited and can be appropriately selected depending on the purpose. For example, a liquid composition containing the solid electrolyte and, if necessary, the binder is mixed with the electrode mixture. The adhesive is applied onto the material layer and the resin insulating layer, solidified and dried.

There are no particular limitations on the coating method, and examples include liquid ejection methods such as the inkjet method, spray coating method, and dispenser method, 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, and reverse printing method.

[Embodiments in which a resin insulating layer or an electrode laminate is formed by directly applying a liquid composition to a substrate]
FIG. 7 is a schematic diagram showing an example of a resin insulating layer manufacturing apparatus (liquid ejection apparatus) for implementing the manufacturing method of the electrode laminate of this embodiment.
The resin insulation layer manufacturing apparatus 500 is an apparatus for manufacturing a resin insulation layer using the above-mentioned liquid composition. The resin insulation layer manufacturing apparatus includes a printing section 100 that performs an application process of applying a liquid composition onto a printing substrate 4 to form a liquid composition layer, a polymerization section 200 that performs a polymerization process of applying heat or light to the liquid composition layer to polymerize it, and a heating section 300 that performs a heat process of heating a porous resin precursor 6 and removing the solvent in the pores to obtain a porous resin. The resin insulation layer manufacturing apparatus includes a conveying section 5 that conveys the printing substrate 4, and the conveying section 5 conveys the printing substrate 4 at a preset speed in the order of the printing section 100, the polymerization section 200, and the heating section 300.
The printing substrate 4 may be a substrate in which an electrode mixture layer is provided on an electrode substrate. Alternatively, the printing substrate 4 may be an electrode substrate that does not have an electrode mixture layer, in which case the electrode mixture layer is provided after the formation of the resin insulating layer.

--Printing unit 100--
The printing unit 100 includes a printing device 1a, which is an example of an application means for realizing an application process of applying a liquid composition for forming a resin insulation layer on the printing substrate 4, a storage container 1b for storing the liquid composition, and a supply tube 1c for supplying the liquid composition stored in the storage container 1b to the printing device 1a.
The storage container 1b stores the liquid composition 7, and the printing unit 100 ejects the liquid composition 7 from the printing device 1a and applies the liquid composition 7 onto the printing substrate 4 to form a thin film of the liquid composition layer. The storage container 1b may be integrated with the resin insulation layer manufacturing apparatus, or may be removable from the resin insulation layer manufacturing apparatus. Alternatively, the storage container 1b may be a container used for adding to a storage container integrated with the resin insulation layer manufacturing apparatus or a storage container removable from the resin insulation layer manufacturing apparatus.
The container 1b and the supply tube 1c may be selected arbitrarily as long as they can stably store and supply the liquid composition 7. The materials constituting the container 1b and the supply tube 1c preferably have a light-shielding property in the relatively short wavelength region of ultraviolet and visible light. This prevents the liquid composition 7 from being polymerized by external light.

--Polymerization section 200--
As shown in FIG. 7, in the case of photopolymerization, the polymerization unit 200 has a light irradiation device 2a, which is an example of a polymerization means for carrying out a polymerization step, and a polymerization inert gas circulation device 2b for circulating a polymerization inert gas. The light irradiation device 2a irradiates the liquid composition layer formed by the printing unit 100 with light in the presence of the polymerization inert gas, and photopolymerizes the liquid composition to obtain a porous resin precursor 6.
The light irradiation device 2a is appropriately selected according to the absorption wavelength of the photopolymerization initiator contained in the liquid composition layer, and is not particularly limited as long as it can initiate and advance the polymerization of the compound in the liquid composition layer, and 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 light with a shorter wavelength generally tends to reach deeper parts, it is preferable to select a light source according to the thickness of the porous film to be formed.
Next, regarding the irradiation intensity of the light source of the light irradiation device 2a, if the irradiation intensity is too strong, polymerization will proceed rapidly before phase separation occurs sufficiently, so that it is difficult to obtain a porous structure. If the irradiation intensity is too weak, phase separation will proceed to a microscale or greater, and porosity variations and coarsening will occur easily. In addition, the irradiation time will be longer, and productivity will tend to decrease. Therefore, the irradiation intensity is preferably 10 mW/cm ² or more and 1 W/cm ² or less, and more preferably 30 mW/cm ² or more and 300 mW/cm ² or less.

The polymerization inert gas circulation device 2b plays a role of lowering the concentration of polymerization active oxygen contained in the atmosphere and allowing the polymerization reaction of the polymerizable compound near the surface of the liquid composition layer to proceed without being hindered. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above-mentioned functions, and examples thereof include nitrogen, carbon dioxide, and argon.
The _O2 concentration of the polymerization inert gas is preferably less than 20% (an environment with a lower oxygen concentration than the atmosphere) in consideration of the effective inhibition reduction effect, more preferably 0% to 15%, and even more preferably 0% to 5%. In addition, the polymerization inert gas circulation device 2b is preferably provided with a temperature control means capable of controlling the temperature in order to realize stable polymerization progress conditions.

In the case of thermal polymerization, the polymerization section 200 may be a heating device. The heating device is not particularly limited and may be appropriately selected depending on the purpose. Examples of the heating device include a substrate heater (e.g., a hot plate), an IR heater, and a hot air heater, and these may be combined.
The heating temperature, time, and light irradiation conditions can be appropriately selected depending on the polymerizable compound contained in the liquid composition 7 and the thickness of the formed film.

--Removal Unit 300--
7, the removal section 300 has a heating device 3a, and performs a solvent removal step in which the porous resin precursor 6 formed in the polymerization section 200 is heated by the heating device 3a to dry and remove the remaining solvent. This makes it possible to form a porous resin. The removal section 300 may perform the solvent removal under reduced pressure.
The removal section 300 also carries out a polymerization promotion step of heating the porous resin precursor 6 with the heating device 3a to further promote the polymerization reaction carried out in the polymerization section 200, and an initiator removal step of heating, drying and removing the photopolymerization initiator remaining in the porous resin precursor 6 with the heating device 3a. Note that the polymerization promotion step and the initiator removal step may be carried out before or after the solvent removal step, rather than simultaneously with the solvent removal step.
Furthermore, the removal unit 300 performs a polymerization completion step of heating the porous material under reduced pressure after the solvent removal step. The heating device 3a is not particularly limited as long as it satisfies the above-mentioned functions, and examples thereof include an IR heater and a hot air heater.
The heating temperature and time can be appropriately selected depending on the boiling point of the solvent contained in the porous resin precursor 6 and the thickness of the formed film.

FIG. 8 is a schematic diagram showing another example of a resin insulating layer manufacturing apparatus (liquid ejection apparatus) for implementing the manufacturing method of the electrode laminate of this embodiment.
The liquid ejection device 300 ′ is capable of circulating the liquid composition through the liquid ejection head 306 , the tank 307 , and the tube 308 by controlling the pump 310 and the valves 311 and 312 .
In addition, the liquid ejection device 300' is provided with an external tank 313, and when the liquid composition in the 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 and the valves 311, 312, and 314.
By using the above-mentioned resin insulating layer manufacturing apparatus, the liquid composition can be discharged to a targeted location on an object to which the composition is to be applied.

Another example of the method for producing the resin insulating layer of this embodiment is shown in FIG.
The method for producing the electrode 210 having a porous resin provided on a substrate includes a step of sequentially discharging the liquid composition 12A onto the substrate 211 using a liquid discharger 300'.
First, an elongated substrate 211 is prepared. Then, the substrate 211 is wound around a cylindrical core, and set on a feed roller 304 and a take-up roller 305 so that the side on which the porous resin 212 is formed is the upper side in Fig. 9. Here, the feed roller 304 and the take-up roller 305 rotate counterclockwise, and the substrate 211 is transported from right to left in Fig. 9. Then, droplets of the liquid composition 12A are ejected from a liquid ejection head 306 installed above the substrate 211 between the feed roller 304 and the take-up roller 305, in the same manner as in Fig. 8, onto the substrate 211 which is being transported successively.
A plurality of liquid ejection heads 306 may be installed in a direction substantially parallel to or substantially perpendicular to the transport direction of the substrate 211. Next, the substrate 211 onto which the droplets of the liquid composition 12A have been ejected is transported to a polymerization section 309 by a delivery roller 304 and a take-up roller 305. As a result, a porous resin 212 is formed, and an electrode 210 having a porous resin provided on the substrate is obtained. Thereafter, the electrode 210 having the polymer electrolyte provided thereon is cut to a desired size by punching or the like.
The overlapping portion 309 may be provided either above or below the base material 211, or a plurality of overlapping portions may be provided.
The polymerization section 309 is not particularly limited as long as it does not come into direct contact with the liquid composition 12A, and examples of the polymerization section 309 include a resistance heater, an infrared heater, a fan heater, etc. in the case of thermal polymerization, and an ultraviolet ray irradiation device, etc. in the case of photopolymerization. A plurality of polymerization sections 309 may be provided.

The conditions for heating or light irradiation are not particularly limited and can be appropriately selected depending on the purpose. The liquid composition 12A is polymerized by polymerization to form a porous resin.
As shown in FIG. 10, the tank 307A may be supplied with the liquid composition from a tank 313A connected to the tank 307A, and the liquid ejection head 306 may have a plurality of liquid ejection heads 306A and 306B.

[Embodiments in which a resin insulating layer or an electrode laminate is formed by indirectly applying a liquid composition to a substrate]
Figures 11 and 12 are configuration diagrams showing an example of a printing unit that employs an inkjet method and a transfer method as an application method in a manufacturing apparatus for a resin insulation layer of this embodiment, where FIG. 11 is a configuration diagram showing a printing unit that uses a drum-shaped intermediate transfer body, and FIG. 12 is a configuration diagram showing a printing unit that uses an endless belt-shaped intermediate transfer body.
The printing unit 400 ′ shown in FIG. 11 is an inkjet printer that transfers a liquid composition or a porous resin to a substrate via an intermediate transfer body 4001 to form a porous resin on the substrate.

The printing section 400 ′ includes an inkjet section 420 , a transfer drum 4000 , a pre-treatment unit 4002 , an absorbing unit 4003 , a heating unit 4004 and a cleaning unit 4005 .
The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The heads 101 eject a liquid composition onto an intermediate transfer body 4001 supported by a transfer drum 4000, and form a liquid composition layer 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 a substrate of the maximum size that can be used. The head 101 has a nozzle surface on its lower surface on which nozzles are formed, and the nozzle surface faces the surface of the intermediate transfer body 4001 via a minute gap. In the case of this embodiment, the intermediate transfer body 4001 is configured to circulate on a circular orbit, so the plurality of heads 101 are arranged radially.

The transfer drum 4000 faces the pressure cylinder 621 and forms a transfer nip. The pretreatment unit 4002 applies, for example, a reaction liquid for increasing the viscosity of the liquid composition onto the intermediate transfer body 4001 before the liquid composition is discharged by the head 101. The absorption unit 4003 absorbs liquid components from the liquid composition layer on the intermediate transfer body 4001 before transfer. The heating unit 4004 heats the liquid composition layer on the intermediate transfer body 4001 before transfer. By heating the liquid composition layer, the liquid composition is thermally polymerized to form a porous resin. In addition, the solvent is removed, improving the transferability to the substrate. The cleaning unit 4005 cleans the intermediate transfer body 4001 after transfer and removes foreign matter such as ink and dust remaining on the intermediate transfer body 4001.
The outer peripheral surface of the pressure drum 621 is in pressure contact with the intermediate transfer body 4001, and the porous resin on the intermediate transfer body 4001 is transferred to the substrate when the substrate passes through a transfer nip between the pressure drum 621 and the intermediate transfer body 4001. The pressure drum 621 may be configured to have at least one gripping mechanism for holding the leading end of the substrate on its outer peripheral surface.

The printing unit 400 ″ shown in FIG. 12 is an inkjet printer that transfers a liquid composition or a porous resin onto a substrate via an intermediate transfer belt 4006 to form a porous resin on the substrate.
The printing unit 400'' ejects droplets of the liquid composition from a plurality of heads 101 provided in the inkjet unit 420 to form a liquid composition layer on the outer circumferential surface of the intermediate transfer belt 4006. The liquid composition layer formed on the intermediate transfer belt 4006 is heated by a heating unit 4007 and thermally polymerized to form a porous resin, which is then turned into a film on the intermediate transfer belt 4006.

The porous resin film on the intermediate transfer belt 4006 is transferred to the substrate in the transfer nip where the intermediate transfer belt 4006 faces the transfer roller 622. The surface of the intermediate transfer belt 4006 after transfer is cleaned by a cleaning roller 4008.
The intermediate transfer belt 4006 is stretched over a drive roller 4009a, an opposing roller 4009b, a plurality of (four in this example) shape maintaining rollers 4009c, 4009d, 4009e, and 4009f, and a plurality of (four in this example) support rollers 4009g, and moves in the direction of the arrow in the figure. The support roller 4009g, which is provided opposite the head 101, maintains the tension state of the intermediate transfer belt 4006 when ink droplets are ejected from the head 101.

(Electrochemical element)
The electrochemical device of the present invention is an electrochemical device having the above-mentioned electrode laminate of the present invention and further having an outer casing. The electrochemical device is an all-solid-state battery having a solid electrolyte layer.
The exterior packaging is not particularly limited as long as it can seal the electrode laminate, and any known exterior packaging can be appropriately selected depending on the purpose.

FIG. 15 shows an example of an all-solid-state battery which is an electrochemical device of the present invention.
15, a positive electrode 20 and a negative electrode 40 are laminated with a solid electrolyte 30 interposed therebetween. Here, the positive electrode 20 is laminated on both sides of the negative electrode 40.
Further, a lead wire 50 is connected to the positive electrode substrate 21 , and a lead wire 51 is connected to the negative electrode substrate 41 .
There is no particular limit to the number of stacked positive electrodes 20 and negative electrodes 40. The number of positive electrodes 20 and the number of negative electrodes 40 may be the same or different.
The lead wires 50 and 51 are led out to the outside of the exterior 60 .
The shape of the electrochemical element is not particularly limited, and examples thereof include a laminate type, a cylinder type, and a coin type.

(Method of manufacturing electrochemical device and apparatus for manufacturing electrochemical device)
The method for manufacturing an electrochemical element of the present invention includes an electrode manufacturing step of manufacturing an electrode laminate by the above-mentioned method for manufacturing an electrode laminate of the present invention, and an element fabrication step of manufacturing an electrochemical element using the electrode laminate, and may further include other steps as necessary.
The electrochemical element manufacturing apparatus of the present invention has an electrode manufacturing section that manufactures an electrode laminate using the above-mentioned electrode laminate manufacturing apparatus of the present invention, and an element production section that manufactures an electrochemical element using the electrode laminate, and may further have other means as necessary.

<Electrode manufacturing process and electrode manufacturing department>
The electrode manufacturing process includes the application process, polymerization process, electrode mixture layer forming process, pressing process, and solid electrolyte layer forming process, which are explained in the above-mentioned manufacturing method of the electrode laminate of the present invention, and further includes other means such as an electrode processing process, as necessary.
The electrode manufacturing section has a container, an application means, a polymerization means, an electrode mixture layer forming means, a pressing means, and a solid electrolyte layer forming means, all of which are described in the electrode laminate manufacturing apparatus of the present invention, and further has other means, such as an electrode processing means, as necessary.
The electrode manufacturing process and the electrode manufacturing unit can manufacture an electrode laminate having an electrode substrate, an electrode mixture layer on the electrode substrate, a resin insulation layer on the outer periphery of the electrode mixture layer, and a solid electrolyte layer on the electrode mixture layer and the resin insulation layer.

<Device Formation Step and Device Formation Division>
The device fabrication step is a step of manufacturing an electrochemical device using the electrode laminate.
The device production section is a means for producing an electrochemical device using the electrode laminate.
The method for producing an electrochemical element using the electrode laminate is not particularly limited, and a publicly known method for producing an electrochemical element can be appropriately selected depending on the purpose. For example, a method for producing an energy storage element can be mentioned in which at least one of the following steps is performed: providing a counter electrode, winding or stacking, and housing in a container.
The element fabrication step does not need to include all steps of element fabrication, and may include only a part of the steps.

<Electrode processing step and electrode processing section>
The electrode processing unit is a means for processing the electrode laminate on which the resin layer is formed downstream of the application unit. The electrode processing unit may perform at least one of cutting, folding, and lamination. The laminated electrode processing unit can, for example, cut the laminated electrode on which the resin layer is formed to prepare a laminate of the laminated electrodes. The electrode processing unit can wind or stack the laminated electrode on which the resin layer is formed.
The electrode processing section has, for example, an electrode processing device, and cuts, folds, stacks, or winds the laminated electrode on which the porous resin layer is formed, according to the desired battery form.
The electrode processing step performed by the electrode processing unit is, for example, a step of processing a laminated electrode on which a resin layer has been formed downstream of the application step. The electrode processing step may include at least one of a cutting step, a folding step, and a bonding step.

<Applications of electrochemical elements>
The uses of the electrochemical element are not particularly limited, and examples thereof include mobile objects such as vehicles, smartphones, notebook computers, pen-input personal computers, mobile personal computers, electronic book players, mobile phones, mobile fax machines, mobile copiers, mobile printers, headphone stereos, video movie machines, liquid crystal televisions, handy cleaners, portable CDs, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power sources, motors, lighting equipment, toys, game devices, clocks, strobes, cameras, and other electric devices. Among these, vehicles and electric devices are particularly preferred.
Examples of the mobile body include ordinary automobiles, large special purpose automobiles, small special purpose automobiles, trucks, large motorcycles, ordinary motorcycles, and the like.

[Mobile object]
19 shows an example of a mobile body equipped with an all-solid-state battery that is an electrochemical element of the present invention. Mobile body 70 is, for example, an electric vehicle. Mobile body 70 includes a motor 71, an electrochemical element 72, and wheels 73 that are an example of a means of transportation. Electrochemical element 72 is the electrochemical element of the present invention described above. Electrochemical element 72 drives motor 71 by supplying power to motor 71. Driven motor 71 can drive wheels 73, and as a result, mobile body 70 can move.
According to the above-mentioned configuration, short-circuiting between the positive and negative electrodes is prevented, and the vehicle is driven by electric power from an electrochemical element having excellent battery characteristics, so that the vehicle can be moved safely and efficiently.
The moving body 70 is not limited to an electric vehicle, but may be a PHEV, HEV, or a locomotive or motorcycle that can run using a diesel engine and an electrochemical element in combination. The moving body may also be a transport robot used in a factory or the like that can run using only an electrochemical element or a combination of an engine and an electrochemical element. The moving body may also be an object that does not move in its entirety, but only a part of it, such as an assembly robot that is arranged on a factory production line and that can operate an arm or the like using only an electrochemical element or a combination of an engine and an electrochemical element.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

<Synthesis of sulfide solid electrolyte>
As the sulfide solid electrolyte, an argyrodite-type sulfide solid electrolyte Li ₆ PS ₅ Cl (LPSC) was synthesized according to the known literature 1, “J. Power Sources. 2018, 396, 33-40”.
The solid electrolyte paint was prepared as follows.
The solvent used was octane (manufactured by Tokyo Chemical Industry Co., Ltd.) The dehydrated solvent was confirmed to have a moisture content of 100 ppm or less using a Karl Fischer moisture concentration meter.
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 (Solspersem ^™ 21000, manufactured by Lubrizol) were added and mixed to obtain a solid electrolyte coating material.

[Evaluation of sulfide solid electrolyte resistance to non-aqueous solvents]
Each non-aqueous solvent shown in Table 1-1 was dried in a glove box under an argon atmosphere with 4A molecular sieves (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) until the moisture value was 5 ppm or less. Next, 1 part by mass of sulfide solid electrolyte Li ₆ PS ₅ Cl was added to 9.0 parts by mass of each non-aqueous solvent, and allowed to stand at room temperature for one week. After standing, the non-aqueous solvent was separated by vacuum filtration and washed with 5 ppm or less dehydrated heptane on a vacuum filter to obtain a cake. The obtained cake was heated and dried at 150 ° C. for 1 hour in a glove box to obtain solvent-treated Li ₆ PS ₅ Cl.

60 mg of the obtained Li ₆ PS ₅ Cl was pressed at 364 MPa with a diameter of 5 mm to prepare a pellet, and the ionic conductivity was measured with a Solatoron analytical 1400 (manufactured by Solatoron analytical Co., Ltd.).
When the sulfide solid electrolyte was measured without being immersed in a solvent, the ionic conductivity was 2.40 S/m. When the ionic conductivity decreased by one digit or more, it was judged that practical use was difficult and was judged as "X". Otherwise, it was judged that there was no problem in practical use and was judged as "O".
The measured ionic conductivity values and the evaluation results are shown in Table 1-1.

[Calculation of Millikan charge difference]
When each non-aqueous solvent shown in Table 1 was a tertiary alcohol, the difference between the Millikan charge of the hydrogen atom in the hydroxyl group and the Millikan charge of the oxygen atom (ΔMulliken(O-H)) was calculated. When the non-aqueous solvent was a primary or secondary amine, the difference between the Millikan charge of the hydrogen atom in the amino group and the Millikan charge of the nitrogen atom (ΔMulliken(N-H)) was calculated.
When the non-aqueous solvent is a primary amine and there are two hydrogen atoms adjacent to the nitrogen atom, the difference between the average value of the Millikan charges of the two hydrogen atoms and the Millikan charge of the nitrogen atom was taken as the Millikan charge difference (ΔMulliken(N-H)).
As the Millikan charge, the charge amount on the atom obtained by calculation with MOPAC7 (Hamiltonian is AM1) using Winmostar v11.1.2 (manufactured by CrossAbility Co., Ltd.) was used.
The Millikan charge differences are shown in Table 1-1.
The non-aqueous solvents used in Table 1-1 and the names of the manufacturers are shown in Table 1-2.

As a result, it was found that when ΔMulliken is less than 0.520 in the case of a tertiary alcohol solvent, or when ΔMulliken is less than 0.470 in the case of an amine solvent, the ionic conductivity is significantly reduced, and therefore the sulfide solid electrolyte does not have resistance, making it difficult to use in practice.
On the other hand, it was found that when ΔMulliken is 0.520 or more in a tertiary alcohol solvent, and when ΔMulliken is 0.470 or more in an amine solvent, the decrease in ion conductivity is suppressed, and therefore the sulfide solid electrolyte is resistant.

Example 1
<Preparation of resin insulation layer>
<<Preparation of Liquid Composition>>
As shown in Table 2-1, 50 parts by mass of NK Ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a polymerizable compound, 50 parts by mass of tetrahydrolinalool (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a non-aqueous solvent, and a polymerization initiator were mixed to prepare a liquid composition of Example 1. Note that, as the polymerization initiator, 1% by mass (0.5 parts by mass) of 1-benzoylcyclohexanol (manufactured by Tokyo Chemical Industry Co., Ltd.) relative to the total amount of the polymerizable compounds was used.
The polymerizable compounds used and the names of the manufacturers are shown in Table 2-2.

<<Preparation of resin insulation layer for warpage evaluation>>
Each liquid composition was applied to the entire area of one side of an aluminum foil substrate (50 mm x 50 mm, average thickness: 20 μm) using a bar coater. The applied area was then irradiated with ultraviolet light (light source: UV-LED (Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) to cure. Next, the cured product was heated at 120°C for 1 minute using a hot plate to remove the solvent, and a resin insulating layer of Example 1 was obtained.

[Evaluation of Warpage of Resin Insulation Layer]
With one of the four sides of the obtained resin insulation layer placed on a horizontal plane, the maximum height of the warpage among the other sides was measured as the warpage evaluation value, and the warpage was evaluated based on the following evaluation criteria. The results are shown in Table 2-1.
-Evaluation criteria-
A: The warpage evaluation value is 3 mm or less, which is good.
Δ: The warpage evaluation value is more than 3 mm and 5 mm or less, and although there is some warpage, it does not cause any problems in use.
×: The warpage evaluation value is more than 5 mm, and the warpage is large and problematic in use.

(Examples 2 to 23 and Comparative Examples 1 to 4)
Except for changing the formulation in Example 1 to that shown in Table 2-1, the liquid compositions and resin insulating layers of Examples 2 to 23 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, and warpage evaluation was performed. Note that 1% by mass of 1-benzoylcyclohexanol was used as the polymerization initiator relative to the total amount of the polymerizable compounds. The results are shown in Table 2-1.

These results show that the inclusion of a non-aqueous solvent in the liquid composition reduces warping, and that the warping is at a level that does not pose a problem in use or is good. Examples 15 to 17 show that a reduction in the content of the non-aqueous solvent or a reduction in the content of the polymerizable compound increases warping, but it is at a level that does not pose a problem in use. On the other hand, as shown in Comparative Examples 1 to 4, it was found that the absence of a non-aqueous solvent results in a level that poses a problem in use.

(Example 24)
An electrode having a resin insulating layer, an electrode laminate, and an all-solid-state battery as an electrochemical element were produced by the following procedures, and the battery performance was evaluated.

<Surface coating of ion-conductive oxide on active material>
A nickel-based positive electrode active material (lithium nickel cobalt manganese oxide, hereinafter sometimes referred to as "NCM1"; average primary particle size 3.5 μm, manufactured by Toshima Manufacturing Co., Ltd.) was used as the positive electrode active material. LiNbO ₃ was used as the ion conductive oxide for surface-coating the NCM1 particles. The LiNbO ₃ layer was formed by hydrolyzing an alkoxide solution containing lithium and niobium on the surface of the NCM1 powder particles, with reference to the publicly known document 2 "J. Mater. Chem. A. 2021, 9, 4117-4125". First, metallic lithium (manufactured by Honjo Metals Co., Ltd.) was dissolved in anhydrous ethanol (manufactured by Kanto Chemical Co., Ltd.) to prepare an ethanol solution of lithium ethoxide. Furthermore, niobium pentaethoxide (Nb(OC ₂ H ₅ ) ₅ ) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was added to this solution to obtain an alkoxide solution containing lithium and niobium. The NCM1 powder was made into a fluidized bed using a rolling fluidizer (MP-01, manufactured by Powrex Corporation), and the alkoxide solution was sprayed onto the fluidized bed to obtain a precursor powder in which the surfaces of the NCM1 powder particles were coated with alkoxide. This powder was heated at 350°C in a dry air atmosphere to synthesize LNO/NCM1 in which a _LiNbO3 layer was formed on the NCM1 surface.

<Method of producing positive electrode>
<Positive electrode>
A positive electrode coating material was prepared by dispersing 45.3 mass% of LNO/NMC1 as a positive electrode active material, 2.2 mass% of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as a conductive material, 1.4 mass% of polybutyl methacrylate (PBMA, manufactured by Aldrich Chemical Industries, Ltd.) as a binder, and 14.7 mass% of a sulfide solid electrolyte in 36.4 mass% of anisole (manufactured by Tokyo Chemical Industry Co., Ltd.).
This positive electrode paint was applied to one side of an aluminum foil substrate (50 mm x 50 mm, average thickness: 15 μm) as an electrode substrate, and then dried to form a positive electrode composite layer of 20 mm x 20 mm, and a positive electrode having a margin of 15 cm on all four sides of the positive electrode composite layer was obtained. The average thickness of the positive electrode composite layer was 95 μm, and the battery capacity per unit area was 2.91 mAh / cm ² .

<Method of producing negative electrode>
<Negative Electrode>
A lithium metal (manufactured by Honjo Metals Co., Ltd.) having an average thickness of 50 μm was attached to a stainless steel foil substrate (50 mm × 50 mm, average thickness: 20 μm) as an electrode substrate, and then an indium foil (manufactured by Nilaco Corporation) having a thickness of 50 μm was attached to the substrate to form a negative electrode having a size of 25 mm × 25 mm.

<Preparation of electrodes>
The liquid composition of Example 1 was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industry Co., Ltd.) The positive electrode was placed on a stage, and the distance d between the positive electrode composite layer and the resin insulating layer was set to 0.5 mm. The liquid composition was discharged and applied so that the width of the resin insulating layer was 10 mm.
Immediately afterwards, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a nitrogen atmosphere to cure the coating. Next, the cured product was heated at 120° C. for 1 minute using a hot plate to remove the solvent, and the electrode of Example 24 was produced (see FIGS. 1 and 6 ).

At this time, the average thickness of the resin insulating layer was 124 μm, and the warping of the resin insulating layer was 0 mm.
The warpage of the resin insulating layer was measured with one of the four sides of the obtained electrode placed on a horizontal plane, and the maximum height of the warpage of the other sides of the resin insulating layer in the electrode was taken as the warpage evaluation value.

The electrode was sealed with an aluminum laminate, and then pressurized at 500 MPa for 5 minutes using a cold isostatic press (CIP). After pressing, the electrode was removed from the aluminum laminate. A solid electrolyte layer was applied onto the positive electrode by a bar coating method to obtain an electrode laminate of Example 24 (see FIG. 2).
After coating, the laminate was sealed again and pressurized by CIP at 500 MPa for 5 minutes. The electrode and the negative electrode were arranged to face each other to form a single cell layer (see FIG. 3 ). After the electrodes were each provided with a lead wire, the laminate was vacuum sealed to produce an all-solid-state battery as an electrochemical element of Example 24.

The battery voltage of the solid-state battery produced using the procedure below was measured and found to be 2.04 V. The capacity per unit area was 141 mAh/g at the initial discharge capacity. Constant-current charging up to 3.6 V was possible without any problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[Method of measuring capacitance per unit area of electrode]
The capacity per unit area of the electrode was measured using a charge/discharge measuring device (TOSCAT3001, manufactured by Toyo Systems Co., Ltd.) according to the following procedure.
First, the prepared electrode was punched out into a circular shape having a diameter of 10 mm.
Next, the capacity of the electrode containing a sulfide solid electrolyte in the positive electrode was evaluated by the following method.
The positive electrode was punched out in an argon atmosphere to obtain a round electrode having a diameter of 10 mm and a capacity per unit area.
80 mg of solid electrolyte 1 was placed in a polyethylene terephthalate (PET) tube of a bipolar cell (manufactured by Hosen Co., Ltd.), a press pin was placed on it, and the solid electrolyte was molded for 1 minute at a nominal pressure of 10 MPa using a uniaxial press (P-6, manufactured by Riken Seiki Co., Ltd.).
Next, the surface of the positive electrode composite layer of the positive electrode punched to a diameter of 10 mm was placed in contact with the surface of the solid electrolyte in the PET tube, a press pin was set, and molding was performed for 1 minute at a nominal pressure of 30 MPa using a uniaxial press (P-6, manufactured by Riken Seiki Co., Ltd.).
On the opposite side of the pressed positive electrode composite layer, lithium of an average thickness of 50 μm was attached to a 10 μm SUS foil (manufactured by Honjo Metals Co., Ltd.) and indium of an average thickness of 50 μm (manufactured by Nilaco Co., Ltd.) was layered on top of the foil. Then, using a uniaxial press (P-6, manufactured by Riken Seiki Co., Ltd.), molding was performed for 3 seconds at a nominal pressure of 12 MPa. With the press pin placed on it, the PET tube was placed in the bipolar cell and sealed at a nominal pressure of 25 N m with a digital torque ratchet (KTC Tool).
This electrochemical element was initially charged and discharged at a constant current of 3.6 V at room temperature (25° C.) at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and then discharged at a constant current of 2.4 V. This charge and discharge was then carried out twice, and the second discharge capacity was measured as the initial capacity per unit area of the positive electrode.
Similarly, the negative electrode was charged and discharged in the range of −0.55 V to 1.4 V at a current value that was 20% of the capacity per unit area calculated from the theoretical capacity of the negative electrode active material, and the capacity per unit area of the negative electrode was calculated.

(Example 25)
The liquid composition of Example 5 was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industry Co., Ltd.). A positive electrode was placed on a stage, and the distance d between the outer periphery of the positive electrode and the resin insulating layer was set to 0.5 mm. The resin insulating layer was discharged and applied to a width of 10 mm. The average thickness of the resin insulating layer was 113 μm, and the warpage of the resin insulating layer was 0 mm (see FIG. 1 and FIG. 6).
Thereafter, in the same manner as in Example 1, an electrode of Example 25, an electrode laminate, and an all-solid-state battery as an electrochemical element were produced.
The battery voltage of the fabricated all-solid-state battery was measured and found to be 2.09 V. Thereafter, constant-current charging was performed without any problems 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, and no short circuit was observed.

(Example 26)
The liquid composition of Example 11 was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industry Co., Ltd.). The positive electrode was placed on a stage, and the distance d between the positive electrode composite layer and the resin insulating layer was set to 0.5 mm. The resin insulating layer was discharged and applied so that the width of the resin insulating layer was 10 mm. The average thickness of the resin insulating layer was 121 μm, and the warpage of the resin insulating layer was 0 mm (see FIG. 1 and FIG. 6).
Thereafter, in the same manner as in Example 1, an electrode of Example 26, an electrode laminate, and an all-solid-state battery as an electrochemical element were produced.
The battery voltage of the fabricated all-solid-state battery was measured and found to be 2.09 V. Thereafter, constant-current charging was performed without any problems 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, and no short circuit was observed.

(Comparative Example 5)
The liquid composition of Comparative Example 1 was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industry Co., Ltd.). The positive electrode was placed on a stage, and the distance d between the outer periphery of the positive electrode and the resin insulating layer was set to 0.5 mm, and the resin insulating layer was discharged and applied to a width of 10 mm. The average thickness of the resin insulating layer was 112 μm, and the warp of the resin insulating layer was 4 mm.
Thereafter, in the same manner as in Example 1, an electrode of Comparative Example 5, an electrode laminate, and an all-solid-state battery as an electrochemical element were produced.

The battery voltage of the produced all-solid-state battery was measured and found to be 0.11 V, indicating a tendency to short circuit. Thereafter, when the battery was charged to 3.6 V at a constant current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, the battery did not rise to 3.6 V.
After applying pressure, the cell was disassembled and cracks were found in the solid electrolyte layer, which is thought to be the reason why the voltage dropped to around 0V.

For example, aspects of the present invention are as follows.
<1> A polymerizable compound represented by the following general formula (1),
A liquid composition comprising a non-aqueous solvent represented by the following general formula (2):
When A in the general formula (2) is a hydroxyl group, the difference in Millikan charge between a hydrogen atom and an oxygen atom in the hydroxyl group is 0.520 or more;
When A in the general formula (2) is an amino group, the difference in Millikan charge between the hydrogen atom and the nitrogen atom in the amino group is 0.470 or more.
(In the general formula (1), R ¹ represents an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and n represents an integer of 2 to 6.)
(In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, A represents a hydroxyl group or an amino group represented by -NR ⁵ H, and R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.)
<2> The liquid composition according to <1>, wherein ^R2 and ^R3 each independently represent a non-cyclic hydrocarbon group.
<3> A storage container, comprising the liquid composition according to <1> or <2> stored therein.
<4> A resin insulating layer obtained by polymerizing the liquid composition according to <1> or <2>.
<5> An electrode substrate;
an electrode mixture layer on the electrode substrate;
The electrode is characterized by having the resin insulating layer described in <4> on the outer periphery of the electrode mixture layer.
<6> The electrode according to <5>,
The electrode laminate is characterized by having a solid electrolyte layer on the electrode.
<7> An electrochemical device comprising the electrode laminate according to <6>.
<8> A step of applying the liquid composition according to <1> or <2> to an outer periphery of an electrode substrate;
a polymerization step of polymerizing the liquid composition by applying heat or light to form a resin insulating layer;
an electrode mixture layer forming step of forming an electrode mixture layer on the electrode substrate,
The electrode manufacturing method is characterized in that the electrode mixture layer and the resin insulating layer are formed adjacent to each other.
<9> The method for producing an electrode according to <8>, wherein the application is performed by an ink-jet method.
<10> An application step of applying the liquid composition according to <1> or <2> to an outer periphery of an electrode substrate;
a polymerization step of polymerizing the liquid composition by applying heat or light to form a resin insulating layer;
an electrode mixture layer forming step of forming an electrode mixture layer on the electrode substrate;
a pressing step of pressing the electrode mixture layer and the resin insulating layer;
and forming a solid electrolyte layer on the electrode mixture layer and the resin insulating layer,
The electrode mixture layer forming step is carried out before the application step or after the polymerization step,
The method for producing an electrode laminate is characterized in that the electrode mixture layer and the resin insulating layer are formed adjacent to each other.
<11> A container containing the liquid composition according to <1> or <2>,
an application means for applying the liquid composition to an outer periphery of an electrode substrate;
a polymerization means for polymerizing the liquid composition by applying heat or light to the liquid composition to form a resin insulating layer;
an electrode mixture layer forming means for forming an electrode mixture layer on the electrode substrate;
a pressing means for pressing the electrode mixture layer and the resin insulating layer in a direction toward the electrode substrate;
a solid electrolyte layer forming means for forming a solid electrolyte layer on the electrode mixture layer and the resin insulating layer,
The electrode mixture layer and the resin insulating layer are formed adjacent to each other.
<12> An electrode laminate manufacturing process for manufacturing an electrode laminate by the electrode laminate manufacturing process according to <10>;
and producing an electrochemical element using the electrode laminate.
<13> An electrode laminate manufacturing means for manufacturing an electrode laminate by the electrode laminate manufacturing apparatus according to <11>;
and an element forming means for producing an electrochemical element using the electrode laminate.

The liquid composition described in any one of <1> to <2>, the container described in <3>, the resin insulating layer described in <4>, the electrode described in <5>, the electrode laminate described in <6>, the electrochemical element described in <7>, the method for manufacturing an electrode described in any one of <8> to <9>, the method for manufacturing an electrode laminate described in <10>, the manufacturing apparatus for an electrode laminate described in <11>, the method for manufacturing an electrochemical element described in <12>, and the manufacturing apparatus for an electrochemical element described in <13> can solve the above-mentioned problems in the past and achieve the object of the present invention.

1a: Printing device 1b: Ink container 1c: Ink supply tube 2a: Light irradiation device 2b: Polymerizable inert gas circulation device 3a: Heating device 4: Printing substrate 5: Transport section 6: Porous resin precursor (resin insulating layer precursor)
7: Guide member 10: Resin insulating layer 20: First electrode mixture layer 21: First electrode substrate 25: Electrode 35: Electrode laminate 40: Second electrode mixture layer 41: Second electrode substrate 45: Electrochemical element 100: Printing section 200: Polymerization section 300: Removal section 500: Manufacturing device for resin insulating layer d: Distance between resin insulating layer and electrode mixture layer

International Publication No. 2020-022111

Claims (13)

A polymerizable compound represented by the following general formula (1),
A liquid composition comprising a non-aqueous solvent represented by the following general formula (2):
When A in the general formula (2) is a hydroxyl group, the difference in Millikan charge between a hydrogen atom and an oxygen atom in the hydroxyl group is 0.520 or more;
A liquid composition characterized in that, when A in the general formula (2) is an amino group, the difference in Millikan charge between a hydrogen atom and a nitrogen atom in the amino group is 0.470 or more.
(In the general formula (1), R ¹ represents an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and n represents an integer of 2 to 6.)
(In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrocarbon group, the total number of carbon atoms of R ² , R ³ and R ⁴ is 4 or more, A represents a hydroxyl group or an amino group represented by -NR ⁵ H, and R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.) The liquid composition according to claim 1 , wherein R ² and R ³ each independently represent a non-cyclic hydrocarbon group. A container in which the liquid composition according to claim 1 or 2 is contained. A resin insulating layer formed by polymerizing the liquid composition according to claim 1 or 2. An electrode substrate;
an electrode mixture layer on the electrode substrate;
An electrode comprising the resin insulating layer according to claim 4 on an outer periphery of the electrode mixture layer. The electrode according to claim 5 ;
and a solid electrolyte layer on the electrode. An electrochemical element comprising the electrode laminate according to claim 6. An application step of applying the liquid composition according to claim 1 or 2 to an outer periphery of an electrode substrate;
a polymerization step of polymerizing the liquid composition by applying heat or light to form a resin insulating layer;
an electrode mixture layer forming step of forming an electrode mixture layer on the electrode substrate,
The electrode manufacturing method according to the present invention is characterized in that the electrode mixture layer and the resin insulating layer are formed adjacent to each other. The method for manufacturing an electrode according to claim 8, wherein the application is performed by an inkjet method. An application step of applying the liquid composition according to claim 1 or 2 to an outer periphery of an electrode substrate;
a polymerization step of polymerizing the liquid composition by applying heat or light to form a resin insulating layer;
an electrode mixture layer forming step of forming an electrode mixture layer on the electrode substrate;
a pressing step of pressing the electrode mixture layer and the resin insulating layer;
and forming a solid electrolyte layer on the electrode mixture layer and the resin insulating layer,
The electrode mixture layer forming step is carried out before the application step or after the polymerization step,
A method for producing an electrode laminate, characterized in that the electrode mixture layer and the resin insulating layer are formed adjacent to each other. A container containing the liquid composition according to claim 1 or 2;
an application means for applying the liquid composition to an outer periphery of an electrode substrate;
a polymerization means for polymerizing the liquid composition by applying heat or light to the liquid composition to form a resin insulating layer;
an electrode mixture layer forming means for forming an electrode mixture layer on the electrode substrate;
a pressing means for pressing the electrode mixture layer and the resin insulating layer in a direction toward the electrode substrate;
a solid electrolyte layer forming means for forming a solid electrolyte layer on the electrode mixture layer and the resin insulating layer,
An apparatus for manufacturing an electrode laminate, wherein the electrode mixture layer and the resin insulating layer are formed adjacent to each other. An electrode laminate manufacturing process for manufacturing an electrode laminate by the electrode laminate manufacturing process according to claim 10;
and producing an electrochemical element using the electrode laminate. an electrode laminate manufacturing means for manufacturing an electrode laminate by the electrode laminate manufacturing apparatus according to claim 11;
and an element forming means for producing an electrochemical element using the electrode laminate.