JP2023019621A - Electrode material, liquid composition, electrode, electrochemical element, electrode manufacturing method, and electrochemical element manufacturing method - Google Patents

Abstract

[Problem] To provide an electrode material that can obtain a liquid composition with excellent dispersibility and stability while suppressing adverse effects on electrochemical properties [Solution] The electrode material is a polymer having a partial structure in the side chain in which either a monocyclic or polycyclic aryl group, or a monocyclic or polycyclic heteroaryl group is bonded to an alkoxy group via a carbonyl group. [Selected Figure] None

Description

TECHNICAL FIELD The present invention relates to an electrode material, a liquid composition, an electrode, an electrochemical device, a method for producing an electrode, and a method for producing an electrochemical device.

Electrochemical devices such as lithium-ion secondary batteries are mounted on mobile devices, hybrid vehicles, electric vehicles, and the like, and their demand is increasing. In addition, needs for thin batteries to be mounted on various wearable devices and medical patches are increasing, and demands for electrochemical devices are diversifying.

Conventionally, as a method for manufacturing an electrode constituting an electrochemical element, for example, a die coater, a comma coater, a reverse roll coater, or the like is used to apply a liquid composition to form an electrode mixture layer on an electrode substrate. Methods of forming are known. For example, an electrode mixture layer is formed by screen-printing a liquid composition for an electrode mixture layer on an electrode substrate.

However, in order to perform screen printing in a shape that meets needs, it is necessary to prepare a plate for each need. Therefore, a method of forming an electrode mixture layer by ejecting a liquid composition for an electrode mixture layer onto an electrode substrate using a liquid ejection apparatus has been studied (see, for example, Patent Documents 1 and 2). ).

A liquid ejection method is a method of ejecting fine droplets of a liquid composition from ejection holes of a liquid ejection head. A piezoelectric method, a thermal method, a valve method, and the like are known as methods for ejecting liquid droplets from a liquid ejection head. Among them, the piezo method can precisely control the discharge amount of the liquid composition by controlling the voltage, and since it does not heat, it is less affected by the usage environment and has high durability.
A liquid composition that can be ejected by a liquid ejection method generally has a viscosity of several mPa·s to several hundred mPa·s at 25° C. from the viewpoint of storage stability and ejection stability. It should be less than the viscosity of the composition at 25°C. In particular, when using a piezo-type liquid ejection head, it is necessary to adjust the viscosity and surface tension of the liquid composition to appropriate values in order to improve the ejection stability.

An object of the present invention is to provide an electrode material capable of obtaining a liquid composition having excellent dispersibility and stability while suppressing adverse effects on electrochemical properties.

The electrode material of the present invention as a means for solving the above problems comprises a monocyclic or polycyclic aryl group, a monocyclic or polycyclic heteroaryl group, an alkoxy group, and a carbonyl It is a polymer having a partial structure in the side chain that is bonded via a group.

ADVANTAGE OF THE INVENTION According to this invention, the electrode material which can obtain the liquid composition which has the outstanding dispersibility and stability can be provided, suppressing the bad influence on an electrochemical characteristic.

FIG. 1 is a cross-sectional view showing an example of the negative electrode used in the present invention. FIG. 2 is a schematic diagram showing an example of the method for producing the negative electrode used in the present invention. FIG. 3 is a schematic diagram showing another example of the method for producing the negative electrode used in the present invention. FIG. 4 is a schematic diagram showing a modification of the liquid ejection device of FIGS. 2 and 3. FIG. FIG. 5 is a cross-sectional view showing an example of the positive electrode used in the present invention. FIG. 6 is a cross-sectional view showing an example of an electrode element that constitutes the electrochemical element of the present invention. FIG. 7 is a cross-sectional view showing an example of the electrochemical device of the present invention. FIG. 8A is a graph showing an example of the results of evaluation of electrochemical stability in Examples and Comparative Examples. FIG. 8B is a graph showing an example of the results of evaluation of electrochemical stability in Examples and Comparative Examples. FIG. 9 is a graph showing an example of the results of evaluation of electrochemical stability in Examples and Comparative Examples.

(Electrode material)
The electrode material of the present invention has a partial structure in which either a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group and an alkoxy group are bonded via a carbonyl group. is a polymer having in the side chain, and further contains other materials as necessary.

In the prior art, the liquid composition to be ejected by the liquid ejection method includes, for example, an active material, a conductive aid, a binder, a dispersant, a solvent, and the like, which are necessary for stably holding the liquid composition to be ejected. formed from, etc.
However, materials such as dispersants and solvents that are necessary to stably hold the liquid composition are unnecessary materials after the liquid composition is applied to the substrate, and unexpected electrochemical reactions and There is a concern that the deterioration product may adversely affect the characteristics of the element in the electrochemical element.
Moreover, in order to obtain a liquid composition that can be discharged by a liquid discharge method, it is important to improve the degree of freedom in selecting materials such as a dispersion medium from the viewpoint of reducing the environmental load and optimizing the process.
In particular, in recent years, the use of NMP solvent, which is generally used in the production of lithium ion secondary batteries, has been reduced, and alternative materials have been desired.
Furthermore, in recent years, for the purpose of improving the safety of lithium-ion secondary batteries, there has been a demand for an all-solid-state battery that uses a solid electrolyte instead of a flammable electrolytic solution. However, among solid electrolytes, sulfide-based solid electrolytes, which have particularly high ionic conductivity and good properties, have the problem of generating hydrogen sulfide in a protic solvent. It is also known that sulfide-based solid electrolytes are decomposed in highly polar solvents such as NMP. Therefore, when preparing a slurry of a sulfide-based solid electrolyte, it is necessary to use a low-polar aprotic solvent that does not damage the electrolyte.

The present inventors have found a partial structure in which a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group and an alkoxy group are bonded via a carbonyl group. It has been found that by using a polymer having a side chain, it is possible to obtain a liquid composition having excellent dispersibility and stability while suppressing adverse effects on electrochemical properties.

The electrode material is not particularly limited as long as it is a material that has the above structure and is used for the production of electrodes, and can be appropriately selected according to the purpose. preferable.

- Dispersant -
A dispersant is a compound capable of dispersing and stably holding various materials in a liquid composition for ejection. It is preferably used.

-binder-
The binder is not particularly limited as long as it is a compound capable of binding negative electrode materials to each other, positive electrode materials to each other, negative electrode material to a negative electrode substrate, or positive electrode material to a positive electrode substrate. From the viewpoint of suppressing the above, it is preferable that the compound is less likely to increase the viscosity of the liquid composition.

The monocyclic or polycyclic aryl group in the electrode material may be either a condensed polycyclic group or a non-condensed polycyclic group, such as a phenyl group, a naphthyl group, a pyrenyl group, a fluorenyl group, an azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, biphenyl group, terphenyl group and the like.
Examples of the monocyclic or polycyclic heteroaryl group include pyridinyl group, pyrimidinyl group, quinolinyl group, isoquinolinyl group, indolyl group, benzofuranyl group, benzothienyl group, acridinyl group, phenazinyl group and carbazolyl group. is mentioned.

The alkyl group preferably has 1 to 30 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, heptyl group, ethylhexyl group, and octyl. group, decyl group, dodecyl group, 2-butyloctyl group, octadecyl group and the like.

The alkylene glycol ether group is represented by the following general formula (a).
[general formula (a)]
-(RO) _n-
(However, in the general formula (a), R is an alkylene group, and n is an integer of 3 or more.)

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

Examples of the linear alkylene group include methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group and the like.

The branched alkylene group is a group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group. A branched alkylene group includes a methylmethylene group, an ethylmethylene group, a propylmethylene group, a butylmethylene group, a methylethylene group, an ethylethylene group, a propylethylene group, a methylpropylene group, a 2-ethylpropylene group, a dimethylpropylene group, and a methylbutylene group. etc.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group.
Examples of the monocyclic cycloalkylene group include a cyclopentylene group.

The electrode material is preferably a polymer having a structural unit represented by the following general formula (I).

一般式（Ｉ）
ただし、前記一般式（Ｉ）中、Ａｒ^１は、単環式又は多環式のアリール基、及び単環式又は多環式のヘテロアリール基のいずれかを表し、前記アリール基及び前記ヘテロアリール基は置換基を有していてもよく、Ｘ^１及びＸ^２はそれぞれ独立に、炭素原子、酸素原子、窒素原子から選択されるいずれかを表し、Ｘ^１及びＸ^２が炭素原子又は窒素原子の場合、これらはさらに水素又は置換あるいは無置換のアルキル基を有し、Ｒ^１は、それぞれ独立に、水素原子、置換若しくは無置換のアルキル基、又は置換若しくは無置換のシクロアルキル基を表し、Ｙは二価の連結基を表す。

general formula (I)
However, in the general formula (I), Ar ¹ represents either a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group, and the aryl group and the heteroaryl The group may have a substituent, X ¹ and X ² each independently represent any one selected from a carbon atom, an oxygen atom and a nitrogen atom, and X ¹ and X ² are a carbon atom or a nitrogen atom , these further have a hydrogen atom or a substituted or unsubstituted alkyl group, and each R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, Y represents a divalent linking group.

The monocyclic or polycyclic aryl group for Ar ¹ in the general formula (I) may be either a condensed polycyclic group or a non-condensed polycyclic group, such as a phenyl group, a naphthyl group, a pyrenyl group, fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, biphenyl group, terphenyl group and the like.
Examples of monocyclic or polycyclic heteroaryl groups include pyridinyl, pyrimidinyl, quinolinyl, isoquinolinyl, indolyl, benzofuranyl, benzothienyl, acridinyl, phenazinyl, and carbazolyl groups. mentioned.

Substituents in the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are not particularly limited and may be appropriately selected depending on the intended purpose. , a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a cycloalkyl group having 3 to 12 carbon atoms and a phenyl group substituted with an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group, and a carboxyl group etc. These substituents may have a plurality of the same groups introduced therein, or may have a plurality of different groups introduced thereto.

The substituted or unsubstituted alkyl group for R ¹ in the general formula (I) is preferably an alkyl group having 1 to 30 carbon atoms from the viewpoint of availability of raw materials, and an alkyl group having 1 to 18 carbon atoms. is more preferred. In addition, the alkyl group may be either linear or branched.

Examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, heptyl group, ethylhexyl group, octyl group and decyl group. , dodecyl group, 2-butyloctyl group, octadecyl group and the like.

The substituted or unsubstituted cycloalkyl group for R ¹ is preferably a cycloalkyl group having 3 or more and 30 or less carbon atoms, more preferably a cycloalkyl group having 3 or more and 18 or less carbon atoms, from the viewpoint of raw material availability.

The cycloalkyl group may be either monocyclic or polycyclic.

Examples of the cycloalkyl group having 3 to 30 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

The substituent for R ¹ is not particularly limited and can be appropriately selected depending on the intended purpose. and phenyl, hydroxyl and carboxyl groups substituted with alkoxy groups having 1 to 12 carbon atoms. These substituents may have a plurality of the same groups introduced therein, or may have a plurality of different groups introduced thereto.

The Y is a divalent linking group. The divalent linking group is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include an alkylene group.

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

Examples of the linear alkylene group include methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group and the like.

The branched alkylene group is a group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group. A branched alkylene group includes a methylmethylene group, an ethylmethylene group, a propylmethylene group, a butylmethylene group, a methylethylene group, an ethylethylene group, a propylethylene group, a methylpropylene group, a 2-ethylpropylene group, a dimethylpropylene group, and a methylbutylene group. etc.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group.

Examples of the monocyclic cycloalkylene group include a cyclopentylene group.

Examples of the divalent linking group include -R ² -CO-R ³ -, -R ² -COO-R ³ -, -R ² -CONH-R ³ -, -R ² -NHCONH-R ³ - A group represented by and the like can be mentioned. R ² and R ³ each independently have a divalent group selected from the linear alkylene group, branched alkylene group, and cycloalkylene group.

As a method for synthesizing a polymer having a structural unit represented by the above general formula (I), esterification of an aromatic carboxylic acid derivative and an alcohol compound and Friedel-Crafts reaction of an aromatic compound and an acid halide are used. It is obtained by polymerizing the (meth)acrylic monomer synthesized as one component of the polymer.

The weight average molecular weight of the polymer in the electrode material of the present invention is preferably 1,000 or more and 1,000,000 or less, more preferably 1,000 or more and 100,000 or less.

Examples of the polymer having the structural unit represented by formula (I) include the following. The polymer having the structural unit represented by formula (I) is not limited to these. However, n is an integer of 1 or more.

(liquid composition)
The liquid composition of the present invention contains the electrode material, solvent, and active material of the present invention and, if necessary, other components.

<Solvent>
The solvent is not particularly limited as long as it can disperse the active material, and can be appropriately selected depending on the purpose. Examples include water, ethylene glycol, propylene glycol, N-methyl-2-pyrrolidone, and cyclohexanone. , acetate, mesitylene, toluene, xylene, anisole, 2-n-butoxymethanol, 2-dimethylethanol, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, lactate, tetramethylurea, and the like. be done. In particular, when a sulfide-based solid electrolyte is used, an aprotic solvent with low polarity is preferred. These may be used individually by 1 type, and may use 2 or more types together.

<Active material>
As the active material, a positive electrode active material or a negative electrode active material that can be applied to an electrochemical device can be used.

The positive electrode active material is not particularly limited as long as it can reversibly occlude and release alkali metal ions, but an alkali metal-containing transition metal compound can be used.

Examples of the alkali metal-containing transition metal compound include lithium-containing transition metal compounds such as composite oxides containing one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron and vanadium and lithium. is mentioned.

Examples of the lithium-containing transition metal compound include lithium cobaltate, lithium nickelate, and lithium manganate.

As the alkali metal-containing transition metal compound, a polyanionic compound having an XO ₄ 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 preferable in terms of cycle characteristics, and lithium vanadium phosphate in terms of lithium diffusion coefficient and input/output characteristics of electrochemical devices. is particularly preferred.

From the viewpoint of electron conductivity, it is preferable that the surface of the polyanionic compound is coated with a conductive agent such as a carbon material to form a composite.

The negative electrode active material is not particularly limited as long as it can reversibly occlude and release alkali metal ions, but carbon materials containing graphite having a graphite-type crystal structure can be used.

Examples of the carbon material include natural graphite, artificial graphite, non-graphitizable carbon (hard carbon), and easily graphitizable carbon (soft carbon).

Examples of the negative electrode active material other than the carbon material include lithium titanate and titanium oxide.

From the viewpoint of the energy density of the electrochemical device, it is preferable to use, for example, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxides, silicon nitrides, and tin oxides as the negative electrode active materials.

Note that when the active material contains lithium, the solvent is preferably a non-aqueous solvent. In this case, the content of water in the liquid composition is preferably 5% by mass or less, more preferably 1% by mass or less. When the water content in the liquid composition is 5% by mass or less, the lithium contained in the active material reacts with water to form a compound such as lithium carbonate, which reduces the discharge capacity of the electrochemical device. can be suppressed. In addition, it is possible to suppress the generation of gas due to decomposition of compounds such as lithium carbonate during charging and discharging of the electrochemical device.

The mode diameter of the active material is preferably 3 μm or less, more preferably 1 μm or less. When the mode diameter of the active material is 3 μm or less, the ejection stability and storage stability of the liquid composition are improved.

The cumulative 10% volume particle diameter (D ₁₀ ) of the active material is preferably 0.1 µm or more, more preferably 0.15 µm or more. When the _D10 of the active material is 0.1 μm or more, the storage stability of the liquid composition is improved.

The content of the active material in the liquid composition is preferably 10% by mass or more, more preferably 15% by mass or more. When the content of the active material in the liquid composition is 10% by mass or more, the number of times of printing required to form an electrode mixture layer with a predetermined basis weight is reduced.

<Other ingredients>
Examples of the other components include binders other than the electrode materials, conductive aids, insulating materials, electrolyte materials, and the like.

- Binders other than the above electrode materials -
As the binder other than the above electrode materials, a solvent-soluble polymer compound, a solvent-dispersed polymer compound, a monomer compound, or the like can be used. After applying a liquid composition containing a monomer compound by an inkjet method, the monomer compound is polymerized. The monomer compound preferably contains, for example, one or more molecules having a polymerizable site, and can bind the electrode materials together and the electrode material and the electrode substrate by progressing polymerization at 25°C.

The polymer compound that dissolves in the solvent may have a viscosity below that for inkjet printing after dissolution.
The polymer compound is not particularly limited as long as it has a viscosity equal to or lower than the above viscosity and can be appropriately selected depending on the purpose. Examples include polyamide compounds, polyimide compounds, polyamideimide compounds, ethylene- Propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), isoprene rubber, polyethylene glycol (PEO), and the like. These may be used individually by 1 type, and may use 2 or more types together.

In order not to increase the viscosity of the liquid composition, polymer particles may be used as a binder. In this case, the average particle diameter of the polymer particles should be smaller than the nozzle diameter of the inkjet head, and is preferably 0.01 μm or more and 1 μm or less.
Materials constituting the polymer particles include, for example, polyvinylidene fluoride, acrylic resin, styrene-butadiene copolymer, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, and polybutylene terephthalate. etc. These may be used individually by 1 type, and may use 2 or more types together.

- Conductive agent -
Examples of the conductive aid that can be used include carbon materials such as conductive carbon black, carbon nanofibers, carbon nanotubes, graphene, and graphite particles.
Here, the conductive aid may be compounded with the active material as described above.

Conductive carbon black can be produced by, for example, a furnace method, an acetylene method, a gasification method, or the like.

As the conductive aid other than the carbon material, for example, metal particles such as aluminum, and metal fibers can be used.

The mass ratio of the conductive aid 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 aid to the active material is 10% by mass or less, the storage stability of the liquid composition of the present embodiment is improved.

The viscosity of the liquid composition at 25° C. is preferably 200 mPa·s or less, more preferably 100 mPa·s or less. When the viscosity of the liquid composition at 25° C. is 200 mPa·s or less, the ejection stability of the liquid composition is improved.
The lower limit of the viscosity of the liquid composition at 25° C. is not particularly limited, and is the viscosity of the solvent alone.
The viscosity of the liquid composition can be measured, for example, using a TV25 viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 100 rpm and a temperature of 25°C.

The liquid composition can be produced by dissolving or dispersing a composition containing the electrode material of the present invention and an active material in a solvent.

Here, the liquid composition can be used in the production of electrodes for electrochemical devices.
The electrochemical element is not particularly limited as long as it can store electricity, and examples thereof include batteries and capacitors.

(Method for manufacturing electrode)
The electrode manufacturing method of the present invention includes a step of discharging the liquid composition of the present invention onto an electrode substrate, and further includes other steps as necessary.
It is preferable that the electrode manufacturing method further include a step of pressurizing the electrode substrate onto which the liquid composition has been discharged. This makes it difficult for the components constituting the electrode mixture layer to come off, improving the reliability of the electrochemical device.

The material constituting the electrode substrate (current collector) is not particularly limited as long as it has conductivity and is stable with respect to the applied potential.

<Negative Electrode>
FIG. 1 shows an example of the negative electrode used in the present invention.
The negative electrode 10 has a negative electrode mixture layer 12 formed on one side of a negative electrode substrate 11 and containing a negative electrode active material and the electrode material of the present invention.
The negative electrode mixture layer 12 may be formed on both surfaces of the negative electrode substrate 11 .

The shape of the negative electrode 10 is not particularly limited, and examples thereof include a flat plate shape.

Examples of materials that constitute the negative electrode substrate 11 include stainless steel, nickel, aluminum, and copper.

<Method for manufacturing negative electrode>
FIG. 2 shows an example of the manufacturing method of the negative electrode used in the present invention.

The manufacturing method of the negative electrode 10 includes a step of ejecting the liquid composition 12A onto the negative electrode substrate 11 using the liquid ejection device 300 .
Here, the liquid composition 12A contains the electrode material, negative electrode active material, and solvent of the present invention.

The liquid composition 12A is stored in a tank 307 and is supplied from the tank 307 to the liquid ejection head 306 via a tube 308 .

Further, the liquid ejection device 300 may be provided with a mechanism for capping the nozzles in order to prevent drying when the liquid composition 12A is not ejected from the liquid ejection head 306 .

When manufacturing the negative electrode 10, the negative electrode substrate 11 is placed on a heatable stage 400, droplets of the liquid composition 12A are ejected onto the negative electrode substrate 11, and then heated. At this time, the stage 400 may move, and the liquid ejection head 306 may move.

When heating the liquid composition 12A ejected onto the negative electrode substrate 11, the stage 400 may be used for heating, or a heating mechanism other than the stage 400 may be used for heating.

The heating mechanism is not particularly limited as long as it does not directly contact the liquid composition 12A, and examples thereof include resistance heaters, infrared heaters, and fan heaters. A plurality of heating mechanisms may be installed.

The heating temperature is not particularly limited as long as it can volatilize the solvent, and is preferably in the range of 70° C. to 150° C. from the viewpoint of power consumption.

Moreover, when heating the liquid composition 12A ejected onto the negative electrode substrate 11, it may be irradiated with ultraviolet light.

FIG. 3 shows another example of the manufacturing method of the negative electrode in the present invention.
The manufacturing method of the negative electrode 10 includes a step of ejecting the liquid composition 12A onto the negative electrode substrate 11 using the liquid ejection device 300 .

First, an elongated negative electrode substrate 11 is prepared. Then, the negative electrode substrate 11 is wound around a cylindrical core, and set on the delivery roller 304 and the take-up roller 305 so that the side on which the negative electrode mixture layer 12 is formed faces the upper side in FIG. Here, the feed roller 304 and the take-up roller 305 rotate counterclockwise, and the negative electrode substrate 11 is conveyed from right to left in FIG. Then, liquid droplets of the liquid composition 12A are discharged onto the conveyed negative electrode substrate 11 from the liquid discharge head 306 installed above the negative electrode substrate 11 between the delivery roller 304 and the take-up roller 305 . A droplet of the liquid composition 12A is discharged so as to cover at least a portion of the negative electrode substrate 11 .

A plurality of liquid ejection heads 306 may be installed in a direction substantially parallel or substantially perpendicular to the conveying direction of the negative electrode substrate 11 .

Next, the negative electrode substrate 11 to which the liquid composition 12A has been discharged is transported to the heating mechanism 309 by the delivery roller 304 and the take-up roller 305 . As a result, the solvent contained in the liquid composition 12A on the negative electrode substrate 11 volatilizes, the negative electrode mixture layer 12 is formed, and the negative electrode 10 is obtained. After that, the negative electrode 10 is cut into a desired size by punching or the like.

The heating mechanism 309 is not particularly limited as long as it does not directly contact the liquid composition 12A, and examples thereof include resistance heaters, infrared heaters, and fan heaters.

The heating mechanism 309 may be installed either above or below the negative electrode substrate 11, or may be installed in plurality.

The heating temperature is not particularly limited as long as it can volatilize the solvent, and is preferably in the range of 70° C. to 150° C. from the viewpoint of power consumption.

Moreover, when heating the liquid composition 12A ejected onto the negative electrode substrate 11, it may be irradiated with ultraviolet light.

FIG. 4 shows a modification of the liquid ejection device 300. As shown in FIG.
The liquid ejection device 300 ′ can circulate the liquid composition 12 A through the liquid ejection head 306 , the tank 307 and the tube 308 by controlling the pump 310 and the valves 311 and 312 .

Further, the liquid ejection device 300' is provided with an external tank 313, and when the liquid composition 12A in the tank 307 is reduced, the external tank is It is also possible to supply liquid composition 12A from 313 to tank 307 .

By using the liquid ejection devices 300 and 300', the liquid composition 12A can be ejected onto the negative electrode substrate 11 at a targeted position. In addition, by using the liquid ejecting devices 300 and 300', the upper and lower surfaces of the negative electrode substrate 11 and the negative electrode mixture layer 12, which are in contact with each other, can be bonded together. Furthermore, the thickness of the negative electrode mixture layer 12 can be made uniform by using the liquid ejection devices 300 and 300'.

<Positive electrode>
FIG. 5 shows an example of the positive electrode used in the present invention.
The positive electrode 20 has a positive electrode mixture layer 22 formed on one side of a positive electrode substrate 21 and containing a positive electrode active material and the electrode material of the present invention. Note that the positive electrode mixture layer 22 may be formed on both surfaces of the positive electrode substrate 21 .

The shape of the positive electrode 20 is not particularly limited, and examples thereof include a flat plate shape.

Examples of materials that constitute the positive electrode substrate 21 include stainless steel, aluminum, titanium, and tantalum.

<Manufacturing method of positive electrode>
The manufacturing method of the positive electrode 20 is the same as the manufacturing method of the negative electrode 10 except that the liquid composition is discharged onto the positive electrode substrate 21 .
Here, the liquid composition includes the positive electrode active material, the electrode material of the present invention, and a solvent.

(Manufacturing method of electrochemical device)
The method for producing an electrochemical device of the present invention includes the steps of the method for producing an electrode of the present invention and, if necessary, other steps.

<Electrode element>
FIG. 6 shows an example of an electrode element that constitutes the electrochemical element of the present invention.
The electrode element 40 is formed by stacking the negative electrode 15 and the positive electrode 25 with the separator 30 interposed therebetween. Here, the positive electrode 25 is laminated on both sides of the negative electrode 15 . A lead wire 41 is connected to the negative electrode substrate 11 , and a lead wire 42 is connected to the positive electrode substrate 21 .

The negative electrode 15 is the same as the negative electrode 10 except that the negative electrode mixture layers 12 are formed on both sides of the negative electrode substrate 11 .

The positive electrode 25 is the same as the positive electrode 20 except that the positive electrode mixture layers 22 are formed on both sides of the positive electrode substrate 21 .
The number of layers of the negative electrode 15 and the positive electrode 25 of the electrode element 40 is not particularly limited.

Also, the number of negative electrodes 15 and the number of positive electrodes 25 of the electrode element 40 may be the same or different.

<Separator>
The separator 30 is provided between the negative electrode 15 and the positive electrode 25 in order to prevent a short circuit between the negative electrode 15 and the positive electrode 25 .

Examples of the separator 30 include paper such as kraft paper, vinylon mixed paper, and synthetic pulp mixed paper, cellophane, polyethylene graft membrane, polyolefin nonwoven fabric such as polypropylene melt blown nonwoven fabric, polyamide nonwoven fabric, glass fiber nonwoven fabric, micropore membrane, and the like. .

The size of the separator 30 is not particularly limited as long as it can be used in an electrochemical device.
The separator 30 may have a single layer structure or a laminated structure.
In addition, when using a solid electrolyte, the separator 30 can be omitted.

<Electrochemical element>
FIG. 7 shows a secondary battery as an example of the electrochemical device of the present invention.

In the secondary battery 1 , an electrolyte layer 51 is formed by injecting an electrolyte aqueous solution or a non-aqueous electrolyte into the electrode element 40 , and the electrolyte layer 51 is sealed with an exterior 52 . In the secondary battery 1 , the lead wires 41 and 42 are drawn out of the exterior 52 .

The secondary battery 1 may have other members as needed.
The secondary battery 1 is not particularly limited, and examples thereof include a lithium ion secondary battery.

The shape of the secondary battery 1 is not particularly limited, and examples thereof include a laminate type, a cylinder type in which a sheet electrode and a separator are spirally formed, a cylinder type with an inside-out structure in which a pellet electrode and a separator are combined, and a pellet electrode and a separator. Laminated coin type etc. are mentioned.

<Aqueous electrolyte solution>
Electrolyte salts constituting the aqueous electrolyte solution include, for example, sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, ammonium chloride, zinc chloride, zinc acetate, zinc bromide, zinc iodide, zinc tartrate, zinc perchlorate, and the like. is mentioned.

<Non-aqueous electrolyte>
A solid electrolyte or a non-aqueous electrolyte can be used as the non-aqueous electrolyte.
Here, the non-aqueous electrolytic solution is an electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent.

－Solid electrolyte－
A material for forming a solid electrolyte layer can be used as the non-aqueous electrolyte. The material constituting the solid electrolyte layer is not particularly limited as long as it is a solid substance that has electronic insulation and exhibits ionic conductivity, and can be appropriately selected according to the purpose. Material-based solid electrolytes and oxide-based solid electrolytes are preferable from the viewpoint of having high ionic conductivity.
Examples of the sulfide-based solid electrolyte include Li ₁₀ GeP ₂ S ₁₂ and Li ₆ PS ₅ X (where X is F, Cl, Br, or I) having an aldirodite crystal structure.
Examples of the oxide-based solid electrolyte include LLZ (Li ₇ La ₃ Zr ₂ O ₁₂ ) having a garnet-type crystal structure and LATP (Li _1+x Al _x Ti20 _x (PO ₄ ) ₃ ) having a NASICON-type crystal structure. 0.1≦x≦0.4), LLT (Li _0.33 La _0.55 TiO ₃ ) having a perovskite crystal structure, amorphous LIPON (Li _2.9 PO _3.3 N _0.4 ), etc. is mentioned. These may be used individually by 1 type, and may use 2 or more types together.
Examples of electrolyte materials to be dissolved or dispersed in a liquid to form these solid electrolyte layers include Li ₂ S, P ₂ S ₅ and LiCl, which are precursors of solid electrolytes, and Li ₂ , which is a material of solid electrolytes. Examples include S-PS ₅ series glass and Li ₇ P ₃ S ₁₁ glass ceramics.

A material for forming a gel electrolyte layer can also be used as the electrolyte.
The gel electrolyte is not particularly limited as long as it exhibits ionic conductivity. For example, polymers constituting the network structure of the gel electrolyte include polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, and polyvinyl chloride. , copolymers of vinylidene fluoride and propylene hexafluoride, and polyethylene carbonate.
Moreover, an ionic liquid is mentioned as a solvent molecule hold|maintained at the said gel electrolyte.
Examples of the ionic liquid include methyl-1-propylpyrrolidinium bis(fluorosulfonylimide), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonylimide), 1-methyl-1-propylpiperidinium Bis(fluorosulfonylimide), 1-ethyl-3-methylimidazolium bis(fluorosulfonylimide), 1-methyl-3-propylimidazolium bis(fluorosulfonylimide), N,N-diethyl-N-methyl-N -(2-methoxyethyl)ammonium bis(fluorosulfonyl)imide.
Further, the ionic liquid may be a mixture of a liquid such as tetraglyme, propylene carbonate, fluoroethylene carbonate, ethylene carbonate or diethyl carbonate and a lithium salt.
_The lithium salt is not particularly limited and can _be appropriately selected _depending on the intended purpose. ), lithium trifluoromethosulfonate (LiCF ₃ SO ₃ ), lithium bis(trifluoromethylsulfonyl)imide (LiN(CF ₃ SO ₂ ) ₂ ), lithium bis(pentafluoroethylsulfonyl)imide (LiN(C ₂ F ₅ SO ₂ ) ₂ ) and the like.
In addition, these may be used individually by 1 type, and may use 2 or more types together.
A solution in which the above-mentioned polymer compound and ionic liquid or lithium salt are dissolved may be used as the electrolyte material to be dissolved or dispersed in the liquid to form these gel electrolyte layers. In addition, as an electrolyte material to be dissolved or dispersed in a liquid, a material that is a precursor of a gel electrolyte (for example, polyethylene oxide or polypropylene oxide having acrylate groups at both ends) is combined with an ionic liquid or a solution in which a lithium salt is dissolved. other) may be used.
When these solid electrolytes and gel electrolytes are used, they can be used as a liquid composition together with the active material.

-Non-aqueous solvent-
The non-aqueous solvent is not particularly limited and can be appropriately selected depending on the intended purpose. For example, it is preferable to use an aprotic organic solvent.

As the aprotic organic solvent, for example, a carbonate-based organic solvent such as a chain carbonate or a cyclic carbonate can be used. Among these, chain carbonates are preferred because they have high dissolving power for electrolyte salts.
Also, the aprotic organic solvent preferably has a low viscosity.

Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and the like.

The content of the chain carbonate in the non-aqueous solvent is preferably 50% by mass or more. When the content of the chain carbonate in the non-aqueous solvent is 50% by mass or more, even if the non-aqueous solvent other than the chain carbonate is a cyclic substance with a high dielectric constant (for example, a cyclic carbonate, a cyclic ester), the cyclic Substance content is reduced. Therefore, even if a non-aqueous electrolytic solution with a high concentration of 2 mol/L (M) or more is prepared, the viscosity of the non-aqueous electrolytic solution is low, and the penetration of the non-aqueous electrolytic solution into the electrode and the diffusion of ions are favorable. Become.

Examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC) and vinylene carbonate (VC).

Examples of the non-aqueous solvent other than the carbonate-based organic solvent include ester-based organic solvents such as cyclic esters and chain esters, and ether-based organic solvents such as cyclic ethers and chain ethers.

Examples of the cyclic ester include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, γ-valerolactone and the like.

Examples of the chain ester include alkyl propionate, dialkyl malonate, alkyl acetate (e.g., methyl acetate (MA), ethyl acetate), and alkyl formate (e.g., methyl formate (MF), ethyl formate). etc.

Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane and the like.

Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and the like.

<Electrolyte salt>
The electrolyte salt is not particularly limited as long as it has high ionic conductivity and can be dissolved in a non-aqueous solvent.
The electrolyte salt preferably contains a halogen atom.

Examples of cations constituting the electrolyte salt include lithium ions.

Anions constituting the electrolyte salt include, for example, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ^- and the like.

_The lithium salt is not particularly limited and can _be appropriately selected _depending on the intended purpose. ), lithium trifluoromethosulfonate (LiCF ₃ SO ₃ ), lithium bis(trifluoromethylsulfonyl)imide (LiN(CF ₃ SO ₂ ) ₂ ), lithium bis(pentafluoroethylsulfonyl)imide (LiN(C ₂ F ₅ SO ₂ ) ₂ ) and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, LiPF ₆ is preferable from the point of ionic conductivity, and LiBF ₄ is preferable from the point of stability. These may be used individually by 1 type, and may use 2 or more types together.

The concentration of the electrolyte salt in the non-aqueous electrolyte can be appropriately selected depending on the purpose. When the water-based electrochemical device is a reserve type, it is preferably 2 mol/L or more and 4 mol/L or less.

<Use of electrochemical device>
The use of the electrochemical element is not particularly limited and can be appropriately selected according to the purpose. Printers, headphone stereos, video movies, liquid crystal televisions, handy cleaners, portable CDs, minidiscs, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power sources, motors, lighting equipment, toys, game devices, clocks , strobes, and cameras.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

In the examples below, the particle size distribution of the active material, the viscosity of the liquid composition, and the particle size distribution were measured by the following methods.

<Particle size distribution of active material>
After dispersing the active material in water, the particle size distribution of the active material was measured at a temperature of 25° C. using a laser diffraction particle size distribution analyzer (Mastersizer 3000, manufactured by Malvern).

<Viscosity of liquid composition>
The viscosity of the liquid composition was measured using a TV25 viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 100 rpm and a temperature of 25°C.

<Particle size distribution of liquid composition>
The particle size distribution of the liquid composition was measured at a temperature of 25° C. using a laser diffraction particle size distribution analyzer (Mastersizer 3000, manufactured by Malvern).

(Production example 1 of positive electrode active material)
-Production of positive electrode active material 1-
Vanadium pentoxide, lithium hydroxide, phosphoric acid, sucrose, and water are mixed to form a precipitate, spray-dried with a spray dryer, and then pulverized with a jet mill to obtain lithium vanadium phosphate (Li ₃ V ₂ ( A precursor of PO ₄ ) ₃ ) particles was obtained. Next, the precursor of lithium vanadium phosphate particles was calcined at 900° C. in a nitrogen atmosphere to obtain lithium vanadium phosphate particles having a carbon content of 3 mass %. Next, the lithium vanadium phosphate particles were pulverized with a jet mill so that the cumulative 90% volume particle diameter _D90 was less than 3 μm to obtain positive electrode active material 1. The obtained positive electrode active material 1 had a mode diameter of 0.7 μm.

(Production example 2 of positive electrode active material)
-Production of positive electrode active material 2-
In Production Example 1 of the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, lithium iron _phosphate (Lithium iron phosphate ( A positive electrode active material 2 was obtained in the same manner as in Production Example 1 of the positive electrode active material, except that LiFePO ₄ ) particles (manufactured by Sigma-Aldrich) were pulverized by a jet mill. The obtained positive electrode active material 2 had a mode diameter of 0.6 μm.

(Production example 3 of positive electrode active material)
-Production of positive electrode active material 3-
In Production Example 1 of the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, lithium cobalt _oxide (LiCoO ₂ ) A positive electrode active material 3 was obtained in the same manner as in Production Example 1 of the positive electrode active material, except that particles (manufactured by Sigma-Aldrich) were pulverized by a jet mill. The obtained positive electrode active material 3 had a mode diameter of 0.9 μm.

(Production Example 4 of Positive Electrode Active Material)
-Production of positive electrode active material 4-
In Production Example 1 of the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, lithium nickel _oxide (LiNi _{0.8Co0.15Al0.05O2} ) particles ( _manufactured by Sigma _- Aldrich Co.) were pulverized by a jet mill in the same manner as in Production Example 1 of the positive electrode active material, to obtain a positive electrode active material _. Got 4. The obtained positive electrode active material 4 had a mode diameter of 1.2 μm.

(Production Example 5 of Positive Electrode Active Material)
-Production of positive electrode active material 5-
In Production Example 1 of the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, Ni-Mn-Co was used so that the cumulative 90% volume particle diameter D ₉₀ was less than 3 μm. System (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ) particles (manufactured by Sigma-Aldrich) were pulverized by a jet mill in the same manner as in Production Example 1 of the positive electrode active material, A positive electrode active material 5 was obtained. The obtained positive electrode active material 5 had a mode diameter of 0.9 μm.

(Production example 6 of positive electrode active material)
-Production of positive electrode active material 6-
In Production Example 1 of the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, lithium _manganate (LiMn ₂ O ₄ ) particles (manufactured by Sigma-Aldrich) were pulverized by a jet mill to obtain a positive electrode active material 6 in the same manner as in Production Example 1 of the positive electrode active material. The obtained positive electrode active material 6 had a mode diameter of 1.2 μm.

(Production Example 1 of Negative Electrode Active Material)
-Production of negative electrode active material 1-
In Production Example 1 of _the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, artificial graphite (MT carbon Negative Electrode Active Material 1 was obtained in the same manner as in Production Example 1 of Positive Electrode Active Material, except that the material pulverized by a jet mill was used. The obtained negative electrode active material 1 had a mode diameter of 1.8 μm.

(Production Example 2 of Negative Electrode Active Material)
-Production of negative electrode active material 2-
In Production Example 1 of the positive electrode active material, instead of lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ) particles, lithium _titanate (Li ₄ Ti ₅ O ₁₂ ) particles (manufactured by Sigma-Aldrich) pulverized by a jet mill were used to obtain a negative electrode active material 2 in the same manner as in Production Example 1 of the positive electrode active material. The obtained negative electrode active material 2 had a mode diameter of 0.7 μm.

＜重合体１（実－１）の合成＞
次に、特開２０１６－１９６６２１号公報に記載の方法に準じて、以下のようにして、重合体１（実－１）を合成した。
具体的には、まず、モノマー（Ｍ－１）及びアクリル酸を、メチルエチルケトンを溶媒、ＡＩＢＮを重合開始剤として用いることにより、重合体１（実－１）を得た。ＧＰＣから求めたポリスチレン換算の重量平均分子量は２２，０００であった。

(Example 1)
<Synthesis of Monomer 1 (M-1)>
According to the method described in JP-A-2016-196621, monomer 1 (M-1) was synthesized as follows.
Specifically, first, 2-naphthalenecarboxylic acid 6-hydroxyhexyl ester was obtained from 1,6-hexanediol and 2-naphthalenecarbonyl chloride manufactured by Tokyo Kasei Kogyo.
Then, a monomer (M-1) was obtained by reacting 2-naphthalenecarboxylic acid 6-hydroxyhexyl ester with 2-methacryloyloxyethyl isocyanate.

<Synthesis of Polymer 1 (Real-1)>
Next, according to the method described in JP-A-2016-196621, polymer 1 (actual-1) was synthesized as follows.
Specifically, first, a polymer 1 (Ex-1) was obtained by using a monomer (M-1) and acrylic acid, methyl ethyl ketone as a solvent, and AIBN as a polymerization initiator. The polystyrene equivalent weight average molecular weight determined by GPC was 22,000.

Linear sweep voltammetry to sweep the potential from 3V to 4.6V after cyclic voltammetry (CV) measurement in the range of 0.05V to 4.2V (vs Li/Li+) for the synthesized polymer 1 (actual-1). Electrochemical properties were evaluated by (LSV) measurements.
For the evaluation of electrochemical stability, a triode cell (manufactured by EC Frontier, micro analysis cell VB7) using a working electrode Pt (diameter φ1.6 mm), a counter electrode Pt (diameter φ3 mm), and a reference electrode Li foil was used. , 5% by mass of polymer was added to the electrolytic solution (1.5 M LiBF ₄ in EC/DMC = 1/1). Polymer 1 (Ex-1) was found to be electrochemically stable within the measurement range. The results of CV measurement of Polymer 1 (Ex-1) are shown in FIGS. 8A and 8B.

(Example 2)
<Synthesis of Polymer 2 (Real-2)>
Polymer 2 (Ex-2) was synthesized in the same manner as in Example 1 except that acrylic acid was changed to methyl acrylate in <Synthesis of Polymer 1 (Ex-1)> of Example 1.

Electrochemical properties of Polymer 2 (Ex-2) were evaluated in the same manner as in Example 1. As a result, like Polymer 1 (Example-1), it was found to be electrochemically stable within the measurement range.

(Example 3)
Polymer 3 (Ex-3) was synthesized in the same manner as in Example 1 except that in <Synthesis of Polymer 1 (Ex-1)> of Example 1, acrylic acid was eliminated. n represents repetition.

Electrochemical properties of Polymer 3 (Ex-3) were evaluated in the same manner as in Example 1. As a result, like Polymer 1 (Example-1), it was found to be electrochemically stable within the measurement range.

(Example 4)
Polymer 4 ( Example-4) was synthesized. n represents repetition.

Electrochemical properties of Polymer 4 (Ex-4) were evaluated in the same manner as in Example 1. As a result, like Polymer 1 (Example-1), it was found to be electrochemically stable within the measurement range.

(Comparative Examples 1 to 6)
Comparative compound 1 (ratio -1) to comparative compound 4 (ratio -4) represented by the following formula synthesized by etherification using a naphthol or phenol derivative and oligoethylene glycol as raw materials in the same manner as in Examples 1 to 4 , and comparative compound 5 (ratio -5) and comparative compound 6 (ratio -6) synthesized in the same manner as in Example 1 were evaluated for electrochemical stability. Similarly, in LSV measurement, current values observed at 4.2 V are shown in FIG.
Incidentally, n in Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 represented by the following formula was about 10.

From the results of FIG. 9, almost no current was observed for the compounds 1 to 4 of Examples 1 to 4 at 4.2 V, whereas for the comparative compounds 1 to 6 of Comparative Examples 1 to 6, all of the currents were observed at 4.2 V. An irreversible electrochemical oxidation reaction occurred, which was an unfavorable result for electrochemical device applications.
Therefore, it was found that compounds 1 to 4 of Examples 1 to 4 can be suitably used as dispersants in liquid compositions containing active materials, insulating materials, electrolyte materials, and the like.

(Example 5)
<Preparation of positive electrode forming liquid composition>
93.1% by mass of the positive electrode active material 1, 0.9% by mass of the polymer 1 (actual-1), 3% by mass of carbon black, and 3% by mass of polyamideimide. N-Methylpyrrolidone was added so that the concentration was 35.8% by mass to prepare a positive electrode forming liquid composition.
The obtained positive electrode forming liquid composition had a viscosity at 25° C. of 16 mPa·s, a mode diameter of 0.8 μm, and a cumulative 90% volume particle diameter _D90 of 3.5 μm.

Next, when the particle size distribution of the positive electrode forming liquid composition was measured again 24 hours after the positive electrode forming liquid composition was prepared, no change was observed in the particle size distribution. The composition had good storage stability.

Next, using a liquid discharger (EV2500, manufactured by Ricoh Co., Ltd.), the positive electrode forming liquid composition of Example 5 was discharged onto an aluminum foil as a positive electrode substrate to form a positive electrode. At this time, the positive electrode-forming liquid composition of Example 5 can be continuously discharged, and the positive electrode-forming liquid composition of Example 5 has good discharge stability, and discharge failure does not occur. I didn't. That is, the positive electrode forming liquid composition of Example 5 had good printing efficiency.

(Example 6)
In Example 5, the positive electrode forming liquid composition of Example 6 was prepared in the same manner as in Example 5, except that the polymer 2 (Example-2) was used instead of the polymer 1 (Example-1). made things.
The resulting positive electrode forming liquid composition had a viscosity at 25° C. of 14 mPa·s, a mode diameter of 0.7 μm, and a cumulative 90% volume particle diameter _D90 of 3.1 μm.

Next, when the particle size distribution of the positive electrode forming liquid composition of Example 6 was remeasured 24 hours after the preparation of the positive electrode forming liquid composition, no change was observed in the particle size distribution. The positive electrode-forming liquid composition had good storage stability.

Using a liquid ejection device (EV2500, manufactured by Ricoh Co., Ltd.), the positive electrode forming liquid composition of Example 6 was ejected onto an aluminum foil serving as a positive electrode substrate. At this time, the positive electrode forming liquid composition of Example 6 can be continuously discharged, and the positive electrode forming liquid composition of Example 6 has good discharge stability, and discharge failure does not occur. I didn't. That is, the positive electrode forming liquid composition of Example 6 had good printing efficiency.

一般式（Ｉ）
ただし、前記一般式（Ｉ）中、Ａｒ^１は、単環式又は多環式のアリール基、及び単環式又は多環式のヘテロアリール基のいずれかを表し、前記アリール基及び前記ヘテロアリール基は置換基を有していてもよく、Ｘ^１及びＸ^２はそれぞれ独立に、炭素原子、酸素原子、窒素原子から選択されるいずれかを表し、Ｘ^１及びＸ^２が炭素原子又は窒素原子の場合、これらはさらに水素又は置換あるいは無置換のアルキル基を有し、Ｒ^１は、それぞれ独立に、水素原子、置換若しくは無置換のアルキル基、又は置換若しくは無置換のシクロアルキル基を表し、Ｙは二価の連結基を表す。
＜３＞ 前記一般式（Ｉ）における二価の連結基Ｙが、－Ｒ^２－ＣＯ－Ｒ^３－、－Ｒ^２－ＣＯＯ－Ｒ^３－、－Ｒ^２－ＣＯＮＨ－Ｒ^３－、及び－Ｒ^２－ＮＨＣＯＮＨ－Ｒ^３－の少なくともいずれかである、前記＜２＞に記載の電極材料である。
ただし、Ｒ^２及びＲ^３は、それぞれアルキレン基を表す。
＜４＞ 分散剤及びバインダーの少なくともいずれかである、前記＜１＞から＜３＞のいずれかに記載の電極材料である。
＜５＞ 前記＜１＞から＜４＞のいずれかに記載の電極材料、活物質、及び溶剤を含有することを特徴とする液体組成物である。
＜６＞ 前記活物質の含有量が１０質量％以上である、前記＜５＞に記載の液体組成物である。
＜７＞ 前記活物質が、リチウム含有遷移金属酸化物、リチウム含有遷移金属リン酸化合物、及び炭素材料から選択される少なくとも１種である、前記＜５＞から＜６＞のいずれかに記載の液体組成物である。
＜８＞ 前記活物質がリチウムを含みかつ非含水性である、前記＜５＞から＜７＞のいずれかに記載の液体組成物である。
＜９＞ ２５℃における粘度が２００ｍＰａ・ｓ以下である、前記＜５＞から＜８＞のいずれかに記載の液体組成物である。
＜１０＞ 電極基体と、該電極基体上に前記＜１＞から＜４＞のいずれかに記載の電極材料及び活物質を含有する層と、を有することを特徴とする電極である。
＜１１＞ 前記＜１０＞に記載の電極を有することを特徴とする電気化学素子である。
＜１２＞ 電極基体上に前記＜５＞から＜９＞のいずれかに記載の液体組成物を吐出する工程を含むことを特徴とする電極の製造方法である。
＜１３＞ 前記液体組成物が吐出された電極基体を加圧する工程を更に含む、前記＜１２＞に記載の電極の製造方法である。
＜１４＞ 前記＜１２＞から＜１３＞のいずれかに記載の電極の製造方法からなる工程を含むことを特徴とする電気化学素子の製造方法である。 Embodiments of the present invention are, for example, as follows.
<1> either a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group,
The electrode material is characterized by being a polymer having a partial structure in a side chain in which an alkoxy group and a carbonyl group are bonded together.
<2> The electrode material according to <1> above, which has a structural unit represented by the following general formula (I).

general formula (I)
However, in the general formula (I), Ar ¹ represents either a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group, and the aryl group and the heteroaryl The group may have a substituent, X ¹ and X ² each independently represent any one selected from a carbon atom, an oxygen atom and a nitrogen atom, and X ¹ and X ² are a carbon atom or a nitrogen atom , these further have a hydrogen atom or a substituted or unsubstituted alkyl group, and each R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, Y represents a divalent linking group.
<3> The divalent linking group Y in the general formula (I) is -R ² -CO-R ³ -, -R ² -COO-R ³ -, -R ² -CONH-R ³ -, and - The electrode material according to <2> above, which is at least one of R ² —NHCONH—R ³ —.
However, R ² and R ³ each represent an alkylene group.
<4> The electrode material according to any one of <1> to <3>, which is at least one of a dispersant and a binder.
<5> A liquid composition comprising the electrode material according to any one of <1> to <4>, an active material, and a solvent.
<6> The liquid composition according to <5>, wherein the content of the active material is 10% by mass or more.
<7> The active material according to any one of <5> to <6>, wherein the active material is at least one selected from lithium-containing transition metal oxides, lithium-containing transition metal phosphate compounds, and carbon materials. It is a liquid composition.
<8> The liquid composition according to any one of <5> to <7>, wherein the active material contains lithium and is non-hydrous.
<9> The liquid composition according to any one of <5> to <8>, having a viscosity of 200 mPa·s or less at 25°C.
<10> An electrode comprising: an electrode substrate; and a layer containing the electrode material and an active material according to any one of <1> to <4> on the electrode substrate.
<11> An electrochemical device comprising the electrode according to <10>.
<12> A method for producing an electrode, comprising the step of discharging the liquid composition according to any one of <5> to <9> onto an electrode substrate.
<13> The method for producing an electrode according to <12>, further comprising pressurizing the electrode substrate onto which the liquid composition has been discharged.
<14> A method for manufacturing an electrochemical device, comprising a step of the method for manufacturing an electrode according to any one of <12> to <13>.

The electrode material according to any one of <1> to <4>, the liquid composition according to any one of <5> to <9>, the electrode according to <10>, and the electrode according to <11>. According to the electrochemical element, the method for manufacturing the electrode according to any one of <12> to <13>, and the method for manufacturing the electrochemical element according to <14>, the various problems in the past are solved, and the present invention The object of the invention can be achieved.

Reference Signs List 1 secondary battery 10 negative electrode 11 negative electrode substrate 12 negative electrode mixture layer 12A liquid composition 15 negative electrode 20 positive electrode 21 positive electrode substrate 22 positive electrode mixture layer 25 positive electrode 30 separator 40 electrode element 41 lead wire 42 lead wire 51 electrolyte layer 52 exterior 300 liquid Discharge device 300' Liquid discharge device 306 Liquid discharge head

JP 2009-152180 A JP 2010-97946 A

Claims (14)

any of a monocyclic or polycyclic aryl group and a monocyclic or polycyclic heteroaryl group;
An electrode material characterized by being a polymer having, in a side chain, a partial structure in which an alkoxy group and a are bonded via a carbonyl group. 2. The electrode material according to claim 1, which has a structural unit represented by the following general formula (I).

general formula (I)
However, in the general formula (I), Ar ¹ represents either a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group, and the aryl group and the heteroaryl The group may have a substituent, X ¹ and X ² each independently represent any one selected from a carbon atom, an oxygen atom and a nitrogen atom, and X ¹ and X ² are a carbon atom or a nitrogen atom , these further have a hydrogen atom or a substituted or unsubstituted alkyl group, and each R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, Y represents a divalent linking group. The divalent linking group Y in the general formula (I) is -R ² -CO-R ³ -, -R ² -COO-R ³ -, -R ² -CONH-R ³ -, and -R ² - 3. The electrode material according to claim 2, which is at least one of NHCONH--R ³ -.
However, R ² and R ³ each represent an alkylene group. 4. The electrode material according to any one of claims 1 to 3, which is at least one of a dispersant and a binder. A liquid composition comprising the electrode material according to any one of claims 1 to 4, an active material, and a solvent. 6. The liquid composition according to claim 5, wherein the content of said active material is 10% by mass or more. 7. The liquid composition according to any one of claims 5 and 6, wherein the active material is at least one selected from lithium-containing transition metal oxides, lithium-containing transition metal phosphate compounds, and carbon materials. 8. The liquid composition according to any one of claims 5 to 7, wherein the active material contains lithium and is non-hydrous. 9. The liquid composition according to any one of claims 5 to 8, having a viscosity at 25°C of 200 mPa·s or less. An electrode comprising: an electrode substrate; and a layer containing the electrode material according to any one of claims 1 to 4 and an active material on the electrode substrate. An electrochemical device comprising the electrode according to claim 10 . 10. A method of manufacturing an electrode, comprising the step of discharging the liquid composition according to any one of claims 5 to 9 onto an electrode substrate. 13. The method of manufacturing an electrode according to claim 12, further comprising pressurizing the electrode substrate onto which the liquid composition has been discharged. 14. A method for manufacturing an electrochemical device, comprising steps comprising the method for manufacturing an electrode according to any one of claims 12 to 13.

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