Dispersant, liquid composition, electrode, electrochemical device, method for manufacturing electrode, and method for manufacturing electrochemical device

Abstract

To provide electrode materials capable of obtaining liquid compositions having excellent dispersibility and stability while suppressing adverse effects on electrochemical properties.SOLUTION: An electrode material is a polymeric material having a side chain with a partial structure in which a monocyclic or polycyclic aryl group, and either a monocyclic or polycyclic heteroaryl group, and an alkoxy group, are bonded via a carbonyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides Dispersants The present invention relates to a liquid composition, an electrode, an electrochemical device, a method for manufacturing an electrode, and a method for manufacturing an electrochemical device. [Background technology]

[0002] Demand for electrochemical elements, including lithium-ion secondary batteries, is expanding as they are installed in mobile devices, hybrid vehicles, electric vehicles, etc. In addition, there is a growing need for thin batteries to be installed in various wearable devices and medical patches, and the requirements for electrochemical elements are becoming more diverse.

[0003] Conventionally, known methods for manufacturing electrodes constituting electrochemical elements include forming an electrode mixture layer on an electrode substrate by applying a liquid composition using, for example, a die coater, a comma coater, a reverse roll coater, etc. For example, the electrode mixture layer is formed by screen-printing the liquid composition for the electrode mixture layer on the electrode substrate.

[0004] However, in order to screen print in a shape that meets needs, a plate needs to be prepared for each need. Therefore, a method of forming an electrode mixture layer by discharging a liquid composition for an electrode mixture layer onto an electrode substrate using a liquid discharge device has been investigated (see, for example, Patent Documents 1 and 2).

[0005] The liquid ejection method is a method of ejecting fine droplets of a liquid composition from ejection holes in a liquid ejection head. Known methods for ejecting droplets from a liquid ejection head include a piezoelectric method, a thermal method, and a valve method. Among these, the piezoelectric method can precisely control the ejection amount of the liquid composition by controlling the voltage. Furthermore, since no heating is required, the piezoelectric method is less affected by the operating environment and has high durability. From the viewpoints of storage stability and ejection stability, liquid compositions that can be ejected by liquid ejection methods generally have a viscosity of several mPa·s to several hundred mPa·s at 25° C., which must be lower than the viscosity of conventional liquid compositions at 25° C. In particular, when a piezo-type liquid ejection head is used, the viscosity and surface tension of the liquid composition must be adjusted to appropriate values ​​in order to improve ejection stability. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide an electrode material that can provide a liquid composition having excellent dispersibility and stability while suppressing adverse effects on electrochemical properties. [Means for solving the problem]

[0007] The present invention provides a method for solving the above problems. Dispersant for batteries using non-aqueous electrolyte has 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. and 40% or more of the side chains have a structural unit represented by the following general formula (I): It is a polymer. [ka] General formula (I) However, in the general formula (I), Ar 1 represents a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group, and the aryl group and the heteroaryl group may have a substituent; X 1 and X 2 represents an oxygen atom, and R 1 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, and Y represents -(CH 2 ) 2 -NH-COO-(CH 2 ) 6 - or -(CH 2 ) 6 - represents. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an electrode material that can obtain a liquid composition having excellent dispersibility and stability while suppressing adverse effects on electrochemical properties. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing an example of the negative electrode used in the present invention. [Figure 2] FIG. 2 is a schematic diagram showing an example of a method for producing the negative electrode used in the present invention. [Figure 3] FIG. 3 is a schematic diagram showing another example of the method for producing the negative electrode used in the present invention. [Figure 4] FIG. 4 is a schematic diagram showing a modification of the liquid ejection device of FIGS. [Figure 5] FIG. 5 is a cross-sectional view showing an example of the positive electrode used in the present invention. [Figure 6] FIG. 6 is a cross-sectional view showing an example of an electrode element constituting the electrochemical device of the present invention. [Figure 7] FIG. 7 is a cross-sectional view showing an example of the electrochemical device of the present invention. [Figure 8A] FIG. 8A is a graph showing an example of the results of evaluating electrochemical stability in Examples and Comparative Examples. [Figure 8B] FIG. 8B is a graph showing an example of the results of evaluating the electrochemical stability in Examples and Comparative Examples. [Figure 9] FIG. 9 is a graph showing an example of the results of evaluating the electrochemical stability in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0010] (electrode material) The electrode material of the present invention is a polymer having, in its side chain, a partial structure 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, and further contains other materials as necessary.

[0011] In conventional technology, a liquid composition to be ejected by a liquid ejection method is formed from, for example, an active material, a conductive aid, a binder, as well as a dispersant, a solvent, etc. that are necessary to stably maintain the liquid composition to be ejected. However, materials such as dispersants and solvents that are necessary to stably maintain the liquid composition are no longer necessary after the liquid composition has been applied to a substrate, and there is a concern that unexpected electrochemical reactions and degradation products may adversely affect the characteristics of the electrochemical element within the element. Furthermore, in obtaining a liquid composition that can be ejected by a liquid ejection method, it is also important to improve the degree of freedom in the selection of materials such as dispersion media from the viewpoints of reducing environmental load and optimizing processes. In particular, in recent years, there has been a demand for reducing the use of NMP solvent, which is generally used in the production of lithium-ion secondary batteries, and for alternative materials to it. Furthermore, in recent years, the development of all-solid-state batteries using solid electrolytes instead of flammable liquid electrolytes has been anticipated in order to improve the safety of lithium-ion secondary batteries. However, among solid electrolytes, sulfide-based solid electrolytes, which have particularly high ionic conductivity and excellent properties, have the problem of generating hydrogen sulfide in protic solvents. Furthermore, sulfide-based solid electrolytes are known to decompose in highly polar solvents such as NMP. Therefore, when preparing a slurry of sulfide-based solid electrolytes, it is necessary to use a low-polarity aprotic solvent that does not damage the electrolyte.

[0012] The present inventors have found that by using a polymer having, in its side chain, a partial structure 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, it is possible to obtain a liquid composition that has excellent dispersibility and stability while suppressing adverse effects on electrochemical properties.

[0013] The electrode material is not particularly limited as long as it has the above structure and can be used to prepare an electrode, and can be appropriately selected depending on the purpose, but is preferably at least one of a dispersant and a binder.

[0014] -Dispersant- A dispersant is a compound that can disperse and stably maintain various materials in a liquid composition to be ejected, and is suitably used as a dispersant in a liquid composition containing an active material, an insulating material, an electrolyte material, etc.

[0015] -binder- The binder is not particularly limited as long as it is a compound that 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, from the viewpoint of suppressing nozzle clogging during ejection from an inkjet head nozzle, it is preferable that the binder is a compound that does not easily increase the viscosity of the liquid composition.

[0016] The monocyclic or polycyclic aryl group in the electrode material may be either a fused polycyclic group or a non-fused polycyclic group, and examples thereof include a phenyl group, a naphthyl group, a pyrenyl group, a fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, a biphenyl group, and a terphenyl group. Examples of the monocyclic or polycyclic heteroaryl group include a pyridinyl group, a pyrimidinyl group, a quinolinyl group, an isoquinolinyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, an acridinyl group, a phenazinyl group, and a carbazolyl group.

[0017] The alkyl group preferably has 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an ethylhexyl group, an octyl group, a decyl group, a dodecyl group, a 2-butyloctyl group, and an octadecyl group.

[0018] The alkylene glycol ether group is represented by the following general formula (a). [General formula (a)] -(RO) n - (In the general formula (a), R is an alkylene group, and n is an integer of 3 or more.)

[0019] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0020] Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, and an n-pentylene group.

[0021] 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. Examples of the branched alkylene group include 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.

[0022] 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.

[0023] The electrode material is preferably a polymer having a structural unit represented by the following general formula (I).

[0024] [ka] General formula (I) However, in the general formula (I), Ar 1 represents a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group, and the aryl group and the heteroaryl group may have a substituent; X 1 and X 2 each independently represents a carbon atom, an oxygen atom, or a nitrogen atom; X 1 and X 2When R is a carbon atom or a nitrogen atom, it further has a hydrogen atom or a substituted or unsubstituted alkyl group, and R 1 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, and Y represents a divalent linking group.

[0025] Ar in the general formula (I) 1 The monocyclic or polycyclic aryl group may be either a fused polycyclic group or a non-fused polycyclic group, and examples thereof include a phenyl group, a naphthyl group, a pyrenyl group, a fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, a biphenyl group, and a terphenyl group. Furthermore, examples of the monocyclic or polycyclic heteroaryl group include a pyridinyl group, a pyrimidinyl group, a quinolinyl group, an isoquinolinyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, an acridinyl group, a phenazinyl group, and a carbazolyl group.

[0026] The substituent in the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a halogen atom, a cyano group, an alkyl group having from 1 to 12 carbon atoms, a phenyl group, a phenyl group substituted with a cycloalkyl group having from 3 to 12 carbon atoms or an alkoxy group having from 1 to 12 carbon atoms, a hydroxyl group, a carboxyl group, etc. These substituents may have a plurality of the same groups introduced therein, or a plurality of different groups introduced therein.

[0027] R in the general formula (I) 1 In terms of availability of raw materials, the substituted or unsubstituted alkyl group in the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms. The alkyl group may be either a straight chain or a branched chain.

[0028] Examples of the alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an ethylhexyl group, an octyl group, a decyl group, a dodecyl group, a 2-butyloctyl group, and an octadecyl group.

[0029] R 1 In terms of availability of raw materials, the substituted or unsubstituted cycloalkyl group in the formula (I) is preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably a cycloalkyl group having 3 to 18 carbon atoms.

[0030] The cycloalkyl group may be either monocyclic or polycyclic.

[0031] 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.

[0032] R 1 The substituent in is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenyl group substituted with a cycloalkyl group having 3 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group, a carboxyl group, etc. A plurality of the same groups or a plurality of different groups may be introduced as these substituents.

[0033] The Y is a divalent linking group. The divalent linking group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include an alkylene group.

[0034] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0035] Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, and an n-pentylene group.

[0036] 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. Examples of the branched alkylene group include 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.

[0037] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group.

[0038] Examples of the monocyclic cycloalkylene group include a cyclopentylene group.

[0039] 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 -, etc. 2 and R 3 each independently has a divalent group selected from the linear alkylene group, branched alkylene group, and cycloalkylene group.

[0040] The polymer having the structural unit represented by the general formula (I) can be synthesized by esterifying an aromatic carboxylic acid derivative with an alcohol compound, or by the Friedel-Crafts reaction of an aromatic compound with an acid halide, and polymerizing the resulting (meth)acrylic monomer as one component of the polymer.

[0041] 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, and more preferably 1,000 or more and 100,000 or less.

[0042] Examples of polymers having a structural unit represented by the general formula (I) include those shown below. Polymers having a structural unit represented by the general formula (I) are not limited to these. However, n is an integer of 1 or more.

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] (liquid composition) The liquid composition of the present invention contains the electrode material of the present invention, a solvent, and an active material, and further contains other components as required.

[0048] <Solvent> The solvent is not particularly limited as long as it can disperse the active material, and can be selected appropriately depending on the purpose. Examples include water, ethylene glycol, propylene glycol, N-methyl-2-pyrrolidone, cyclohexanone, acetate, mesitylene, toluene, xylene, anisole, 2-n-butoxymethanol, 2-dimethylethanol, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, lactate, and tetramethylurea. In particular, when using a sulfide-based solid electrolyte, aprotic solvents with low polarity are preferred. These solvents may be used alone or in combination.

[0049] <Active material> As the active material, a positive electrode active material or a negative electrode active material that can be applied to an electrochemical element can be used.

[0050] The positive electrode active material is not particularly limited as long as it is capable of reversibly absorbing and releasing alkali metal ions, and alkali metal-containing transition metal compounds can be used.

[0051] 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.

[0052] Examples of the lithium-containing transition metal compound include lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide.

[0053] The alkali metal-containing transition metal compound may also be a polyanionic compound having an XO4 tetrahedron (X=P, S, As, Mo, W, Si, etc.) in its crystal structure. 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 input / output characteristics of electrochemical devices.

[0054] From the viewpoint of electron conductivity, the polyanionic compound is preferably composited by coating the surface with a conductive aid such as a carbon material.

[0055] The negative electrode active material is not particularly limited as long as it is capable of reversibly absorbing and releasing alkali metal ions, but carbon materials containing graphite having a graphite-type crystal structure can be used.

[0056] Examples of the carbon material include natural graphite, artificial graphite, non-graphitizable carbon (hard carbon), and easily graphitizable carbon (soft carbon).

[0057] Examples of the negative electrode active material other than the carbon material include lithium titanate and titanium oxide.

[0058] In terms of the energy density of the electrochemical device, it is preferable to use a high-capacity material such as silicon, tin, a silicon alloy, a tin alloy, silicon oxide, silicon nitride, or tin oxide as the negative electrode active material.

[0059] When the active material contains lithium, the solvent is preferably a nonaqueous solvent. In this case, the water content 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 compounds such as lithium carbonate, which can prevent a decrease in the discharge capacity of the electrochemical device. Furthermore, the decomposition of compounds such as lithium carbonate during charging and discharging of the electrochemical device can be prevented, which can prevent gas generation.

[0060] 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.

[0061] Cumulative 10% volume particle diameter of the active material (D 10) is preferably 0.1 μm or more, more preferably 0.15 μm or more. 10 When the particle size is 0.1 μm or more, the storage stability of the liquid composition is improved.

[0062] 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 printing cycles required to form an electrode mixture layer with a predetermined basis weight is reduced.

[0063] <Other ingredients> Examples of the other components include binders other than the electrode materials, conductive additives, insulating materials, and electrolyte materials.

[0064] -Binders other than the above electrode materials- As binders other than the electrode materials, polymer compounds soluble in a solvent, polymer compounds dispersed in a solvent, monomer compounds, etc. can be used. A liquid composition containing the monomer compounds is applied by an inkjet method, and then the monomer compounds are polymerized. The monomer compounds preferably contain, for example, one or more molecules having a polymerizable moiety, and can bond electrode materials to each other and to the electrode substrate as polymerization proceeds at 25°C.

[0065] The polymer compound that dissolves in the solvent may have a viscosity that is not higher than that at which inkjet printing is possible after dissolution. The polymer compound is not particularly limited as long as it can ensure binding properties at the above viscosity or less, and can be appropriately selected depending on the purpose, and examples thereof include polyamide compounds, polyimide compounds, polyamideimide compounds, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), isoprene rubber, polyethylene glycol (PEO), etc. These may be used alone or in combination of two or more.

[0066] Polymer particles may be used as a binder to prevent the viscosity of the liquid composition from increasing. In this case, the polymer particles should have an average particle diameter smaller than the nozzle diameter of the inkjet head, preferably 0.01 μm or more and 1 μm or less. Examples of materials constituting the polymer particles include polyvinylidene fluoride, acrylic resin, styrene-butadiene copolymer, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, etc. These may be used alone or in combination of two or more.

[0067] -Conductive additive- As the conductive assistant, for example, carbon materials such as conductive carbon black, carbon nanofibers, carbon nanotubes, graphene, and graphite particles can be used. Here, as described above, the conductive additive may be compounded with the active material.

[0068] The conductive carbon black can be produced by, for example, a furnace method, an acetylene method, a gasification method, or the like.

[0069] As the conductive additive other than the carbon material, for example, metal particles such as aluminum particles and metal fibers can be used.

[0070] The mass ratio of the conductive additive to the active material is preferably 10% by mass or less, and more preferably 8% by mass or less. When the mass ratio of the conductive additive to the active material is 10% by mass or less, the storage stability of the liquid composition of this embodiment is improved.

[0071] The viscosity of the liquid composition at 25° C. is preferably 200 mPa·s or less, and 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 type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 100 rpm and a temperature of 25°C.

[0072] 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.

[0073] The liquid composition can be used to manufacture electrodes for electrochemical devices. The electrochemical element is not particularly limited as long as it is capable of storing electricity, and examples thereof include a battery and a capacitor.

[0074] (Electrode manufacturing method) The method for producing an electrode of the present invention includes a step of discharging the liquid composition of the present invention onto an electrode substrate, and may further include other steps as necessary. The method for producing an electrode preferably further includes a step of pressurizing the electrode substrate onto which the liquid composition has been discharged, which makes it difficult for the components constituting the electrode mixture layer to peel off, thereby improving the reliability of the electrochemical device.

[0075] There are no particular limitations on the material that constitutes the electrode substrate (current collector), as long as it is conductive and stable against the applied potential.

[0076] <Negative electrode> FIG. 1 shows an example of the negative electrode used in the present invention. Negative electrode 10 has a negative electrode substrate 11 and a negative electrode mixture layer 12 formed on one surface thereof, the negative electrode mixture layer 12 containing a negative electrode active material and the electrode material of the present invention. Negative electrode mixture layer 12 may be formed on both sides of negative electrode substrate 11 .

[0077] The shape of the negative electrode 10 is not particularly limited, and may be, for example, a flat plate shape.

[0078] Examples of materials that can be used to form the negative electrode substrate 11 include stainless steel, nickel, aluminum, and copper.

[0079] <Method of manufacturing the negative electrode> FIG. 2 shows an example of a method for producing the negative electrode used in the present invention.

[0080] The method for producing the negative electrode 10 includes a step of discharging the liquid composition 12A onto the negative electrode substrate 11 using the liquid discharge device 300. Here, the liquid composition 12A contains the electrode material of the present invention, a negative electrode active material, and a solvent.

[0081] The liquid composition 12 A is stored in a tank 307 and is supplied from the tank 307 to a liquid ejection head 306 via a tube 308 .

[0082] Furthermore, the liquid ejection device 300 may be provided with a mechanism for capping the nozzle to prevent the liquid composition 12A from drying out when it is not being ejected from the liquid ejection head 306.

[0083] 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 the negative electrode substrate 11 is heated. At this time, the stage 400 or the liquid ejection head 306 may be moved.

[0084] Furthermore, when the liquid composition 12A discharged onto the negative electrode substrate 11 is heated, it may be heated by the stage 400 or by a heating mechanism other than the stage 400.

[0085] The heating mechanism is not particularly limited as long as it does not come into direct contact with the liquid composition 12A, and examples thereof include a resistance heater, an infrared heater, a fan heater, etc. Note that a plurality of heating mechanisms may be installed.

[0086] The heating temperature is not particularly limited as long as it is a temperature at which the solvent can be volatilized, and is preferably in the range of 70°C to 150°C from the viewpoint of power consumption.

[0087] Furthermore, when the liquid composition 12A discharged onto the negative electrode substrate 11 is heated, ultraviolet light may be irradiated thereto.

[0088] FIG. 3 shows another example of the method for producing a negative electrode according to the present invention. The method for producing the negative electrode 10 includes a step of discharging the liquid composition 12A onto the negative electrode substrate 11 using the liquid discharge device 300.

[0089] First, an elongated negative electrode substrate 11 is prepared. The negative electrode substrate 11 is then 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 negative electrode composite layer 12 is to be formed faces upward in FIG. 3. The feed roller 304 and the take-up roller 305 rotate counterclockwise, and the negative electrode substrate 11 is transported from right to left in FIG. 3. Then, droplets of liquid composition 12A are ejected onto the transported negative electrode substrate 11 from a liquid ejection head 306 installed above the negative electrode substrate 11 between the feed roller 304 and the take-up roller 305. The droplets of liquid composition 12A are ejected so as to cover at least a portion of the negative electrode substrate 11.

[0090] A plurality of liquid ejection heads 306 may be installed in a direction substantially parallel to or substantially perpendicular to the direction in which the negative electrode substrate 11 is transported.

[0091] Next, negative electrode substrate 11 onto which liquid composition 12A has been ejected is transported to heating mechanism 309 by delivery roller 304 and take-up roller 305. As a result, the solvent contained in liquid composition 12A on negative electrode substrate 11 volatilizes, forming negative electrode composite layer 12 and obtaining negative electrode 10. Thereafter, negative electrode 10 is cut to a desired size by punching or the like.

[0092] The heating mechanism 309 is not particularly limited as long as it does not come into direct contact with the liquid composition 12A, and examples thereof include a resistance heater, an infrared heater, and a fan heater.

[0093] The heating mechanism 309 may be installed either above or below the negative electrode substrate 11, or a plurality of heating mechanisms may be installed.

[0094] The heating temperature is not particularly limited as long as it is a temperature at which the solvent can be volatilized, and is preferably in the range of 70°C to 150°C from the viewpoint of power consumption.

[0095] Furthermore, when the liquid composition 12A discharged onto the negative electrode substrate 11 is heated, ultraviolet light may be irradiated thereto.

[0096] FIG. 4 shows a modified example of the liquid ejection device 300. As shown in FIG. The liquid ejection device 300 ′ is capable of circulating 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 .

[0097] In addition, the liquid ejection device 300' is provided with an external tank 313, and when the liquid composition 12A in the tank 307 decreases, it is possible to supply the liquid composition 12A from the external tank 313 to the tank 307 by controlling the pump 310 and the valves 311, 312, and 314.

[0098] By using the liquid ejection devices 300 and 300', it is possible to eject the liquid composition 12A onto a targeted location on the negative electrode substrate 11. Furthermore, by using the liquid ejection devices 300 and 300', it is possible to bond the contacting surfaces of the negative electrode substrate 11 and the negative electrode composite material layer 12 together. Furthermore, by using the liquid ejection devices 300 and 300', it is possible to make the thickness of the negative electrode composite material layer 12 uniform.

[0099] <Positive electrode> FIG. 5 shows an example of the positive electrode used in the present invention. In the positive electrode 20, a positive electrode mixture layer 22 containing a positive electrode active material and the electrode material of the present invention is formed on one surface of a positive electrode substrate 21. The positive electrode mixture layer 22 may be formed on both surfaces of the positive electrode substrate 21.

[0100] The shape of the positive electrode 20 is not particularly limited, and may be, for example, a flat plate shape.

[0101] Examples of materials that can be used to form the positive electrode substrate 21 include stainless steel, aluminum, titanium, and tantalum.

[0102] <Positive electrode manufacturing method> The method for producing the positive electrode 20 is the same as the method for producing the negative electrode 10, except that the liquid composition is discharged onto the positive electrode substrate 21. Here, the liquid composition contains a positive electrode active material, the electrode material of the present invention, and a solvent.

[0103] (Method of manufacturing an electrochemical element) 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 may further include other steps as necessary.

[0104] <Electrode element> FIG. 6 shows an example of an electrode element constituting the electrochemical device of the present invention. The electrode element 40 is formed by laminating a negative electrode 15 and a positive electrode 25 with a separator 30 interposed therebetween. The positive electrodes 25 are 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.

[0105] Negative electrode 15 is similar to negative electrode 10 except that negative electrode mixture layer 12 is formed on both sides of negative electrode substrate 11 .

[0106] Positive electrode 25 is similar to positive electrode 20 except that positive electrode mixture layers 22 are formed on both sides of positive electrode substrate 21 . There is no particular limit to the number of layers of the negative electrodes 15 and positive electrodes 25 of the electrode element 40.

[0107] Furthermore, the number of negative electrodes 15 and the number of positive electrodes 25 in the electrode element 40 may be the same or different.

[0108] <Separator> The separator 30 is provided between the negative electrode 15 and the positive electrode 25 to prevent short-circuiting between the negative electrode 15 and the positive electrode 25 .

[0109] 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, and micropore membrane.

[0110] There is no particular limitation on the size of the separator 30 as long as it can be used in an electrochemical element. The separator 30 may have a single layer structure or a laminated structure. When a solid electrolyte is used, the separator 30 can be omitted.

[0111] <Electrochemical element> FIG. 7 shows a secondary battery as an example of the electrochemical device of the present invention.

[0112] In the secondary battery 1, an electrolyte layer 51 is formed by injecting an aqueous electrolyte solution or a non-aqueous electrolyte into the electrode element 40, and the secondary battery 1 is sealed with an exterior case 52. In the secondary battery 1, the lead wires 41 and 42 are drawn out to the outside of the exterior case 52.

[0113] The secondary battery 1 may include other components as necessary. The secondary battery 1 is not particularly limited, and examples thereof include a lithium ion secondary battery.

[0114] 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 wound, a cylinder type with an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are stacked.

[0115] <Aqueous electrolyte solution> Examples of electrolyte salts that constitute the aqueous electrolyte solution include sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, ammonium chloride, zinc chloride, zinc acetate, zinc bromide, zinc iodide, zinc tartrate, and zinc perchloride.

[0116] <Non-aqueous electrolyte> As the non-aqueous electrolyte, a solid electrolyte or a non-aqueous electrolytic solution can be used. Here, the non-aqueous electrolyte is an electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent.

[0117] -Solid electrolyte- The non-aqueous electrolyte may be a material for forming a solid electrolyte layer. The material for forming the solid electrolyte layer is not particularly limited as long as it is a solid substance that has electronic insulation and ion conductivity, and can be appropriately selected depending on the purpose. For example, sulfide-based solid electrolytes and oxide-based solid electrolytes are preferred from the viewpoint of having high ionic conductivity. The sulfide-based solid electrolyte may be, for example, Li 10 GeP2S 12 and Li6PS5X (X is F, Cl, Br, or I) having an argyrodite crystal structure. The oxide-based solid electrolyte is, for example, LLZ (Li7La3Zr2O 12 ), LATP (Li 1+x Al x Ti20 x (PO4)3) (0.1≦x≦0.4), LLT (Li 0.33 La 0.55 TiO3), amorphous LIPON (Li 2.9 PO 3.3 N 0.4 These may be used alone or in combination of two or more. Examples of electrolyte materials that can be dissolved or dispersed in a liquid to form these solid electrolyte layers include precursors of solid electrolytes such as Li2S, P2S5, and LiCl, as well as solid electrolyte materials such as Li2S-PS5 glass and Li7P3S 11 Glass ceramics and the like.

[0118] Furthermore, 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 ion conductivity. For example, polymers constituting the network structure of the gel electrolyte include polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, copolymers of vinylidene fluoride and propylene hexafluoride, and polyethylene carbonate. The solvent molecules held in the gel electrolyte include ionic liquids. 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), and N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(fluorosulfonyl)imide. The ionic liquid may be a mixture of a liquid such as tetraglyme, propylene carbonate, fluoroethylene carbonate, ethylene carbonate, or diethyl carbonate with a lithium salt. The lithium salt is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include lithium hexafluorophosphate (LiPF), lithium borofluoride (LiBF), lithium arsenic hexafluoride (LiAsF), lithium trifluoromethasulfonate (LiCFSO), lithium bis(trifluoromethylsulfonyl)imide (LiN(CFSO)), and lithium bis(pentafluoroethylsulfonyl)imide (LiN(CFSO)). These may be used alone or in combination of two or more. The electrolyte material dissolved or dispersed in the liquid to form these gel electrolyte layers may be a solution of the above-mentioned polymer compound and an ionic liquid or a lithium salt. Alternatively, the electrolyte material dissolved or dispersed in the liquid may be a precursor of the gel electrolyte (for example, a combination of polyethylene oxide or polypropylene oxide having acrylate groups at both ends with a solution of an ionic liquid or a lithium salt). When such a solid electrolyte or gel electrolyte is used, it can be used as a liquid composition together with the active material.

[0119] -Non-aqueous solvent- The non-aqueous solvent is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable to use, for example, an aprotic organic solvent.

[0120] As the aprotic organic solvent, for example, a carbonate-based organic solvent such as a chain carbonate, a cyclic carbonate, etc. Among these, a chain carbonate is preferred because of its high dissolving power for the electrolyte salt. In addition, it is preferable that the aprotic organic solvent has a low viscosity.

[0121] Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (EMC).

[0122] 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 (e.g., a cyclic carbonate or a cyclic ester), the content of the cyclic substance is reduced. Therefore, even if a non-aqueous electrolyte solution with a high concentration of 2 mol / L (M) or more is prepared, the viscosity of the non-aqueous electrolyte solution is reduced, and the non-aqueous electrolyte solution penetrates into the electrodes and ions diffuse well.

[0123] Examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC).

[0124] Examples of the non-aqueous solvent other than the carbonate organic solvent include ester organic solvents such as cyclic esters and chain esters, and ether organic solvents such as cyclic ethers and chain ethers.

[0125] Examples of the cyclic ester include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone.

[0126] 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).

[0127] Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and 1,4-dioxolane.

[0128] Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, and diethylene glycol dialkyl ether ether.

[0129] <Electrolyte salt> The electrolyte salt is not particularly limited as long as it has high ionic conductivity and is soluble in a non-aqueous solvent. The electrolyte salt preferably contains a halogen atom.

[0130] Examples of the cations constituting the electrolyte salt include lithium ions.

[0131] Examples of the anion constituting the electrolyte salt include BF4 - , PF6 - , AsF6 - , CF3SO3 - , (CF3SO2)2N - , (C2F5SO2)2N - Examples include:

[0132] The lithium salt is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include lithium hexafluorophosphate (LiPF), lithium borofluoride (LiBF), lithium hexafluoride (LiAsF), lithium trifluoromethasulfonate (LiCFSO), lithium bis(trifluoromethylsulfonyl)imide (LiN(CFSO)), and lithium bis(pentafluoroethylsulfonyl)imide (LiN(CFSO)). These may be used alone or in combination of two or more. Among these, LiPF is preferred from the viewpoint of ionic conductivity, and LiBF is preferred from the viewpoint of stability. These may be used alone or in combination of two or more.

[0133] The concentration of the electrolyte salt in the nonaqueous electrolytic solution can be appropriately selected depending on the purpose, but if the nonaqueous electrochemical device is of a swing type, it is preferably 1 mol / L or more and 2 mol / L or less, and if the nonaqueous electrochemical device is of a reserve type, it is preferably 2 mol / L or more and 4 mol / L or less.

[0134] <Applications of electrochemical elements> The use of the electrochemical element is not particularly limited and can be appropriately selected depending on the purpose. Examples include 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, handheld vacuum cleaners, portable CDs, minidiscs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting equipment, toys, game devices, clocks, strobe lights, and cameras. [Example]

[0135] Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

[0136] In the following examples, 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.

[0137] <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 measuring device (Mastersizer 3000, manufactured by Malvern Instruments).

[0138] <Viscosity of Liquid Composition> The viscosity of the liquid composition was measured using a TV25 type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 100 rpm and a temperature of 25°C.

[0139] <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 measuring device (Mastersizer 3000, manufactured by Malvern Instruments).

[0140] (Production Example 1 of Positive Electrode Active Material) -Production of positive electrode active material 1- Vanadium pentoxide, lithium hydroxide, phosphoric acid, sucrose, and water were mixed to form a precipitate, which was spray-dried using a spray dryer and then pulverized using a jet mill to obtain a precursor of lithium vanadium phosphate (Li3V2(PO4)3) particles. The precursor of the lithium vanadium phosphate particles was then calcined at 900°C in a nitrogen atmosphere to obtain lithium vanadium phosphate particles with a carbon content of 3% by mass. The cumulative 90% volume particle diameter D 90 The lithium vanadium phosphate particles were pulverized using a jet mill so that the mode diameter became less than 3 μm, thereby obtaining a positive electrode active material 1. The obtained positive electrode active material 1 had a mode diameter of 0.7 μm.

[0141] (Positive Electrode Active Material Production Example 2) -Production of positive electrode active material 2- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 Positive electrode active material 2 was obtained in the same manner as in Positive electrode active material Production Example 1, except that lithium iron phosphate (LiFePO4) particles (manufactured by Sigma-Aldrich) were used that were crushed using a jet mill so that the mode diameter was less than 3 μm. The obtained positive electrode active material 2 had a mode diameter of 0.6 μm.

[0142] (Positive Electrode Active Material Production Example 3) -Production of Positive Electrode Active Material 3- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 Positive electrode active material 3 was obtained in the same manner as in Positive electrode active material Production Example 1, except that lithium cobalt oxide (LiCoO) particles (manufactured by Sigma-Aldrich) were used that were crushed using a jet mill so that the mode diameter was less than 3 μm. The obtained positive electrode active material 3 had a mode diameter of 0.9 μm.

[0143] (Positive Electrode Active Material Production Example 4) -Production of Positive Electrode Active Material 4- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 The thickness of the lithium nickel oxide (LiNi 0.8 Co 0.15 Al 0.05 Positive electrode active material 4 was obtained in the same manner as in Positive electrode active material Production Example 1, except that O2) particles (manufactured by Sigma-Aldrich) crushed using a jet mill were used. The resulting positive electrode active material 4 had a mode diameter of 1.2 μm.

[0144] (Positive Electrode Active Material Production Example 5) -Production of Positive Electrode Active Material 5- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 The Ni-Mn-Co system (LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 Positive electrode active material 5 was obtained in the same manner as in Positive electrode active material Production Example 1, except that O2) particles (manufactured by Sigma-Aldrich) crushed using a jet mill were used. The resulting positive electrode active material 5 had a mode diameter of 0.9 μm.

[0145] (Positive Electrode Active Material Production Example 6) -Production of Positive Electrode Active Material 6- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 Positive electrode active material 6 was obtained in the same manner as in Positive electrode active material Production Example 1, except that lithium manganese oxide (LiMnO) particles (manufactured by Sigma-Aldrich Corp.) were used that were crushed using a jet mill so that the mode diameter was less than 3 μm. The obtained positive electrode active material 6 had a mode diameter of 1.2 μm.

[0146] (Negative Electrode Active Material Production Example 1) -Production of negative electrode active material 1- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 Negative electrode active material 1 was obtained in the same manner as in Positive electrode active material Production Example 1, except that artificial graphite (manufactured by MT Carbon Co., Ltd.) was used, which was pulverized using a jet mill so that the mode diameter was less than 3 μm. The obtained negative electrode active material 1 had a mode diameter of 1.8 μm.

[0147] (Negative Electrode Active Material Production Example 2) -Production of negative electrode active material 2- In Example 1 of the positive electrode active material production, instead of lithium vanadium phosphate (Li3V2(PO4)3) particles, a 90% cumulative volume particle diameter D 90 The thickness of the lithium titanate (Li4Ti5O 12 Negative electrode active material 2 was obtained in the same manner as in Positive electrode active material Production Example 1, except that ZnO particles (manufactured by Sigma-Aldrich) pulverized with a jet mill were used. The resulting negative electrode active material 2 had a mode diameter of 0.7 μm.

[0148] Example 1 <Synthesis of Monomer 1 (M-1)> Monomer 1 (M-1) was synthesized in the following manner according to the method described in JP 2016-196621 A. Specifically, first, 2-naphthalenecarboxylic acid 6-hydroxyhexyl ester was obtained from 1,6-hexanediol (Tokyo Chemical Industry Co., Ltd.) and 2-naphthalenecarbonyl chloride. Next, the monomer (M-1) was obtained by reacting 2-naphthalenecarboxylic acid 6-hydroxyhexyl ester with 2-methacryloyloxyethyl isocyanate. [ka] <Synthesis of Polymer 1 (Example 1)> Next, polymer 1 (Example 1) was synthesized as follows in accordance with the method described in JP-A-2016-196621. Specifically, first, a polymer 1 (Example 1) was obtained by using a monomer (M-1) and acrylic acid in a solvent of methyl ethyl ketone and AIBN as a polymerization initiator. The weight average molecular weight (Mw) of the polymer, calculated as polystyrene, determined by GPC was 22,000. [ka]

[0149] The electrochemical properties of the synthesized polymer 1 (Experiment-1) were evaluated by cyclic voltammetry (CV) measurements in the range of 0.05 V to 4.2 V (vs. Li / Li+), followed by linear sweep voltammetry (LSV) measurements sweeping the potential from 3 V to 4.6 V. To evaluate the electrochemical stability, a three-electrode cell (EC Frontier, Microanalysis Cell VB7) was used, consisting of a Pt working electrode (diameter φ1.6 mm), a Pt counter electrode (diameter φ3 mm), and a Li foil reference electrode. 5% by mass of the polymer was added to the electrolyte (EC / DMC = 1 / 1, 1.5 M LiBF4). Polymer 1 (Example 1) was found to be electrochemically stable within the measurement range. The results of the CV measurement of Polymer 1 (Example 1) are shown in Figures 8A and 8B.

[0150] Example 2 <Synthesis of Polymer 2 (Example 2)> Polymer 2 (Example 2) was synthesized in the same manner as in Example 1 <Synthesis of Polymer 1 (Example 1)>, except that acrylic acid was changed to methyl acrylate. [ka]

[0151] The electrochemical properties of Polymer 2 (Example 2) were evaluated in the same manner as in Example 1. As a result, it was found to be electrochemically stable within the measurement range, similar to Polymer 1 (Example 1).

[0152] Example 3 Polymer 3 (Example 3) was synthesized in the same manner as in Example 1 <Synthesis of Polymer 1 (Example 1)>, except that acrylic acid was omitted. n represents a repeating unit. [ka]

[0153] The electrochemical properties of Polymer 3 (Example 3) were evaluated in the same manner as in Example 1. As a result, it was found to be electrochemically stable within the measurement range, similar to Polymer 1 (Example 1).

[0154] Example 4 Polymer 4 (Example 4) was synthesized in the same manner as in Example 1 <Synthesis of Polymer 1 (Example 1)>, except that the monomer (M-1) was changed to the following monomer (M-2). n represents a repeating unit. [ka]

[0155] The electrochemical properties of Polymer 4 (Example 4) were evaluated in the same manner as in Example 1. As a result, it was found to be electrochemically stable within the measurement range, similar to Polymer 1 (Example 1).

[0156] (Comparative Examples 1 to 6) The electrochemical stability of comparative compounds 1 (Comparative-1) to 4 (Comparative-4), which are represented by the following formulas and synthesized by etherification using naphthol or phenol derivatives and oligoethylene glycol as raw materials, and comparative compounds 5 (Comparative-5) and 6 (Comparative-6), which were synthesized in the same manner as in Example 1, was evaluated in the same manner as in Examples 1 to 4. Similarly, the current values ​​observed at 4.2 V in the LSV measurements are shown in Figure 9. In addition, n in Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 represented by the following formulas was approximately 10.

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] From the results in FIG. 9, almost no current was observed at 4.2 V for compounds 1 to 4 in Examples 1 to 4, whereas irreversible electrochemical oxidation reactions occurred at 4.2 V for all of comparative compounds 1 to 6 in Comparative Examples 1 to 6, which were undesirable results for use in electrochemical elements. 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.

[0164] Example 5 <Preparation of Positive Electrode Forming Liquid Composition> A liquid composition for forming a positive electrode was prepared by adding N-methylpyrrolidone to a solid content consisting of 93.1 mass% of positive electrode active material 1, 0.9 mass% of the above polymer 1 (Example 1), 3 mass% of carbon black, and 3 mass% of polyamideimide, so that the solid content concentration was 35.8 mass%. The obtained liquid composition for forming a positive electrode had a viscosity of 16 mPa·s at 25°C, a mode diameter of 0.8 μm, and a cumulative 90% volume particle diameter D 90was 3.5 μm.

[0165] Next, 24 hours after the preparation of the positive electrode-forming liquid composition, the particle size distribution of the positive electrode-forming liquid composition was measured again. No change in the particle size distribution was observed, and the positive electrode-forming liquid composition of Example 5 had good storage stability.

[0166] Next, using a liquid ejection device (EV2500, manufactured by Ricoh Co., Ltd.), the positive electrode-forming liquid composition of Example 5 was ejected onto aluminum foil as a positive electrode substrate to form a positive electrode. At this time, the positive electrode-forming liquid composition of Example 5 could be ejected continuously, and the positive electrode-forming liquid composition of Example 5 had good ejection stability and no ejection defects occurred. In other words, the positive electrode-forming liquid composition of Example 5 had good printing efficiency.

[0167] Example 6 A 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) in Example 5. The obtained liquid composition for forming a positive electrode had a viscosity of 14 mPa·s at 25°C, a mode diameter of 0.7 μm, and a cumulative 90% volume particle diameter D 90 was 3.1 μm.

[0168] Next, 24 hours after the preparation of the positive electrode-forming liquid composition, the particle size distribution of the positive electrode-forming liquid composition of Example 6 was measured again. No change in the particle size distribution was observed, and the positive electrode-forming liquid composition of Example 6 had good storage stability.

[0169] Using a liquid ejection device (EV2500, manufactured by Ricoh Co., Ltd.), the positive electrode forming liquid composition of Example 6 was ejected onto aluminum foil as a positive electrode substrate. At this time, the positive electrode forming liquid composition of Example 6 could be ejected continuously, and the positive electrode forming liquid composition of Example 6 had good ejection stability and no ejection defects occurred. In other words, the positive electrode forming liquid composition of Example 6 had good printing efficiency.

[0170] The present invention includes, for example, the following aspects. <1> a monocyclic or polycyclic aryl group and a monocyclic or polycyclic heteroaryl group; The electrode material is characterized by being a polymer having a partial structure in which an alkoxy group and an alkoxy group are bonded via a carbonyl group in the side chain. <2> The above-mentioned compound having a structural unit represented by the following general formula (I): <1> The electrode material is described in [ka] General formula (I) However, in the general formula (I), Ar 1 represents a monocyclic or polycyclic aryl group or a monocyclic or polycyclic heteroaryl group, and the aryl group and the heteroaryl group may have a substituent; X 1 and X 2 each independently represents a carbon atom, an oxygen atom, or a nitrogen atom; X 1 and X 2 When R is a carbon atom or a nitrogen atom, it further has a hydrogen atom or a substituted or unsubstituted alkyl group, and R 1 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, and 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 -R 2 -NHCONH-R 3 - at least one of the above <2> The electrode material is described in However, R 2 and R 3 Each of the groups represents an alkylene group. <4> The above-mentioned component is at least one of a dispersant and a binder. <1> from <3> The electrode material is any one of the above. <5> The aforementioned <1> from <4> 1. A liquid composition comprising the electrode material according to any one of the above items 1 to 8, an active material, and a solvent. <6> The content of the active material is 10% by mass or more. <5> The liquid composition according to claim 1. <7> The active material is at least one selected from a lithium-containing transition metal oxide, a lithium-containing transition metal phosphate compound, and a carbon material. <5> from <6> The liquid composition according to any one of the above items. <8> the active material contains lithium and is non-hydrous; <5> from <7> The liquid composition according to any one of the above items. <9> The viscosity at 25°C is 200 mPa·s or less. <5> from <8> The liquid composition according to any one of the above items. <10> an electrode substrate, and the above-mentioned electrode substrate <1> from <4> and a layer containing the electrode material according to any one of the above items and an active material. <11> The aforementioned <10> 1. An electrochemical device characterized by having the electrode described above. <12> On the electrode substrate <5> from <9> 10. A method for manufacturing an electrode, comprising the step of ejecting the liquid composition according to any one of the above items. <13> The method further comprises a step of pressurizing the electrode substrate onto which the liquid composition has been ejected. <12> 2. A method for producing the electrode according to claim 1. <14> The aforementioned <12> from <13> 1. A method for producing an electrochemical element, comprising the steps of the method for producing an electrode according to any one of the above.

[0171] The aforementioned <1> from <4> The electrode material according to any one of <5> from <9> The liquid composition according to any one of <10> The electrode according to <11> The electrochemical element according to <12> from <13> The method for producing an electrode according to any one of the preceding claims, <14> According to the method for producing an electrochemical element described above, the various problems encountered in the past can be solved and the object of the present invention can be achieved. [Explanation of symbols]

[0172] 1 Secondary battery 10 negative electrode 11 Negative electrode substrate 12 Negative electrode composite 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 Line 42 Lead Line 51 Electrolyte layer 52 Exterior 300 Liquid discharge device 300' liquid dispensing device 306 Liquid ejection head [Prior art documents] [Patent documents]

[0173] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-152180 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-97946

Claims

1. a monocyclic or polycyclic aryl group and a monocyclic or polycyclic heteroaryl group; and a partial structure in which an alkoxy group and a carbonyl group are bonded to each other in a side chain, A dispersant for a battery using a non-aqueous electrolyte, characterized in that it is a polymer having a structural unit represented by the following general formula (I) in 40% or more of its side chains: 【Chemistry 1】 General formula (I) 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 group may have a substituent; X 1 and X 2 represent an oxygen atom; R 1 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group; and Y represents —(CH 2 ) 2 —NH—COO—(CH 2 ) 6 — or —(CH 2 ) 6 —.

2. A liquid composition comprising the dispersant according to claim 1, an active material, and a solvent.

3. The liquid composition according to claim 2 , wherein the content of the active material is 10% by mass or more.

4. 4. The liquid composition according to claim 2, wherein the active material is at least one selected from the group consisting of a lithium-containing transition metal oxide, a lithium-containing transition metal phosphate compound, and a carbon material.

5. 5. The liquid composition according to claim 2, wherein the active material contains lithium and is non-hydrous.

6. 6. The liquid composition according to claim 2, which has a viscosity at 25°C of 200 mPa·s or less.

7. 10. An electrode comprising: an electrode substrate; and a layer containing the dispersant according to claim 1 and an active material on the electrode substrate.

8. An electrochemical device comprising the electrode according to claim 7.

9. A method for manufacturing an electrode, comprising the step of discharging the liquid composition according to any one of claims 2 to 6 onto an electrode substrate.

10. The method for manufacturing an electrode according to claim 9 , further comprising the step of pressurizing the electrode substrate onto which the liquid composition has been ejected.

11. A method for producing an electrochemical device, comprising the steps of the method for producing an electrode according to any one of claims 9 and 10.

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