WO2011074270A1 - Coating liquid - Google Patents

Abstract

Disclosed is a coating liquid which contains: a thermal base generator or a photobase generator; a polysaccharide such as glycerylated chitosan; an acid and/or an acid derivative such as a polyvalent organic acid or a derivative thereof; a solvent; and a conductivity-imparting agent and/or an electrode active material. An undercoat layer or an electrode active material layer is formed by applying the coating liquid over a collector and generating a base. A secondary battery such as a lithium ion battery or an electric double layer capacitor is fabricated using an electrode that comprises the undercoat layer or the electrode active material layer.

Description

Coating liquid

The present invention relates to a coating liquid. In more detail, this invention relates to the coating liquid for manufacturing the electrode used for electrochemical elements, such as a secondary battery and an electrical double layer capacitor.

Known electrochemical devices include secondary batteries such as lithium ion batteries (sometimes referred to as lithium ion secondary batteries) and nickel metal hydride batteries, and capacitors such as electric double layer capacitors and hybrid capacitors.
The electrode of an electrochemical element generally comprises a current collector and an electrode active material layer. The electrode is usually produced by applying a coating liquid containing an electrode active material, a binder, and a solvent to a current collector and drying it. In order to reduce the internal resistance or impedance of secondary batteries and electric double layer capacitors, it has been proposed to interpose an undercoat layer between the electrode active material layer and the current collector.

By the way, it is said that a film obtained with a coating solution containing a polysaccharide such as chitosan has high ion permeability or ion mobility, and can reduce the internal resistance or impedance of a lithium ion battery or an electric double layer capacitor. ing.
For example, Patent Document 1 discloses that an electrode active material layer or an undercoat layer is produced by applying a coating liquid containing a hydroxyalkyl chitosan and an organic acid and / or a derivative thereof onto a current collector and drying it. Proposed. Organic acids and their derivatives have the role of crosslinking hydroxyalkylchitosan.

Patent Documents 2 and 3 disclose that an undercoat layer and an electrode active material layer are collected by applying a coating solution containing a crosslinked polysaccharide and a carbon particle on a current collector and drying it. It is described that it is provided between the electric body. Organic compounds such as maleic anhydride are exemplified as compounds used for crosslinking polysaccharides. It is generally known that it is necessary to make chitosan acidic in order to dissolve it in water.

WO2008 / 015828 WO2007 / 043515 JP 2007-226969 A

An acidic component may remain in the electrode active material layer or the undercoat layer obtained with a coating solution containing an organic acid. This acidic component may erode a current collector made of aluminum or copper. In particular, since chitosan is hydrophilic, it tends to absorb moisture in the air, and there is a tendency that the risk of erosion of the current collector increases due to acidic components and water. When the current collector is eroded, the internal resistance and impedance may increase.

In view of the above circumstances, the present inventor first tried to neutralize a coating solution containing a polysaccharide and an organic acid in order to make the electrode active material layer and the undercoat layer neutral. However, when a base is added to the coating solution for neutralization, an organic acid salt is generated, the crosslinking function is lowered, and the dispersion of the electrode active material is deteriorated. Also, neutralization was attempted by applying a base solution to the surface of the electrode active material layer or undercoat layer where the acid component remained, but the base could not reach the inside of the layer, so a sufficient effect was obtained. There wasn't.
Accordingly, an object of the present invention is to provide an electrochemical device having excellent storage stability and low internal resistance or impedance, and a coating solution used for the production thereof.

The present inventor has intensively studied to achieve the above object. As a result, the coating solution contains a base generator, decomposes the base generator after crosslinking with an acid to generate a base, and neutralizes the undercoat layer or electrode active material layer, thereby improving storage stability. It has been found that an electrochemical element having excellent internal resistance or impedance can be obtained. The present invention has been completed by further studies based on this finding.

That is, the present invention includes the following.
<1> A coating solution for producing an electrochemical device, comprising a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, a conductivity imparting material and / or an electrode active material.
<2> The coating solution according to <1>, wherein the base generator is a thermal base generator.
<3> The coating solution according to <2>, wherein the thermal base generator is urea or a urea derivative.
<4> The coating solution according to <1>, wherein the base generator is a photobase generator.
<5> The photobase generator is 2-nitrobenzyl cyclohexyl carbamate, 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, 1,1-dimethyl-2-phenylethyl-N-isopropyl carbamate, triphenylmethanol, <4> The coating solution according to <4>, which is o-carbamoylhydroxylamide, N-cyclohexyl-4-methylphenylsulfonamide, or o-carbamoyloxime.
<6> The coating solution according to any one of <1> to <5>, wherein the acid and / or the acid derivative is a polyvalent organic acid and / or a polyvalent organic acid derivative.
<7> The coating solution according to any one of <1> to <6>, wherein the acid derivative is an acid anhydride.

<8> A film formed using the coating liquid according to any one of <1> to <7>.
<9> A laminate for an electrode comprising: a current collector; and a layer a formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, and a conductivity-imparting material.

<10> A current collector, a layer a formed using a coating liquid containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and a conductivity-imparting material, and an electrode active material layer electrode.
<11> An electrode having a current collector and a layer b formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and an electrode active material.

<12> An electrochemical device having the electrode according to <10> or <11>.
<13> A power supply system having the electrochemical element according to <12>.
<14> An automobile having the electrochemical element according to <12>.
<15> A transport device having the electrochemical element according to <12>.
<16> A portable device having the electrochemical element according to <12>.
<17> A power generation system having the electrochemical element according to <12>.

An electrode active material layer or an undercoat layer having excellent storage stability can be formed on the current collector by applying the coating liquid of the present invention to the current collector and then generating a base. When an electrode having the electrode active material layer or the undercoat layer is used, an electrochemical element having excellent storage stability and low internal resistance or impedance can be obtained.

The coating liquid according to the present invention contains a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, a conductivity imparting material and / or an electrode active material.

The base generator used in the coating liquid according to the present invention is decomposed by a stimulus such as heat or light, thereby generating a base. The base generator used in the present invention is not particularly limited, but a thermal base generator that decomposes by heat and / or a photobase generator that decomposes by light is preferable.

The thermal base generator used in the present invention is not particularly limited, but preferably does not contain a metal. Specifically, carbamate derivatives such as 1-methyl-1- (4-biphenylyl) ethyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate; urea and N, N-dimethyl-N′-methyl urea Urea derivatives; dihydropyridine derivatives such as 1,4-dihydronicotinamide; dicyandiamide, phenylsulfonylacetic acid guanidine, p-methanesulfonylphenylsulfonylacetic acid guanidine, phenylpropiolic acid guanidine, p-phenylene-bis-phenylpropiolic acid guanidine, phenylsulfonylacetic acid Examples thereof include tetramethylammonium and tetramethylammonium phenylpropiolate. These can be used alone or in combination of two or more.
Among these, urea derivatives such as urea and N, N-dimethyl-N′-methylurea are preferable in that they can generate a base even by hydrothermal hydrolysis and can remove moisture in the coating solution. . The thermal base generator preferably has a temperature at which a base is generated higher than a temperature at which a crosslinking reaction described later occurs. If the temperature at which the base is generated is too lower than the temperature at which the crosslinking reaction occurs, crosslinking tends to be insufficient.

The photobase generator used in the present invention is not particularly limited. For example, photoactive carbamates such as triphenylmethanol, benzylcarbamate and benzoincarbamate; amides such as o-carbamoylhydroxylamide, o-carbamoyloxime, aromatic sulfonamide, alpha-lactam and N- (2-allylethynyl) amide and Other amides; oxime esters, α-aminoacetophenone and the like can be mentioned. These can be used alone or in combination of two or more.
Of these, 2-nitrobenzyl cyclohexyl carbamate, 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, 1,1-dimethyl-2-phenylethyl-N-isopropyl carbamate, triphenyl methanol, o-carbamoyl hydroxyl Amide, N-cyclohexyl-4-methylphenylsulfonamide, or o-carbamoyloxime may be mentioned as preferred.
In order to improve the function of the photobase generator, a photosensitizer may be added.

The hot base generator generates a base when heated. The photobase generator generates a base when irradiated with light. The generated base neutralizes the acidic component of the undercoat layer or the electrode active material layer. As a result, erosion of the current collector can be effectively prevented. Even after an electrode manufactured with the coating solution is stored for a long period of time, the electrochemical element having the electrode maintains a low internal resistance or impedance.

The base generator is preferably contained in the coating solution in an amount that generates enough base to neutralize the acidic component of the undercoat layer or electrode active material layer.
The specific amount of the base generator varies depending on the type and amount of the acid and acid derivative, but is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts per 100 parts by mass of the total amount of the acid and acid derivative. Part by mass. If the amount of the base generator is too small, the acidic component cannot be sufficiently neutralized. Conversely, if the amount of the base generator is too large, the basicity tends to become strong.

The polysaccharide used in the coating solution according to the present invention is a polymer compound in which a large number of monosaccharides (including monosaccharide substitutes and derivatives) are polymerized by glycosidic bonds. The polymer compound generates a large number of monosaccharides by hydrolysis. Usually, 10 or more monosaccharides are polymerized. The polysaccharide may have a substituent, for example, a polysaccharide in which an alcoholic hydroxyl group is substituted with an amino group (amino sugar), a one in which a carboxyl group or an alkyl group is substituted, or a deacetylated polysaccharide Etc. are included. The polysaccharide may be either a homopolysaccharide or a heteropolysaccharide. Hydroxyl polysaccharides or derivatives thereof, carboxyalkyl polysaccharides are preferred, and hydroxyalkyl polysaccharides are preferred because they can increase the solubility in polar solvents and increase the mobility of ions by crosslinking with acids and / or acid derivatives. preferable. Hydroxyalkyl polysaccharides or derivatives and carboxyalkyl polysaccharides can be produced by known methods.

Specific examples of polysaccharides include agarose, amylose, amylopectin, arabinan, arabinogalactan, alginic acid, inulin, carrageenan, galactan, glucan, xylan, xyloglucan, carboxyalkylchitin, chitin, glycogen, glucomannan, keratan sulfate, colomine Acid, chondroitin sulfate A, chondroitin sulfate B, chondroitin sulfate C, cellulose, dextran, starch, hyaluronic acid, fructan, pectic acid, pectin, heparic acid, heparin, hemicellulose, pentozan, β-1,4'-mannan, α -1,6'-mannan, lichenan, levan, lentinan, chitosan, pullulan, curdlan, carrageenan and the like.
Of these, chitin, chitosan, hydroxyalkylchitosan, carboxyalkylchitosan, caprolactone-modified chitosan, hydroxyalkylcellulose or carboxyalkylcellulose are preferred because of their high ion permeability; chitosan, hydroxyalkylchitosan, carboxyalkylchitosan, caprolactone-modified chitosan More preferred is at least one selected from the group consisting of hydroxyalkyl cellulose and carboxyalkyl cellulose.
These polysaccharides can be used individually by 1 type or in combination of 2 or more types.
Examples of hydroxyalkyl chitosan include hydroxyethyl chitosan, hydroxypropyl chitosan, glycerylated chitosan and the like.
Examples of hydroxyalkyl cellulose include hydroxyethyl cellulose and hydroxypropyl cellulose.
Examples of carboxyalkyl chitosan include carboxymethyl chitosan and carboxyethyl chitosan.
Examples of carboxyalkyl cellulose include carboxymethyl cellulose and carboxyethyl cellulose.

The acid and acid derivative used in the coating solution according to the present invention are not particularly limited as long as the polysaccharide can be cross-linked, but those capable of cross-linking the polysaccharide by a thermal reaction are preferable. The acid and acid derivative preferably have a temperature at which the crosslinking reaction occurs at 100 to 400 ° C. If the temperature is 100 ° C. or lower, the crosslinking reaction is too fast and difficult to handle. Above 400 ° C, the current collector may be affected. The acid or acid derivative is preferably a polyvalent organic acid or a polyvalent organic acid derivative. Examples of acid derivatives include esters, acid halides, acid anhydrides, and the like. Of these, acid anhydrides are preferred. Carboxylic anhydride reacts with polysaccharides and moisture to become polyvalent carboxylic acid. As the organic acid, a polybasic acid is preferable in that it has a high crosslinking effect. As the polybasic acid, tribasic acid, tetrabasic acid or pentabasic acid is preferable.

Preferred acids or acid derivatives include 1,2,3,4-butanetetracarboxylic acid, phthalic acid, adipic acid, trimellitic acid, pyromellitic acid, maleic acid, salicylic acid, citric acid, malic acid, pyrrolidone carboxylic acid, Examples thereof include succinic acid, phthalic anhydride, adipic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride. These acids or acid derivatives can be used alone or in combination of two or more.
The total amount of the acid and the acid derivative is not particularly limited, but is preferably 20 to 300 parts by mass, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the polysaccharide. If the total amount of acid and acid derivative is too small, it is difficult to obtain a crosslinking effect. When the total amount of the acid and the acid derivative is too large, a lot of acidic components tend to remain.

There is no restriction | limiting in particular in the solvent used for the coating liquid which concerns on this invention, For example, an aprotic polar solvent, a protic polar solvent, water, etc. are used. Such a solvent is preferably one that evaporates at a temperature below the temperature at which the crosslinking reaction starts. Specifically, the boiling point at normal pressure is preferably 50 to 300 ° C., more preferably 100 to 220 ° C.
Examples of the aprotic polar solvent include ethers, carbonates, amides and the like. Examples of the protic polar solvent include alcohols and polyhydric alcohols. A solvent can be used individually by 1 type or in combination of 2 or more types.

The amount of the solvent used in the coating liquid according to the present invention is not particularly limited as long as it can be adjusted to a viscosity suitable for the coating work. For example, the amount of the solvent used is such that the viscosity of the coating solution at the temperature at which the coating operation is performed is preferably 100 to 100,000 mPa · s, more preferably 1,000 to 50,000 mPa · s, and still more preferably 5, The amount is 000 to 20,000 mPa · s. For example, when the coating operation is performed at 25 ° C., the amount of solvent used is preferably 50 to 99 parts by weight, more preferably 70 to 95 parts by weight, and still more preferably 80 to 95 parts in 100 parts by weight of the coating solution. Part by mass.

The conductivity imparting material used in the coating liquid according to the present invention is a conductive carbon material containing carbon as a main component. As the conductive carbon material, carbon black such as acetylene black and ketjen black; vapor grown carbon fiber; graphite and the like are suitable. These conductive carbon materials can be used singly or in combination of two or more.
The conductivity imparting material preferably has a powder electrical resistance of 1 × 10 ⁻¹ Ω · cm or less in 100% green compact.

The conductivity-imparting material may be particles such as a spherical shape, or may have an anisotropic shape such as a fiber shape, a needle shape, or a rod shape.
The particulate conductivity imparting material is not particularly limited by the particle size, but preferably has a volume-based average particle size of 10 nm to 50 μm, more preferably 10 nm to 100 nm.
An anisotropic conductivity imparting material has a large surface area per weight and a large contact area with the current collector, electrode active material, etc., so even if it is added in a small amount, it is between the current collector and the electrode active material or the electrode active material. The conductivity between substances can be increased. Examples of the anisotropic conductivity imparting material include carbon nanotubes and carbon nanofibers. Carbon nanotubes and carbon nanofibers have a fiber diameter of usually 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm, and a fiber length of usually 1 to 100 μm, preferably 1 to 30 μm. It is suitable for improvement.
The total amount of the base generator, polysaccharide, acid and / or acid derivative in the coating solution for forming the layer a described later is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the conductivity-imparting material. It is. The solid content of the coating solution for forming the layer a is preferably 1 to 50% by mass.

The electrode active material used in the coating liquid according to the present invention is not particularly limited as long as it is used in an electrochemical element such as a lithium ion battery or an electric double layer capacitor.

The electrode active material used for lithium ion batteries is different for positive and negative electrodes.

The positive electrode active material used for the lithium ion battery is not particularly limited as long as it is a substance capable of inserting and extracting lithium ions. Specifically, lithium cobalt oxide (LiCoO _2), lithium manganate (LiMn ₂ O _4), lithium nickel oxide (LiNiO _2); Co, 3 ternary lithium compounds of Mn and _{Ni (Li (Co x Mn y} Ni _z ) O ₂ ), sulfur-based compounds (TiS ₂ ), olivine-based compounds (LiFePO ₄ ) and the like can be mentioned as suitable ones.
The total amount of the base generator, the polysaccharide, the acid and / or the acid derivative in the coating solution for forming the positive electrode layer b of the lithium ion battery is preferably 100 parts by mass of the positive electrode active material. 0.1 to 30 parts by mass.

The negative electrode active material used for the lithium ion battery is not particularly limited. Specific examples include graphite carbon such as graphite, amorphous graphite carbon, and oxide.
The total amount of the base generator, the polysaccharide, the acid and / or the acid derivative in the coating solution for forming the negative electrode layer b of the lithium ion battery is preferably 100 parts by mass of the negative electrode active material. 0.1 to 30 parts by mass.

In the coating liquid for forming the layer b of the lithium ion battery electrode, it is preferable to use the aforementioned conductivity imparting material and the electrode active material in combination in order to increase the conductivity of the obtained layer b. The amount of the conductivity imparting material is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the electrode active material. The solid content of the coating liquid for forming the layer b is preferably 50 to 99% by mass.

The electrode active material used for the electric double layer capacitor can be the same for the positive electrode and the negative electrode.
The electrode active material used for the electric double layer capacitor is preferably activated carbon.
The activated carbon preferably has a large specific surface area from the viewpoint of increasing the electric capacity. Specifically, the activated carbon preferably has a BET specific surface area of 800 to 2500 m ² / g. The activated carbon preferably has an average particle size (D50) of 1 μm to 50 μm. Here, the average particle diameter (D50) of the activated carbon is a volume-based 50% cumulative particle diameter (μm) measured with a Microtrac particle size distribution meter.

Examples of the activated carbon include coconut shell activated carbon and fibrous activated carbon. The activated carbon is not particularly limited by its activation method, and those obtained by a steam activation method, a chemical activation method, or the like can be employed. In addition, in order to obtain a high capacity | capacitance capacitor, what performed the alkali activation process, ie, alkali activated carbon, is suitable. The alkali activated carbon is obtained, for example, by heat-treating coconut shell, coke, polymer carbide, non-graphitizable carbide or graphitizable carbide in the presence of an alkali metal compound. Examples of graphitizable carbides include those obtained by heat-treating pitches such as petroleum pitch, coal pitch, and their organic solvent soluble components, and carbides of polyvinyl chloride compounds. . Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, and potassium carbonate.

The activated carbon preferably has a hardened bulk density (tap density) in the range of 0.3 g / cm ³ to 0.9 g / cm ³ . If the compacted bulk density is too small, the packing density is decreased, and the electric capacity per volume of the electric double layer capacitor and per cell tends to decrease. If the hardened bulk density is too large, the electric capacity per weight decreases, and the amount of electrolyte that can be retained tends to decrease, so the capacity retention rate may decrease.

The total amount of the base generator, the polysaccharide, the acid and / or the acid derivative in the coating liquid for forming the layer b of the electrode for the electric double layer capacitor is preferably 0 with respect to 100 parts by mass of the electrode active material. 1 to 20 parts by mass.

In the coating liquid for forming the layer b of the electrode for an electric double layer capacitor, it is preferable to use the aforementioned conductivity imparting material and the electrode active material in combination in order to increase the conductivity of the layer b obtained. The amount of the conductivity imparting material is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the electrode active material. The solid content of the coating liquid for forming the layer b is preferably 50 to 99% by mass.

Furthermore, various additives may be added to the coating liquid of the present invention as necessary. For example, other crosslinking agents, dispersants, wetting agents, thickeners, coupling agents, anti-settling agents, anti-skinning agents, polymerization inhibitors, antifoaming agents, electrostatic coating modifiers, sagging inhibitors, colors Examples include a minute inhibitor, a leveling agent, an effect accelerator, and a repellency inhibitor.

The method for preparing the coating liquid according to the present invention is not particularly limited. For example, a method in which a base generator, a polysaccharide, an acid and / or an acid derivative are dissolved in a solvent, and a conductivity-imparting material and / or an electrode active material is added and dispersed in the solution is preferably mentioned. it can. Moreover, according to the viscosity of a coating liquid, etc., a well-known kneader and a stirrer can be selected suitably, and it can be used for preparation of a coating liquid.

The electrode laminate according to the present invention includes a current collector, a layer a formed using a coating liquid containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, and a conductivity-imparting material; It is what has. The laminate for an electrode according to the present invention can be used in place of a conventionally known current collector in the production of an electrode.

The electrode according to the present invention includes a current collector, a layer a formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and a conductivity-imparting material, And a current collector and a layer b formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and an electrode active material. It is.
The layer a corresponds to an undercoat layer in the background art, and the layer b corresponds to an electrode active material layer in the background art.

The layer a or the layer b can be formed by a method including applying the coating liquid according to the present invention to a current collector and then generating a base.
The coating method of the coating liquid is not particularly limited, and a known coating method or drying method used in the production of an undercoat layer or an electrode active material layer used for a lithium ion battery or an electric double layer capacitor can be directly employed. .

Examples of the coating method include a casting method, a bar coater method, a dip method, and a printing method. Among these, from the point that it is easy to control the thickness of the coating film, bar coater, gravure coat, gravure reverse coat, roll coat, Meyer bar coat, blade coat, knife coat, air knife coat, comma coat, slot diamond coat, A slide die coat and a dip coat are preferred. Further, in order to adjust the coating amount, the concentration of the coating solution can be adjusted with the above solvent.
The application may be performed on a part of the current collector, on the entire surface, or on one surface or both surfaces. In the case of applying to both sides, the application operation may be performed on each side, or the application operation may be performed on both sides simultaneously.
When a thermal base generator is used in the coating liquid, the coating film may be dried simultaneously with the heat treatment described later or separately. Drying can be performed in air, under an inert gas, or under vacuum. Of these, it is preferable to perform in the atmosphere because of low cost. When a photobase generator is used in the coating solution, drying can be performed before light irradiation. The drying method is not particularly limited, but it is preferably performed within a temperature range of 100 to 400 ° C., preferably for 10 seconds to 10 minutes.

In the step of generating a base, heat treatment or light irradiation is performed according to the type of base generator contained in the coating solution.
The temperature during the heat treatment varies depending on the coating speed, heating method, etc., but is preferably 100 to 400 ° C. If the heat treatment temperature is too low, neutralization tends to be insufficient, and if the heat treatment temperature is too high, the current collector tends to be annealed. The heat treatment time is preferably 10 seconds to 10 minutes. If the heat treatment time is too short, neutralization tends to be insufficient. If the heat treatment time is too long, productivity is lowered and cost is likely to increase.

The light irradiation method is not particularly limited. As a light source for light irradiation, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, a flood bulb for photography, the sun A known light source that irradiates light such as ultraviolet light and visible light such as a lamp can be given.
The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm ² , although it depends on the thickness of layer a or b and the type of photobase generator. The irradiation energy can be controlled by the illuminance of the light source and the irradiation time.

The current collector is not particularly limited as long as it is used in a lithium ion battery, an electric double layer capacitor, or the like.
The current collector includes not only a non-perforated foil but also a punched metal foil or a perforated foil such as a net. The current collector is not particularly limited as long as it is composed of a conductive material, and examples thereof include those made of a conductive metal and those made of a conductive resin. Particularly preferred are aluminum and copper. As the aluminum foil, pure aluminum-based A1085 material, A3003 material, or the like is usually used. As the copper foil, rolled copper foil or electrolytic copper foil is usually used.
The current collector may have a smooth surface, but a surface roughened by an electrical or chemical etching process, that is, an etching foil is also suitable.

The current collector is not particularly limited by the thickness, but it is usually preferable to have a thickness of 5 μm to 100 μm. If the thickness is 5 μm or less, the strength may be insufficient and the foil may be broken in the coating process. On the other hand, when the thickness exceeds 100 μm, the ratio of the current collector in the predetermined volume increases, which may lead to a decrease in capacity.
In lithium ion batteries, aluminum is often used for the positive electrode and copper is often used for the negative electrode.
In an electric double layer capacitor, aluminum is often used for both the positive electrode and the negative electrode.
The aluminum current collector is preferably an aluminum foil, an aluminum etching foil or an aluminum punching foil. The copper current collector is preferably a copper foil, a copper etching foil or a copper punching foil.

The layer a is formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, and a conductivity-imparting material.
The layer b is formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, and an electrode active material.
An electrode active material layer is usually formed on the layer a. In the electrode according to the present invention, the electrode active material layer formed on the layer a is formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and an electrode active material. The layer b may be a well-known electrode active material layer.

The thickness of the layer a is preferably 0.01 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less. If the thickness is too thin, desired effects such as a decrease in internal resistance or impedance tend not to be obtained. On the other hand, the resistance or impedance does not become smaller than a certain value even if the thickness is increased too much.
The thickness of the electrode active material layer or layer b in the electric double layer capacitor is preferably 10 μm or more and 500 μm or less.
The thickness of the electrode active material layer or layer b in the lithium ion battery is preferably 0.1 μm or more and 500 μm or less. When the thickness is 0.1 μm or less, the desired effect tends not to be obtained. When the thickness is 500 μm or more, it is easy for the current collector to fall off.

In addition, the layer a or the layer b formed with the coating liquid according to the present invention can be peeled off from the current collector and used as a film. The membrane has high ion permeability or ion mobility.

The electrochemical device according to the present invention has the electrode according to the present invention described above, and further usually has a separator and an electrolytic solution. The electrodes in the electrochemical device according to the present invention may both be the electrodes according to the present invention, or one of them may be the electrode according to the present invention and the other may be a known electrode.
A separator and electrolyte solution will not be restrict | limited especially if used in secondary batteries, such as a lithium ion battery, an electric double layer capacitor, a hybrid capacitor.

The electrochemical element according to the present invention can be applied to a power supply system. And this power supply system includes automobiles; transport equipment such as railways, ships and airplanes; portable equipment such as mobile phones, personal digital assistants and portable electronic computers; office equipment; solar power generation systems, wind power generation systems, fuel cell systems, etc. It can be applied to the power generation system.

Next, the present invention will be described more specifically with reference to examples and comparative examples. The scope of the present invention is not limited by this embodiment. The coating liquid, film, electrode laminate, electrode, electrochemical device, power supply system, automobile, transportation equipment, portable device, and power generation system according to the present invention are appropriately modified and implemented without departing from the scope of the present invention. can do.

Production Example 1: Preparation of solutions 1 to 6 According to the formulation shown in Table 1, polysaccharides and acids and / or acid derivatives were added and dissolved in a solvent to obtain solutions 1 to 6.

Production Example 2: Preparation of Solutions 7 to 15 According to the formulation shown in Table 2, polysaccharides, acids and / or acid derivatives, and base generators were added and dissolved in solvents to obtain solutions 7 to 15.

<Example 1>
(Manufacture of coating liquid for undercoat layer manufacturing)
10 parts by mass of acetylene black (average particle size 40 nm) as a conductivity imparting material and 790 parts by mass of solution 790 were stirred and mixed at a rotation speed of 60 rpm for 120 minutes with a planetary mixer. The mixed solution was diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the thickness of the resulting undercoat layer was 5 μm to obtain a slurry-like coating solution for producing an undercoat layer.

(Manufacture of aluminum foil with an undercoat layer)
An aluminum foil having a thickness of 30 μm made of A1085 material washed with alkali was prepared. Using an applicator with a gap of 10 μm, an undercoat layer production coating solution was applied onto an aluminum foil by a casting method. Then, it heated at 180 degreeC for 3 minute (s), was made to dry, a crosslinking reaction, and neutralization reaction, and obtained the aluminum foil provided with the undercoat layer.

(Evaluation of pH of undercoat layer)
The aluminum foil provided with the undercoat layer was immersed in pure water and sealed. The pH was measured after 24 hours. The amount of water was 0.02 ml with respect to 1 cm ^{2 of} application area. The results are shown in Table 3.

(Evaluation as a lithium ion battery)
To 95 parts by mass of lithium cobaltate as a positive electrode active material, 2 parts by mass of polyvinylidene fluoride as a binder, and 3 parts by mass of acetylene black (average particle size 40 nm) as a conductivity-imparting material, N— Methyl-2-pyrrolidone was added to produce a positive electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 200 μm.
The positive electrode paste was applied to an aluminum foil provided with an undercoat layer, dried, and an electrode active material layer having a thickness of 200 μm was formed on the undercoat layer to obtain a positive electrode for a lithium ion secondary battery.

92 parts by mass of graphite as a negative electrode active material, 3 parts by mass of polyvinylidene fluoride as a binder, and 5 parts by mass of acetylene black (average particle diameter 40 nm) as a conductivity-imparting material, N-methyl- 2-Pyrrolidone was added to produce a negative electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 250 μm.
The negative electrode paste was applied to an electrolytic copper foil having a thickness of 9 μm and dried to form an electrode active material layer having a thickness of 250 μm, thereby obtaining a negative electrode for a lithium ion secondary battery.

A porous polyethylene separator was incorporated between the positive electrode and the negative electrode obtained above, and these were impregnated with an organic electrolyte solution to assemble a lithium ion battery.
The organic electrolyte is a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1/1, the electrolyte is LiPF ₆ , and the concentration is 1 mol / liter, trade name LIPASTER-EDMC / PF1 manufactured by Toyama Pharmaceutical Co., Ltd. used.

The initial capacity retention ratio and internal resistance of the lithium ion battery were measured. The results are shown in Table 3.
The initial capacity retention rate was determined by measuring the capacity after 100 cycles at a current rate of 20 C using a battery charging / discharging device HJ-2010 model manufactured by Hokuto Denko Co., Ltd. as the measuring instrument. The percentage relative to is expressed as a percentage.
The internal resistance was measured at a measurement frequency of 1 kHz by an AC impedance method using a HIOKI3551 battery tester.

Moreover, the aluminum foil provided with the undercoat layer obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the aluminum foil stored in the environment, a lithium ion battery was manufactured in the same manner as described above. The internal resistance of this lithium ion battery was measured. The results are shown in Table 3.

(Evaluation as an electric double layer capacitor)
85 parts by mass of activated carbon (alkaline activated charcoal having a specific surface area of 1500 m ² / g) as an electrode active material, 10 parts by mass of polyvinylidene fluoride as a binder, and 5 parts by mass of acetylene black (average particle diameter 40 nm) as a conductivity-imparting material To this part, N-methyl-2-pyrrolidone as a solvent was added to produce an electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 200 μm.

The electrode paste is applied to the aluminum foil having the undercoat layer obtained above and dried, and an electrode active material layer having a thickness of 200 μm is formed on the undercoat layer. Obtained.
Next, two electric double layer capacitor electrodes were punched out with a diameter of 20 mmφ in accordance with the size of the capacitor container for evaluation. Two electrodes are stacked with a glass nonwoven fabric separator in between, placed in an evaluation capacitor container, poured into the container with an organic electrolyte, immersed in the electrode, and finally covered with a container, An electric double layer capacitor for evaluation was produced.
As the organic electrolytic solution, trade name LIPASTE-P / EAFIN manufactured by Toyama Pharmaceutical Co., Ltd., having a solvent of propylene carbonate, an electrolyte of (C ₂ H ₅ ) ₄ NBF ₄ and a concentration of 1 mol / liter was used.

The impedance and electric capacity of the electric double layer capacitor were measured. The results are shown in Table 4.
The impedance was measured under the condition of 1 kHz using an impedance measuring instrument (PAN110-5AM) manufactured by KIKUSUI.
The electric capacity was measured using a charge / discharge test apparatus (HJ-101SM6) manufactured by Hokuto Denko Corporation at a current density of 1.59 mA / cm ² at a voltage of 0 to 2.5 V, during the second constant current discharge. The electric capacity (F / cell) per cell of the electric double layer capacitor was calculated from the measured discharge curve. The capacity retention rate (%) was calculated by a formula of (electric capacity at the 50th cycle) / (electric capacity at the second cycle) × 100.

The aluminum foil provided with the undercoat layer obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the aluminum foil stored in the environment, an electric double layer capacitor was manufactured in the same manner as described above. The impedance of this electric double layer capacitor was measured. The results are shown in Table 4.

<Examples 2 to 6>
A coating liquid for producing an undercoat layer was prepared in the same manner as in Example 1 except that Solution 8, Solution 10, Solution 11, Solution 12 and Solution 13 were used instead of Solution 7, respectively. The aluminum foil provided with was obtained. Then, the pH of the undercoat layer, the characteristics of the lithium ion battery, and the electric double layer capacitor were measured in the same manner as in Example 1. The results are shown in Table 3 and Table 4.

<Example 7>
A coating solution for producing an undercoat layer was produced in the same manner as in Example 1 except that the solution 9 was used instead of the solution 7.
An aluminum foil provided with an undercoat layer was produced in the same manner as in Example 1 except that this coating liquid for producing an undercoat layer was used and the drying conditions were changed to 250 ° C. for 1 minute.
Then, the pH of the undercoat layer, the characteristics of the lithium ion battery, and the electric double layer capacitor were measured in the same manner as in Example 1. The results are shown in Table 3 and Table 4.

<Examples 8 and 9>
A coating solution for producing an undercoat layer was produced in the same manner as in Example 1 except that the solution 14 and the solution 15 were used instead of the solution 7, respectively.
Using this coating solution for undercoat layer production, the drying conditions were changed to 180 ° C. for 3 minutes, and after drying, ultraviolet rays (wavelength 365 nm) were applied using an ultraviolet lamp, and the irradiation energy was 900 mJ / cm ^2. Thus, an aluminum foil provided with an undercoat layer was manufactured in the same manner as in Example 1 except that irradiation was performed for 10 minutes at an ultraviolet illuminance of 1.5 mW / cm ² .
Then, the pH of the undercoat layer, the characteristics of the lithium ion battery, and the electric double layer capacitor were measured in the same manner as in Example 1. The results are shown in Table 3 and Table 4.

<Comparative Examples 1 to 6>
A coating liquid for producing an undercoat layer was prepared in the same manner as in Example 1 except that the solutions 1 to 6 were used in place of the solution 7 to obtain an aluminum foil provided with the undercoat layer. Then, the pH of the undercoat layer, the characteristics of the lithium ion battery, and the electric double layer capacitor were measured in the same manner as in Example 1. The results are shown in Table 3 and Table 4.

<Example 10>
(Manufacture of copper foil with an undercoat layer)
A copper foil provided with an undercoat layer was obtained in the same manner as in Example 1 except that an electrolytic copper foil having a thickness of 9 μm was used instead of the aluminum foil.

(Evaluation of pH of undercoat layer)
The pH of the copper foil provided with the undercoat layer obtained above was evaluated by the same method as in Example 1. The results are shown in Table 5.

(Evaluation as a lithium ion battery)
92 parts by mass of graphite as a negative electrode active material, 3 parts by mass of polyvinylidene fluoride as a binder, and 5 parts by mass of acetylene black (average particle diameter 40 nm) as a conductivity-imparting material, N-methyl- 2-Pyrrolidone was added to produce a negative electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 250 μm.
A negative electrode active material layer having a thickness of 250 μm is formed on the undercoat layer by applying the negative electrode paste to the copper foil provided with the undercoat layer and drying the resulting copper foil. A negative electrode was obtained.

To 95 parts by mass of lithium cobaltate as a positive electrode active material, 2 parts by mass of polyvinylidene fluoride as a binder, and 3 parts by mass of acetylene black (average particle size 40 nm) as a conductivity-imparting material, N— Methyl-2-pyrrolidone was added to produce a positive electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 200 μm.
The positive electrode paste was applied to an aluminum foil having a thickness of 30 μm made of alkali-washed A1085 material and dried to form a positive electrode active material layer having a thickness of 200 μm to obtain a positive electrode for a lithium ion secondary battery. .

A lithium polyethylene separator was assembled by incorporating a porous polyethylene separator between the positive electrode and the negative electrode obtained above and impregnating the separator with an organic electrolyte.
The organic electrolyte is a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1/1, the electrolyte is LiPF ₆ , and the concentration is 1 mol / liter, trade name LIPASTER-EDMC / PF1 manufactured by Toyama Pharmaceutical Co., Ltd. used.

In the same manner as in Example 1, the initial capacity retention rate and internal resistance of the lithium ion battery were measured. Table 5 shows the measurement results.
Moreover, the copper foil provided with the undercoat layer obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the copper foil stored in the environment, a lithium ion battery was manufactured in the same manner as described above. The internal resistance of this lithium ion battery was measured. Table 5 shows the measurement results.

<Example 11>
A coating solution for producing an undercoat layer was obtained in the same manner as in Example 10 except that the solution 9 was used instead of the solution 7.
A copper foil provided with an undercoat layer was obtained in the same manner as in Example 10 except that the drying condition was changed to 250 ° C. and 1 minute using the coating solution. Then, the pH of the undercoat layer and the characteristics of the lithium ion battery were measured by the same method as in Example 10. The results are shown in Table 5.

<Examples 12 to 16>
A copper foil provided with an undercoat layer was obtained in the same manner as in Example 10 except that Solution 8, Solution 10, Solution 11, Solution 12, and Solution 13 were used instead of Solution 7, respectively. Then, the pH of the undercoat layer and the characteristics of the lithium ion battery were measured by the same method as in Example 10. The results are shown in Table 5.

<Examples 17 to 18>
A coating solution for producing an undercoat layer was produced in the same manner as in Example 10 except that the solution 14 and the solution 15 were used in place of the solution 7, respectively.
Using this coating solution, the drying conditions are changed to 180 ° C. for 3 minutes, and after drying, ultraviolet rays (wavelength 365 nm) are applied using an ultraviolet lamp to 1.5 mW so that the irradiation energy is 900 mJ / cm ^2. A copper foil provided with an undercoat layer was obtained in the same manner as in Example 10 except that irradiation was performed for 10 minutes at an ultraviolet illuminance of / cm ² . Then, the pH of the undercoat layer and the characteristics of the lithium ion battery were measured by the same method as in Example 10. The results are shown in Table 5.

<Comparative Examples 7-12>
A copper foil provided with an undercoat layer was obtained in the same manner as in Example 10 except that the solutions 1 to 6 were used in place of the solution 7, respectively. Then, the pH of the undercoat layer and the characteristics of the lithium ion battery were measured by the same method as in Example 10. The results are shown in Table 5.

<Example 19>
(Manufacture of coating liquid for manufacturing electrode active material layer of electric double layer capacitor)
Planetary, 85 parts by mass of activated carbon (alkaline activated charcoal having a specific surface area of 1500 m ² / g) as an electrode active material, 5 parts by mass of acetylene black (average particle size 40 nm) as a conductivity imparting material, and 750 parts by mass of a solution The mixture was stirred and mixed at a rotation speed of 60 rpm for 120 minutes with a mixer. The mixed solution is diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the resulting electrode active material layer has a thickness of 200 μm to obtain a slurry-like electrode active material layer production coating solution. It was.

(Manufacture of electrodes)
An aluminum foil having a thickness of 30 μm made of A1085 material washed with alkali was prepared. Using an applicator with a gap of 250 μm, the above-mentioned coating liquid for producing an electrode active material layer was applied onto an aluminum foil by a casting method. Then, it heated at 180 degreeC for 3 minute (s), and the drying, crosslinking reaction, and neutralization reaction were made, and the electrode was obtained.

(Evaluation of pH of electrode active material layer)
The pH evaluation of the electrode active material layer obtained above was performed by the same method as the pH evaluation of the undercoat layer in Example 1. The results are shown in Table 6.

(Evaluation as an electric double layer capacitor)
Two of the electrodes obtained above were punched out with a diameter of 20 mm in accordance with the size of the evaluation capacitor container. Two electrodes are stacked with a glass nonwoven fabric separator in between, placed in an evaluation capacitor container, poured into the container with an organic electrolyte, immersed in the electrode, and finally covered with a container, An electric double layer capacitor for evaluation was produced.
As the organic electrolytic solution, trade name LIPASTE-P / EAFIN manufactured by Toyama Pharmaceutical Co., Ltd., having a solvent of propylene carbonate, an electrolyte of (C ₂ H ₅ ) ₄ NBF ₄ and a concentration of 1 mol / liter was used.

In the same manner as in Example 1, the impedance and capacitance of the electric double layer capacitor obtained above were measured. The results are shown in Table 6.
The electrode obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the electrode stored in the environment, an electric double layer capacitor was manufactured in the same manner as described above. The impedance of this electric double layer capacitor was measured. The results are shown in Table 6.

<Example 20>
A coating solution for producing an electrode active material layer was produced in the same manner as in Example 19 except that the solution 9 was used instead of the solution 7.
An electrode was obtained in the same manner as in Example 19 except that the coating solution was used and the drying conditions were changed to 250 ° C. for 1 minute.
In the same manner as in Example 19, the pH of the electrode active material layer and the characteristics of the electric double layer capacitor were measured. The results are shown in Table 6.

<Examples 21 to 25>
An electrode was obtained in the same manner as in Example 19 except that Solution 8, Solution 10, Solution 11, Solution 12, and Solution 13 were used instead of Solution 7, respectively.
In the same manner as in Example 19, the pH of the electrode active material layer and the characteristics of the electric double layer capacitor were measured. The results are shown in Table 6.

<Examples 26 to 27>
A coating solution for producing an electrode active material layer was produced in the same manner as in Example 19 except that the solution 14 and the solution 15 were used instead of the solution 7, respectively.
Using this coating solution, the drying conditions were changed to 180 ° C. for 3 minutes, and after drying, ultraviolet rays (wavelength 365 nm) were applied using an ultraviolet lamp to 1.5 mW so that the irradiation energy was 900 mJ / cm ^2. An electrode was obtained in the same manner as in Example 19 except that irradiation was performed at an ultraviolet illuminance of / cm ² for 10 minutes.
In the same manner as in Example 19, the pH of the electrode active material layer and the characteristics of the electric double layer capacitor were measured. The results are shown in Table 6.

<Comparative Examples 13 to 18>
An electrode was obtained in the same manner as in Example 19 except that solutions 1 to 6 were used instead of solution 7, respectively.
In the same manner as in Example 19, the pH of the electrode active material layer and the characteristics of the electric double layer capacitor were measured. The results are shown in Table 6.

<Example 28>
(Manufacture of coating solution for manufacturing positive electrode of lithium ion battery)
95 parts by mass of lithium cobaltate as a positive electrode active material, 5 parts by mass of acetylene black (average particle size 40 nm) as a conductivity-imparting material, and 40 parts by mass of a solution 7 are 120 minutes at a rotation speed of 60 rpm with a planetary mixer. Stir and mix. The mixed solution is diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the thickness of the obtained positive electrode active material layer becomes 200 μm, and a slurry-like coating solution for producing a lithium ion battery positive electrode is obtained. Got.

(Manufacture of positive electrode)
An aluminum foil having a thickness of 30 μm made of A1085 material washed with alkali was prepared. Using the applicator with a gap of 250 μm, the above-mentioned coating solution for producing a positive electrode was applied on an aluminum foil by a casting method. Then, it heated at 180 degreeC for 3 minute (s), and the drying, the crosslinking reaction, and the neutralization reaction were made, and the positive electrode was obtained.

(Manufacture of coating solution for manufacturing negative electrode of lithium ion battery)
92 parts by mass of graphite as a negative electrode active material, 5 parts by mass of acetylene black (average particle size 40 nm) as a conductivity imparting material, and 750 parts by mass of a solution are stirred and mixed at a rotation speed of 60 rpm for 120 minutes using a planetary mixer. I let you. The mixed solution is diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the thickness of the obtained electrode active material layer is 250 μm to obtain a slurry-like coating solution for producing an electric double layer capacitor negative electrode. It was.

(Manufacture of negative electrode)
Using an applicator having a gap of 300 μm, a coating solution for producing a negative electrode was applied onto an electrolytic copper foil having a thickness of 9 μm. Then, it heated at 180 degreeC for 3 minute (s), and the drying, the crosslinking reaction, and the neutralization reaction were made, and the negative electrode was obtained.

(PH evaluation of positive electrode active material layer and negative electrode active material layer)
In the same manner as the pH evaluation of the undercoat layer in Example 1, the pH evaluation of the positive electrode active material layer and the negative electrode active material layer obtained above was performed. The results are shown in Table 7.

(Evaluation as a lithium ion battery)
A porous polyethylene separator was incorporated between the positive electrode and the negative electrode obtained above, and these were impregnated with an organic electrolyte solution to assemble a lithium ion battery.
The organic electrolyte used was a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1/1, the electrolyte was LiPF ₆ , and the product name LIPASTER-EDMC / PF1 manufactured by Toyama Pharmaceutical Co., Ltd., having a concentration of 1 mol / liter. .

In the same manner as in Example 1, the initial capacity retention rate and internal resistance of the lithium ion battery were measured. Table 7 shows the measurement results.
Further, the positive electrode and the negative electrode obtained above were stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the positive electrode and the negative electrode stored in the environment, a lithium ion battery was manufactured by the same method as described above. The internal resistance of this lithium ion battery was measured. Table 7 shows the measurement results.

<Example 29>
A positive electrode manufacturing coating solution and a negative electrode manufacturing coating solution were prepared in the same manner as in Example 28 except that the solution 9 was used instead of the solution 7.
A positive electrode and a negative electrode were obtained in the same manner as in Example 28 except that the coating solution was used and the drying conditions were changed to 250 ° C. for 1 minute.
In the same manner as in Example 28, the pH of the positive electrode active material layer and the negative electrode active material layer and the characteristics of the lithium ion battery were measured. The results are shown in Table 7.

<Examples 30 to 34>
A positive electrode and a negative electrode were obtained in the same manner as in Example 28 except that Solution 8, Solution 10, Solution 11, Solution 12, and Solution 13 were used instead of Solution 7, respectively.
In the same manner as in Example 28, the pH of the positive electrode active material layer and the negative electrode active material layer and the characteristics of the lithium ion battery were measured. The results are shown in Table 7.

<Examples 35 to 36>
A positive electrode manufacturing coating solution and a negative electrode manufacturing coating solution were prepared in the same manner as in Example 28 except that the solution 14 and the solution 15 were used instead of the solution 7, respectively.
Using this coating solution, the drying conditions were changed to 180 ° C. for 3 minutes, and after drying, ultraviolet rays (wavelength 365 nm) were applied using an ultraviolet lamp to 1.5 mW so that the irradiation energy was 900 mJ / cm ^2. A positive electrode and a negative electrode were obtained in the same manner as in Example 28 except that irradiation was performed for 10 minutes at an ultraviolet illuminance of / cm ² .
In the same manner as in Example 28, the pH of the positive electrode active material layer and the negative electrode active material layer and the characteristics of the lithium ion battery were measured. The results are shown in Table 7.

<Comparative Examples 19 to 24>
A positive electrode and a negative electrode were obtained in the same manner as in Example 28 except that the solutions 1 to 6 were used in place of the solution 7, respectively.
In the same manner as in Example 28, the pH of the positive electrode active material layer and the negative electrode active material layer and the characteristics of the lithium ion battery were measured. The results are shown in Table 7.

From the above results, the pH of the undercoat layer or electrode active material layer obtained with the coating solution containing the polysaccharide and the organic acid (comparative example) is low, and the lithium ion battery or electric battery obtained in the comparative example is low. It can be seen that the multilayer capacitor has insufficient characteristics.
On the other hand, a coating solution containing a base generator, a polysaccharide, an organic acid, a solvent, a conductivity-imparting material and / or an electrode active material produced according to the present invention, an undercoat layer or When the electrode active material layer is formed, the undercoat layer or the electrode active material layer has a pH of around 7, and the lithium ion battery and electric double layer capacitor manufactured according to the present invention are of comparative examples. It turns out that it is favorable compared with.

Claims (17)

1. A coating solution for producing an electrochemical element, comprising a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent, a conductivity imparting material and / or an electrode active material.
2. The coating solution according to claim 1, wherein the base generator is a thermal base generator.
3. The coating solution according to claim 2, wherein the thermal base generator is urea or a urea derivative.
4. The coating solution according to claim 1, wherein the base generator is a photobase generator.
5. Photobase generator is 2-nitrobenzyl cyclohexyl carbamate, 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, 1,1-dimethyl-2-phenylethyl-N-isopropyl carbamate, triphenylmethanol, o-carbamoyl The coating solution according to claim 4, which is hydroxylamide, N-cyclohexyl-4-methylphenylsulfonamide or o-carbamoyloxime.
6. The coating solution according to any one of claims 1 to 5, wherein the acid and / or the acid derivative is a polyvalent organic acid and / or a polyvalent organic acid derivative.
7. The coating solution according to any one of claims 1 to 6, wherein the acid derivative is an acid anhydride.
8. A film formed using the coating liquid according to any one of claims 1 to 7.
9. A current collector,
   A layered product for an electrode having a layer a formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and a conductivity-imparting material.
10. A current collector,
    A layer a formed using a coating liquid containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and a conductivity-imparting material;
    An electrode having an electrode active material layer.
11. A current collector,
    An electrode having a layer b formed using a coating solution containing a base generator, a polysaccharide, an acid and / or an acid derivative, a solvent and an electrode active material.
12. An electrochemical element having the electrode according to claim 10 or 11.
13. A power supply system having the electrochemical element according to claim 12.
14. An automobile having the electrochemical element according to claim 12.
15. Transportation equipment having the electrochemical element according to claim 12.
16. A portable device having the electrochemical element according to claim 12.
17. A power generation system having the electrochemical element according to claim 12.