JP2018160450A - Dispersant composition for power storage device slurry, and utilization thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a dispersant composition for a power storage device slurry, which achieves satisfactory dispersion stability; a power storage device slurry composition which achieves satisfactory coatability and coating dryability; and a power storage device arranged by use of the power storage device slurry composition.SOLUTION: A dispersant composition for a power storage device slurry comprises: a component (A); and a component (B). The component (A) is a polymer A including a carboxyl group-containing monomer unit (I) of 15-40 wt.%, exclusive of 40 wt.% and a monomer unit (II) represented by the formula (1) and accounting for 40-85 wt.%, exclusive of 85 wt.%, and having a weight-average molecular weight under 500000. The component (B) is a polymer B including a carboxyl group-containing monomer unit (I) of 0-15 wt.%, exclusive of 15 wt.%, and a monomer unit (II) represented by the formula (1) below and accounting for 70-100 wt.%: CH=CRCOOCHR(1) (where Rrepresents H or CH; Rrepresents H or OH; n is an integer satisfying n=1-20).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dispersant composition for an electricity storage device slurry and use thereof.

  In recent years, in electronic devices, secondary batteries such as lithium ion secondary batteries, nickel hydride secondary batteries, nickel cadmium secondary batteries and capacitors such as electric double layer capacitors that can be repeatedly used by charging have been used. . Secondary batteries are being rapidly developed as batteries for use in portable electronic devices and hybrid vehicles. In addition, capacitors are also being developed in the same manner as backup power supplies and power supplies for small electronic devices. Lithium ion secondary batteries and capacitors are mainly composed of a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte solution, and various studies have been made to improve battery and capacitor characteristics.

  For example, the positive electrode is manufactured by applying a positive electrode slurry containing a positive electrode active material and a solvent to a current collector and drying. The negative electrode is produced by applying and drying a negative electrode slurry containing a negative electrode active material and a solvent on a current collector. The separator is a material capable of isolating the positive electrode and the negative electrode and improving the safety of the battery. For example, a polyolefin porous film has excellent characteristics. In addition, a separator whose surface is coated by applying a slurry for a separator containing organic particles or inorganic particles to the surface of a separator substrate such as a polyolefin porous film and drying the same has been developed. However, in a situation where a secondary battery and a capacitor having a larger capacity are demanded, there has been a demand for a material for an electricity storage device that can further enhance safety.

As a means for ensuring safety, for example, there is a method of providing a shutdown function for preventing further heat generation by blocking the passage of ions between the positive and negative electrodes by the above-described separator in the event of abnormal heat generation. With the shutdown function, the separator melts and becomes non-porous in the event of abnormal heat generation, blocking the passage of ions and further suppressing heat generation. For example, a separator made of a polyolefin porous film is about 80 to 180 ° C. when the battery is abnormally heated.
Further heat generation is suppressed by blocking (shutdown) the passage of ions by melting and making nonporous. However, when the heat generation is severe, the separator made of the porous film may cause a short circuit due to direct contact between the positive electrode and the negative electrode due to shrinkage or film breakage. Thus, the separator made of a polyolefin porous film has insufficient shape stability and sometimes cannot suppress abnormal heat generation due to a short circuit.

For example, Patent Document 1 is formed by laminating a heat-resistant layer containing fine particle filler and a porous film mainly composed of polyolefin as a base material (hereinafter sometimes referred to as “base material porous film”). A separator for a non-aqueous electrolyte secondary battery comprising a laminated porous film; Patent Document 2 discloses a method using a fine particle filler whose surface is modified as a heat-resistant layer of the separator; Patent Document 3 describes a chemical structure of a binder resin. A method of binding a filler is disclosed.

  However, these methods do not solve the dispersibility of the inorganic powder in the electricity storage device slurry, the storage stability of the electricity storage device slurry, the film formation property of the electricity storage device slurry, the drying property, uniformity and heat resistance of the coating film. There is a need for further performance improvements.

JP 2004-227972 A JP 2007-31151 A JP 2006-331760 A

  An object of the present invention is to provide a dispersion composition for an electricity storage device slurry having good dispersion stability, an electricity storage device slurry composition having good coating properties and coating drying properties, and an electricity storage having good coating properties and coating drying properties. It is providing the manufacturing method of a device slurry composition, and the electrical storage device using this electrical storage device slurry composition.

  As a result of intensive studies, the present inventors have found that the dispersant composition for an electricity storage device slurry containing two specific types of polymer components can solve the problem of the present application, and have reached the present invention.

That is, the dispersant composition for an electricity storage device slurry of the present invention contains the following component (A) and the following component (B).
Component (A): The carboxyl group-containing monomer unit (I) is 15% by weight or more and less than 40% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 40% by weight or more and 85% by weight. Polymer component A having a weight average molecular weight of less than 500,000
Component (B): The carboxyl group-containing monomer unit (I) is 0% by weight or more and less than 15% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 70% by weight or more and 100% by weight. Polymer component B, which is
CH ₂ = CR ¹ COOC _n H _2n R ² (1)
(In the formula (1), R ¹ is H or CH ₃ , R ² is H or OH, and n = 1 to 20.)

When the component (A) is 100 parts by weight, the component (B) is preferably 5 to 800 parts by weight.
The component (A) preferably contains at least one selected from the monomer unit (II-1) where n is 1 and the monomer unit (II-2) where n is 2.
The component (A) includes the monomer unit (II-1) and the monomer unit (II-2), and the monomer unit (II-1) and the monomer unit (II- The weight ratio (II-1 / II-2) of 2) is preferably more than 0 and less than 0.8.
The component (B) is a monomer unit (II-1) in which n is 1, a monomer unit (II-2) in which n is 2, and a monomer unit (in which n is 3). II-3) and preferably containing at least one selected from monomer units (II-4) wherein n is 4-20.
The component (B) comprises the monomer unit (II-1), the monomer unit (II-2), the monomer unit (II-3), and the monomer unit (II-4). The monomer unit (II-1), the monomer unit (II-2) in which n is 2, and the monomer in which n is 3 The weight ratio [II-1 / (II-2 + II-3 + II-4)] of the unit (II-3) and the total of the monomer units (II-4) wherein n is 4 to 20 is represented by the following formula. It is preferable to satisfy (2).
0 <II-1 / (II-2 + II-3 + II-4) <1.2 (2)
When the glass transition point of the component (A) is Tg (A) (° C.) and the glass transition point of the component (B) is Tg (B) (° C.), it is preferable that the following mathematical formula (3) is satisfied.
0 ≦ | Tg (A) −Tg (B) | ≦ 50 (3)
It is preferable that the component (A) and / or the component (B) further contains a nitrogen-containing monomer unit (III).
The component (B) preferably further contains a glycidyl group-containing monomer unit (IV).

An electricity storage device slurry composition containing the following component (A), the following component (B) and inorganic particles (F), and may contain the following component (C):
When the content of the inorganic particles (F) is 100 parts by weight, the respective contents are 0.01 to 20 parts by weight for the component (A) and 0.1 to 40 parts by weight for the component (B). Part and the said component (C) are 0-20 weight part.
Component (A): The carboxyl group-containing monomer unit (I) is 15% by weight or more and less than 40% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 40% by weight or more and 85% by weight. Polymer component A having a weight average molecular weight of less than 500,000
Component (B): The carboxyl group-containing monomer unit (I) is 0% by weight or more and less than 15% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 70% by weight or more and 100% by weight. Polymer component B, which is
CH ₂ = CR ¹ COOC _n H _2n R ² (1)
(In the formula (1), R ¹ is H or CH ₃ , R ² is H or OH, and n = 1 to 20.)
Component (C): Surfactant

The positive electrode of the present invention is a positive electrode having a positive electrode coating film on a current collector, and the coating film is formed by a non-volatile component of the electricity storage device slurry composition.
The negative electrode of the present invention is a negative electrode having a negative electrode coating film on a current collector, and the coating film is formed of a nonvolatile component of the electricity storage device slurry composition.
The separator of this invention is a separator which has a coating film for separators, Comprising: The said coating film is formed with the non volatile matter of the said electrical storage device slurry composition.
The electricity storage device of the present invention is an electricity storage device including a negative electrode, a positive electrode, a separator, and an electrolyte solution, and at least one of the negative electrode, the positive electrode, and the separator is formed by a nonvolatile component of the electricity storage device slurry composition. It has the film which becomes.

  The slurry containing the dispersant composition for an electricity storage device slurry of the present invention has good dispersion stability. The electricity storage device slurry composition of the present invention is excellent in coating property and coating drying property. The film for an electricity storage device produced using the electricity storage device slurry composition of the present invention is excellent in heat resistance and liquid retention.

Schematic of the dispersing agent composition for electrical storage device slurries.

  The dispersant composition for an electricity storage device slurry of the present invention essentially contains the component (A) and the component (B). First, each component which comprises the dispersing agent composition for electrical storage device slurries is demonstrated in detail. In addition, the electrical storage device slurry of this invention contains the slurry for secondary batteries, and the slurry for capacitors.

[Component (A)]
Component (A) is a polymer component A obtained by polymerizing a polymerizable monomer. Component (A) has a carboxyl group-containing monomer unit (I) of 15 wt% or more and less than 40 wt% with respect to the entire polymerizable monomer, and is a single amount of the above chemical formula (1) with respect to the entire polymerizable monomer The polymer component A has a body unit (II) of 40% by weight or more and less than 85% by weight and a weight average molecular weight of less than 500,000.
The component (A) functions as a dispersion aid for inorganic particles and an applicability improver for the electricity storage device slurry composition. Moreover, it functions also as a binder of inorganic particles after apply | coating an electrical storage device slurry to a base material and drying water.

  In the component (A), the weight ratio of the carboxyl group-containing monomer unit (I) is 15% by weight or more and less than 40% by weight, and is preferably 15 to 36% by weight from the viewpoint of dispersion stability. -32 wt% is more preferred, 15-28 wt% is particularly preferred, and 15-24 wt% is most preferred. If it is less than 15% by weight or 40% by weight or more, the dispersion stability may be deteriorated.

  Examples of the carboxyl group-containing monomer unit (I) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and citraconic acid.

In the component (A), the weight ratio of the monomer unit (II) of the chemical formula (1) to the entire polymerizable monomer is 40% by weight or more and less than 85% by weight, and from the viewpoint of dispersion stability, 45 -85 wt% is more preferable, 50-85 wt% is more preferable, 55-85 wt% is particularly preferable, and 60-85 wt% is most preferable. If it is less than 40% by weight or more than 85% by weight, the dispersion stability may be deteriorated. The said whole polymerizable monomer shall mean the whole monomer unit which comprises a polymer. Hereinafter, the description of the entire polymerizable monomer in the present application is the same.
As the monomer unit of the chemical formula (1), methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, methacryl Pentyl acid, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, undecyl methacrylate , Dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, pentadecyl acrylate, pentadec methacrylate , Hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, nonadecyl acrylate, nonadecyl methacrylate, icosyl acrylate, icosyl methacrylate (of the above monomer units, The alkyl chain may be optionally branched, and H at any one position of the alkyl chain may be substituted with OH), or one or more of them may be used in combination. Examples of the monomer unit in which H is substituted with OH include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and methacrylic acid 2 -Hydroxypropyl, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like. From the viewpoint of dispersibility, the monomer unit contained in the component (A) is preferably methyl acrylate, ethyl acrylate, or methyl methacrylate.

  When the component (A) contains at least one selected from the monomer unit (II-1) in which n is 1 and the monomer unit (II-2) in which n is 2, the components (A) are used in combination. Since compatibility with the said component (B) improves, it is preferable.

  The component (A) includes the monomer unit (II-1) in which n is 1 and the monomer unit (II-2) in which n is 2, and the monomer unit (II -1) and the monomer unit (II-2) having a weight ratio (II-1 / II-2) of more than 0 and less than 0.8, compatibility with other polymer components is improved. Therefore, it is preferably more than 0 and less than 0.7, more preferably more than 0 and less than 0.6%, most preferably more than 0 and less than 0.5. If it is 0.8 or more, the dispersion stability may be deteriorated.

It is preferable that the component (A) further contains a nitrogen-containing monomer unit (III) because an improvement in the heat resistance of the coating can be expected.
Examples of the nitrogen-containing monomer unit (III) include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, acrylamide, methacrylamide, methylenebisacrylamide, N-methylolacrylamide, N-hydroxyethyl. Acrylamide, N-hydroxyethyl methacrylamide, N-hydroxypropyl acrylamide, N-hydroxypropyl methacrylamide, N-hydroxybutyl acrylamide, N-hydroxybutyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylate Luamide, N-ethoxymethyl acrylamide, N-ethoxymethyl methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, etc. may be mentioned, and one or more may be used in combination. Of these, acrylonitrile, acrylamide, and N, N-diethylacrylamide are preferable.

The weight average molecular weight of the component (A) is less than 500,000, and from the viewpoint of dispersibility, it is preferably 460,000 or less, more preferably 420,000 or less, further preferably 380,000 or less, and most preferably 340,000 or less. Above 500,000, dispersibility is insufficient.
A preferable lower limit of the weight average molecular weight of the component (A) is 150,000.
In addition, the measuring method of a weight average molecular weight is demonstrated in detail in an Example.

  The neutralizing agent (E) used for neutralization of the component (A) is not particularly limited, but it is preferable that the neutralizing agent (E) is water-soluble because it is excellent in dispersibility of inorganic particles. The solubility of the neutralizing agent (E) in water is not particularly limited. For example, it is preferably 2.0 g / 100 ml or more, more preferably 4.0 g / 100 ml or more, and even more preferably 6.0 g / 100 ml. Above, particularly preferably 8.0 g / 100 ml or more, most preferably 10.0 g / 100 ml or more. Examples of the neutralizing agent (E) include sodium hydroxide.

  Although there is no limitation in particular regarding the neutralization degree (mol% with respect to a carboxyl group monomer) of the said component (A) and sodium hydroxide, For example, Preferably it is 50-150%, More preferably, it is 60-140%, More preferably Is 70 to 130%, particularly preferably 70 to 120%, most preferably 80 to 120%. If the neutralization degree is less than 50%, the dispersibility of the electricity storage device slurry may not be sufficient.

  The solubility of the component (A) neutralized product in water is not particularly limited, but it is preferable to exhibit water solubility because the dispersibility of the inorganic particles is excellent. The solubility of the component (A) neutralized sodium hydroxide in water is not particularly limited. For example, it is preferably 0.1 g / 100 ml or more, more preferably 0.5 g / 100 ml or more, and still more preferably. 1.0 g / 100 ml or more, particularly preferably 2.0 g / 100 ml or more, most preferably 3.0 g / 100 ml or more. When the solubility of the neutralized sodium hydroxide of component (A) in water is less than 0.1 g / 100 ml, the dispersibility of the electricity storage device slurry may not be sufficient.

  The 3% aqueous solution viscosity at 25 ° C. of the sodium hydroxide neutralized product of component (A) is preferably 200 to 50000 mPa · s, and preferably 200 to 40000 mPa · s from the viewpoints of dispersion stability and coatability. More preferably, it is more preferable in it being 200-30000 mPa * s, 200-25000 mPa * s is especially preferable, and 200-20000 mPa * s is the most preferable. If it is less than 200 mPa · s, the dispersion stability may deteriorate, and if it exceeds 50000 mPa · s, the applicability may deteriorate. In addition, even if it uses neutralizing agents other than sodium hydroxide, the preferable range of a neutralization degree, the solubility to water, and 3% aqueous solution viscosity does not change.

  The weight loss at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas and heating from 40 ° C. at a heating rate of 10 ° C./min) is not particularly limited, but preferably 0 -50% by weight, more preferably 1-40% by weight, still more preferably 2-30% by weight, particularly preferably 3-20% by weight, and most preferably 5-15% by weight. When the weight loss at 300 ° C. by thermogravimetry of the component (A) is more than 50% by weight, the heat resistance may not be sufficient.

When the zeta potential of the component (A) is in a specific range, it is preferable because the dispersibility is excellent.
The zeta potential of the 5 wt% aqueous dispersion at a measurement temperature of 25 ° C. is preferably 0 to −100 mV, more preferably −10 to −90 mV, still more preferably −20 to −80 mV, and particularly preferably −30 to −70 mV. Most preferably, it is −35 to −65 mV. When the zeta potential of the 5 wt% aqueous dispersion of the component (A) is less than -100 mV, handling properties may not be excellent. On the other hand, when the zeta potential of the 5% by weight concentration aqueous dispersion of the component (A) is more than 0 mV, the dispersibility of the slurry for an electricity storage device may not be sufficient.

  The glass transition point Tg (A) (° C.) of the component (A) is preferably −10 to 70 (° C.), more preferably −10 to 65 (° C.), and further preferably −10 to 60 (° C.). -10 to 55 (° C) is particularly preferable. If it is less than −10 (° C.), the dispersibility may be insufficient, and if it exceeds 70 (° C.), the film flexibility may be insufficient.

[Component (B)]
Component (B) has a carboxyl group-containing monomer unit (I) with respect to the entire polymerizable monomer of 0 wt% or more and less than 15 wt%, and is a single amount of the above chemical formula (1) with respect to the entire polymerizable monomer This is a polymer component B in which the body unit (II) (where n = 1 to 20) is 70% by weight to 100% by weight.
The component (B) functions as a dispersion aid for inorganic particles, particularly a conductive aid component, and an applicability improver for an electricity storage device slurry composition. Moreover, it functions also as a binder with the inorganic particles after apply | coating the slurry for electrical storage devices to a base material and drying water. Moreover, the dispersibility of an inorganic particle improves synergistically by using together with the said component (A).

  In the component (B), the weight ratio of the monomer unit (II) of the chemical formula (1) to the entire polymerizable monomer is 70 wt% or more and 100 wt% or less, and from the viewpoint of dispersion stability, 74 -99 wt% is more preferable, 78-98 wt% is further preferable, 82-98 wt% is particularly preferable, and 86-98 wt% is most preferable. If it is less than 70% by weight, the synergistic effect when used in combination with the component (A) is weakened, and the dispersion stability may be deteriorated.

  Examples of the monomer unit of the chemical formula (1) include the same ones as described in the component (A), and one or more of them may be used in combination, but when used in combination with the component (A). From the viewpoint of the synergistic effect, the monomer unit contained in the component (B) is preferably methyl methacrylate, ethyl acrylate, propyl acrylate, or butyl acrylate.

  The component (B) is a monomer unit (II-1) in which n is 1, a monomer unit (II-2) in which n is 2, and a monomer unit (in which n is 3). It is preferable to include at least one selected from II-3) and monomer units (II-4) in which n is 4 to 20, since an improvement in liquid retention of the electrolytic solution can be expected.

The component (B) is a monomer unit (II-1) where n is 1, a monomer unit (II-2) where n is 2, and a monomer unit where n is 3. (II-3) and at least one selected from monomer units (II-4) wherein n is 4 to 20, the monomer unit (II-1) and the monomer unit (II-2), a weight ratio [II-1 / (II-2 + II-3 + II-4)] to the sum of the monomer units (II-3) and the monomer units (II-4), When the following formula (2) is satisfied, dispersibility is improved due to a synergistic effect with the component (A), and the weight ratio is more preferably more than 0 and less than 1.1, and more preferably more than 0 and less than 1.0. Preferably, more than 0 and less than 0.9 is most preferable.
0 <II-1 / (II-2 + II-3 + II-4) <1.2 (2)

It is preferable that the component (B) further contains a nitrogen-containing monomer unit (III) because an improvement in the heat resistance of the coating can be expected.
Examples of the nitrogen-containing monomer unit (III) include the same as those described in the component (A).

It is preferable that the component (B) further includes a glycidyl group-containing monomer unit (IV) because an effect of improving heat resistance can be expected. The glycidyl group-containing monomer unit (IV) is not particularly limited, but glycidyl (meth) acrylate, hydroxymethyl acrylate glycidyl ether, 2-hydroxyethyl acrylate glycidyl ether, 3-hydroxypropyl acrylate glycidyl ether, 4-hydroxy Examples thereof include butyl acrylate glycidyl ether, glycidyl vinyl ether, glycidyl allyl ether, and diglycidyl ether.
The solubility of the component (B) in water is not particularly limited, but it is preferable to exhibit water-insolubility because of excellent coating properties.
The solubility of the component (B) in water at 25 ° C. is not particularly limited. For example, it is preferably 10 g / 1000 ml or less, more preferably 5 g / 1000 ml or less, still more preferably 1 g / 1000 ml or less, particularly preferably 0.5 g / 1000 ml or less, most preferably 0.1 g / 1000 ml or less. When the solubility of the component (B) in water exceeds 10 g / 1000 ml, the binding property of the electricity storage device slurry may not be sufficient. A preferable lower limit of the solubility of the component (B) in water is 0 g / 1000 ml.

  The 20% aqueous dispersion viscosity at 25 ° C. of the component (B) is preferably 0.1 to 1000 mPa · s, more preferably 1 to 500 mPa · s, from the viewpoints of dispersion stability and coatability. 2 to 400 mPa · s is more preferable, 3 to 300 mPa · s is particularly preferable, and 4 to 200 mPa · s is most preferable. If it is less than 0.1 mPa · s, the dispersion stability may deteriorate. If it exceeds 1000 mPa · s, the applicability may deteriorate.

  The weight loss at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas and heating from 40 ° C. at a heating rate of 10 ° C./min) is not particularly limited, but preferably 20 % By weight or less, more preferably 15% by weight or less, further preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 3% by weight or less. If the weight loss at 300 ° C. by thermogravimetry of the polymer component is more than 20% by weight, the binding property may not be sufficient.

It is preferable that the zeta potential of the component (B) is in a specific range because the dispersibility is excellent.
The zeta potential of the 5 wt% aqueous dispersion at a measurement temperature of 25 ° C. is preferably 0 to −100 mV, more preferably −10 to −90 mV, still more preferably −20 to −80 mV, and particularly preferably −30 to −70 mV. Most preferably, it is −35 to −65 mV. When the zeta potential of the 5% by weight aqueous dispersion of the component (B) is less than −100 mV, handling properties may not be excellent. On the other hand, when the zeta potential of the 5 wt% aqueous dispersion of the component (B) is more than 0 mV, the dispersibility of the slurry for an electricity storage device may not be sufficient.

  The component (B) may be in the form of a polymer particle emulsion in which polymer particles are dispersed in water. The concentration of the polymer particles in the case of the polymer particle emulsion is not particularly limited. For example, it is preferably 1 to 80% by weight, more preferably 10 to 70% by weight, still more preferably 15 to 60% by weight, particularly Preferably it is 15-50 weight%, Most preferably, it is 20-50 weight%. If the concentration of the polymer particles in the case of the polymer particle emulsion is less than 1% by weight, the dispersibility may not be excellent. On the other hand, if the concentration of the polymer particles is more than 80% by weight, handling properties may not be excellent.

  The average particle size of the component (B) is not particularly limited, but is preferably 0.001 to 100 μm, more preferably 0.01 to 10 μm, still more preferably 0.05 to 1 μm, and particularly preferably 0.1 to 0.1 μm. 0.8 μm. When the average particle size of the component (B) is less than 0.001 μm, production may be difficult, which may not be preferable. On the other hand, when the average particle diameter of the component (B) is more than 100 μm, the dispersion stability may be deteriorated, which is not preferable.

  The glass transition point Tg (B) (° C.) of the component (B) is preferably −70 to 50 (° C.), more preferably −60 to 45 (° C.), and further preferably −55 to 40 (° C.). -50 to 35 (° C) is particularly preferable. If it is less than −70 (° C.), the dispersibility may be insufficient, and if it exceeds 50 (° C.), the film formability may be insufficient.

  When the component (A) is 100 parts by weight, from the viewpoint of dispersibility, the component (B) is preferably 5 to 800 parts by weight, more preferably 10 to 700 parts by weight, and further 15 to 600 parts by weight. Preferably, 20 to 600 parts by weight is most preferable. If it is less than 5 parts by weight, the synergistic effect of the component (A) and the component (B) may be insufficient, and if it exceeds 800 parts by weight, the dispersion stability may be insufficient.

When the glass transition point of the component (A) is Tg (A) (° C.), the glass transition point of the component (B) is Tg (B) (° C.), and the following formula (3) is satisfied, the component (A) From the viewpoint of the synergistic effect of component (B), the value of | Tg (A) −Tg (B) | is more preferably 1 or more and 50 or less, further preferably 5 or more and 50 or less, and particularly preferably 8 or more and 50 or less.
0 ≦ | Tg (A) −Tg (B) | ≦ 50 (3)

[Component (C)]
The dispersant composition of the present invention may contain a surfactant component C which is component (C). When the surfactant component C is contained in the dispersant composition, it plays a role of improving the dispersion stability and coating property of the slurry.
Examples of the surfactant component C include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Examples of the anionic surfactant include fatty acid salts such as sodium oleate, potassium palmitate and triethanolamine; alkyl sulfate esters such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate and sodium cetyl sulfate. Polyoxyalkylene alkyl ether acetates such as sodium polyoxyethylene tridecyl ether acetate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; polyoxyalkylene alkyl ether sulfates; stearoyl methyl taurine Na, lauroyl methyl taurine Na, myristoyl Higher fatty acid amide sulfonates such as methyl taurine Na and palmitoyl methyl taurine Na; N-amino such as lauroyl sarcosine sodium Rusarcosine salts; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether and sodium polyoxyethylene stearyl ether phosphate; di-2-ethylhexyl sulfosuccinate Long-chain sulfosuccinates such as sodium sulfate, sodium dioctylsulfosuccinate, long-chain N-acyl glutamates such as sodium monosodium N-lauroylglutamate, disodium N-stearoyl-L-glutamate; polyacrylic acid, polymethacrylic acid , Polymaleic acid, polymaleic anhydride, copolymer of maleic acid and isobutylene, copolymer of maleic anhydride and isobutylene, copolymer of maleic acid and diisobutylene, Copolymer of maleic acid and diisobutylene, copolymer of acrylic acid and itaconic acid, copolymer of methacrylic acid and itaconic acid, copolymer of maleic acid and styrene, maleic anhydride and styrene Copolymer of acrylic acid and methacrylic acid, copolymer of acrylic acid and methyl acrylate, copolymer of acrylic acid and vinyl acetate, copolymer of acrylic acid and maleic acid Products such as alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts and amine salts of copolymers of acrylic acid and maleic anhydride Polycarboxylate; naphthalene sulfonic acid, alkyl naphthalene sulfonic acid, formalin condensate of naphthalene sulfonic acid, alkyl naphthalene Formalin condensates of phonic acid and their alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), naphthalene sulfonic acids such as ammonium salts and amine salts Salt; melamine sulfonic acid, alkyl melamine sulfonic acid, formalin condensate of melamine sulfonic acid, formalin condensate of alkyl melamine sulfonic acid, and alkali metal salts thereof (lithium salt, sodium salt, potassium salt, etc.), alkaline earth Metal salts (magnesium salts, calcium salts, etc.), melamine sulfonates such as ammonium salts and amine salts, etc .; lignin sulfonic acids, and alkali metal salts thereof (lithium salts, sodium salts, potassium salts, etc.), alkaline earths Metal salt (magnesium salt, calcium Etc.), lignin sulfonic acid salts such as ammonium salts and amine salts and the like, may be alone or in combination of two or more.

  Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkylmethylammonium salts and alkylamine salts. 1 type or 2 types or more may be used in combination.

Examples of the nonionic surfactant include POE (30) lauryl ether, POE (12) lauryl ether, POE (9) myristyl ether, POE (3) lauryl ether, POP (2) POE (8) stearyl ether. Polyoxyalkylene oxide-added alkyl ethers such as POE (50) oleyl ether; polyoxyethylene (24) polyoxyalkylene styrenated phenyl ethers such as styrenated phenyl ether; multivalents such as sorbitan monopalmitate and sorbitan monooleate Ester compound of alcohol and monovalent fatty acid; polyoxyalkylene alkyl phenyl ether such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether; polyoxyethylene monolaur Polyoxyalkylene fatty acid esters such as polyoxyethylene monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerin monostearate and glycerin monopalmitate Glycerin fatty acid esters such as glycerin monolaurate; polyoxyalkylene castor oil; polyoxyalkylene hydrogenated castor oil; polyoxyalkylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkyl glycerin ether; polyoxyalkylene cholesteryl ether; alkyl polyglucoside; Fatty acid ester; polyoxyalkylene alkylamine; polyoxyethylene-polyoxypropylene bromide Kuporima and the like.
The POE represents polyoxyethylene, the POP represents polyoxypropylene, and the POE (12) represents 12 mole addition of polyoxyethylene.

  Examples of the amphoteric surfactant include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt. Imidazoline-based amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaines and the like; N -Amino acid type amphoteric surfactants such as laurylglycine, N-lauryl β-alanine, N-stearyl β-alanine and the like may be mentioned, and one or more may be used in combination.

  The content of the component (C) is not particularly limited. When the total content of the component (A) and the component (B) is 100 parts by weight, usually 0.1 to 500 parts by weight, Preferably it is 0.5-250 weight part, More preferably, it is 1-100 weight part, Especially preferably, it is 2-70 weight part, Most preferably, it is 2-50 weight part. When the content of the component (C) is less than 0.1 parts by weight, dispersibility and coatability are not sufficient. On the other hand, when the content of the component (C) is more than 500 parts by weight, handling properties are not excellent.

[Defoaming component (D)]
When the dispersant composition for an electricity storage device slurry of the present invention contains an antifoam component (D), it is preferable from the viewpoint of improving the handleability and applicability of the electricity storage device slurry.
Although there is no limitation in particular as said component (D), For example, fat-type antifoamers, such as castor oil, sesame oil, linseed oil, and animal and vegetable oil; Fatty acid type antifoamers, such as a stearic acid, an oleic acid, and a palmitic acid; Fatty acid ester antifoaming agents such as isoamyl acid, distearyl succinate, ethylene glycol distearate, butyl stearate; polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol, etc. Alcohol-based antifoaming agents; ether-based antifoaming agents such as 3-heptylcellosolve, nonylcellosolve, 3-heptylcarbitol, polyalkylene glycol; phosphate ester-based antifoaming agents such as tributyl phosphate and tris (butoxyethyl) phosphate ; Diamylamine Amine-based antifoaming agents; Amide-based antifoaming agents such as polyalkylene amide and acylate polyamine; Sulfate-based antifoaming agents such as sodium lauryl sulfate; Polysiloxane-based antifoaming agents such as dimethylpolysiloxane; Paraffin-based minerals Examples thereof include mineral oils such as oils, cyclopentene, cyclohexane, phytelite, and naphthenic mineral oils such as oleanane; silica fine powder antifoaming agents and the like, and one or more may be used in combination. Of these, it is preferable that the antifoaming agent is at least one selected from a polysiloxane antifoaming agent and fine silica powder because of excellent antifoaming properties.

  The content of the component (D) is not particularly limited, but preferably 0.0001 to 10 parts by weight when the total content of the component (A) and the component (B) is 100 parts by weight. More preferably 0.0005 to 1 part by weight, still more preferably 0.001 to 0.5 part by weight, particularly preferably 0.005 to 0.1 part by weight, and most preferably 0.01 to 0.05 part by weight. It is. If the content of the antifoaming agent is less than 0.0001 part by weight, the antifoaming property may not be sufficient. On the other hand, if the content of the antifoaming agent exceeds 10 parts by weight, the coatability may not be excellent.

[Neutralizer component (E)]
The neutralizer component (E) is a component that neutralizes the component (A) and makes it water-soluble.
Although there is no limitation in particular as a component (E), For example, sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, magnesium hydroxide, etc. Hydroxide, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, calcium carbonate, barium carbonate, strontium carbonate, magnesium carbonate, sodium bicarbonate, lithium bicarbonate, potassium bicarbonate, cesium bicarbonate, bicarbonate Carbonate compounds such as rubidium, calcium bicarbonate, barium bicarbonate, strontium bicarbonate, magnesium bicarbonate, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethyl Min, mono (iso) propylamine, di (iso) propylamine, mono (iso) butylamine, mono (iso) pentylamine, mono (iso) hexylamine, mono (iso) heptylamine, mono (iso) octylamine, Monoethanolamine, diethanolamine, triethanolamine, mono (iso) propanolamine, di (iso) propanolamine, tri (iso) propanolamine, mono (iso) butanolamine, mono (iso) pentanolamine, mono (iso) Hexanolamine, mono (iso) heptanolamine, mono (iso) octanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-di (iso) propylethanolamine, N-methyldiethanolamine , N-Echi Diethanolamine, N- (iso) propyldiethanolamine, N- (iso) butyldiethanolamine, N-tert-butyldiethanolamine, N- (iso) pentyldiethanolamine, N- (iso) hexyldiethanolamine, N-cyclopentylmonoethanolamine, N-cyclohexyl monoethanolamine, N-cyclooctyl monoethanolamine, N-cyclopentyl diethanolamine, N-cyclohexyl diethanolamine, N-cyclooctyl diethanolamine, 2-amino-2-methyl-1-propanol, 1,3-bisaminomethyl Hexane, 2- (2-aminoethoxy) ethanol, 3-methoxypropylamine, 3-amino-4-octanol, polyethyleneimine, alkylamine polyoxy Alkylene adduct, tert-alkylamine polyoxyalkylene adduct, spermine, aniline, pyrrolidine, pyrimidine, pyrazine, piveridine, piverazine, morpholine, 4,4'-methylenebismorpholine, 4,4'-ethylenebismorpholine, imidazoles Amino acids and the like, and may be used alone or in combination of two or more.

（式（４）中、Ｒ^３は炭素数が１〜２０のアルキル基であり、ｍは１〜２０、ｎは０〜２０の整数である。）
Ｒ^３のアルキル基の分岐の有無は特に制限はないが、第１級より第２級が好ましく、第２級よりも第３級がより好ましい。
Ｒ^３の炭素数が１〜８の場合、スラリー分散性の観点から、ｍ＋ｎの数は１５以下が好ましく、１０以下がより好ましく、６以下がさらに好ましく、４以下が特に好ましく、２が最も好ましい。
ｍ＋ｎの数が１５超だと、配合量が増加するおそれがあり、ｍ＋ｎの数が２未満だとスラリー分散性が低下するおそれがある。
Ｒ^３の炭素数が９〜２０の場合、スラリー分散性の観点から、ｍ＋ｎの数は、６以上４０以下が好ましく、８以上３２以下がより好ましく、１０以上２４以下が特に好ましく、１２以上２０以下が最も好ましい。
ｍ＋ｎの数が４０超だと、ハンドリング性が低下するおそれがあり、６未満だとスラリー分散性が低下する場合がある。
また、化学式（４）で示される成分のうち、Ｒ^３の炭素数が１〜８の場合の成分と、Ｒ^３の炭素数が〜２０の場合の成分を併用すると、相乗的にスラリー分散性、塗布性が向上するので好ましい。
中和剤成分（Ｅ）の含有量としては特に制限はないが、前記成分（Ａ）の含有量を１００重量部としたときに、好ましくは１〜２００重量部、より好ましくは５〜１５０重量部、さらに好ましくは１０〜１００重量部、特に好ましくは１０〜５０重量部である。１重量部未満であると分散性が不足するおそれがあり、２００重量部超だとハンドリング性が低下する場合がある。 Among the above-described neutralizing agent components (E) containing nitrogen, the components represented by the following chemical formula (4) are particularly preferable from the viewpoint of slurry dispersibility.

(In the formula (4), ^{R 3} is an alkyl group having 1 to 20 carbon atoms, m is 1-20, n is an integer of 0 to 20.)
The presence or absence of branching of the alkyl group of R ³ is not particularly limited, but the secondary is preferable to the primary, and the tertiary is more preferable to the secondary.
When R ³ has 1 to 8 carbon atoms, from the viewpoint of slurry dispersibility, the number of m + n is preferably 15 or less, more preferably 10 or less, further preferably 6 or less, particularly preferably 4 or less, and most preferably 2. .
If the number of m + n is more than 15, the blending amount may increase, and if the number of m + n is less than 2, the slurry dispersibility may be lowered.
When the carbon number of R ³ is 9 to 20, from the viewpoint of slurry dispersibility, the number of m + n is preferably 6 or more and 40 or less, more preferably 8 or more and 32 or less, particularly preferably 10 or more and 24 or less, and 12 or more and 20 The following are most preferred.
When the number of m + n is more than 40, the handling property may be lowered, and when it is less than 6, the slurry dispersibility may be lowered.
In addition, among the components represented by the chemical formula (4), when the component when the carbon number of R ³ is 1 to 8 and the component when the carbon number of R ³ is ~ 20 are used in combination, the slurry dispersibility synergistically. This is preferable because the coating property is improved.
Although there is no restriction | limiting in particular as content of a neutralizer component (E), When content of the said component (A) is 100 weight part, Preferably it is 1-200 weight part, More preferably, it is 5-150 weight. Parts, more preferably 10 to 100 parts by weight, particularly preferably 10 to 50 parts by weight. If it is less than 1 part by weight, the dispersibility may be insufficient, and if it exceeds 200 parts by weight, the handling property may be lowered.

[Other monomer units]
The dispersant composition for an electricity storage device slurry of the present invention may optionally contain other monomer units other than the monomer units listed above. Other monomer units are not particularly limited, and examples include ethylene, propylene, butylene, butadiene, isoprene, styrene, alkylene oxide, vinyl halide, vinylidene halide, vinyl acetate, and vinyl alcohol. Two or more kinds may be used in combination.

[Dispersant composition for power storage device slurry, its production method and form]
The manufacturing method of the dispersing agent composition for electricity storage device slurry is not particularly limited. Component (A): Polymer component A, Component (B): Polymer component B, Component (C): Surfactant, Component (D ): Antifoaming agent, component (E): a method of mixing a neutralizing agent and the like.
The mixing is not particularly limited, and can be performed using an apparatus having a very simple mechanism such as a container and a stirring blade. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned. Moreover, you may use the mixer which can perform a general rocking | swiveling or stirring. Examples of the mixer include a ribbon type mixer and a vertical screw type mixer. A mixer can be mentioned. Super mixer (made by Kawata Co., Ltd.) and high speed mixer (made by Fukae Co., Ltd.), Newgram Machine (made by Seishin Enterprise Co., Ltd.), SV Mixer (manufactured by Shinko Environmental Solution Co., Ltd.), Filmics (Primix Co., Ltd.), Jet Pasta (Nihon Spindle Manufacturing Co., Ltd.), KRC Nida (manufactured by Kurimoto Steel Works), Rotating and Revolving Mixer (Sinky Corporation) , Photochemical Co., Ltd.) or the like. Other examples include crushers such as jaw crusher, gyratory crusher, cone crusher, roll crusher, impact crusher, hammer crusher, rod mill, ball mill, vibration rod mill, vibration ball mill, disk type mill, jet mill, cyclone mill, etc. It may be used.
Further, an ultrasonic emulsifier, a continuous biaxial kneader, a high-pressure emulsifier, a microreactor, or the like may be used.

  The surface tension at 25 ° C. of the 0.1 wt% aqueous solution of the dispersant composition for power storage device slurry is not particularly limited, but is preferably 20 to 50 mN / m, more preferably 25 to 45 mN / m, Especially preferably, it is 25-40 mN / m, Most preferably, it is 25-35 mN / m. If it is less than 20 mN / m, the drying property may not be excellent. If it exceeds 50 mN / m, the coatability may be poor.

  The dispersant composition for an electricity storage device slurry is measured for foaming power by the Ross Miles test method under the measurement conditions of a concentration of 0.1% by weight and a temperature of 25 ° C. described in detail in the following examples. The foaming power immediately after flowing down the dispersant composition is 50 mm or less, preferably 40 mm or less, more preferably 30 mm or less, still more preferably 20 mm or less, and particularly preferably 10 mm or less. The foaming power 5 minutes after flowing down is 25 mm or less, preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, and particularly preferably 5 mm or less. When the foaming force immediately after flowing down is more than 50 mm according to the Ross Miles test method, the applicability of the slurry for an electricity storage device is not sufficient. Moreover, the applicability | paintability of the slurry for electrical storage devices is not enough in the foaming power 5 minutes after flowing down being more than 25 mm.

  The zeta potential at the measurement temperature of 25 ° C. of the dispersant composition for power storage device slurry is not particularly limited, but is preferably −20 to −100 mV, more preferably −25 to −80 mV, and particularly preferably −30 to −70 mV. Most preferably, it is −35 to −60 mV. If it is less than −100 mV, handling properties may be poor. If it exceeds -20 mV, the dispersibility may not be excellent.

  The effective concentration of the dispersant composition for the electricity storage device slurry is not particularly limited as the pH in the 20 wt% aqueous dispersion, but is preferably 2.0 to 12.0, more preferably 2.5 to 11.5, Especially preferably, it is 3.0-11.0, Most preferably, it is 3.0-10.0. If pH is less than 2.0, applicability | paintability may be bad. If it exceeds 12.0, the handleability may be poor.

  The contact angle after 1600 msec from dropping the droplet of the dispersant composition to the polyolefin resin surface of the dispersant composition for the electricity storage device slurry is not particularly limited, but preferably 10 to 60 °, The angle is preferably 15 to 60 °, particularly preferably 20 to 50 °, and most preferably 30 to 40 °. If it is less than 10 °, the dispersibility may not be excellent. If it exceeds 60 °, applicability may be poor.

  The contact angle after 1600 msec after dropping the droplet of the dispersant composition for the storage device slurry on the surface of the inorganic oxide plate of the dispersant composition for the storage device slurry is not particularly limited, 60 °, more preferably 15 to 60 °, particularly preferably 20 to 50 °, and most preferably 30 to 40 °. If it is less than 10 °, the dispersibility may not be excellent. If it exceeds 60 °, applicability may be poor. The raw material of the inorganic oxide plate used for contact angle measurement is alumina (aluminum oxide).

  The non-volatile concentration of the dispersant composition for the electricity storage device slurry is not particularly limited. For example, it is usually 1 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight, and most preferably 30 to 60% by weight. If it is less than 1% by weight, the dispersibility may not be excellent. If it exceeds 90% by weight, the stability may be poor.

The power storage device slurry dispersant composition may be a composition composed of a combination of at least two agents. Although there is no particular limitation, for example, when the combination is a first agent that essentially contains the component (B) and a second agent that contains any component other than the component (B), handling properties It is preferable because of its superiority.
As the first agent, for example, the component (B) is essentially contained, and other than the component (B), the component (A), the component (C), the component (D), the component (E) and other components and More preferably, it contains water.
As the second agent, for example, it is more preferable to contain a component (A) other than the component (B), a component (C), a component (D), a component (E), other components and water.

[Storage device slurry composition, production method and use thereof]
The electricity storage device slurry composition of the present invention is obtained by a production method in which inorganic particles (F) are dispersed in a solvent in the presence of the dispersant composition for electricity storage device slurry described above.
The method for producing the power storage device slurry composition of the present invention is not particularly limited. For example, the power storage device slurry composition is obtained by mixing the power storage device slurry dispersant composition and the solvent, and the dispersant adjustment step. The manufacturing method etc. which include the inorganic particle (F) dispersion | distribution process of disperse | distributing an inorganic particle (F) to the obtained liquid mixture are mentioned.

Although there is no limitation in particular as a dispersing agent adjustment process which mixes the dispersing agent composition for electrical storage device slurries, and a solvent, For example, the 2nd agent containing the said component (A) is mixed with a solvent, and adjustment liquid (1) is prepared. Examples of the adjustment step (1) to be obtained and the adjustment step (2) for mixing the first agent containing the component (B) and the component (E) with the adjustment liquid (1) to obtain the adjustment liquid (2).
As an example of the mixing order as the adjustment step, the step of adjusting the first agent after the adjustment of the second agent is given as an example, but this order may be changed. In addition, the said component (C) and the said component (D) are arbitrarily contained in either the 1st agent and the 2nd agent.

The inorganic particles (F) will be described later because they vary depending on the use of the electricity storage device slurry composition.
Although there is no limitation in particular as content of the said component (A) in an electrical storage device slurry composition, 0.01-10 weight part with respect to 100 weight part of inorganic particles (F), Preferably it is 0.05-8. Parts by weight, more preferably 0.1 to 6 parts by weight, still more preferably 0.2 to 5 parts by weight, and particularly preferably 0.3 to 4 parts by weight. If it exceeds 10 parts by weight, the battery and capacitor performance is not excellent. On the other hand, if it is less than 0.01 parts by weight, the coatability is not sufficient.

  Although there is no limitation in particular as content of the said component (B) in an electrical storage device slurry composition, 0.1-50 weight part with respect to 100 weight part of inorganic particles (F), Preferably 0.3-20 Parts by weight, more preferably 0.5 to 15 parts by weight, still more preferably 0.8 to 10 parts by weight, and particularly preferably 1 to 7 parts by weight. If it exceeds 50 parts by weight, the battery and capacitor performance is not excellent. On the other hand, if it is less than 0.1 parts by weight, the coatability is not sufficient.

  In the electricity storage device slurry composition, the foaming force is measured by the Ross Miles test method under the measurement conditions of a concentration of 0.1% by weight and a temperature of 25 ° C. described in detail in the following examples. The immediately foaming force is 50 mm or less, preferably 40 mm or less, more preferably 30 mm or less, still more preferably 20 mm or less, and particularly preferably 10 mm or less. The foaming power 5 minutes after flowing down is 25 mm or less, preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, and particularly preferably 5 mm or less. If the foaming force immediately after flowing down is more than 50 mm according to the Ross Miles test method, the coatability is not sufficient. Moreover, applicability | paintability is not enough in the foaming power 5 minutes after immediately after flowing down exceeding 25 mm.

  Although there is no limitation in particular as specific gravity of an electrical storage device slurry composition, For example, Usually, 1-4, Preferably it is 1.1-3, More preferably, it is 1.2-2.5, More preferably, it is 1.3-2. Particularly preferred is 1.4 to 1.9, and most preferred is 1.5 to 1.8. When the specific gravity of the electricity storage device slurry composition is more than 4, dispersion stability may not be excellent. On the other hand, if the specific gravity of the electricity storage device slurry composition is less than 1, applicability may not be excellent.

  The effective concentration of the electricity storage device slurry composition is not particularly limited as the pH in the 20% by weight aqueous dispersion, but is preferably 4.0 to 12.5, more preferably 5.0 to 12.0, and particularly preferably. 5.5 to 11.5, most preferably 6.0 to 11.0. If pH is less than 4.0, applicability | paintability may be bad. If it exceeds 12.5, the handleability may be poor.

The solvent in which the inorganic particles (F) are dispersed is not particularly limited and may be an organic solvent or water. Water is preferred because of its low cost and low risk of toxicity, but if necessary, an aprotic solvent such as N-methyl-2-pyrrolidone or alcohols may be used as a solvent.
The water contained in the electricity storage device slurry composition of the present invention may be any of tap water, ion exchange water, distilled water and the like.

  Although there is no limitation in particular as content of the solvent in an electrical storage device slurry composition, For example, 1-10000 weight part with respect to 100 weight part of inorganic particles (F), Preferably it is 10-1000 weight part, More preferably It is 50 to 500 parts by weight, more preferably 60 to 300 parts by weight, particularly preferably 80 to 200 parts by weight, and most preferably 100 to 150 parts by weight. When the content of the solvent in the electricity storage device slurry composition is more than 10,000 parts by weight with respect to 100 parts by weight of the inorganic particles (F), battery performance may not be excellent. On the other hand, when the content of the solvent in the electricity storage device slurry composition is less than 1 part by weight with respect to 100 parts by weight of the inorganic particles (F), applicability may not be sufficient.

In addition to the components described above, the electricity storage device slurry composition of the present invention includes a hydrotrope agent, protective colloid agent, antibacterial agent, antifungal agent, colorant, antioxidant, deodorant, cross-linking agent, catalyst, It may further contain an emulsion stabilizer, a chelating agent and the like.
In order to obtain the power storage device slurry composition of the present invention, there is no particular limitation on the method of mixing each component such as the power storage device slurry dispersant composition, inorganic particles (F), water, and the like, such as a container and a stirring blade. This can be done using a device with a very simple mechanism. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned. Moreover, you may use the mixer which can perform a general rocking | swiveling or stirring. Examples of the mixer include a mixer that can perform rocking stirring or stirring such as a ribbon type mixer and a vertical screw type mixer. Super mixer (made by Kawata Co., Ltd.) and high speed mixer (made by Fukae Co., Ltd.), Newgram Machine (made by Seishin Enterprise Co., Ltd.), SV A mixer (manufactured by Shinko Environmental Solution Co., Ltd.), Filmics (Primix Co., Ltd.), Jet Pasta (Nihon Spindle Manufacturing Co., Ltd.), KRC Kneader (manufactured by Kurimoto Steel Works Co., Ltd.) or the like may be used. Other examples include crushers such as jaw crusher, gyratory crusher, cone crusher, roll crusher, impact crusher, hammer crusher, rod mill, ball mill, vibration rod mill, vibration ball mill, disk type mill, jet mill, cyclone mill, etc. It may be used. Further, an ultrasonic emulsifier, a continuous biaxial kneader, a high-pressure emulsifier, a microreactor, or the like may be used.

  Moreover, the manufacturing method of the electrical storage device slurry composition of this invention may include the process of disperse | distributing each component which comprises the dispersing agent composition for electrical storage device slurry separately to a solvent. In addition, the quantity of each component at the time of disperse | distributing to a solvent separately follows each component content of an above-described electrical storage device slurry composition.

The step of separately dispersing each component constituting the dispersant composition for an electricity storage device slurry in a solvent is not particularly limited. For example, the step of mixing the component (A) and a solvent to obtain a mixture (a ), The mixed solution and the component (B) are mixed to obtain a dispersant composition (b), and the mixed solution or the dispersant composition is mixed with the component (E) (c) And the manufacturing method including the process (d) which mixes the said dispersing agent composition and inorganic particle (F), and obtains a slurry composition is mentioned. The order of the step (c) may be “after step (a)” or “after step (b)”.
When using at least one selected from the component (C), the component (D), and other components, at least one selected from the component (C), the component (D), and other components. The mixing step may be any of the step (a), the step (b), the step (c), and the step (d). However, when mixed in the step (a), the dispersant composition becomes uniform, so Since an effect is easy to be acquired, it is preferable. Although there is no limitation in particular as an application of the electrical storage device slurry composition of this invention, Surface coating uses, such as a positive electrode use, a negative electrode use, a positive electrode, a negative electrode, a separator, etc. are mentioned.
Hereinafter, various uses will be described in detail.

(Secondary battery positive electrode use)
The electricity storage device slurry composition of the present invention can be used as a secondary battery positive electrode application. Examples of the inorganic particles (F) of the electricity storage device slurry composition when the electricity storage device slurry composition is used as a positive electrode for a secondary battery include a positive electrode active material and a conductive additive. The slurry composition for the secondary battery positive electrode is usually applied to a current collector sheet, dried and thinned to be used as a secondary battery positive electrode.

The secondary battery positive electrode active material is not particularly limited. For example, lithium iron phosphate (LiFePO ₄ ), lithium manganese phosphate (LiMnPO ₄ ), lithium cobalt phosphate (LiCoPO ₄ ), iron pyrophosphate (Li ₂ ). FeP ₂ O ₇ ), lithium cobaltate composite oxide (LiCoO ₂ ), spinel type lithium manganate lithium cobaltate composite oxide (LiMn ₂ O ₄ ), lithium manganate composite oxide (LiMnO ₂ ), lithium nickelate composite Oxide (LiNiO ₂ ), lithium niobate composite oxide (LiNbO ₂ ), lithium ferrate composite oxide (LiFeO ₂ ), lithium magnesium oxide composite oxide (LiMgO ₂ ), lithium calcium oxide composite oxide (LiCaO ₂ ) , cuprate lithium composite oxide (LiCuO ₂ , Lithium composite oxide zincate (LiZnO _2), molybdate lithium composite oxide (LiMoO _2), lithium tantalate complex oxide (LiTaO _2), tungstic acid lithium composite oxide (LiWO _2), lithium - nickel - cobalt - aluminum composite oxide _{(LiNi 0.8 Co 0.15 Al 0.05 O} 2), lithium - nickel - cobalt - manganese composite oxide _{(LiNi 0.33 Co 0.33 Mn 0.33 O} 2, LiNi 0 _.8 Co _0.1 Mn _0.1 O ₂ ), manganese nickel oxide (LiNi _0.5 Mn _1.5 O ₄ ), manganese oxide (MnO ₂ ), lithium-rich nickel-cobalt-manganese composite oxide, water Nickel oxide (Ni (OH) ₂ ), vanadium oxide, sulfur oxide, silicate An oxide etc. are mentioned and one sort or two sorts or more may be sufficient.

  The conductive auxiliary agent is not particularly limited. For example, carbon black such as furnace black, acetylene black, and ketjen black; graphene; carbon nanotube such as carbon nanofiber, single-walled carbon nanotube, and multi-walled carbon nanotube; silver, copper Metal fine particles such as tin, zinc, zinc oxide, nickel and manganese; composite metal fine particles such as indium tin oxide and the like.

  The current collector of the secondary battery positive electrode is not particularly limited as long as it is a material having electronic conductivity and capable of supplying current to the positive electrode material. For example, C, Ti, Cr, Mo, Ru, Rh, Ta , W, Os, Ir, Pt, Au, Al, Ni and other conductive materials, and alloys containing two or more of these conductive materials (for example, stainless steel) can be used. The current collector is preferably C, Al, Ni, stainless steel or the like from the viewpoint of high electrical conductivity and good stability in the electrolytic solution and oxidation resistance, and more preferably Al or the like from the viewpoint of material cost. The shape of the current collector is not particularly limited, and for example, a foil-like substrate, a three-dimensional substrate, or the like can be used. A primer layer may be formed on the current collector surface in advance. The primer layer has a conductive auxiliary such as carbon black, an organic component such as an acrylic resin or a surfactant for assisting the formation of the primer layer, and phosphoric acid. Inorganic salts such as salts and silicates may be included.

The method for coating the electricity storage device slurry composition on the current collector of the positive electrode is not particularly limited as long as it is a method capable of uniformly wet coating, for example, a capillary coating method, a spin coating method, a slit die coating method, Spray coating, dip coating, roll coating, screen printing, flexographic printing, bar coater, gravure coater, die coater, etc. can be employed.
The method for removing the solvent from the coating film is generally a method by drying. The drying temperature of the solvent is not particularly limited, but is usually 10 to 200 ° C, preferably 30 to 190 ° C, more preferably 50 to 180 ° C, particularly preferably 80 to 170 ° C, and most preferably 80 to 160 ° C. is there. When the drying temperature of the solvent is higher than 200 ° C., the function of the positive electrode may be deteriorated, which is not preferable.

The surface coat film formed by applying and drying the electricity storage device slurry composition of the present invention on the surface of the current collector may be formed on one side of the current collector, or may be formed on both sides.
The film thickness of the positive electrode film for one side formed by applying and drying the electricity storage device slurry composition of the present invention on the surface of the current collector is not particularly limited, but for example, usually 1 to 500 μm, preferably 10 to 10 μm. It is 400 μm, more preferably 20 to 300 μm, particularly preferably 20 to 200 μm, and most preferably 20 to 150 μm. When the film thickness of the positive electrode film for one side is less than 1 μm, the battery performance may be deteriorated, which is not preferable. When the film thickness of the surface coat film for one side is more than 500 μm, the handling property may be lowered, which is not preferable.

(Use for secondary battery negative electrode)
The electricity storage device slurry composition of the present invention can be used as a secondary battery negative electrode application. Examples of the inorganic particles (F) of the power storage device slurry composition when the power storage device slurry composition is used as a secondary battery negative electrode include a negative electrode active material, a conductive auxiliary agent, and the like. The electricity storage device slurry composition for secondary battery negative electrode application is usually applied to a current collector sheet, dried to form a thin film, and can be used as a secondary battery negative electrode.

The secondary battery negative electrode active material is not particularly limited, but for example, carbon materials such as natural graphite, artificial graphite, expanded graphite, activated carbon, carbon fiber, coke, soft carbon, and hard carbon; silicon-based; SiO, SnO, _{SnO 2, CuO, Li 4 Ti} 5 O 12 and the like of the metal oxide; Si-Al, Al-Zn , Si-Mg, Al-Ge, Si-Ge, Si-Ag, Zn-Sn, Ge-Ag, Alloys such as Ge—Sn, Ge—Sb, Ag—Sn, Ag—Ge, Sn—Sb; tin phosphate glass-based materials can be used, and one or more of them may be used.

  The current collector of the secondary battery negative electrode is not particularly limited as long as it is a material having electronic conductivity and capable of supplying current to the negative electrode material. For example, Cu, Ni, C, Ti, Cr, Mo, Ru , Rh, Ta, W, Os, Ir, Pt, Au, Al, and other conductive materials, and alloys containing two or more of these conductive materials (for example, stainless steel) can be used. The current collector is preferably Cu, C, Al, stainless steel or the like from the viewpoint of high electrical conductivity and good stability in the electrolyte and oxidation resistance, and Cu or the like is more preferable from the viewpoint of material cost. The shape of the current collector is not particularly limited, and for example, a foil-like base material, a three-dimensional base material, and the like can be used. Specifically, a rolled copper foil, an electrolytic copper foil, and the like are preferable. A primer layer may be formed on the current collector surface in advance. The primer layer has a conductive auxiliary agent such as carbon black, an organic component such as an acrylic resin or a surfactant for assisting the formation of the primer layer, and phosphoric acid. Inorganic salts such as salts and silicates may be included.

  The method for coating the electricity storage device slurry composition on the current collector of the negative electrode is not particularly limited as long as it can be uniformly wet-coated, and examples thereof include a capillary coating method, a spin coating method, a slit die coating method, Spray coating, dip coating, roll coating, screen printing, flexographic printing, bar coater, gravure coater, die coater, etc. can be employed.

The method for removing the solvent from the coating film is generally a method by drying. The drying temperature of the solvent is not particularly limited, but is usually 10 to 200 ° C, preferably 30 to 190 ° C, more preferably 50 to 180 ° C, particularly preferably 80 to 170 ° C, and most preferably 90 to 160 ° C. is there. When the drying temperature of the solvent is higher than 200 ° C., the function of the negative electrode may be deteriorated, which is not preferable.
The surface coat film formed by applying and drying the electricity storage device slurry composition of the present invention on the surface of the current collector may be formed on one side of the current collector, or may be formed on both sides.
The film thickness of the negative electrode film for one side formed by applying and drying the electricity storage device slurry composition of the present invention on the surface of the current collector is not particularly limited, but for example, usually 1 to 500 μm, preferably 10 to 10 μm. It is 400 μm, more preferably 20 to 300 μm, particularly preferably 20 to 200 μm, and most preferably 20 to 150 μm. When the film thickness of the negative electrode film for one side is less than 1 μm, the battery performance may be deteriorated, which is not preferable. When the film thickness of the surface coat film for one side is more than 500 μm, the handling property may be lowered, which is not preferable.

(Capacitor electrode application)
The electricity storage device slurry composition of the present invention can be used for capacitor electrode (positive electrode and negative electrode) applications. Examples of the inorganic particles (F) of the electricity storage device slurry composition when the electricity storage device slurry composition is used for capacitor positive electrode and negative electrode applications include capacitor active materials and conductive assistants. An electricity storage device slurry composition for use as a capacitor electrode is usually applied to a current collector sheet, dried and thinned to be used as a capacitor electrode.

  The active material for a capacitor is not particularly limited, and may be any material as long as it can reversibly support a cation and an anion, and examples thereof include carbon materials, silicon compounds, titanium compounds, and tin compounds. From the viewpoint of cost, a carbon-based material is preferable, and specific examples include activated carbon, carbon whisker, carbon nanotube, and graphite. One or more kinds may be used, and activated carbon and graphite are preferable from the viewpoint of cost.

  Regarding the current collector foil used for the capacitor electrode and the method for coating and drying the capacitor electrode, the same method as for the positive and negative electrodes of the secondary battery can be applied.

(For surface coating)
The electricity storage device slurry composition of the present invention can be used as a separator for surface coating, or as a positive electrode or negative electrode surface coating as described above. Non-conductive particles etc. are mentioned as an inorganic particle (F) of an electrical storage device slurry composition in case an electrical storage device slurry composition is used as a surface coat use. Non-conductive particles are not particularly limited. For example, silica (silicon oxide), α-alumina, β-alumina, γ-alumina, θ alumina and other aluminas (aluminum oxide), titania (titanium oxide), magnesia, and the like. (Magnesium oxide), zirconia (zirconium oxide), calcium oxide, barium oxide, tin oxide, strontium oxide, niobium oxide, cerium oxide, tungsten oxide, indium oxide, gallium oxide, yttrium oxide, iron oxide, antimony oxide, white carbon, etc. Inorganic oxide particles; inorganic nitride particles such as aluminum nitride and silicon nitride; ion crystal particles such as calcium fluoride, barium fluoride, barium sulfide and calcium sulfide; covalently bonded crystal particles such as silicon and diamond; mica, Talc, bentona DOO, kaolin, aluminum silicate, silicates such as sericite; calcium carbonate, magnesium carbonate, carbonates such as barium carbonate and the like, may be one or more. Of these, α-alumina is preferred because of its particularly high thermal and chemical stability.

  The average particle size of the non-conductive particles is not particularly limited, but is usually 0.001 to 100 μm, preferably 0.01 to 10 μm, more preferably 0.1 to 1 μm, and particularly preferably 0.1 to 0.8 μm. Most preferably, the thickness is 0.2 to 0.7 μm. If the average particle size of the non-conductive particles is less than 0.001 μm, the production may be difficult, which may not be preferable. On the other hand, when the average particle diameter of the non-conductive particles is more than 100 μm, the dispersibility may be deteriorated, which is not preferable.

The BET specific surface area of the non-conductive particles is not particularly limited, but is usually 0.1 to 30 m ² / g, preferably 1 to 18 m ² / g, more preferably 4 to 14 m ² / g, particularly preferably. Is 5-10 m ² / g, most preferably 8-10 m ² / g. When the non-conductive particles have a BET specific surface area of less than 0.1 m ² / g, the film-forming property may be deteriorated, which is not preferable. On the other hand, when the BET specific surface area of the non-conductive particles is more than 30 m ² / g, the handling properties may be deteriorated, which may not be preferable.

The electric conductivity of the non-conductive particles is not particularly limited. For example, it is preferably 100 μS / cm or less, more preferably 80 μS / cm or less, particularly preferably 40 μS / cm or less, and most preferably 20 μS / cm or less. is there. When the electrical conductivity of the non-conductive particles exceeds 100 μS / cm, the battery performance may be deteriorated, which may not be preferable.
The nonconductive particles may contain a free metal (or metal ion). Although there is no limitation in particular as a free metal, For example, iron, a silica, magnesium, sodium, copper etc. are mentioned.

The content of the free metal is not particularly limited, but is usually 10,000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or less, particularly preferably 10 ppm or less, and most preferably 1 ppm or less. When the content of free metal exceeds 10,000 ppm, the battery and capacitor performance may be deteriorated, which is not preferable.
The zeta potential of the electricity storage device slurry composition for surface coating is not particularly limited, but the zeta potential of the 5 wt% aqueous dispersion at a measurement temperature of 25 ° C. is preferably −10 to −100 mV, more preferably − 10 to -90 mV, more preferably -20 to -80 mV, particularly preferably -30 to -70 mV, most preferably -30 to -65 mV. When the zeta potential of the electricity storage device slurry composition for surface coating at a concentration of 5% by weight is less than −100 mV, handling properties may not be excellent. On the other hand, if the zeta potential of the secondary battery slurry composition for surface coating at a concentration of 5% by weight exceeds -10 mV, the dispersibility may not be sufficient.
Here, the case where the electrical storage device slurry composition of the present invention is used as a surface coating for a secondary battery separator will be described in detail.

In secondary batteries, a separator is usually used to prevent a short circuit between the positive electrode and the negative electrode. For example, in the case of a lithium ion battery, when a short circuit occurs inside the battery, the separator has a shutdown function that blocks the hole of the separator, making it impossible for lithium ions to move in the shorted part. By losing the function, it plays a role of maintaining the safety of the lithium ion secondary battery. However, when the battery temperature exceeds, for example, 150 ° C. due to instantaneous heat generation, the separator may contract rapidly and the short-circuited portion between the positive electrode and the negative electrode may expand. In this case, the battery temperature may reach a state where it is abnormally heated to several hundred degrees C or more, which is a problem in terms of safety. Therefore, as means for solving the above problems, an inorganic oxide porous film containing an inorganic oxide filler having insulating properties is formed on the surface of the positive electrode, the negative electrode or the separator constituting the lithium ion secondary battery.
The method for applying the slurry composition for coating a secondary battery separator to the separator is not particularly limited as long as it is a method that enables uniform wet coating, and examples thereof include a capillary coating method, a spin coating method, a slit die coating method, Spray coating, dip coating, roll coating, screen printing, flexographic printing, bar coater, gravure coater, die coater, etc. can be employed.

  The method for removing the solvent from the coating film is generally a method by drying. The drying temperature of the solvent is preferably a temperature not higher than the softening point of the separator, and is usually 10 to 200 ° C, preferably 30 to 150 ° C, more preferably 40 to 120 ° C, particularly preferably 50 to 100 ° C, and most preferably 60. ~ 90 ° C. When the drying temperature of the solvent is higher than 200 ° C., the function of the separator may be deteriorated, which is not preferable.

The resin constituting the composition of the separator is not particularly limited. For example, polyolefin resins such as polyethylene, polypropylene, and polybutylene; polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyamide resins such as nylon; polyamideimide resins; polyacetal resins; polystyrene resins; methacrylic resins; polyvinyl chloride resins; polycarbonate resins; polyphenylene sulfide resins, cellulose resins, and the like.
There is no limitation in particular as a shape of a separator, For example, a microporous film, a nonwoven fabric, etc. are mentioned.
The surface of the separator may be coated with a polyvinylidene fluoride resin, a polyaramid resin, or the like before applying the slurry composition for coating a secondary battery separator.
The separator may be subjected to a hydrophilization treatment before the slurry composition for coating a secondary battery separator is applied. Examples of the hydrophilization treatment include chemical treatment with acid or alkali, corona treatment, and plasma treatment.
The surface coat film formed by applying and drying the slurry composition for coating a secondary battery separator of the present invention on the separator surface may be formed on one side of the separator or on both sides.

The film thickness of the surface coat film for one surface formed by applying and drying the slurry composition for coating a secondary battery separator of the present invention on the separator surface is not particularly limited. The thickness is preferably 0.3 to 10 μm, more preferably 0.5 to 5 μm, particularly preferably 1 to 4 μm, and most preferably 1 to 3 μm. When the film thickness of the surface coat film for one side is less than 0.1 μm, the heat resistance may deteriorate, which may be undesirable. When the film thickness of the surface coat film for one side is more than 30 μm, the function of the separator may be deteriorated, which is not preferable.
The thickness of the separator coated with the slurry for coating a secondary battery separator of the present invention and dried and surface-coated is not particularly limited. Is 10 to 30 μm, particularly preferably 15 to 25 μm, and most preferably 20 to 25 μm. When the film thickness of the surface-coated separator is less than 1 μm, the heat resistance may deteriorate, which may not be preferable. When the film thickness of the surface coat film for one side is more than 100 μm, the function of the separator may be deteriorated, which is not preferable.

It is preferable that the contact angle of the solvent with respect to the separator whose surface is coated by applying the slurry composition for coating a secondary battery separator of the present invention is in a specific range because battery performance is excellent.
The contact angle of water with respect to the separator whose surface is coated by applying and drying the slurry composition for coating a secondary battery separator of the present invention is not particularly limited. For example, it is normal when 1600 msec elapses after water is dropped. It is 60 ° or less, preferably 50 ° or less, more preferably 40 ° or less, further preferably 30 ° or less, and particularly preferably 20 ° or less. If the contact angle of water with the surface-coated separator exceeds 60 °, battery performance may not be excellent.

The contact angle of the electrolytic solution with respect to the separator whose surface is coated by applying the slurry composition for coating a secondary battery separator of the present invention is not particularly limited. For example, when 1600 msec has elapsed since the electrolytic solution was dropped. Is usually 80 ° or less, preferably 70 ° or less, more preferably 60 ° or less, still more preferably 55 ° or less, and particularly preferably 50 ° or less. When the contact angle of the electrolytic solution with respect to the surface-coated separator is more than 80 °, battery performance may not be excellent.
Examples of the electrolytic solution used for measuring the contact angle include alkyl carbonate compounds such as dimethyl carbonate, ethylene carbonate, diethyl carbonate, propylene carbonate, butylene carbonate, and methyl ethyl carbonate; ester compounds such as γ-butyrolactone and methyl formate; 1 Examples include ether compounds such as 2 dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide, and the like.

[Material for power storage device and method for producing the same]
Examples of the material for the electricity storage device of the present invention include the positive electrode, the negative electrode, and the separator described above for each use of the above electricity storage device slurry composition. That is, the positive electrode of the present invention is a secondary battery having a positive electrode coating on a current collector and a positive electrode for a capacitor, and the coating is formed of a nonvolatile component of the above-mentioned electricity storage device slurry composition. The negative electrode of the present invention is a secondary battery having a negative electrode coating film on a current collector and a negative electrode for a capacitor, and the coating film is formed of a nonvolatile component of the above-described electricity storage device slurry composition. The separator of this invention is a separator which has a coating film for separators, Comprising: The said coating film is formed with the non volatile matter of the said electrical storage device slurry composition.

Although the manufacturing method of the material for electrical storage devices of the present invention is not particularly limited, for example, the step (a) of mixing the component (A) and a solvent to obtain a mixed solution, the mixed solution and the component (B) A step (b) of obtaining a dispersant composition by mixing, a step (c) of mixing the component (E) in the mixed solution or the dispersant composition, and the dispersant composition and inorganic particles (F). (D) to obtain a slurry composition by mixing and applying the slurry composition to at least one selected from a positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode and a separator, and drying The manufacturing method including the process (e) of forming a film is mentioned. The order of the step (c) may be “after step (a)” or “after step (b)”. The step of mixing at least one selected from the component (C), the component (D), and the other components may be any of the step (a), the step (b), the step (c), and the step (d). However, mixing in the step (a) is preferable because the effect of the present application can be easily obtained by making the dispersant composition uniform.
In addition, about the application | coating method and the drying method, the method already described by each use of the said electrical storage device slurry composition is employable.

[Secondary battery]
The secondary battery of this invention can be produced using the positive electrode, negative electrode, and separator which were produced using the dispersing agent composition for electrical storage device slurry of this invention, and the manufacturing method is not specifically limited. For example, the above-described negative electrode and positive electrode are overlapped with a separator and wound, folded, or laminated according to the shape of the battery to produce an electrode body, put in the battery container, and inject the electrolyte into the battery container to seal it. May be.
The battery shape is not particularly limited, and examples thereof include a coin type, a cylindrical type, a square type, and a sheet type.
The battery packaging method is not particularly limited, and examples thereof include a metal case, a mold resin, and an aluminum laminate film.

The type of secondary battery is not particularly limited, and lithium ion secondary batteries such as lithium ion batteries and lithium ion polymer batteries; alkaline secondary batteries such as nickel metal hydride batteries and nickel cadmium batteries; sodium sulfur batteries; redox flow batteries An air battery or the like.
Although there is no limitation in particular as electrolyte solution, in the case of a lithium ion battery, what melt | dissolved lithium salt as a supporting electrolyte in a non-aqueous solvent can be used, for example. Examples of the lithium salt include LiPF ₆ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlCl ₄ , LiClO ₄ , CF ₃ SO ₃ Li, C ₄ H ₉ SO ₃ Li, CF ₃ COOLi, (CF ₃ CO) ₂ NLi , (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) ₂ NLi, and the like, and one or more of them may be used. The solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, alkyl carbonate compounds such as dimethyl carbonate, ethylene carbonate, diethyl carbonate, propylene carbonate, butylene carbonate, and methyl ethyl carbonate; γ -Ester compounds such as butyrolactone and methyl formate; ether compounds such as 1,2 dimethoxyethane and tetrahydrofuran; and sulfur-containing compounds such as sulfolane and dimethyl sulfoxide. Other additives may be mixed in the electrolytic solution, and examples thereof include vinylene carbonate.
The electrolytic solution when the secondary battery is a nickel metal hydride battery is not particularly limited and may be an alkaline aqueous solution. Examples thereof include an aqueous solution containing potassium hydroxide or sodium hydroxide.

[Capacitor]
Examples of the capacitor include an electric double layer capacitor, a ceramic capacitor, an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, a mylar capacitor, and a film capacitor. From the viewpoint of the storage amount, an electric double layer capacitor, a ceramic capacitor, and an aluminum electrolytic capacitor An electric double layer capacitor is particularly preferable. In this application, an electric double layer capacitor will be described. The electric double layer capacitor of the present invention can be produced using the positive electrode, the negative electrode and the separator produced using the dispersant composition for an electricity storage device slurry of the present invention, and the production method thereof is not particularly limited. For example, the above-described negative electrode and positive electrode are overlapped via a separator, wound or folded or laminated according to the shape to prepare an electrode body, put it in a container, and inject the electrolyte into the container to seal it Good. The shape of the electric double layer capacitor is not particularly limited, and examples thereof include a coin type, a cylindrical type, a square type, and a sheet type.

The electricity storage device of the present invention can be used as a power source for various electric appliances (including vehicles that use electricity).
Examples of electrical equipment include air conditioners, washing machines, televisions, refrigerators, freezers, air conditioners, laptop computers, tablets, smartphones, computer keyboards, computer displays, desktop computers, CRT monitors, computer racks, printers, and integrated computers. , Mouse, hard disk, computer peripherals, iron, clothes dryer, window fan, walkie-talkie, blower, ventilation fan, music recorder, music player, oven, range, toilet seat with washing function, hot air heater, car component, car navigation, flashlight, Humidifier, portable karaoke machine, ventilation fan, dryer, dry cell, air purifier, mobile phone, emergency light, game machine, blood pressure monitor, coffee mill, coffee maker, kotatsu, copy machine, disc changer, radio, shaver Juicer, shredder, water purifier, lighting equipment, dehumidifier, dish dryer, rice cooker, stereo, stove, speaker, trouser press, vacuum cleaner, body fat scale, weight scale, health meter, movie player, electric carpet, electric kettle , Rice cooker, electric razor, table lamp, electric pot, electronic game machine, portable game machine, electronic dictionary, electronic notebook, microwave oven, electromagnetic cooker, calculator, electric cart, electric wheelchair, electric tool, electric toothbrush, red bean , Haircut equipment, telephones, watches, intercoms, air circulators, lightning insecticide, copiers, hot plates, toasters, dryers, electric drills, water heaters, panel heaters, crushers, soldering irons, video cameras, video decks, facsimiles , Fan heater, food processor, futon dryer, headphone , Electric kettle, hot carpet, microphone, massage machine, bean bulb, mixer, sewing machine, mochi machine, floor heating panel, lantern, remote control, cold storage, water cooler, refrigeration stocker, cold air blower, word processor, bubbler, electronic Musical instruments, motorcycles, toys, lawn mowers, walkers, bicycles, automobiles, hybrid cars, plug-in hybrid cars, electric cars, railways, ships, airplanes, emergency storage batteries, etc.

  Below, the Example of this invention is described concretely with the comparative example. The present invention is not limited to these examples.

[Measurement of viscosity]
20% concentration aqueous dispersions of component (A) and component (B) were prepared and measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd .: BL type) in an atmosphere at 25 ° C.

[Foaming power]
The measurement was performed under a measurement condition at a temperature of 25 ° C. by the Ross Miles test method based on the method of JIS K3362. An aqueous solution having an effective concentration of 0.1% by weight of the composition was used as a test solution, 50 ml of the test solution was poured along the tube wall of the Ross Miles measuring device, and 200 ml of the test solution was also placed in the upper falling pipette. Set the pipette so that the liquid drop of the test liquid falls in the center of the cylinder of the Ross Miles measuring device, let the test liquid flow down from a height of 90 cm, and the height of the foam immediately after the flow ends (immediately after the flow down) and immediately after the flow down The height of the foam after 5 minutes was measured. Here, the effective concentration refers to the weight ratio of the absolutely dry component when the composition is heat-treated at 105 ° C. to remove the solvent and reach a constant weight with respect to the weight of the composition.

(Weight average molecular weight)
The polymer component was dissolved in tetrahydrofuran so that the nonvolatile content concentration was about 0.2% by mass, and then gel permeation chromatography (GPC) was measured under the following measurement conditions. Subsequently, a calibration curve was prepared from the GPC measurement result of polyethylene glycol having a known molecular weight, and the weight average molecular weight was calculated.
(Measurement condition)
Device name: HLC-8220 (manufactured by Tosoh Corporation)
Column: KF-G, KF-402HQ, KF-403HQ each connected in series (all manufactured by Shodex)
Eluent: Tetrahydrofuran Injection volume: 10 μl
Eluent flow rate: 0.3 ml / min

〔surface tension〕
An aqueous solution having an effective concentration of 0.1% by weight was used as a test solution, and an automatic surface tension meter (manufactured by KRUSS, product number Tensiometer K100) was used, and measurement was performed at a temperature of 25 ° C. by the Wilhelmy method.

[Contact angle]
The measurement was performed using a contact angle meter (product number DM-901, manufactured by Kyowa Interface Science Co., Ltd.) using an aqueous solution having an effective concentration of 5% by weight of the dispersant composition for power storage device slurry as a test solution. As the alumina plate, a dense alumina plate (50 × 50 × 2 mm, sold by ASONE) was used.

[Measurement of glass transition point]
It measured using the dynamic-viscoelasticity measuring apparatus (The TI instrument company make, product number Q800).

[Measurement of thermogravimetry (TGA)]
Using a differential thermal balance (manufactured by Rigaku Corporation, product number Thermo plus EVO), the measurement was performed under the measurement conditions of a setting start temperature of 20 ° C., a setting final temperature of 300 ° C., and a heating rate of 10 ° C. per minute.

[Measurement of average particle size and zeta potential]
Measurement was performed using a particle size / zeta potential measurement system (ELSZ-1000, manufactured by Otsuka Electronics Co., Ltd.).

[Component (A)]
About the component (A) used by the Example and the comparative example, those specific manufacturing methods and physical property are shown to the manufacture examples A-1 to A-7 of the following Table 1, and manufacture comparison examples A-8 to A-10. Show.

[Component (B)]
About the component (B) used by the Example and the comparative example, those specific manufacturing methods and physical properties are shown to the manufacture examples B-1 to B-7 of the following Table 2, and manufacture comparison example B-8.

[Defoaming component (D)]
The antifoaming agents used in Examples and Comparative Examples are shown below.
Polysiloxane antifoaming agent 1: dimethylpolysiloxane, viscosity 100 mPa · s
Polysiloxane antifoaming agent 2: dimethylpolysiloxane, viscosity 1000 mPa · s
Silica fine powder defoaming agent: Silica fine powder mineral oil defoaming agent hydrophobized with trimethylethoxysilane: Paraffin mineral oil

[Inorganic particles (F)]
The inorganic particles (F) used in Examples and Comparative Examples are shown below.
α-alumina 1: primary particle size 0.3 μm, BET specific surface area 8.4 m ² / g
α-alumina 2: primary particle size 0.8 μm, BET specific surface area 4.9 m ² / g
γ-alumina: primary particle size 0.3 μm, BET specific surface area 4.7 m ² / g
θ alumina: primary particle size 0.3 μm, BET specific surface area 5.3 m ² / g
Silica: primary particle size 0.3 μm, BET specific surface area 5.4 m ² / g
Lithium cobaltate; primary particle size 7.3 μm, BET specific surface area 0.4 m ² / g
Lithium-nickel-cobalt-manganese composite oxide (LiNi _0.33 Co _0.33 Mn _0.33 O ₂ ; primary particle diameter 11.5 μm, BET specific surface area 0.3 m ² / g
Lithium manganate composite oxide (LiMnO ₂ ); primary particle size 10.1 μm, BET specific surface area 0.3 m ² / g
Lithium iron phosphate (LiFeO ₄ ); primary particle size 12.1 μm, BET specific surface area 0.3 m ² / g
Activated carbon; primary particle size 5.8 μm, BET specific surface area 1600 m ² / g
Graphite; primary particle size 11.1 μm, BET specific surface area 0.4 m ² / g
Hard carbon; primary particle size 13.3 μm, BET specific surface area 0.2 m ² / g
Acetylene black; average particle diameter 70.1 nm, BET specific surface area 68 m ² / g
Carbon nanofiber: fiber diameter 150.0 nm, BET specific surface area 13 m ² / g

[Production Example A-1]
First, 20 g of acrylic acid and 80 g of ethyl acrylate were prepared as polymerizable monomers, and 0.4 g of lauryl sulfonic acid soda salt was prepared as an emulsifier.
The polymerizable monomer and emulsifier prepared above and 400 g of ion-exchanged water are mixed and stirred with a homogenizer, and reacted in a 1000 ml separable flask at 80 ° C. for 3 hours in a nitrogen stream. A-1 was obtained. This acrylic polymer component A-1 is water-insoluble and has a non-volatile concentration of 20.4% by weight, a viscosity of 12 mPa · s, a weight average molecular weight of 220,000, a zeta potential of −28 mV, and a thermogravimetric measurement of 4.1%. The glass transition point was 7 ° C.

[Production Examples A-2 to A-8, Production Comparative Examples A-9 to A-11]
In Production Examples A-2 to A-8 and Production Comparative Examples A-9 to A-11, Production Example A-1 is the same as Production Example A-1, except that the raw materials are also changed as shown in Table 1. Each polymer component was obtained, and the physical properties and the like were evaluated in the same manner as in Production Example A-1.

[Production Example B-1]
First, 43 g of methyl methacrylate, 20 g of ethyl acrylate, 32 g of butyl acrylate and 5.0 g of glycidyl methacrylate were prepared as polymerizable monomers, and 1.0 g of POE (30) lauryl ether was used as an emulsifier. And 1.0 g of POE (10) -1- (allyloxymethyl) alkyl ether ammonium sulfate were prepared.
The polymerizable monomer and emulsifier prepared above and 150 g of ion-exchanged water are mixed and stirred with a homogenizer, and reacted in a 500 ml separable flask at 80 ° C. for 3 hours in a nitrogen stream to produce an acrylic polymer emulsion. B-1 was obtained. This acrylic polymer emulsion B-1 is water-insoluble and has a non-volatile concentration of 40.1% by weight, a viscosity of 15 mPa · s, an average particle size of 235 nm, a zeta battery of −24 mV, a thermogravimetric measurement of 0.9%, The glass transition point was 27 ° C.

[Production Examples B-2 to B-7 and Production Comparative Example B-8]
In Production Examples B-2 to B-7 and Production Comparative Example B-8, a polymer emulsion is produced in the same manner as in Production Example B-1, except that the raw materials are also changed as shown in Table 2 in Production Example B-1. And the physical properties and the like were evaluated in the same manner as in Production Example B-1.

[Production Example 1]
60 g of an acrylic polymer diluent containing 12 g of polymer component A-1 as component (A), 85 g of an acrylic polymer emulsion containing 34 g of polymer component B-1 as component (B), tert 15 g of the —C12-14 alkylamine POE (15 mol) adduct and 251 g of ion-exchanged water were uniformly mixed to obtain a dispersant composition for an electricity storage device slurry. The amount of ion-exchanged water was 350 g including the ion-exchanged water contained in polymer component A-1 and polymer component B-1. The dispersant composition for the electricity storage device slurry has a non-volatile content of 12.4%, a viscosity of 2500 mPa · s, a pH of 6.9, a surface tension of 35.4 mN / m, a zeta potential of −39 mV, and a foaming power of 18 mm immediately after, The value after 5 minutes was 3 mm, the contact angle to the alumina plate as an inorganic oxide plate was 41 ° when 1600 msec elapsed, and the contact angle to the polyolefin resin was 27 ° when 1600 msec elapsed.

[Production Examples 2 to 16 and Production Comparative Examples 17 to 22]
In Production Examples 2 to 16 and Production Comparative Examples 17 to 22, except that the raw materials were changed as shown in Tables 3 to 5, respectively, a dispersion composition for an electricity storage device slurry was obtained in the same manner as in Production Example 1, Physical properties and the like were evaluated in the same manner as in Production Example 1. The results are shown in Tables 3-5.

[Example 1]
100 g of α-alumina 1 as an inorganic powder, 60 g of dispersant composition 1 for power storage device slurry as a dispersant, and 100 g of ion-exchanged water were uniformly mixed to obtain a power storage device slurry composition.
The resulting electricity storage device slurry composition had a non-volatile content concentration of 41.2% by weight, a viscosity of 72 mPa · s, an average particle size of 480 nm, a pH of 5.9, a zeta potential of −36 mV, and a foaming power of 12 mm immediately after the foaming power of 5 minutes. The later value was 3 mm.
When the dispersion stability of the dispersant composition for electricity storage device slurry was evaluated using this electricity storage device slurry composition, the weight of the precipitate was 10% by weight or more and less than 20% by weight, and the dispersion stability was slightly superior. .
The electricity storage device slurry composition obtained above was applied to a polyolefin resin separator having a thickness of 20 μm and dried in an oven at 80 ° C. The drying time was within 30 seconds, and the drying property was excellent. The coated area of the separator surface after drying was 95% or more, and the coating property was excellent. The surface coat film thickness was 3 μm.

[Examples 2 to 16]
In Examples 2 to 16, an electricity storage device slurry composition was obtained in the same manner as in Example 1 except that the raw materials were changed as shown in Tables 6 and 7 in Example 1, and the physical properties and the like were also in Example 1. And evaluated in the same manner. The results are shown in Tables 6 and 7.

Example 17
97 g of lithium cobaltate as an inorganic powder, 3 g of acetylene black, 30 g of the dispersant composition 1 for a storage device slurry as a dispersant and 40 g of ion-exchanged water were uniformly mixed to obtain a storage device slurry composition. The obtained electricity storage device slurry composition has a non-volatile content concentration of 60.1% by weight, a viscosity of 6200 mPa · s, an average particle size of 12.5 μm, a pH of 8.3, a zeta potential of −47 mV, and a foaming force of 25 mm immediately after, The value after 5 minutes was 6 mm.
When the dispersion stability of the dispersant composition for electricity storage device slurry was evaluated using this electricity storage device slurry composition, the weight of the precipitate was less than 5% by weight, and the dispersion stability was excellent.
The electricity storage device slurry composition obtained above was applied to an aluminum foil having a thickness of 20 μm and dried in an oven at 150 ° C. to obtain a positive electrode film for a secondary battery. The coated area of the current collector after drying was 95% or more, and the coating property was excellent without cracking on the surface. The drying time was also within 300 seconds, and the drying property was excellent. The film thickness of the positive electrode film for secondary batteries was 40 μm.

[Examples 18 to 33]
In Examples 18 to 33, an electricity storage device slurry composition was obtained in the same manner as in Example 17 except that the raw materials were changed as shown in Tables 8 and 9, and the physical properties and the like were evaluated in the same manner as in Example 17. . The results are shown in Tables 8 and 9.

Example 34
95 g of graphite as an inorganic powder, 5 g of acetylene black, 50 g of the dispersant composition 1 for a power storage device slurry as a dispersant, and 50 g of ion-exchanged water were uniformly mixed to obtain a power storage device slurry composition. The resulting electricity storage device slurry composition has a nonvolatile content concentration of 52.1% by weight, a viscosity of 4100 mPa · s, an average particle size of 18.1 μm, a pH of 6.8, a zeta potential of −41 mV, and a foaming power of 18 mm immediately after, The value after 5 minutes was 3 mm.
When the dispersion stability of the dispersant composition for electricity storage device slurry was evaluated using this electricity storage device slurry composition, the weight of the precipitate was less than 5% by weight, and the dispersion stability was excellent.
The electricity storage device slurry composition obtained above was applied to a copper foil having a film thickness of 18 μm and dried in an oven at 150 ° C. to obtain a negative electrode film for a secondary battery. The coated area of the current collector after drying was 95% or more, and there was no crack on the surface and the coating property was excellent. The drying time was also within 300 seconds, and the drying property was excellent. The film thickness of the secondary battery negative electrode film was 50 μm.

[Examples 35 to 47]
In Examples 35 to 47, except that the raw materials were changed as shown in Tables 10 and 11, power storage device slurry compositions were obtained in the same manner as in Example 34, and the physical properties and the like were evaluated in the same manner as in Example 34. . The results are shown in Tables 10 and 11.

Example 48
85 g of activated carbon as inorganic powder, 10 g of acetylene black, 50 g of dispersant composition 1 for power storage device slurry as a dispersant, and 105 g of ion-exchanged water were uniformly mixed to obtain a power storage device slurry composition. The obtained electricity storage device slurry composition has a non-volatile content concentration of 40.8% by weight, a viscosity of 6700 mPa · s, an average particle size of 7.1 μm, a pH of 7.2, a zeta potential of −36 mV, and a foaming power of 35 mm immediately after, The value after 5 minutes was 28 mm.
When the dispersion stability of the dispersant composition for electricity storage device slurry was evaluated using this electricity storage device slurry composition, the weight of the precipitate was 5% by weight or more and less than 10% by weight, and the dispersion stability was excellent.
The electricity storage device slurry composition obtained above was applied to an aluminum foil having a thickness of 20 μm and dried in an oven at 150 ° C. to obtain an electrode film for a capacitor. The coated area of the current collector after drying was 90% or more and less than 95%. The drying time was also within 300 seconds, and the drying property was excellent. The film thickness of the capacitor electrode film was 40 μm.

Example 49
In Example 49, an electricity storage device slurry composition was obtained in the same manner as in Example 48 except that the raw materials were changed as shown in Table 11, and the physical properties and the like were evaluated in the same manner as in Example 48. The results are shown in Table 11.

[Comparative Example 1]
100 g of α-alumina 1 as an inorganic powder, 60 g of dispersant composition 17 for power storage device slurry as a dispersant, and 100 g of ion-exchanged water were uniformly mixed to obtain a power storage device slurry composition. The obtained electricity storage device slurry composition has a non-volatile content concentration of 40.1% by weight, a viscosity of 420 mPa · s, an average particle size of 900 nm, a pH of 7.4, a zeta potential of −31 mV, and a foaming force of 31 mm immediately after, The value after 5 minutes was 15 mm.
When the dispersion stability of the dispersant composition for an electricity storage device slurry was evaluated using this electricity storage device slurry composition, the weight of the precipitate was 10% by weight or more and less than 30% by weight, and the dispersion stability was inferior.
The electricity storage device slurry composition obtained above was applied to a polyolefin resin separator having a thickness of 20 μm and dried in an oven at 80 ° C. The drying time is over 30 seconds and is inferior in drying properties. The area of the coated surface of the separator after drying is less than 80%, which is inferior in applicability. The surface coat film thickness was 1 μm.

[Comparative Examples 2 to 12]
In Comparative Examples 2 to 12, each of the power storage device slurry compositions was obtained in the same manner as in Comparative Example 1 except that the raw materials were changed as shown in Table 12 and Table 13 in Comparative Example 1, and the physical properties and the like were also Comparative Examples. Evaluation was performed in the same manner as in 1. The results are shown in Tables 12 and 13.

As can be seen from Tables 6 to 11, since the electricity storage device slurry compositions of Examples 1 to 49 contain the component (A) and the component (B), the dispersion stability, applicability, and drying properties of the film are improved. Excellent.
On the other hand, as can be seen from Tables 12 and 13, when there is no component (B) (Comparative Examples 1 and 7, Production Comparative Example 17), when there is no component (A) (Comparative Examples 2 and 8, Production Comparative Example 18), When the component (B) contains 15% by weight or more of the carboxyl group-containing monomer unit (I) (Comparative Examples 3 and 9, Production Comparative Example 19), the component (A) is a carboxyl group-containing monomer unit (I ) 40% by weight or more (Comparative Examples 4 and 10, Production Comparative Example 20), when component (A) contains less than 15% by weight of carboxyl group-containing monomer unit (I) (Comparative Examples 5 and 11, Production Comparative Example 21), and when the weight average molecular weight of component (A) is 500,000 or more (Comparative Examples 6 and 12, Production Comparative Example 22), any of the problems of the present application cannot be solved.
When the dispersion composition 9 for the electricity storage device slurry is included (Examples 10, 26, 41) and when the dispersion composition 14 for the electricity storage device slurry is included (Examples 15, 31, 46), the evaluation result is Somewhat better.
When the power storage device slurry dispersant composition 12 is included (Examples 13, 29, and 44), the problems of the present application can be solved, but the power storage device slurry composition has a high foaming power and is slightly inferior in handling properties.
When the dispersion composition 13 for the electricity storage device slurry is included (Examples 14, 30, 45), when the dispersion composition 10 for the electricity storage device slurry is included (Examples 11, 27, 42), and the dispersion agent for the electricity storage device slurry Compared with the case where the composition 15 is included (Examples 16, 32, and 47), the evaluation results are slightly superior.
Regarding the dispersion stability of the electricity storage device slurry composition, the evaluation results for electrode application (Examples 17 to 49) were generally better than the evaluation results for separator application (Examples 1 to 16). It was.

[Evaluation of dispersion stability]
The produced power storage device slurry composition was stored in a 100 ml centrifuge tube at room temperature for 24 hours, and the weight of the sediment was measured. The evaluation criteria for dispersion stability are as follows.
A: The weight of the precipitate is less than 5% by weight, and the dispersion stability is excellent.
(Double-circle): The weight of a sediment is 5 weight% or more and less than 10 weight%, and is excellent in dispersion stability.
◯: The weight of the sediment is 10% by weight or more and less than 20% by weight, which is slightly excellent in dispersion stability.
(Triangle | delta): The weight of a sediment is 20 weight% or more and less than 30 weight%, and is somewhat inferior to dispersion stability.
X: The weight of a sediment is 30 weight% or more, and it is inferior to dispersion stability.

[Evaluation of coating properties]
(In case of separator)
The electricity storage device slurry composition was applied to the surface of the polyolefin-based separator at 15 g / m ² , heated to a temperature of 80 ° C. and dried. The area covered with the separator surface was measured. The evaluation criteria for applicability are as follows.
A: The coated area is 95% or more, and the coating property is excellent.
A: The covering area is 90% or more and less than 95%, and the coating property is excellent.
(Triangle | delta): A coating area is 80% or more and less than 90%, and is inferior to applicability | paintability.
X: The coating area is less than 80%, and the applicability is poor.
(For electrodes)
The electricity storage device slurry composition was applied to the surface of the current collector at 10 mg / cm ² , heated to a temperature of 150 ° C. and dried. The area covered with the current collector surface was measured. The evaluation criteria for applicability are as follows.
○: The coated area is 95% or more, and the coating surface is not cracked during drying, and the coating property is excellent.
X: Cracks occurred on the coated surface at the time of drying, and the coated area was less than 95%, and the coating property was inferior.

[Evaluation of dryness]
(In case of separator)
The electricity storage device slurry composition is applied to the surface of the polyolefin-based separator at 15 g / m ^2, and the time until the coating surface is dried at a temperature of 80 ° C. is measured visually. The dryness evaluation criteria are as follows.
○: If the drying time is 30 seconds or less, the waiting time is small and the drying property is good.
X: If the drying time exceeds 30 seconds, the waiting time is long and the workability is hindered, so the drying property is not good.
(For electrodes)
10 mg / cm ^{2 of the} electricity storage device slurry composition is applied to the surface of the current collector, and the time until the coated surface dries at a temperature of 150 ° C. is measured visually. The dryness evaluation criteria are as follows.
○: If the drying time is 300 seconds or less, the waiting time is small and the drying property is good.
X: If the drying time exceeds 300 seconds, the waiting time is long and the workability is hindered, so the drying property is not good.

[Evaluation of heat resistance]
A sample of 10 cm long × 10 cm wide of the produced surface-coated separator was stored in a constant temperature bath at 120 ° C. for 8 hours and heated, and then the length of each sample was measured to calculate the shrinkage. The evaluation criteria for heat resistance are as follows. The heat resistance of the surface-coated separator was evaluated based on the smaller shrinkage ratio, either vertical or horizontal.
Shrinkage rate (%) = (length or width of surface coat separator after heating for 8 hours / 10) × 100
A: Shrinkage is 95% or more and excellent in heat resistance.
A: The shrinkage rate is 90% or more and less than 95%, and the heat resistance is excellent.
(Triangle | delta): Shrinkage is 80% or more and less than 90%, and is inferior to heat resistance.
X: Shrinkage is less than 80%, and heat resistance is poor.

[Evaluation of water retention properties]
Using a contact angle meter (product number DM-901, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle when 1600 msec had elapsed after dropping water on the surface coat separator was evaluated.
(Double-circle): A contact angle is less than 20 degrees and is excellent in the liquid retention of water.
◯: The contact angle is 20 ° or more and less than 30 °, and the liquid retainability is excellent.
(Triangle | delta): A contact angle is 30 degrees or more and less than 40 degrees, and is inferior to the liquid retention of water.
X: A contact angle is 40 degrees or more, and it is inferior to the liquid retention of water.

[Evaluation of electrolyte retention]
Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number DM-901), an equivalent mixed solution of ethylene carbonate and dimethyl carbonate was dropped onto either the surface coat separator or the electrode, and the contact angle when 1600 msec elapsed was determined. Measured and evaluated.
(Double-circle): A contact angle is less than 20 degrees, and it is excellent in the liquid retention property of electrolyte solution.
◯: The contact angle is 20 ° or more and less than 30 °, and the electrolyte retainability is excellent.
(Triangle | delta): A contact angle is 30 degrees or more and less than 40 degrees, and is inferior to the liquid holding property of electrolyte solution.
X: A contact angle is 40 degrees or more, and it is inferior to the liquid retention property of electrolyte solution.

1 Polymer component (A)
2 Polymer component (B)
3 Inorganic particles (F)

Claims (14)

The dispersing agent composition for electrical storage device slurries containing the following component (A) and the following component (B).
Component (A): The carboxyl group-containing monomer unit (I) is 15% by weight or more and less than 40% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 40% by weight or more and 85% by weight. Polymer component A having a weight average molecular weight of less than 500,000
Component (B): The carboxyl group-containing monomer unit (I) is 0% by weight or more and less than 15% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 70% by weight or more and 100% by weight. Polymer component B, which is
CH ₂ = CR ¹ COOC _n H _2n R ² (1)
(In the formula (1), R ¹ is H or CH ₃ , R ² is H or OH, and n = 1 to 20.)   The dispersant composition for an electricity storage device slurry according to claim 1, wherein the component (B) is 5 to 800 parts by weight when the component (A) is 100 parts by weight.   The component (A) includes at least one selected from the monomer unit (II-1) in which n is 1 and the monomer unit (II-2) in which n is 2. Or the dispersing agent composition for electrical storage device slurries of 2 or 2.   The component (A) includes the monomer unit (II-1) and the monomer unit (II-2), and the monomer unit (II-1) and the monomer unit (II- The dispersant composition for an electricity storage device slurry according to claim 3, wherein the weight ratio (II-1 / II-2) of 2) is more than 0 and less than 0.8.   The component (B) is a monomer unit (II-1) in which n is 1, a monomer unit (II-2) in which n is 2, and a monomer unit (in which n is 3). The dispersant composition for an electricity storage device slurry according to any one of claims 1 to 4, comprising at least one selected from II-3) and a monomer unit (II-4) wherein n is 4 to 20. . The component (B) comprises the monomer unit (II-1), the monomer unit (II-2), the monomer unit (II-3), and the monomer unit (II-4). The monomer unit (II-1), the monomer unit (II-2) in which n is 2, and the monomer in which n is 3 The weight ratio [II-1 / (II-2 + II-3 + II-4)] of the unit (II-3) and the total of the monomer units (II-4) wherein n is 4 to 20 is represented by the following formula. The dispersant composition for an electricity storage device slurry according to claim 5, which satisfies (2).
0 <II-1 / (II-2 + II-3 + II-4) <1.2 (2) The glass transition point of the component (A) is Tg (A) (° C), the glass transition point of the component (B) is Tg (B) (° C), and the following mathematical formula (3) is satisfied. 6. The dispersant composition for power storage device slurry according to any one of 6 above.
0 ≦ | Tg (A) −Tg (B) | ≦ 50 (3)   The dispersant composition for an electricity storage device slurry according to any one of claims 1 to 7, wherein the component (A) and / or the component (B) further contains a nitrogen-containing monomer unit (III).   The dispersant composition for an electricity storage device slurry according to any one of claims 1 to 8, wherein the component (B) further comprises a glycidyl group-containing monomer unit (IV). An electricity storage device slurry composition containing the following component (A), the following component (B) and inorganic particles (F), and may contain the following component (C):
When the content of the inorganic particles (F) is 100 parts by weight, the respective contents are 0.01 to 20 parts by weight for the component (A) and 0.1 to 40 parts by weight for the component (B). Part, The electrical storage device slurry composition whose said component (C) is 0-20 weight part.
Component (A): The carboxyl group-containing monomer unit (I) is 15% by weight or more and less than 40% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 40% by weight or more and 85% by weight. Polymer component A having a weight average molecular weight of less than 500,000
Component (B): The carboxyl group-containing monomer unit (I) is 0% by weight or more and less than 15% by weight, and the monomer unit (II) represented by the following chemical formula (1) is 70% by weight or more and 100% by weight. Polymer component B, which is
CH ₂ = CR ¹ COOC _n H _2n R ² (1)
(In the formula (1), R ¹ is H or CH ₃ , R ² is H or OH, and n = 1 to 20.)
Component (C): Surfactant   A positive electrode for an electricity storage device having a positive electrode coating film on a current collector, wherein the coating film is formed of a nonvolatile component of the electricity storage device slurry composition according to claim 10.   A negative electrode for an electricity storage device having a negative electrode coating film on a current collector, wherein the coating film is formed of a nonvolatile component of the electricity storage device slurry composition according to claim 10.   The separator for electrical storage devices which is a separator which has a film for separators, Comprising: The said film is formed with the non volatile matter of the electrical storage device slurry composition of Claim 10.   It is an electrical storage device containing a negative electrode, a positive electrode, a separator, and electrolyte solution, Comprising: At least 1 of the said negative electrode, the said positive electrode, and the said separator is formed with the non volatile matter of the electrical storage device slurry composition of Claim 10. An electricity storage device having a coating.

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