JP5446178B2 - Positive electrode mixture paste for lithium secondary battery - Google Patents

Description

The present invention relates to a positive electrode mixture paste used for producing a positive electrode constituting a lithium secondary battery and a method for producing the same.
In addition, the present invention is a lithium secondary comprising an electrode having excellent discharge characteristics or charge characteristics at a large current, cycle characteristics, and conductivity of an electrode mixture, and a small contact resistance between the electrode current collector and the electrode mixture. It relates to batteries.

  In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. These electronic devices have always been required to minimize the volume and reduce the weight, and the batteries to be mounted are also required to be small, light, and have a large capacity. Also, in large-sized secondary batteries for automobiles and the like, it is desired to realize a large-sized nonaqueous electrolyte secondary battery instead of the conventional lead-acid battery.

  In order to meet such demands, lithium secondary batteries are being actively developed. As an electrode of a lithium secondary battery, a positive electrode in which an electrode mixture composed of a positive electrode active material containing lithium ions, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of a metal foil, and lithium ion removal A negative electrode is used in which an electrode mixture composed of an insertable negative electrode active material, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of a metal foil.

Generally, lithium transition metal composite oxides such as lithium cobaltate, lithium manganate, and lithium nickelate are used as the positive electrode active material, but these have low electron conductivity and are sufficient for use alone. Battery performance is not obtained. Therefore, attempts have been made to improve the conductivity by reducing the internal resistance of the positive electrode by adding a carbon material such as carbon black (for example, acetylene black) as a conductive additive. In addition, in order to efficiently reduce internal resistance with a smaller amount of carbon black, both the positive electrode active material and the conductive auxiliary carbon material are required to be uniformly mixed at a finer level in the electrode. .
In particular, reducing the internal resistance of the electrode is very important in enabling discharge with a large current and improving charge and discharge efficiency.

  However, the positive electrode active material, which is an inorganic component having high hydrophilicity, and the carbon material such as carbon black, which has high hydrophobicity, are greatly different from each other in physical properties on the particle surface, and as such, can be uniformly dispersed and mixed in the positive electrode mixture paste. This makes it difficult to achieve the maximum performance of the positive electrode active material and the carbon material that is the conductive additive, and a high improvement in battery performance cannot be expected. Also, if the dispersion of the positive electrode active material and the conductive additive in the positive electrode mixture is insufficient, a resistance distribution occurs on the electrode plate due to partial aggregation, and the current concentrates when used as a battery, Inconveniences such as partial heat generation and deterioration may occur.

  In addition, when a positive electrode mixture layer is formed on a current collector such as a metal foil, the charge and discharge are repeated many times, and the interface between the current collector and the positive electrode mixture layer or the positive electrode active material and the conductive material inside the positive electrode mixture. There is a problem in that the adhesion at the auxiliary agent interface is deteriorated and the battery performance is lowered. This is because the positive electrode active material and the positive electrode mixture layer are repeatedly expanded and contracted by doping and dedoping of lithium ions during charge and discharge, so that the positive electrode mixture layer and the current collector interface, and the positive electrode active material and the conductive auxiliary agent interface This is thought to be because local shear stress is generated and the interfacial adhesion deteriorates. Also in this case, if the dispersion of the positive electrode active material and the conductive additive is insufficient, the decrease in adhesion becomes significant. This is presumably because the presence of coarse aggregated particles makes it difficult to relieve stress.

  In lithium secondary batteries, the dispersion of a carbon material that is an active material and a conductive auxiliary agent is one of the important points. Patent Documents 1 and 2 describe examples in which a surfactant is used as a dispersant when dispersing an active material and carbon black in a solvent. However, since the surfactant has a weak adsorption force to the particle surface, the amount of the surfactant added must be increased in order to obtain good dispersion stability. As a result, the amount of the active material that can be contained is small. Battery capacity will decrease. Further, if the surfactant is not sufficiently adsorbed on the particles, the active material and the carbon material are aggregated. Further, a general surfactant has a remarkably low dispersion effect in an organic solvent as compared with dispersion in an aqueous solution.

  Patent Document 3 discloses a method of improving the dispersion state by adding a dispersion resin when the negative electrode active material and carbon black are dispersed in water. However, with this method, although the dispersibility of the active material and carbon black is improved, the dispersion resin having a large molecular weight coats the particle surface, so that the conductive network is likely to be hindered and the resistance of the electrode is increased. In addition, the effect of improving the dispersion of the active material and carbon black may be offset.

  In addition to the improvement in the dispersibility of the electrode material, an important factor for improving the charge / discharge efficiency is an improvement in the wettability of the electrode with respect to the electrolytic solution. Since the electrode reaction occurs at the contact interface between the electrode material surface and the electrolytic solution, it is important that the electrolytic solution penetrates into the electrode and the electrode material is well wetted. As a method of promoting the electrode reaction, a method of increasing the surface area of the electrode by using a fine active material or a conductive assistant has been studied, but the actual contact area is difficult to increase because of poor wettability to the electrolyte. There is a problem that it is difficult to improve battery performance.

As a method for improving the wettability of the electrode, Patent Document 4 discloses a method of improving the wettability by adsorbing a surfactant such as a higher fatty acid alkali salt to the negative electrode active material and carbon powder. As described above, surfactants are often not sufficiently dispersed in a non-aqueous system, and a uniform electrode coating film cannot be obtained. In these examples, the total performance including the dispersibility of the electrode material was insufficient.
JP-A-63-236258 JP-A-8-190912 JP-T-2006-51679 JP-A-6-60877

  In the positive electrode mixture paste for a lithium secondary battery, the present invention aims to stabilize the dispersion without inhibiting the conductivity of the positive electrode active material, to improve the wettability of the positive electrode active material with respect to the electrolyte, It aims at improving the battery performance of the battery produced using the battery composition of invention.

一般式（１６）中、
Ｘ ¹⁰¹ は、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−、又は−Ｘ ¹⁰³ −Ｙ ¹⁰¹ −Ｘ ¹⁰⁴ −であり、
Ｘ ¹⁰² 、及びＸ ¹⁰⁴ は、それぞれ独立に、−ＮＨ−、又は−Ｏ−であり、
Ｘ ¹⁰³ は、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＮＨＣＯ−、又は−ＮＨ
ＳＯ ₂ −であり、
Ｙ ¹⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ¹⁰¹ は、−ＳＯ ₃ Ｍ ¹⁰¹ 、−ＣＯＯＭ ¹⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ¹⁰¹ ） ₂ であり、
Ｍ ¹⁰¹ は、１〜３価のカチオンの一当量であり、
Ｑ ¹⁰¹ は、−Ｏ−Ｒ ¹⁰² 、−ＮＨ−Ｒ ¹⁰² 、ハロゲン基、−Ｘ ¹⁰¹ −Ｒ ¹⁰¹ 、又は−Ｘ ¹⁰² −Ｙ ¹⁰¹ −Ｚ ¹⁰¹ であり、
Ｒ ¹⁰² は、水素原子、置換基を有してもよいアルキル基、又は置換基を有してもよいアルケニル基であり、
ｎ ¹⁰¹ は、１〜４の整数であり、
Ｒ ¹⁰¹ は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は下記一般式（１７）で表される基である。

一般式（１７）：

一般式（１７）中、
Ｘ ²⁰¹ は、−ＮＨ−、又は−Ｏ−であり、
Ｘ ²⁰² 、及びＸ ²⁰³ は、それぞれ独立に、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、又は−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−であり、
Ｒ ²⁰¹ 、及びＲ ²⁰² は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は−Ｙ ²⁰¹ −Ｚ ²⁰¹ であり、
Ｙ ²⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ²⁰¹ は、−ＳＯ ₃ Ｍ ²⁰¹ 、−ＣＯＯＭ ²⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ²⁰¹ ） ₂ であり、
Ｍ ²⁰¹ は、１〜３価のカチオンの一当量である。
The subject is a positive electrode mixture paste for a lithium secondary battery, comprising a vinylamide resin and a positive electrode active material ,
Furthermore,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
The A comprising at for a lithium secondary battery positive electrode material mixture paste,
A triazine derivative having an acidic functional group is
This is solved by a positive electrode mixture paste for a lithium secondary battery, which is a triazine derivative represented by the following general formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation.

  The present invention also relates to the positive electrode mixture paste for a lithium secondary battery, wherein the basic functional group of the derivative is an amino group.

  The present invention also relates to the positive electrode mixture paste for a lithium secondary battery, wherein the acidic functional group of the derivative is one or more acidic functional groups selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

  Moreover, this invention relates to the said positive mix paste for lithium secondary batteries whose positive electrode active material is lithium iron phosphate.

  The present invention further relates to the positive electrode material mixture paste for a lithium secondary battery, further comprising a binder resin.

  The present invention also relates to the positive electrode mixture paste for a lithium secondary battery, wherein the binder resin is a polymer compound containing a fluorine atom in the molecule.

  The present invention further relates to the positive electrode mixture paste for a lithium secondary battery, further comprising a conductive additive.

一般式（１６）中、
Ｘ ¹⁰¹ は、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−、又は−Ｘ ¹⁰³ −Ｙ ¹⁰¹ −Ｘ ¹⁰⁴ −であり、
Ｘ ¹⁰² 、及びＸ ¹⁰⁴ は、それぞれ独立に、−ＮＨ−、又は−Ｏ−であり、
Ｘ ¹⁰³ は、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＮＨＣＯ−、又は−ＮＨ
ＳＯ ₂ −であり、
Ｙ ¹⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ¹⁰¹ は、−ＳＯ ₃ Ｍ ¹⁰¹ 、−ＣＯＯＭ ¹⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ¹⁰¹ ） ₂ であり、
Ｍ ¹⁰¹ は、１〜３価のカチオンの一当量であり、
Ｑ ¹⁰¹ は、−Ｏ−Ｒ ¹⁰² 、−ＮＨ−Ｒ ¹⁰² 、ハロゲン基、−Ｘ ¹⁰¹ −Ｒ ¹⁰¹ 、又は−Ｘ ¹⁰² −Ｙ ¹⁰¹ −Ｚ ¹⁰¹ であり、
Ｒ ¹⁰² は、水素原子、置換基を有してもよいアルキル基、又は置換基を有してもよいアルケニル基であり、
ｎ ¹⁰¹ は、１〜４の整数であり、
Ｒ ¹⁰¹ は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は下記一般式（１７）で表される基である。

一般式（１７）：

一般式（１７）中、
Ｘ ²⁰¹ は、−ＮＨ−、又は−Ｏ−であり、
Ｘ ²⁰² 、及びＸ ²⁰³ は、それぞれ独立に、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、又は−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−であり、
Ｒ ²⁰¹ 、及びＲ ²⁰² は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は−Ｙ ²⁰¹ −Ｚ ²⁰¹ であり、
Ｙ ²⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ²⁰¹ は、−ＳＯ ₃ Ｍ ²⁰¹ 、−ＣＯＯＭ ²⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ²⁰¹ ） ₂ であり、
Ｍ ²⁰¹ は、１〜３価のカチオンの一当量である。
The present invention also includes a vinylamide resin, a positive electrode active material,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
And a method for producing a positive electrode mixture paste for a lithium secondary battery in which a solvent is dispersed ,
A triazine derivative having an acidic functional group is
The present invention relates to a method for producing a positive electrode mixture paste for a lithium secondary battery, which is a triazine derivative represented by the following general formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation.

一般式（１６）中、
Ｘ ¹⁰¹ は、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−、又は−Ｘ ¹⁰³ −Ｙ ¹⁰¹ −Ｘ ¹⁰⁴ −であり、
Ｘ ¹⁰² 、及びＸ ¹⁰⁴ は、それぞれ独立に、−ＮＨ−、又は−Ｏ−であり、
Ｘ ¹⁰³ は、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＮＨＣＯ−、又は−ＮＨ
ＳＯ ₂ −であり、
Ｙ ¹⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ¹⁰¹ は、−ＳＯ ₃ Ｍ ¹⁰¹ 、−ＣＯＯＭ ¹⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ¹⁰¹ ） ₂ であり、
Ｍ ¹⁰¹ は、１〜３価のカチオンの一当量であり、
Ｑ ¹⁰¹ は、−Ｏ−Ｒ ¹⁰² 、−ＮＨ−Ｒ ¹⁰² 、ハロゲン基、−Ｘ ¹⁰¹ −Ｒ ¹⁰¹ 、又は−Ｘ ¹⁰² −Ｙ ¹⁰¹ −Ｚ ¹⁰¹ であり、
Ｒ ¹⁰² は、水素原子、置換基を有してもよいアルキル基、又は置換基を有してもよいアルケニル基であり、
ｎ ¹⁰¹ は、１〜４の整数であり、
Ｒ ¹⁰¹ は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は下記一般式（１７）で表される基である。

一般式（１７）：

一般式（１７）中、
Ｘ ²⁰¹ は、−ＮＨ−、又は−Ｏ−であり、
Ｘ ²⁰² 、及びＸ ²⁰³ は、それぞれ独立に、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、又は−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−であり、
Ｒ ²⁰¹ 、及びＲ ²⁰² は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は−Ｙ ²⁰¹ −Ｚ ²⁰¹ であり、
Ｙ ²⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ²⁰¹ は、−ＳＯ ₃ Ｍ ²⁰¹ 、−ＣＯＯＭ ²⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ²⁰¹ ） ₂ であり、
Ｍ ²⁰¹ は、１〜３価のカチオンの一当量である。
The present invention also includes a vinylamide resin, a positive electrode active material, a binder resin, a conductive auxiliary agent,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
And a method for producing a positive electrode mixture paste for a lithium secondary battery that is co-dispersed in a solvent ,
A triazine derivative having an acidic functional group is
The present invention relates to a method for producing a positive electrode mixture paste for a lithium secondary battery, which is a triazine derivative represented by the following general formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation.

一般式（１６）中、
Ｘ ¹⁰¹ は、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−、又は−Ｘ ¹⁰³ −Ｙ ¹⁰¹ −Ｘ ¹⁰⁴ −であり、
Ｘ ¹⁰² 、及びＸ ¹⁰⁴ は、それぞれ独立に、−ＮＨ−、又は−Ｏ−であり、
Ｘ ¹⁰³ は、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＮＨＣＯ−、又は−ＮＨ
ＳＯ ₂ −であり、
Ｙ ¹⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ¹⁰¹ は、−ＳＯ ₃ Ｍ ¹⁰¹ 、−ＣＯＯＭ ¹⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ¹⁰¹ ） ₂ であり、
Ｍ ¹⁰¹ は、１〜３価のカチオンの一当量であり、
Ｑ ¹⁰¹ は、−Ｏ−Ｒ ¹⁰² 、−ＮＨ−Ｒ ¹⁰² 、ハロゲン基、−Ｘ ¹⁰¹ −Ｒ ¹⁰¹ 、又は−Ｘ ¹⁰² −Ｙ ¹⁰¹ −Ｚ ¹⁰¹ であり、
Ｒ ¹⁰² は、水素原子、置換基を有してもよいアルキル基、又は置換基を有してもよいアルケニル基であり、
ｎ ¹⁰¹ は、１〜４の整数であり、
Ｒ ¹⁰¹ は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は下記一般式（１７）で表される基である。

一般式（１７）：

一般式（１７）中、
Ｘ ²⁰¹ は、−ＮＨ−、又は−Ｏ−であり、
Ｘ ²⁰² 、及びＸ ²⁰³ は、それぞれ独立に、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、又は−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−であり、
Ｒ ²⁰¹ 、及びＲ ²⁰² は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は−Ｙ ²⁰¹ −Ｚ ²⁰¹ であり、
Ｙ ²⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ²⁰¹ は、−ＳＯ ₃ Ｍ ²⁰¹ 、−ＣＯＯＭ ²⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ²⁰¹ ） ₂ であり、
Ｍ ²⁰¹ は、１〜３価のカチオンの一当量である。
The present invention also includes a vinylamide resin, a positive electrode active material,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
In a dispersion obtained by dispersing in a solvent,
A method for producing a positive electrode mixture paste for a lithium secondary battery, comprising mixing a conductive additive and a binder resin ,
A triazine derivative having an acidic functional group is
The present invention relates to a method for producing a positive electrode mixture paste for a lithium secondary battery, which is a triazine derivative represented by the following general formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation.

一般式（１６）中、
Ｘ ¹⁰¹ は、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−、又は−Ｘ ¹⁰³ −Ｙ ¹⁰¹ −Ｘ ¹⁰⁴ −であり、
Ｘ ¹⁰² 、及びＸ ¹⁰⁴ は、それぞれ独立に、−ＮＨ−、又は−Ｏ−であり、
Ｘ ¹⁰³ は、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、−ＮＨＣＯ−、又は−ＮＨ
ＳＯ ₂ −であり、
Ｙ ¹⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ¹⁰¹ は、−ＳＯ ₃ Ｍ ¹⁰¹ 、−ＣＯＯＭ ¹⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ¹⁰¹ ） ₂ であり、
Ｍ ¹⁰¹ は、１〜３価のカチオンの一当量であり、
Ｑ ¹⁰¹ は、−Ｏ−Ｒ ¹⁰² 、−ＮＨ−Ｒ ¹⁰² 、ハロゲン基、−Ｘ ¹⁰¹ −Ｒ ¹⁰¹ 、又は−Ｘ ¹⁰² −Ｙ ¹⁰¹ −Ｚ ¹⁰¹ であり、
Ｒ ¹⁰² は、水素原子、置換基を有してもよいアルキル基、又は置換基を有してもよいアルケニル基であり、
ｎ ¹⁰¹ は、１〜４の整数であり、
Ｒ ¹⁰¹ は、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は下記一般式（１７）で表される基である。

一般式（１７）：

一般式（１７）中、
Ｘ ²⁰¹ は、−ＮＨ−、又は−Ｏ−であり、
Ｘ ²⁰² 、及びＸ ²⁰³ は、それぞれ独立に、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ ₂ ＮＨ−、−ＣＨ ₂ ＮＨ−、又は−ＣＨ ₂ ＮＨＣＯＣＨ ₂ ＮＨ−であり、
Ｒ ²⁰¹ 、及びＲ ²⁰² は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は−Ｙ ²⁰¹ −Ｚ ²⁰¹ であり、
Ｙ ²⁰¹ は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ ²⁰¹ は、−ＳＯ ₃ Ｍ ²⁰¹ 、−ＣＯＯＭ ²⁰¹ 、又は−Ｐ（Ｏ）（−ＯＭ ²⁰¹ ） ₂ であり、
Ｍ ²⁰¹ は、１〜３価のカチオンの一当量である。
The present invention also provides
One or more selected from the group consisting of vinylamide resins, organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups Treatment agent, or
One or more treatment agents selected from the group consisting of vinylamide resins, organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups;
A method for producing a positive electrode material mixture paste for a lithium secondary battery using a pretreated positive electrode active material ,
A triazine derivative having an acidic functional group is
The present invention relates to a method for producing a positive electrode mixture paste for a lithium secondary battery, which is a triazine derivative represented by the following general formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation.

  Furthermore, the present invention is a lithium secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium, The present invention relates to a lithium secondary battery in which the positive electrode mixture layer is formed using the positive electrode mixture paste for a lithium secondary battery.

  Furthermore, this invention relates to the said lithium secondary battery formed using the positive mix paste for lithium secondary batteries manufactured by the said manufacturing method.

  According to a preferred embodiment of the present invention, a positive electrode mixture paste for a lithium secondary battery excellent in dispersion stability can be obtained without inhibiting the conductivity of the positive electrode active material. Furthermore, by using the positive electrode mixture paste for a lithium secondary battery according to a preferred embodiment of the present invention for the positive electrode of the lithium secondary battery, the positive electrode active material is uniformly mixed at the primary particle level in the positive electrode mixture. In addition, the adhesion between the current collector and the positive electrode mixture, the adhesion between the positive electrode active material and the conductive additive, and the wettability of the positive electrode mixture with respect to the electrolyte solution are improved, and the internal resistance of the positive electrode is reduced. At the same time, charging / discharging efficiency can be improved, and battery performance can be improved comprehensively.

Lithium secondary battery positive electrode material mixture paste of the present invention will be described in detail below.

<Vinylamide resin>
The vinylamide resin used for the positive electrode mixture paste for a lithium secondary battery of the present invention is not particularly limited.
Examples thereof include polyvinyl acetamide, polyacrylamide, polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, a graft copolymer of polyvinyl pyrrolidone, and a copolymer of vinyl pyrrolidone and a comonomer.

 Comonomers that can be copolymerized with vinylpyrrolidone include α-olefin, vinyl acetate, ethyl acrylate, methyl acrylate, methyl methacrylate, dimethylaminomethyl methacrylate, acrylamide, methacrylamide, acrylonitrile, ethylene, styrene, maleic anhydride, Examples include acrylic acid, sodium vinyl sulfate, vinyl chloride, vinyl pyrrolidine, trimethylsiloxy vinyl silane, vinyl propionate, vinyl caprolactam, and methyl vinyl ketone.

  In addition, an acid-modified product obtained by treating the vinylamide resin with an organic acid or an inorganic acid can be used.

  Among the vinyl amide resins, in particular, a treatment with an almost neutral vinyl amide resin such as polyvinyl pyrrolidone, vinyl pyrrolidone-1-butene copolymer, or vinyl pyrrolidone-styrene copolymer, or an organic acid or an inorganic acid. An acid-modified product of polyvinyl pyrrolidone is preferably used.

  The vinylamide resin of the present invention is effective in dispersing the positive electrode active material because the solvent used is excellent in wettability with respect to the solvent regardless of whether the solvent used is water or an aqueous solvent or a solvent system. It is inferred that this is because the interaction between the active material and the active material is smoothly promoted, and the aggregation of the active materials is extremely reduced. In particular, when a highly polar solvent is used, the dispersion effect is extremely high.

<Positive electrode active material>
Although it does not specifically limit as a positive electrode active material used for the positive mix paste for lithium secondary batteries of this invention, Metal oxides which can dope or intercalate lithium ion, and metal compounds, such as a metal sulfide, are used. can do. Examples thereof include transition metal oxides such as Ti, Fe, Co, Ni, and Mn, composite oxides of the transition metal and lithium, and inorganic compounds such as sulfides of the transition metal.

In particular,
Transition metal oxide powders such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , and TiO ₂ ;
A composite oxide powder of lithium and a transition metal, such as lithium nickelate, lithium cobaltate, lithium manganate having a layered structure, and lithium manganate having a spinel structure;
A lithium iron phosphate material which is a phosphate compound having an olivine structure; and
Examples thereof include transition metal sulfide powders such as TiS ₂ and FeS.

  In addition, two or more of the above inorganic compounds may be mixed and used.

As the specific surface area of the positive electrode active material used increases, the number of contact points between the positive electrode active material particles increases, which is advantageous in reducing the internal resistance of the positive electrode. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is 0.1 m ² / g or more and 150 m ² / g or less, preferably 1 m ² / g or more and 120 m ² / g or less, more preferably 1.5 m ² / g or more, it is desirable to use the following 100 m ² / g. When a positive electrode active material having a specific surface area of less than 0.1 m ² / g is used, it may be difficult to obtain sufficient conductivity, and a positive electrode active material having a specific surface area of more than 150 m ² / g may not be easily manufactured. .

  In addition, the particle size of the positive electrode active material to be used is preferably 0.01 to 500 μm, particularly preferably 0.05 to 100 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.

  Among positive electrode active materials, lithium iron phosphate having an olivine structure is a preferable material from the viewpoints of cost and safety.

  Since lithium iron phosphate having a simple olivine structure has very low electronic conductivity compared to lithium cobaltate or the like, it is difficult to obtain excellent battery characteristics. Therefore, in order to improve the electron conductivity, a method is adopted in which a conductive material such as a carbon material is supported on the particles or the primary particle diameter is reduced.

  The carbon material-supported lithium iron phosphate is not particularly limited, but can be produced with reference to Japanese Patent Application Laid-Open Nos. 2003-292308 and 2003-292309.

For example, ferrous phosphate octahydrate (Fe ₃ (PO ₄ ) ₂ .8H ₂ O) and lithium phosphate (Li ₃ PO ₄ ) are used so that the element ratio of lithium to iron becomes 1: 1. And a carbon material (for example, acetylene black, ketjen black, etc.) that is a conductive substance, or an organic compound that is decomposed by firing to become a carbon material, and the carbon material component in the final product is 0. It is obtained by further adding 1 to 50% by mass, pulverizing and mixing with a dry pulverizer, etc., then firing at 600 ° C. for several hours in an inert gas atmosphere, and pulverizing the resulting fired product. It is done.

<Various derivatives having basic functional groups>
As various derivatives having a basic functional group in the present invention, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a basic functional group One or more selected from the group consisting of triazine derivatives. Hereinafter, various derivatives having a basic functional group or derivatives having a basic functional group may be abbreviated.

  In particular, use of a triazine derivative represented by the following general formula (2) or an organic dye derivative represented by the general formula (7) is preferable.

  General formula (2):

[Formula (2) Medium X ¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ² -Y ¹ -X ^3- ,
X ² is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
X ³ is each independently —NH— or —O—.
Y ¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ² , —NH—R ² , a halogen group, —X ¹ —R ¹ , or a substituent represented by any of the following general formulas (3), (4), or (5). Yes,
R ² is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent,
R ¹ is an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (6). Yes,
n ¹ is an integer of 1 to 4.

  General formula (3):

  General formula (4):

  General formula (5):

[In the general formulas (3) to (5),
X ⁴ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or -X ⁵ -Y ² -X ⁶ - a and,
X ⁵ is —NH— or —O—.
X ⁶ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ² is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, having 1 to 20 carbon atoms,
v is an integer from 1 to 10,
R ³ And R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or R ³ And R ⁴ together with an optionally substituted heterocyclic residue containing an additional nitrogen, oxygen or sulfur atom,
R ⁵ , R ⁶ , R ⁷ , And R ⁸ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group,
R ⁹ is an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ]

  General formula (6):

[In general formula (6),
T is a -X ⁸ -R ^10, or W ^1,
U is, -X ⁹ -R ^11, or a W ^2,
W ¹ and W ² are each independently —O—R ²⁰ , —NH—R ²⁰ , a halogen group, or a substituent represented by any one of the general formulas (3), (4), and (5). Group,
R ²⁰ is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent,
X ⁷ is —NH— or —O—.
X ^8, and X ⁹ are each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
Y ³ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
R ¹⁰ and R ¹¹ are each independently an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent. ]}

Examples of the organic dye residue represented by R ^{1 in the} general formula (2) and R ¹⁰ and R ¹¹ in the general formula (6) include diketopyrrolopyrrole dyes, azo such as azo, disazo, and polyazo. Dyes, phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrones, indantrons, pyrantrons, violanthrones, anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, Examples include thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.

Examples of the heterocyclic residues and aromatic ring residues represented by R ^{1 in the} general formula (2) and R ¹⁰ and R ¹¹ in the general formula (6) include thiophene, furan, pyridine, pyrazine, Examples include triazine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. It is done. These heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy) Group, or may be substituted with a halogen, etc.), and a phenylamino group (which may be substituted with an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, or a halogen), etc. You may have the substituent of.

R ³ and R ⁴ in the general formulas (3) and (4) are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or optionally substituted. An aryl group, or R ³ And R ⁴ together with each other is an optionally substituted heterocyclic residue containing a nitrogen, oxygen or sulfur atom.

Y ¹ , Y ² and Y ³ in the general formulas (2) to (6) each independently represent an alkylene group, an alkenylene group or an arylene group which may have a substituent having 20 or less carbon atoms. However, an phenylene group, a biphenylene group, a naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms may be mentioned.

  General formula (7):

{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ² is an integer of 1 to 4,
R ¹² is an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic residue which may have a substituent.

  General formula (8):

  General formula (9):

  General formula (10):

[In the general formulas (8) to (10),
X ¹⁰ represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or -X ¹¹ -Y ⁴ -X ¹² - a and,
X ¹¹ is —NH— or —O—.
X ¹² represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ⁴ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
v ¹ is an integer from ¹ to 10,
R ¹³ , And R ¹⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ³ and R ⁴ together. An optionally substituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ , And R ¹⁸ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group,
R ¹⁹ is an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ]}

Examples of the organic dye residue represented by R ¹² in the general formula (7) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, and flavan. Anthraquinone dyes such as Throne, Antanthrone, Indanthrone, Pyrantron, Biolantron, Quinacridone dyes, Dioxazine dyes, Perinone dyes, Perylene dyes, Thioindigo dyes, Isoindoline dyes, Isoindolinone dyes, Examples thereof include quinophthalone dyes, selenium dyes, and metal complex dyes. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.

Examples of the heterocyclic residue and aromatic ring residue represented by R ¹² in the general formula (7) include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, and benzimidazole. Examples include Ron, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. These heterocyclic residues and aromatic ring residues are alkyl groups (such as methyl, ethyl, and butyl groups), amino groups, alkylamino groups (such as dimethylamino groups, diethylamino groups, and dibutylamino groups), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy) Group, and optionally substituted with halogen, etc.), phenylamino group (which may be substituted with alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.), etc. You may have the substituent of.

R ¹³ in the general formulas (8) and (9) And R ¹⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ^13. And R ¹⁴ together with each other is an optionally substituted heterocyclic residue containing a nitrogen, oxygen or sulfur atom.

Examples of amine components used to form the substituents represented by the general formulas (3) to (5) and the general formulas (7) to (9) include:
Dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N- tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, Dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutyl Aminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoe Ruamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-rupetidin, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N -Aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N Butyl piperazine, N- methyl homopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, and 1-cyclopentyl piperazine and the like.

  As a method of synthesizing an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group having a basic functional group according to the present invention. Although there is no particular limitation, JP-A 54-62227, JP-A 56-118462, JP-A 56-166266, JP 60-88185, JP It can be synthesized by the method described in JP-A-63-305173, JP-A-3-2676, JP-A-11-199796 or the like.

  For example, after introducing substituents represented by the general formulas (11) to (14) into an organic dye, anthraquinone, or acridone, these substituents and amine components (for example, N, N-dimethylaminopropylamine, N- Synthesizing by reacting methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazin-2-ylamino] aniline). Can do.

General formula (11):
-SO ₂ Cl
Formula (12):
-COCl
General formula (13):
-CH ₂ NHCOCH ₂ Cl
General formula (14):
—CH ₂ Cl

  For example, when introducing the substituent represented by the general formula (11), an organic dye, anthraquinone, or acridone is dissolved in chlorosulfonic acid and reacted with a chlorinating agent such as thionyl chloride. The number of substituents represented by the general formula (11) to be introduced into the organic dye, anthraquinone, or acridone can be controlled by conditions such as the reaction temperature and the reaction time.

  In addition, when the substituent represented by the formula (12) is introduced, first, an organic dye having a carboxyl group, anthraquinone, or acridone is synthesized by a known method, and then thionyl chloride or the like in an aromatic solvent such as benzene. And the like, and the like.

During the reaction of the substituents represented by the general formulas (11) to (14) and the amine component, a part of the substituents represented by the general formulas (11) to (14) are hydrolyzed and chlorine is substituted with hydroxyl groups. There are things to do. In that case, the substituent represented by the general formula (11) is a sulfonic acid group, and the substituent represented by the general formula (12) is a carboxylic acid group. A salt with a trivalent metal or the above-mentioned amine may be formed.
When the organic dye is an azo dye, a substituent represented by the general formulas (8) to (10) or the following general formula (15) is previously introduced into the diazo component or the coupling component, and then coupled. An azo organic dye derivative can also be produced by carrying out the reaction.

  Formula (15):

{In general formula (15),
X ¹³ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁴ -Y ⁵ -X ¹⁵ - a and,
X ¹⁴ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Each X ¹⁵ is independently —NH— or —O—;
Y ⁵ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
P ¹ is a substituent represented by any of the above general formulas (3), (4), or (5),
Q ² represents —O—R ²⁴ , —NH—R ²⁴ , a halogen group, —X ¹ —R ²⁵ , or a substituent represented by any one of the above general formulas (3), (4), or (5). And
R ²⁴ is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent,
R ²⁵ is an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the above general formula (6). is there. }

  In addition, the triazine derivative having a basic functional group of the present invention, for example, using cyanuric chloride as a starting material, and adding at least one chlorine of cyanuric chloride to the above general formulas (8) to (10) or general formula (15) Reacting the amine component (eg, N, N-dimethylaminopropylamine, N-methylpiperazine, etc.) that forms the indicated substituents, and then reacting the remaining chlorine of cyanuric chloride with various amines, alcohols, etc. Obtained by.

<Various derivatives having acidic functional groups>
As the various derivatives having an acidic functional group in the present invention, one or more kinds selected from organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group represented by the following general formula (16) are used. . Hereinafter, various derivatives having an acidic functional group or derivatives having an acidic functional group may be abbreviated.

  In particular, use of a triazine derivative represented by the following general formula (16) or an organic dye derivative represented by the general formula (19) is preferable.

  Formula (16):

In general formula ( 16 ),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation, and Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —. Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

  Formula (17):

一般式（１７）中、
Ｘ²⁰¹は、−ＮＨ−、又は−Ｏ−であり、
Ｘ²⁰²、及びＸ²⁰³は、それぞれ独立に、−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ₂ＮＨ−、−ＣＨ₂ＮＨ−、又は−ＣＨ₂ＮＨＣＯＣＨ₂ＮＨ−であり、
Ｒ²⁰¹、及びＲ²⁰²は、それぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基、又は−Ｙ²⁰¹−Ｚ²⁰¹であり、
Ｙ²⁰¹は、炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基、又は置換基を有してもよいアリーレン基であり、
Ｚ²⁰¹は、−ＳＯ₃Ｍ²⁰¹、−ＣＯＯＭ²⁰¹、又は−Ｐ（Ｏ）（−ＯＭ²⁰¹）₂であり、
Ｍ²⁰¹は、１〜３価のカチオンの一当量である。

In general formula ( 17 ),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
^M201 is one equivalent of a monovalent to trivalent cation.

Examples of the organic dye residue represented by R ^{101 in the} general formula (16) and R ²⁰¹ and R ²⁰² in the general formula (17) include azo dyes such as diketopyrrolopyrrole dyes, azo, disazo, and polyazo. Dye, phthalocyanine dye, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantron, violanthrone, anthraquinone dye, quinacridone dye, dioxazine dye, perinone dye, perylene dye, thioindigo And dyes such as azo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, The use of a quinacridone dye or a dioxazine dye is preferable because of excellent dispersibility.

Examples of the heterocyclic residue and aromatic ring residue represented by R ^{101 in the} general formula (16) and R ²⁰¹ and R ²⁰² in the general formula (17) include thiophene, furan, pyridine, pyrazole, pyrrole. Imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, or anthraquinone. In particular, the use of a heterocyclic residue containing at least one of S, N, and O heteroatoms is preferable because of excellent dispersibility.

Y ^{101 in the} general formula (16) and Y ^{201 in the} general formula (17) represent an alkylene group, an alkenylene group or an arylene group which may have a substituent having 20 or less carbon atoms, but are preferably substituted. Examples thereof include a phenylene group, a biphenylene group, a naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms.
Formula (16) substituent alkyl group which may have a represented by R ¹⁰² contained in Q ^101, the alkenyl group is preferably of 20 or less carbon atoms, more preferably carbon atoms The alkyl group which may have 10 or less side chains is mentioned. An alkyl group or alkenyl group having a substituent is a group in which a hydrogen atom of an alkyl group or an alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom, or a bromine atom, a hydroxyl group, or a mercapto group It is.

M ²⁰¹ of M ¹⁰¹ and of the general formula (16) (17) represents one equivalent of a monovalent to trivalent cation, e.g., hydrogen atom (proton), any metal cation, or a quaternary ammonium cation Represents. Further, when two or more Ms are included in the dispersant structure, M may be any one of proton, metal cation and quaternary ammonium cation, or a combination thereof.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the general formula (18) or a mixture.

  General formula (18):

In General Formula (18), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have hydrogen, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Any of the aryl groups that may be present.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ in the general formula (18) may be the same or different. Further, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the carbon number is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

  General formula (19):

In general formula (19),
X ^401, a direct bond, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH -, - X 402 -Y-, or -X ⁴⁰² - Y- ^X403-
X ⁴⁰² _{is, -CONH -, - SO 2 NH} -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
X ⁴⁰³ is —NH— or —O—;
Y ⁴⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, having 1 to 20 carbon atoms,
Z ⁴⁰¹ is —SO ₃ M ⁴⁰¹ , —COOM ⁴⁰¹ , or —P (O) (— OM ⁴⁰¹ ) ₂ ;
M ⁴⁰¹ is one equivalent of a monovalent to trivalent cation,
R ⁴⁰¹ is an organic dye residue,
n ⁴⁰¹ is an integer of 1 to 4.

Examples of the organic dye residue represented by R ⁴⁰¹ in the general formula (19) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, and flavantrons. , Antanthrone, Indanthrone, Pyrantron, Biolantron, etc. Anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone And dyes, selenium dyes, metal complex dyes, and the like. The organic dye residue represented by R ⁴⁰¹ includes a light yellow anthraquinone residue that is not generally called a dye. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, The use of a quinacridone dye or a dioxazine dye is preferable because of excellent dispersibility.

M ⁴⁰¹ in the general formula (19) represents one equivalent of a monovalent to trivalent cation, and represents, for example, a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation. In the case where the dispersant structure has two or more M, M ⁴⁰¹ may be only one of proton, metal cation and quaternary ammonium cation, or a combination thereof.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the general formula (18) or a mixture.

  General formula (18):

In General Formula (18), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have hydrogen, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Any of the aryl groups that may be present.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ in the general formula (18) may be the same or different. Further, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the carbon number is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

  The method for synthesizing the various derivatives having an acidic functional group is not particularly limited. For example, JP-B-39-28884, JP-B-45-11026, JP-B-45-29755, They can be synthesized by the methods described in JP-A No. 64-5070, JP-A No. 2004-217842, and the like.

<Effects of various derivatives having basic or acidic functional groups>
As one of the effects of various derivatives having the above basic or acidic functional groups (hereinafter sometimes simply referred to as “derivatives”), a derivative further added to increase the wettability of the vinylamide resin with the solvent is used as the positive electrode. By acting on the surface of the active material (for example, adsorption), it is considered that dispersion proceeds due to a synergistic effect. Among the positive electrode active materials, in the case of lithium iron phosphate carrying a carbon material, since the surface of the particles is highly hydrophobic, the effect of adsorbing various derivatives having functional groups is further improved, so it is considered that the dispersion effect is also exhibited. It is done.

  Therefore, in the present invention, by using the vinylamide resin and various derivatives having a basic or acidic functional group, a functional group is not directly introduced (covalently bonded) to the surface of the positive electrode active material, and a dispersion resin is not used. Good dispersion can be obtained. From these, good dispersion can be obtained without degrading the conductivity of the positive electrode active material. By using the positive electrode mixture paste for a lithium secondary battery of the present invention in which the positive electrode active material is well dispersed, a positive electrode in which the positive electrode active material is uniformly dispersed can be produced.

  Moreover, in the positive electrode using the positive electrode mixture paste for a lithium secondary battery of the present invention, since various derivatives having a functional group are present on the surface of the positive electrode active material, the wettability of the positive electrode active material to the electrolytic solution is improved. Combined with the above uniform dispersion effect, the wettability of the positive electrode to the electrolyte is improved.

The vinyl amide resin is used as a binder for binding the positive electrode active material and the carbon material as the conductive auxiliary agent, or for binding the positive electrode active material and the carbon material as the conductive auxiliary agent to the collector electrode. 1 type selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group By using in combination with one or more derivatives selected from the group consisting of the above derivatives, or organic dye derivatives having an acidic functional group, and triazine derivatives having an acidic functional group represented by the general formula (16), The dispersion stability of the substance and the adhesion of the positive electrode mixture layer can be further improved.

  That is, adsorption of the vinylamide resin on the surface of the positive electrode active material is promoted by adsorbing the vinylamide resin on the surface of the positive electrode active material while interacting with the derivative acting on the surface of the positive electrode active material (eg, adsorption) and the vinylamide resin. It is considered that the adhesion between the active material and the vinylamide resin is improved, and the dispersion stability of the positive electrode active material is improved by repulsion due to steric hindrance of the vinylamide resin. Further, since the adhesion between the positive electrode active material and the polymer compound containing a fluorine atom in the molecule as the binder resin is also improved, it can be expected that the amount of the binder used is reduced.

<Conductive aid>
As the conductive additive added to the positive electrode mixture paste for a lithium secondary battery in the present invention, a carbon material is most preferable. The carbon material is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, carbon nanotube, carbon nanofiber, carbon fiber, fullerene, etc. alone or in combination of two or more. Can be used. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.

  Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material. Channel black rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and various types such as acetylene black using acetylene gas as a raw material alone, Or two or more types can be used together. Ordinarily oxidized carbon black, hollow carbon and the like can also be used.

  The oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon. However, since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.

As the specific surface area of the carbon black used increases, the number of contact points between the carbon black particles increases, which is advantageous in reducing the internal resistance of the electrode. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is 20 m ² / g or more and 1500 m ² / g or less, preferably 50 m ² / g or more and 1500 m ² / g or less, more preferably 100 m ^2. / G or more and 1500 m ² / g or less are desirable. If carbon black having a specific surface area of less than 20 m ² / g is used, it may be difficult to obtain sufficient conductivity, and carbon black of more than 1500 m ² / g may be difficult to obtain from commercially available materials. is there.

  Moreover, the particle size of the carbon black to be used is preferably 0.005 to 1 μm, and particularly preferably 0.01 to 0.2 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.

Examples of commercially available carbon black include
Furnace blacks manufactured by Tokai Carbon, such as Toka Black # 4300, # 4400, # 4500, and # 5500;
Furnace Black made by Degussa such as Printex L;
Furnace black manufactured by Colombian, such as Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, Conductex SC ULTRA, 975 ULTRA, PUER BLACK100, 115, and 205;
# 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, and # 5400B furnace black manufactured by Mitsubishi Chemical Corporation;
Furnace black from Cabot, such as MONARCH 1400, 1300, 900, Vulcan XC-72R, and Black Pearls 2000;
Furnace black manufactured by TIMCAL, such as Ensaco 250G, Ensaco 260G, Ensaco 350G, and SuperP-Li;
Ketjen Black EC-300J, EC-600JD and other Akzo Ketjen Black;
Examples include, but are not limited to, Denka Black, Denka Black HS-100, FX-35 and other acetylene blacks manufactured by Denki Kagaku Kogyo.

<Solvent>
Examples of the solvent used in the present invention include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, and phosphoric acid. Examples include esters, ethers, nitriles, and water.

  In order to obtain the solubility of the binder resin component and the dispersion stability of the carbon material which is a conductive additive, it is preferable to use a highly polar solvent.

  For example, N-methyl-2-pyrrolidone, an amide solvent obtained by dialkylating nitrogen such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide , Hexamethylphosphoric triamide, and dimethyl sulfoxide, water, alcohol and the like. Two or more types can be used in combination.

<Binder>
The positive electrode mixture paste for a lithium secondary battery of the present invention may further contain a binder component other than the vinylamide resin.

  Examples of the binder used include cellulose resins such as acrylic resin, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicon resin, fluororesin, and carboxymethylcellulose. , Synthetic rubbers such as styrene-butadiene rubber and fluororubber, and conductive resins such as polyaniline and polyacetylene, etc., and modified, blended, or copolymers of these resins may be used.

  Specifically, ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, vinyl pyrrolidone, etc. Examples thereof include a copolymer contained as a structural unit.

  In particular, it is preferable to use a polymer compound having a fluorine atom in the molecule, for example, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene, etc. from the viewpoint of resistance.

  The weight average molecular weight of these resins as a binder is preferably 10,000 to 1,000,000. When the molecular weight is small, the resistance of the binder may decrease. When the molecular weight is increased, the resistance of the binder is improved, but the viscosity of the binder itself is increased, the workability is lowered, and it acts as an aggregating agent.

<Positive electrode mixture paste for lithium secondary battery>
The positive electrode mixture paste of the present invention can be used as a positive electrode mixture paste for a lithium secondary battery. When used as a positive electrode mixture paste, a paste comprising a vinylamide resin, a positive electrode active material, and a solvent, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, a basic One or more derivatives selected from the group consisting of an acridone derivative having a functional group and a triazine derivative having a basic functional group, or an organic dye derivative having an acidic functional group, and an acidic function represented by the general formula (16) It is preferable that a paste containing one or more derivatives selected from the group consisting of a triazine derivative having a group and a carbon material as a conductive additive and a binder component are used as a positive electrode mixture paste.

  The ratio of the positive electrode active material to the total solid content in the positive electrode mixture paste is 80% by weight or more and 98.5% by weight or less of the vinylamide resin and the derivative having a basic functional group or an acidic functional group. Is preferred. Further, the ratio of the solid content of the carbon material as the conductive auxiliary agent in the total solid content in the positive electrode mixture paste is preferably 0.5% by weight or more and 19% by weight or less. The ratio of the binder component (resin component other than the vinylamide resin) in the total solid content in the positive electrode mixture paste is preferably 1% by weight or more and 10% by weight or less. The proper viscosity of the positive electrode mixture paste depends on the method of applying the positive electrode mixture paste, but generally it is preferably 100 mPa · s or more and 30,000 mPa · s or less.

  The positive electrode mixture paste in the present invention not only has excellent dispersibility of the positive electrode active material but also has an effect of relaxing aggregation of the positive electrode active material. Since the dispersibility of the positive electrode active material is excellent, the energy when mixing and dispersing the positive electrode active material and the carbon material as the conductive additive in the solvent is efficiently inhibited without being inhibited by the aggregate of the positive electrode active material ( It is considered that the dispersibility of the carbon material (conducting aid) can be improved as a result.

  In the positive electrode mixture paste of the present invention, carbon material particles as a conductive auxiliary agent can be uniformly coordinated and adhered around the positive electrode active material, and excellent conductivity and adhesion can be imparted to the positive electrode mixture layer. . Further, since the conductivity is improved, the amount of carbon material added as a conductive additive can be reduced, so the amount of positive electrode active material added can be relatively increased, and the capacity, which is a large characteristic of the battery, can be increased. Can be bigger.

  Furthermore, since the positive electrode mixture paste of the present invention has little aggregation of the positive electrode active material and the carbon material (conducting aid), a uniform coating film with high smoothness can be obtained when applied to the current collector, The adhesion between the current collector and the positive electrode mixture is improved. In addition, since the vinylamide resin acts (for example, adsorbs) on the surface of the carbon material (conducting aid), the surface of the positive electrode active material such as a lithium transition metal composite oxide and the surface of the carbon material (conducting aid) Compared with the case where a derivative having a basic functional group or an acidic functional group is not used, the adhesion between the positive electrode active material and the carbon material (conducting aid) is improved by using the derivative in combination, as compared with the case where a derivative having a basic functional group or an acidic functional group is not used. .

<The manufacturing method of the positive mix paste for lithium secondary batteries of this invention>
Next, the manufacturing method of the positive mix paste of this invention is demonstrated.

  The positive electrode mixture paste of the present invention comprises, for example, a vinylamide resin and a positive electrode active material dispersed in a solvent, and, if necessary, a carbon material as a conductive auxiliary agent or an additional binder component (vinylamide). It can manufacture by mixing resin components other than a resin. The order of addition of each component is not limited to this. Moreover, you may add a solvent further as needed.

  A method for producing a positive electrode mixture paste is a method in which a vinylamide resin is completely or partially dissolved in a solvent, and the positive electrode active material is added and mixed in the solution, whereby the resin acts on the positive electrode active material (for example, adsorption). It is preferable to disperse in a solvent.

Furthermore, as other positive electrode mixture paste manufacturing method,
Vinylamide resin,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group represented by the general formula (16) ,
And completely or partially dissolved in the solvent, and the positive electrode active material is added and mixed in the solution, so that the vinylamide resin and derivative act on the positive electrode active material (for example, adsorb) and are dispersed in the solvent. Is preferred.

  The concentration of the positive electrode active material in the dispersion at this time is 1% by weight or more and 90% by weight, although it depends on the characteristic values unique to the positive electrode active material such as the specific surface area and surface functional group amount of the positive electrode active material used. The content is preferably 10% by weight or more and 80% by weight or less. If the concentration of the positive electrode active material is too low, the production efficiency is deteriorated, and the viscosity of the mixture paste tends to be low, and the positive electrode active material is likely to settle with time, and it may be difficult to produce a uniform positive electrode. On the other hand, when the concentration of the positive electrode active material is too high, the viscosity of the dispersion is remarkably increased, and the dispersion efficiency and the handling of the dispersion may be reduced.

  The vinylamide resin added when dispersing the positive electrode active material is 0.01 parts by weight or more and 30 parts by weight or less, preferably 0.05 parts by weight or more and 25 parts by weight or less, with respect to 100 parts by weight of the positive electrode active material. More preferably, it is added at 0.1 to 20 parts by weight.

  In addition, when dispersing the positive electrode active material in the solvent, it is preferable to add a vinylamide resin and a derivative. The amount of the derivative added is determined by the specific surface area of the positive electrode active material used. Generally, the derivative is added in an amount of 0.01 to 30 parts by weight, preferably 0.05 to 25 parts by weight, more preferably 0.1 to 100 parts by weight of the positive electrode active material. It is added in an amount of 20 parts by weight or more and 20 parts by weight or less. If the addition amount is small, a sufficient dispersion effect cannot be obtained, and even if added excessively, a significant dispersion improvement effect may not be obtained.

  As an apparatus for dispersing the vinylamide resin in the solvent while acting (for example, adsorbing) the positive electrode active material, or for dispersing the vinylamide resin and the derivative in the solvent while acting (for example, adsorbing) the positive electrode active material. Can use a disperser usually used for pigment dispersion or the like.

For example,
Mixers such as dispersers, homomixers, or planetary mixers;
Homogenizers such as “Clairemix” manufactured by M Technique, or “Fillmix” of PRIMIX;
Media-type dispersers such as paint conditioners (manufactured by Red Devil), ball mills, sand mills (such as “Dynomill” manufactured by Shinmaru Enterprises), attritors, pearl mills (such as “DCP mill” manufactured by Eirich), or coball mills;
Wet jet mill (genus “Genus PY”, Sugino Machine “Starburst”, Nanomizer “Nanomizer”, etc.) M Technic “Claire SS-5”, or Nara Machinery “MICROS” Medialess dispersers such as; or
In addition, although a roll mill etc. are mentioned, it is not limited to these. Further, as the disperser, it is preferable to use a disperser that has been subjected to a metal mixing prevention treatment from the disperser.

  For example, when using a media-type disperser, a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. And as a medium, it is preferable to use ceramic beads, such as glass beads, zirconia beads, or alumina beads. Moreover, also when using a roll mill, it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.

  In the case of a positive electrode active material in which particles are easily broken or crushed by a strong impact, a medialess disperser such as a roll mill or a homogenizer is preferable to a media type disperser.

In addition, in order to improve the wettability of the positive electrode active material to the solvent and further improve the dispersibility in the solvent,
One or more selected from the group consisting of vinylamide resins, organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups Treatment agent, or
One or more treatment agents selected from the group consisting of vinylamide resins, organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups represented by the general formula (16) ;
Thus, a positive electrode active material that has been treated in advance can be used.

  The processing method at this time is a dry processing machine such as a roll mill such as a two-roll or a three-roll, a high-speed stirrer such as a Henschel mixer or a super mixer, a fluid energy pulverizer such as a micronizer or jet mill, an attritor or the like. Can be mentioned. On the other hand, a kneader is mentioned as a wet processing machine. However, the processing method is not limited to the above method. Depending on the type of the positive electrode active material, the positive electrode active material itself may be destroyed at the time of processing, resulting in a decrease in battery performance. Therefore, it is preferable to select a treatment method suitable for the positive electrode active material.

  When using a dry processing machine, the treatment agent may be added directly, but in order to treat the surface of the positive electrode active material more uniformly, the treatment agent is dissolved or dispersed in a small amount of solvent in advance. A method of adding the positive electrode active material while dissolving the aggregated particles is preferable. Furthermore, it may be preferable to heat in order to increase the processing efficiency.

As a method for adding an additional binder component (a resin component other than a vinylamide resin), an organic dye derivative having the above basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, And one or more derivatives selected from the group consisting of triazine derivatives having basic functional groups, or organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups represented by the general formula (16) While stirring a dispersion obtained by dispersing one or more derivatives selected from the group and a positive electrode active material in a solvent, or a dispersion obtained by further adding a vinylamide resin to the dispersion and dispersing the dispersion. An additional binder component (resin component other than vinylamide resin) is added as a solid and dissolved. In addition, a method in which an additional binder component (a resin component other than a vinylamide resin) is dissolved in a solvent in advance and mixed with the dispersion can be used. Further, after an additional binder component (resin component other than vinylamide resin) is added to the dispersion, the dispersion treatment may be performed again with the dispersion apparatus.

As a method for adding a carbon material as a conductive aid,
One or more derivatives selected from the group consisting of the above organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups Or
One or more derivatives selected from the group consisting of organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group represented by the general formula (16) ,
And a positive electrode active material dispersed in a solvent while stirring, a carbon material as a conductive auxiliary agent is added and dispersed, or a carbon material as a conductive auxiliary agent is dispersed in a solvent in advance. There is a method in which the dispersion is added to the positive electrode active material dispersion and mixed. Furthermore, when the vinylamide resin and the positive electrode active material are dispersed in a solvent, it is more preferable to add various derivatives having a basic or acidic functional group together.

or,
One or more derivatives selected from the group consisting of the above organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups Or
One or more derivatives selected from the group consisting of organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group represented by the general formula (16) ,
In addition, when the positive electrode active material is dispersed in a solvent, a part or all of the carbon material as a conductive additive can be added simultaneously to perform co-dispersion treatment. Furthermore, it is more preferable to add a vinylamide resin together during the co-dispersion treatment.

  As an apparatus for performing mixing and dispersion at this time, the above-described dispersion apparatus used for ordinary pigment dispersion or the like can be used.

  The dispersed particle diameter of the positive electrode active material varies depending on the size of the primary particle diameter of the positive electrode active material to be used, but is 0.05 μm or more and 100 μm or less, preferably 0.1 μm or more and 70 μm or less, and more preferably 0.8 μm. It is desirable to miniaturize to 15 μm or more and 50 μm or less. A positive electrode mixture paste having a dispersed particle size of the positive electrode active material of less than 0.05 μm may be difficult to produce. In addition, when a composition in which the dispersed particle diameter of the positive electrode active material exceeds 100 μm is used, the resistance distribution of the electrode varies and the amount of the conductive auxiliary agent must be increased to reduce the resistance. Problems may occur. The dispersed particle size referred to here can be determined by determination with a grind gauge (in accordance with JIS K5600-2-5). When the dispersed particle size is 1.0 μm or less, the particle size (D50) is 50% when the volume fraction of particles is integrated from the finer particle size distribution in the volume particle size distribution. The particle size distribution is measured with a general particle size distribution meter, for example, a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).

  As described above, the positive electrode mixture paste of the present invention is usually produced, distributed, and used as a dispersion (liquid) containing a solvent or a paste.

This is a conductive aid, an active material,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group represented by the general formula (16) ,
And a vinylamide resin in a dry powder state, it is difficult to uniformly act on the positive electrode active material and the conductive additive, and in the liquid phase method, the positive electrode active material and the conductive additive are used as a solvent. By dispersing, uniformly with respect to the positive electrode active material and the conductive additive,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group represented by the general formula (16) ,
This is because a vinylamide resin can be allowed to act.

  In addition, as described below, when an electrode mixture layer is formed on a current collector, it is preferable to apply a liquid dispersion as uniformly as possible and dry it.

  However, for example, a dispersion produced by a liquid phase method may be considered as a dry powder by once removing the solvent for reasons such as transportation cost. And it can also be considered that this dry powder is redispersed with an appropriate solvent and used to form an electrode mixture layer. Therefore, the positive electrode mixture paste of the present invention is not limited to a liquid dispersion, and may be a composition in a dry powder state.

<Lithium secondary battery>
Next, a lithium secondary battery using the positive electrode mixture paste of the present invention will be described.

  The lithium secondary battery includes a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. An electrode base layer may be formed between the positive electrode mixture layer and the current collector or between the negative electrode mixture layer and the current collector.

  For the electrode, the material and shape of the current collector to be used are not particularly limited, and as the material, a metal or an alloy such as aluminum, copper, nickel, titanium, or stainless steel is used. Copper is preferred as the negative electrode material. As the shape, a flat plate foil is generally used, but a roughened surface, a perforated foil shape, and a mesh shape can also be used.

  As a method for forming the electrode underlayer on the current collector, there is a method in which an electrode base paste in which carbon black as a conductive material and a binder component are dispersed in a solvent is applied to the electrode current collector and dried. The film thickness of the electrode underlayer is not particularly limited as long as the conductivity and adhesion are maintained, but is generally 0.05 μm or more and 20 μm or less, preferably 0.1 μm or more and 10 μm or less. It is.

  The electrode mixture layer is formed on the current collector by directly applying the electrode mixture paste described above on the current collector and drying the electrode mixture layer, and after forming the electrode base layer on the current collector. And a method of applying an agent paste and drying. In addition, when an electrode mixture layer is formed on an electrode underlayer, after applying the electrode underlayer paste on the current collector, the electrode mixture paste may be applied repeatedly in a wet state and dried. good. The thickness of the electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.

  There is no restriction | limiting in particular about the coating method, A well-known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating.

<Electrolyte>
As the electrolytic solution constituting the lithium secondary battery of the present invention, an electrolyte containing lithium is dissolved in a non-aqueous solvent. As electrolytes, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₃ C , LiI, LiBr, LiCl, LiAlCl, LiHF ₂ , LiSCN, or LiBPh _4, but are not limited thereto.

The non-aqueous solvent is not particularly limited.
Carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate;
Lactones such as γ-butyrolactone, γ-valerolactone, and γ-octanoic lactone;
Glymes such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2-dibutoxyethane;
Esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and
Nitriles such as acetonitrile are exemplified. These solvents may be used alone or in combination of two or more.

  Furthermore, the electrolyte solution may be a gelled polymer electrolyte held in a polymer matrix. Examples of the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, and a polysiloxane having a polyalkylene oxide segment.

  The structure of the lithium secondary battery using the positive electrode mixture paste of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, and is a paper type, cylindrical type, button type Various shapes can be formed according to the purpose of use, such as a laminated type.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. About the dispersion | distribution particle size of a positive electrode active material dispersion and an electrode mixture paste, it calculated | required from determination by a grind gauge (according to JISK5600-2-5). The viscosity of the positive electrode active material dispersion was measured with an E type viscometer (“RE80 type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. at a rotation speed of 50 rpm.

  In addition, hereinafter, “one type selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group” The above derivatives are abbreviated as “derivatives having a basic functional group”.

In addition, hereinafter, “one or more derivatives selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group represented by the general formula (16) ” has “an acidic functional group” Abbreviated as “derivative”.

  In the following, “a derivative having a basic functional group” or “a derivative having an acidic functional group” is abbreviated as “a derivative having a basic functional group or an acidic functional group”.

<Preparation of positive electrode active material dispersion>
[Positive electrode active material dispersions 1 to 31]
According to the composition shown in Table 6, the container was charged with various solvents or water and, optionally, a vinylamide resin, and the vinylamide resin was completely or partially dissolved. Next, any one of various derivatives (A) to (P) having basic functional groups or acidic functional groups shown in Tables 1 to 4 was charged and mixed and stirred to completely or partially dissolve the derivatives. Next, the positive electrode active material was added and dispersed with a media mix, which is a medialess disperser, to obtain a positive electrode active material dispersion. Table 7 shows the dispersion evaluation results of the obtained positive electrode active material dispersion.

  The positive electrode active materials, vinylamide resins, and derivatives having basic functional groups or acidic functional groups used in Examples and Comparative Examples are shown below.

<Positive electrode active material>
Lithium manganate LiMn ₂ O ₄ CELLSEED S-LM (manufactured by Nippon Kagaku Kogyo Co., Ltd.): average primary particle size 12.0 μm, specific surface area 0.48 m ² / g.
・ Lithium iron phosphate LiFePO ₄ (TIANJIN STL ENERGY
(Manufactured by TECHNOLOGY): average primary particle size 0.2 μm, specific surface area 15 m ² / g.

<Derivatives (A) to (H) having basic functional groups>
-Dye derivatives having basic functional groups: (A), (B), (C)
Anthraquinone derivatives having basic functional groups: (F)
Acridone derivatives having basic functional groups: (G)
Triazine derivatives having basic functional groups: (D), (E), (H)

<Derivatives (I) to (P) having an acidic functional group>
-Pigment derivatives having acidic functional groups: (M), (N), (O)
Triazine derivatives having an acidic functional group: (I), (J), (K),
・ Salt salt of triazine derivative having acidic functional group: (L)

<Vinylamide resin>
PVP K-30 (manufactured by ISP Japan): polyvinylpyrrolidone (abbreviated as PVP) Weight average molecular weight of about 40 to 80,000.
AGRIMER AL-10LC (manufactured by ISP Japan): alkylated polyvinylpyrrolidone / 1-butene = 90/10 (abbreviated as AGRIMER)
PNVA GE191 (manufactured by Showa Denko): Poly N-vinylacetamide (abbreviated as PNVA) weight average molecular weight of about 1 to 30,000.

<Binder>
(1) KF polymer W # 1100 (manufactured by Kureha):
Polyvinylidene fluoride (PVDF), weight average molecular weight of about 280,000.
(2) PTFE 30-J (Mitsui / Dupont Fluoro Chemical Co.):
60% polytetrafluoroethylene (PTFE) aqueous dispersion

<Carbon black for conductive aid>
-Denka Black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.):
Acetylene black, primary particle size 48 nm, specific surface area 48 m ² / g.
・ Denka Black FX-35 (manufactured by Denki Kagaku Kogyo Co., Ltd.):
Acetylene black, primary particle size 23 nm, specific surface area 133 m ² / g.
Super-P Li (manufactured by TIMCAL):
Furnace black, primary particle size 40 nm, specific surface area 62 m ² / g.
<Adjustment of carbon black dispersion for conductive aid>
[Carbon dispersion (1)]
A glass bottle was charged with 0.5 part of N-methyl-2-pyrrolidone (NMP) and a derivative (A) having a basic functional group, and mixed and stirred to completely or partially dissolve the derivative. Next, 10 parts of carbon black HS-100 (acetylene black, primary particle size 48 nm, specific surface area 48 m ² / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) serving as a conductive auxiliary agent was added, and zirconia beads were further added as a medium. Dispersion was performed with a paint shaker to obtain a carbon dispersion (solid content: 10.5%).

[Carbon dispersion (2)]
A glass bottle was charged with 0.5 part of N-methyl-2-pyrrolidone (NMP) and polyvinylpyrrolidone (PVP) solids to completely or partially dissolve the resin. Next, 0.5 part of the derivative (M) having an acidic functional group was charged and mixed and stirred to completely or partially dissolve the derivative. Next, 10 parts of carbon black Super-PLi (furnace black, primary particle size 40 nm, specific surface area 62 m ² / g, manufactured by TIMCAL) as a conductive auxiliary agent was added, and zirconia beads were further added as a medium. Dispersion was performed using a shaker to obtain a carbon dispersion (solid content: 10.5%).

[Carbon dispersion (3)]
Purified water and 0.125 part of PNVA were charged into a glass bottle and mixed thoroughly. Next, 0.375 part of a derivative (J) having an acidic functional group was charged and mixed and stirred to completely or partially dissolve the derivative. Next, 10 parts of carbon black HS-100 (acetylene black, primary particle size 48 nm, specific surface area 48 m ² / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) serving as a conductive auxiliary agent was added, and zirconia beads were further added as a medium. Dispersion was performed with a paint shaker to obtain a carbon dispersion (solid content: 10.5%).

<Derivatives having basic functional group or acidic functional group, adjustment of positive electrode active material surface-treated with vinylamide resin>
In accordance with the composition and treatment method shown in Table 5, the surface treatment of the positive electrode active material with a derivative having a basic functional group or an acidic functional group and a vinylamide resin was performed. The amount of resin used was expressed in terms of solid content.

[Surface treatment positive electrode active material (1)]
100 parts of lithium iron phosphate as the positive electrode active material (average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY), 0.2 part of derivative (A) having basic functional group, And 25 parts of N-methyl-2-pyrrolidone (NMP) was charged, and the surface-treated positive electrode active material (1) was obtained by processing with two rolls.

[Surface treatment positive electrode active material (2)]
In a kneader, 100 parts of lithium manganate (CELLSEED S-LM, average primary particle size 12.0 μm, specific surface area 0.48 m ² / g, manufactured by Nippon Chemical Industry Co., Ltd.), a derivative having an acidic functional group I) 0.1 part and 25 parts of NMP were charged and kneaded. The obtained processed product was dried and pulverized to obtain a surface-treated positive electrode active material (2).

[Surface treatment positive electrode active material (3)]
In a kneader, 100 parts of lithium iron phosphate (average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) as a positive electrode active material, derivative (E) having a basic functional group 0. One part, 0.1 part of PVP, and 43 parts of N, N-dimethylformamide (DMF) were charged and kneaded.
The obtained treated product was added to 1000 parts of hexane and stirred, and then the aggregate was collected by filtration, dried and pulverized to obtain a surface-treated positive electrode active material (3).

[Surface treatment positive electrode active material (4)]
15 parts of NMP 15 parts of polyvinyl pyrrolidone (PVP) with respect to 100 parts of lithium iron phosphate (average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) as a positive electrode active material The surface-treated positive electrode active material (4) was obtained by dissolving in a dry jet mill and treating with pulverization.

[Surface treatment positive electrode active material (5)]
Lithium iron phosphate as the positive electrode active material (average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) 100 parts, acidic functional group-containing derivative (M) 1.5 parts, and A surface-treated positive electrode active material (5) was obtained by charging 25 parts of N-methyl-2-pyrrolidone (NMP) and treating with two rolls.

<Evaluation of wettability of positive electrode active material with and without surface treatment>
Various positive electrode active materials untreated with the dispersant and various positive electrode active materials treated with the dispersant were dried under reduced pressure at 80 ° C. for 10 hours. Subsequently, the dried product was pulverized with an agate mortar and further dried under reduced pressure at 80 ° C. for 12 hours. The obtained dried product was again pulverized in an agate mortar, and then loaded with 500 kgf / cm ² with a tablet molding machine (Specac) to produce a positive electrode active material pellet (diameter 10 mm, thickness 0.5 mm). did. A droplet in which ethylene carbonate and diethyl carbonate were mixed 1: 1 was dropped on this pellet with a microsyringe, and the time for the droplet to penetrate the pellet was measured. This measurement was performed 5 times for each sample, and those whose average permeation time was less than 1 second was “◎”, those that were 1 second or more and less than 5 seconds were “◯”, 5 seconds or more and 10 seconds. Those that were less than “Δ” were those that were 10 seconds or longer, and “x”. The results of wettability evaluation of the positive electrode active material are shown in Table 5.

NMP: N-methyl-2-pyrrolidone DMF: N, N-dimethylformaldehyde PVP: polyvinylpyrrolidone PNVA: poly N-vinylamide

<Preparation of positive electrode mixture paste for lithium secondary battery>
[Examples 1-2, Examples 5-6, Examples 11-20, 24, 25, Comparative Examples 1 and 3]
Polyvinylidene fluoride PVDF (KF polymer W # 1100, manufactured by Kureha Co.) and N-methyl-2-pyrrolidone were used as binders with respect to the lithium iron phosphate LiFePO ₄ dispersion prepared previously (91 parts as the amount of LiFePO ₄ ). After mixing with a planetary mixer, carbon black or carbon dispersion (4 parts as carbon black amount) is added as a conductive aid, and further kneaded with a planetary mixer, and a positive electrode mixture paste (solid content ratio: 50%, solid Composition ratio: active material / carbon black / binder and dispersant = 91/4/5). (See Table 8)

[Examples 3-4, 7-10, 21, 22, Comparative Example 2]
Polyvinylidene fluoride PVDF (KF polymer W # 1100, manufactured by Kureha), N-methyl-2 as a binder with respect to the lithium manganate LiMn ₂ O ₄ dispersion prepared previously (85 parts as the amount of LiMn ₂ O ₄ ) -After mixing pyrrolidone with a planetary mixer, carbon black or carbon dispersion (9 parts as carbon black amount) is added as a conductive aid, and further kneaded with a planetary mixer, and a positive electrode mixture paste (solid content ratio: 50 %, Solid content composition ratio: positive electrode active material / carbon black / binder and dispersant = 85/9/6). (See Table 8)

[Example 25, Comparative Example 4]
60% polytetrafluoroethylene PTFE aqueous dispersion (PTFE 30-J, Mitsui / Dupont Fluorochemical) as a binder with respect to the previously prepared lithium manganate LiMn ₂ O ₄ dispersion (85 parts as LiMn ₂ O ₄ amount) After mixing purified water with a planetary mixer, carbon black or carbon dispersion (9 parts as carbon black amount) is added as a conductive aid, and further kneaded with a planetary mixer to produce a positive electrode mixture paste (solid 50%, solid composition ratio: positive electrode active material / carbon black / binder and dispersant = 85/9/6). (See Table 9)

[Example 26, Comparative Example 5]
60% polytetrafluoroethylene PTFE aqueous dispersion (PTFE 30-J, manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.) as a binder with respect to the lithium iron phosphate LiFePO ₄ dispersion prepared previously (91 parts as the amount of LiFePO ₄ ) Then, after mixing purified water with a planetary mixer, carbon black or carbon dispersion (4 parts as carbon black amount) is added as a conductive aid, and further kneaded with a planetary mixer, and a positive electrode mixture paste (solid content ratio; 50%, solid content composition ratio; active material / carbon black / binder and dispersant = 91/4/5). (See Table 9)

NMP: N-methyl-2-pyrrolidone DMF: N, N-dimethylformamide PVDF: polyvinylidene fluoride

PTFE: Polytetrafluoroethylene

<Preparation of negative electrode mixture paste for lithium secondary battery>
Polyvinylidene fluoride PVDF (KF polymer W # 1100, manufactured by Kureha), N-methyl-2-pyrrolidone as a binder with respect to 20 parts of carbon dispersion (1) prepared earlier (2 parts as the amount of carbon black) After mixing with a high-speed disper, 93 parts of mesophase carbon (MCMB 6-28, average particle size 5 to 7 μm, specific surface area 4 m ² / g made by Osaka Gas Chemical Co., Ltd.) is added as a negative electrode active material and kneaded with a planetary mixer. A mixture paste (solid content ratio: 60%, solid content composition ratio: negative electrode active material / carbon black / binder and dispersant = 93/2/5) was used.

<Preparation of positive electrode for lithium secondary battery>
[Examples 1 to 26, Comparative Examples 1 to 5]
The various positive electrode mixture pastes prepared above were applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, dried by heating under reduced pressure, rolled by a roll press or the like, and 60 μm thick. A positive electrode mixture layer was prepared. (See Tables 8 and 9)

<Preparation of negative electrode for lithium secondary battery>
The previously prepared various negative electrode mixture pastes were applied onto a 20 μm thick copper foil serving as a current collector using a doctor blade, dried under reduced pressure, and subjected to a rolling process using a roll press or the like to obtain a thickness of 60 μm. A negative electrode mixture layer was prepared.

<Assembly of lithium secondary battery positive electrode evaluation cell>
A separator made of a porous polypropylene film between the working electrode and the counter electrode (# 2400, manufactured by Celgard Co., Ltd.) with the positive electrode fabricated previously punched out to a diameter of 9 mm and used as a working electrode and a metal lithium foil (thickness 0.15 mm) as a counter electrode Is inserted and laminated, filled with an electrolyte (nonaqueous electrolyte in which LiPF ₆ is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate in a ratio of 1: 1), and a bipolar metal cell (Hosen) (HS flat cell). The cell was assembled in a glow box substituted with argon gas, and after the cell was assembled, predetermined battery characteristics were evaluated.

<Characteristic evaluation of lithium secondary battery positive electrode>
[Charge / Discharge Cycle Characteristics Examples 3 to 4, 7 to 10, 21, 22, 25, Comparative Examples 2 and 4]
The produced battery evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at a room temperature (25 ° C.) with a charge rate of 0.2 C and 1.0 C, and at a constant current at the same rate as during charging. Charge / discharge for discharging to a discharge lower limit voltage of 3.0V is defined as one cycle (charge / discharge interval rest time 30 minutes), and this cycle is performed for a total of 20 cycles to evaluate charge / discharge cycle characteristics (Evaluation apparatus: SM-8 manufactured by Hokuto Denko Co., Ltd.) ) Moreover, the cell after evaluation was decomposed | disassembled and the external appearance of the electrode coating film was confirmed visually. The evaluation results are shown in Tables 10 and 11.

[Charge / Discharge Cycle Characteristics Examples 1-2, 5-6, 11-20, 23, 24, 26, Comparative Examples 1, 3, 5]
The produced battery evaluation cell is fully charged at a constant current and constant voltage charge (upper limit voltage 4.5 V) at room temperature (25 ° C.) and at a charge rate of 0.2 C and 1.0 C, and at a constant current at the same rate as during charging. Charging / discharging for discharging to a lower discharge limit voltage of 2.0V is defined as one cycle (charging / discharging interval rest time 30 minutes), and this cycle is performed for a total of 20 cycles, and charging / discharging cycle characteristics evaluation (evaluation apparatus: SM-8 manufactured by Hokuto Denko Co., Ltd.) ) Moreover, the cell after evaluation was decomposed | disassembled and the external appearance of the electrode coating film was confirmed visually. The evaluation results are shown in Tables 10 and 11.

[DC Internal Resistance Measurement Examples 1 to 26, Comparative Examples 1 to 5]
The battery evaluation cell thus prepared was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at room temperature (25 ° C.) and a charge rate of 0.2 C, and 5 at a constant current of 0.2 C and 1.0 C rates. The battery voltage was measured after the second discharge. The voltage value was plotted against the current value, and the slope of the obtained linear relationship was defined as the internal resistance. The evaluation results are shown in Tables 10 and 11. When lithium iron phosphate was used as the positive electrode active material, it was shown as a relative value when the measured internal resistance value of Example 1 was 100. About the case where lithium manganate was used as a positive electrode active material, it showed as a relative value when the internal resistance measured value of Example 3 is set to 100.

  As can be seen from Tables 6 to 11, in the examples, the dispersibility of the positive electrode active material was improved by using a vinylamide resin in the positive electrode mixture paste, so that the dispersion in the positive electrode mixture paste was higher than that in the comparative example. And stability over time were improved. The stability was further improved by using a derivative having a basic or acidic functional group. Further, as compared with the comparative example, a tendency of lowering the internal resistance was observed, and the battery capacity and the 20 cycle capacity maintenance rate were improved.

Claims (13)

A positive electrode mixture paste for a lithium secondary battery comprising a vinylamide resin and a positive electrode active material,
Furthermore,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
The A comprising at for a lithium secondary battery positive electrode material mixture paste,
A triazine derivative having an acidic functional group is
A positive electrode mixture paste for a lithium secondary battery, which is a triazine derivative represented by the following general formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation. Basic functional group derivative of claim 1, wherein the lithium secondary battery positive electrode material mixture paste is an amino group. Acidic functional group derivatives, a carboxyl group, a sulfonic acid group, and one or more acidic functional groups and is claim 1, wherein the lithium secondary battery positive electrode material mixture paste which is selected from the group consisting of phosphoric acid group. The positive electrode active material is lithium iron phosphate. The positive electrode material mixture paste for a lithium secondary battery according to any one of claims 1 to 3 . The positive electrode mixture paste for a lithium secondary battery according to any one of claims 1 to 4 , further comprising a binder resin. The positive electrode mixture paste for a lithium secondary battery according to claim 5 , wherein the binder resin is a polymer compound containing a fluorine atom in the molecule. Furthermore, the positive electrode mixture paste for lithium secondary batteries in any one of Claims 1-6 which contains a conductive support agent. A vinylamide resin, a positive electrode active material,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
And a method for producing a positive electrode mixture paste for a lithium secondary battery in which a solvent is dispersed ,
A triazine derivative having an acidic functional group is
The manufacturing method of the positive mix paste for lithium secondary batteries which is a triazine derivative shown by following General formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation. A vinylamide resin, a positive electrode active material, a binder resin, a conductive aid,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
And a method for producing a positive electrode mixture paste for a lithium secondary battery that is co-dispersed in a solvent ,
A triazine derivative having an acidic functional group is
The manufacturing method of the positive mix paste for lithium secondary batteries which is a triazine derivative shown by following General formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation. A vinylamide resin, a positive electrode active material,
One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group, or ,
One or more derivatives selected from the group consisting of organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups,
In a dispersion obtained by dispersing in a solvent,
A method for producing a positive electrode mixture paste for a lithium secondary battery, comprising mixing a conductive additive and a binder resin ,
A triazine derivative having an acidic functional group is
The manufacturing method of the positive mix paste for lithium secondary batteries which is a triazine derivative shown by following General formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation. One or more selected from the group consisting of vinylamide resins, organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups Treatment agent, or
One or more treatment agents selected from the group consisting of vinylamide resins, organic dye derivatives having acidic functional groups, and triazine derivatives having acidic functional groups;
The method for producing a positive electrode mixture paste for a lithium secondary battery according to any one of claims 8 to 10, wherein a positive electrode active material that has been treated in advance is used .
A triazine derivative having an acidic functional group is
The manufacturing method of the positive mix paste for lithium secondary batteries which is a triazine derivative shown by following General formula (16).

Formula (16):

In general formula (16),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M ¹⁰¹ , —COOM ¹⁰¹ , or —P (O) (— OM ¹⁰¹ ) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (17) It is.

Formula (17):

In general formula (17),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —Y ^201. −Z ²⁰¹ ,
Y ²⁰¹ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
M ²⁰¹ is an equivalent of a monovalent to trivalent cation. A lithium secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium, wherein the positive electrode mixture layer comprises: , lithium secondary battery comprising formed using claim 1-7, wherein the lithium secondary battery positive electrode material mixture paste. It claims 8-11 lithium secondary battery according to claim 12, wherein comprising formed using the produced lithium secondary battery positive electrode material mixture paste by the method according any one.