TWI735041B - Paste composition, electrode material for secondary cell, electrode for secondary cell and secondary cell - Google Patents

Abstract

Provided is a paste composition which can be used to manufacture secondary batteries with high safety against heat. The above-mentioned paste composition includes the hemiacetal ester derivative represented by the formula (1), the polyamine represented by the formula (2), an active material for secondary batteries, and an aqueous medium.

Description

Paste composition, electrode material for secondary battery, electrode for secondary battery, and secondary battery

The present invention relates to a paste composition, an electrode material for a secondary battery, an electrode for a secondary battery, and a secondary battery.

In recent years, rechargeable secondary battery systems have gradually become more and more important. In particular, with the wide spread of portable electronic products, the demand for secondary batteries with advantages such as light weight, high operating power, and high energy density has shown a further increase.

The secondary battery represented by the lithium ion secondary battery is found to have advantages of light weight, high operating voltage, high energy density, and long life. Therefore, it is expected to be widely used in transportation equipment such as automobiles and aircrafts. Now the requirements for space saving, durability, high voltage, high energy density, and high safety are gradually increasing.

On the other hand, in many cases where the characteristics of lithium ion secondary batteries are required to improve, flammable organic solvents are used as electrolytes. In an environment where the temperature rises, there are also high-capacity positive and negative active materials. , So it will emit a lot of heat. This kind of heat can cause the electrolyte to catch fire, and it can also cause an explosion. In these lithium secondary batteries, there may be physical damage caused by spurs or external force shocks caused by rogue objects, which may cause internal short circuits, and cause rapid heating, thermal runaway, or explosions. Therefore, we need to pay attention to how to avoid risks in the future.

Conventional lithium ion secondary batteries use polyvinylidene fluoride resin (PVDF) or polyimide resin as the coating material for the active material. As a solvent for these treatments, organic solvents such as N-methyl-pyrrolidone (NMP) are used in many cases. In the drying step of applying the paste composition on the current collector to obtain the electrode, since evaporation is accompanied by evaporation, the organic solvent should be recovered safely, and special equipment or protective equipment is also necessary. Due to environmental regulations stipulated by laws and regulations, it is often impossible to use organic solvents. Therefore, coating resins that can be used with water-based solvents have gradually become the mainstream.

Patent Document 1 describes "a lithium battery, including: a positive electrode plate and a negative electrode plate; a separator located between the positive electrode plate and the negative electrode plate to define an accommodating area; and an electrolyte solution located The accommodating area; wherein the material surface of the positive electrode plate or the negative electrode plate has a thermally activated protective film, when the lithium battery is heated to a thermally activated temperature, the thermally activated protective film undergoes a cross-linking reaction to prevent thermal runaway , Where the thermal activation temperature is about 80-280°C" (request item 1). The thermally-actuated protective film in the lithium battery utilizes the thermal cross-linking reaction between the vinyl group derived from bismaleimide and the amine group derived from barbituric acid. When the battery is exposed to heat, it uses heat The protective film is activated to cover the positive electrode active material or the negative electrode active material, thereby preventing thermal runaway. In addition, the electrode pad paste composition system presupposes the use of an organic solvent as a dispersion medium. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2010-157512 A

[The problem to be solved by the invention]

The subject of the present invention is to provide a paste composition capable of manufacturing a secondary battery with high safety against overheating. The subject of the present invention is also to provide an electrode material for a secondary battery, an electrode for a secondary battery, and a secondary battery that have high safety against heating. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted repeated and intensive studies and found that a paste composition containing a specific tetracarboxylic acid ester, a specific polyamine, an active material for a secondary battery, and an aqueous medium, The aqueous dispersion can be prepared in a relatively short time (several hours) and can produce a secondary battery with high safety against overheating, thereby completing the present invention.

上述式(1)中，n為0或1，R¹ 、R² 、R³ 、R⁴ 及R⁵ 係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相鍵結而形成環狀構造，X為4價之有機基。 上述式(1)中，n=0時，R² 與R⁴ 或R⁴ 與R⁵ 亦可互相鍵結而形成可具有取代基之芳香族碳六員環。 上述式(2)中，m為2以上之整數，Y為m價之有機基或包含矽氧烷鍵之m價之有機矽基。 [2] 如上述[1]之糊料組成物，其中上述半縮醛酯衍生物為選自由式(1-1)所示之2,3-二氫呋喃衍生物、式(1-2)所示之3,4-二氫-2H-吡喃衍生物，及，式(1-3)所示之1-苯並呋喃衍生物所成群之至少1種。

上述式(1-1)中，R¹ 、R² 、R⁴ 、R⁵ 及X係各自與上述式(1)中之R¹ 、R² 、R⁴ 、R⁵ 及X為相同意義。 上述式(1-2)中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 及X係各自與上述式(1)中之R¹ 、R² 、R³ 、R⁴ 、R⁵ 及X為相同意義。 上述式(1-3)中，R¹ 、R² 及X係各自與上述式(1)中之R¹ 、R² 及X為相同意義。上述式(1-3)中、R⁶ 、R⁷ 、R⁸ 及R⁹ 係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相鍵結而形成環狀構造。 [3] 如上述[1]或[2]之糊料組成物，其中上述聚胺為選自由聚丙烯酸、聚胺基甲酸酯、聚醯胺及聚醯胺醯亞胺所成群之至少1種。 [4] 一種二次電池用電極材料，其係包含式(1)所示之半縮醛酯衍生物、式(2)所示之聚胺，及二次電池用活性物質。

上述式(1)中，n為0或1，R¹ 、R² 、R³ 、R⁴ 及R⁵ 係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相鍵結而形成環狀構造，X為4價之有機基。 上述式(1)中，n=0時，R² 與R⁴ 或R⁴ 與R⁵ 亦可互相鍵結而形成可具有取代基之芳香族碳六員環。 上述式(2)中，m為2以上之整數，Y為m價之有機基或包含矽氧烷鍵之m價之有機矽基。 [5] 如上述[4]之二次電池用電極材料，其中上述半縮醛酯衍生物為選自由式(1-1)所示之2,3-二氫呋喃衍生物、式(1-2)所示之3,4-二氫-2H-吡喃衍生物，及式(1-3)所示之1-苯並呋喃衍生物所成群之至少1種。

上述式(1-1)中，R¹ 、R² 、R⁴ 、R⁵ 及X係各自與上述式(1)中之R¹ 、R² 、R⁴ 、R⁵ 及X為相同意義。 上述式(1-2)中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 及X係各自與上述式(1)中之R¹ 、R² 、R³ 、R⁴ 、R⁵ 及X為相同意義。 上述式(1-3)中，R¹ 、R² 及X係各自與上述式(1)中之R¹ 、R² 及X為相同意義。上述式(1-3)中，R⁶ 、R⁷ 、R⁸ 及R⁹ 係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相鍵結而形成環狀構造。 [6] 如上述[4]或[5]之二次電池用電極材料，其中上述聚胺為選自由聚丙烯酸、聚胺基甲酸酯、聚醯胺及聚醯胺醯亞胺所成群之至少1種。 [7] 一種二次電池用電極，其係具有如上述[4]~[6]中任一項之二次電池用電極材料。 [8] 一種二次電池，其係具有如上述[7]之二次電池用電極。 [發明之效果]That is, the present invention is shown in the following [1] to [8]. [1] A paste composition characterized by comprising: a hemiacetal ester derivative represented by formula (1), a polyamine represented by formula (2), an active material for secondary batteries, and an aqueous medium.

In the above formula (1), n is 0 or 1, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, which may also be formed by bonding with each other Ring structure, X is a tetravalent organic group. In the above formula (1), when n=0, R ² and R ⁴ or R ⁴ and R ⁵ may also be bonded to each other to form an aromatic carbon six-membered ring which may have a substituent. In the above formula (2), m is an integer of 2 or more, and Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond. [2] The paste composition of [1] above, wherein the hemiacetal ester derivative is selected from the 2,3-dihydrofuran derivatives represented by the formula (1-1), and the formula (1-2) The 3,4-dihydro-2H-pyran derivatives shown, and at least one of the group of 1-benzofuran derivatives shown by formula (1-3).

In the above formula ^{(1-1), R 1, R} 2, R 4, R 5 and X are each the lines (1) in the above formula R ^{1, R 2, R 4,} R 5 and X have the same meaning. In the above formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X has the same meaning. In the above formula ^{(1-3), R 1, R} 2 and X are each the line ^1, R ² and X the formula R (1) in the same meaning. In the above formula (1-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. [3] The paste composition of [1] or [2] above, wherein the polyamine is at least selected from the group consisting of polyacrylic acid, polyurethane, polyamide and polyimide 1 kind. [4] An electrode material for a secondary battery, which contains the hemiacetal ester derivative represented by the formula (1), the polyamine represented by the formula (2), and an active material for a secondary battery.

In the above formula (1), n is 0 or 1, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, which may also be formed by bonding with each other Ring structure, X is a tetravalent organic group. In the above formula (1), when n=0, R ² and R ⁴ or R ⁴ and R ⁵ may also be bonded to each other to form an aromatic carbon six-membered ring which may have a substituent. In the above formula (2), m is an integer of 2 or more, and Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond. [5] The electrode material for a secondary battery as in [4] above, wherein the hemiacetal ester derivative is selected from the 2,3-dihydrofuran derivatives represented by the formula (1-1), the formula (1- 2) At least one of the 3,4-dihydro-2H-pyran derivative represented by the formula (1-3) and the 1-benzofuran derivative represented by the formula (1-3).

In the above formula ^{(1-1), R 1, R} 2, R 4, R 5 and X are each the lines (1) in the above formula R ^{1, R 2, R 4,} R 5 and X have the same meaning. In the above formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X has the same meaning. In the above formula ^{(1-3), R 1, R} 2 and X are each the line ^1, R ² and X the formula R (1) in the same meaning. In the above formula (1-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. [6] The electrode material for a secondary battery according to [4] or [5] above, wherein the polyamine is selected from the group consisting of polyacrylic acid, polyurethane, polyamide and polyamide imine At least one of them. [7] An electrode for a secondary battery, which has the electrode material for a secondary battery as described in any one of [4] to [6] above. [8] A secondary battery having the electrode for a secondary battery as described in [7] above. [Effects of Invention]

According to the present invention, it is possible to provide a paste composition which is an aqueous dispersion that can be prepared in a relatively short time (several hours) and can produce a secondary battery with high safety against overheating.

In addition, the present invention can provide an electrode material for a secondary battery, an electrode for a secondary battery, and a secondary battery that have high safety against heating.

In this manual, the range indicated by "~" is regarded as including both ends of the range. For example, the range represented by "A~B" includes A and B.

In an electrode made using the paste composition of the present invention, hemiacetal ester derivatives, polyamines, and active materials for secondary batteries are in a state of a mixture under normal temperature ranges, and the active materials for secondary batteries are not affected by Covered. However, in the overheating temperature region, the vinyl ether is separated from the hemiacetal ester derivative, the tetracarboxylic acid reacts with the polyamine, and the active material for the secondary battery is coated with the polyimide. As a result, the electrode will be destroyed, and the ignition and explosion of the secondary battery will be prevented.

[Paste composition] The paste composition of the present invention includes the hemiacetal ester derivative represented by the formula (1) described later (hereinafter referred to as "hemiacetal ester derivative (1)"), the hemiacetal ester derivative represented by the formula (2) Polyamine (hereinafter referred to as "polyamine (2)"), active materials for secondary batteries, and aqueous media. Hereinafter, each component of the paste composition of the present invention will be described in detail.

＜Hemiacetal ester derivatives (1)＞ The hemiacetal ester derivative (1) is a compound represented by formula (1). The paste composition of the present invention may contain one type or two or more types of hemiacetal ester derivatives (1).

"Explanation of each sign" The meaning of each symbol in formula (1) is as follows.

(n) n is 0 or 1.

(R ¹ , R ² , R ³ , R ⁴ and R ⁵ ) R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a monovalent organic group.

The above-mentioned halogen atom is not particularly limited, but at least one selected from the group consisting of fluorine atom, chlorine atom, bromine atom, and iodine atom is preferred, and fluorine atom is preferred.

The above-mentioned monovalent organic group is not particularly limited. A monovalent hydrocarbon group is preferred, and at least one selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and aryl groups is preferred. Preferably, an alkyl group is more preferable, an alkyl group having 1 to 3 carbon atoms (C _1-3 alkyl) is more preferable, and a methyl group is more preferable. Here, _{examples of the C 1-3} alkyl group include methyl, ethyl, propyl, and isopropyl (2-propyl).

The hydrogen atom of the above-mentioned monovalent hydrocarbon group may be substituted with a halogen atom or a hydroxyl group. Here, the halogen atom is not particularly limited, but at least one selected from the group consisting of fluorine atom, chlorine atom, bromine atom, and iodine atom is preferred, and fluorine atom is preferred.

In addition, the above-mentioned monovalent organic group preferably does not include a functional group reactive with an amino group or a carboxyl group. Here, as a group reactive with an amine group, for example, a carboxyl group, a carboxylic anhydride group, a carbonyl group, an aldehyde group, and a halogenated carbonyl group can be mentioned, but it is not limited to these groups. As the functional group reactive with the carboxyl group, for example, an amino group, a hydroxyl group, a carboxyl group, and a vinyloxy group can be mentioned, but it is not limited to these.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ may also be bonded to each other to form a ring structure. Here, the cyclic structure is not particularly limited, and, for example, an aromatic hydrocarbon ring which may have a substituent or an alicyclic hydrocarbon ring which may have a substituent is mentioned. In particular, when n=0, R ² and R ⁴ or R ⁴ and R ⁵ may also be bonded to each other to form an aromatic carbon six-membered ring which may have a substituent.

(X) X is a 4-valent organic group. Examples of tetravalent organic groups include compounds having chain hydrocarbons in the basic skeleton such as ethylene and propane; compounds having cyclic hydrocarbons in the basic skeleton such as cyclohexane; and benzene, naphthalene, etc. Compounds with aromatic hydrocarbons in the basic skeleton; compounds with a benzophenone skeleton such as benzophenone; compounds with a diphenyl ether skeleton such as diphenyl ether; compounds with a diphenyl ether skeleton such as diphenyl ether Compounds with a sulfide skeleton; compounds with a biphenyl skeleton such as biphenyl; and other compounds are formed by removing any 4 hydrogen atoms. However, it is not limited to these persons.

The above-mentioned tetravalent organic group preferably does not include a functional group reactive with an amine group. Here, as a group having reactivity with an amino group, for example, a carboxyl group, a carboxylic anhydride group, a carbonyl group, an aldehyde group, and a halogenated carbonyl group can be mentioned, but it is not limited to these groups.

"Structure of Hemiacetal Ester Derivative (1) in Paste Composition" In the paste composition of the present invention, in an aqueous medium, the carboxyl group bound to X in formula (1) can also be ionized to become carboxylate Anion. In this case, the paste of the present invention the composition of formula (1) a carboxylate anion portion of the half ester derivatives of the acetal shown in (-COO ^-), and the polyamine (2) of the ammonium cationic moiety (-NH ₃ ⁺ ) can also be paired to form a salt structure as shown in the following formula.

In the above ^{formulas, n, R 1, R 2} , R 3, 3, R 4, R 5 , and X R ^4, R ⁵ and X lines are each of the formula (1) in the ^{n, R 1, R 2,} R is The same meaning.

"Manufacturing Method of Hemiacetal Ester Derivatives (1)" The production method of the hemiacetal ester derivative (1) is not particularly limited. For example, the addition of unsaturated bonds between carbons of the cyclic unsaturated ether compound represented by formula (A) is represented by formula (B) The method of the carboxyl group of the tetracarboxylic acid.

N, R ¹ , R ² , R ³ , R ⁴ and R ⁵ in formula (A), and X in formula (B) are respectively the same as n, R ¹ , R ² , R ^{3 in formula (1)} , R ⁴ , R ⁵ and X have the same meaning.

The hemiacetal ester bond represented by the following formula is formed by adding the unsaturated bond between carbons of the cyclic unsaturated ether compound represented by the formula (A) to the carboxyl group of the tetracarboxylic acid represented by the formula (B) .

^{R 1} in the above formula has the same meaning as ^{R 1} in the formula (1).

The hemiacetal ester bond formed by this operation is resistant to hydrolysis, and is not easy to cause the deprotection of the carboxyl group due to the detachment of the carboxyl protecting group. Therefore, the stability of the hemiacetal ester derivative (1) in an aqueous medium is high, and as a result, the storage stability of the paste composition of the present invention is excellent. The paste composition of the present invention is preferably used as an electrode.

"Specific Examples of Hemiacetal Ester Derivatives (1)" Hereinafter, specific examples of the hemiacetal ester derivative (1) will be described. As hemiacetal ester derivatives (1), suitable examples include those selected from 2,3-dihydrofuran derivatives represented by formula (1-1) described later, and those represented by formula (1-2) described later. At least one of the 3,4-dihydro-2H-pyran derivatives shown, and the 1-benzofuran derivatives represented by the formula (1-3) described later. However, the hemiacetal ester derivative (1) is not limited to the specific examples described below.

(2,3-Dihydrofuran derivative) One of the specific examples of the hemiacetal ester derivative (1) is the 2,3-dihydrofuran derivative represented by the formula (1-1). The formula (1-1) should be equivalent to the case of n=0 in formula (1).

In formula (1-1), R ¹ , R ² , R ⁴ , R ⁵ and X have the same meaning as ^{R 1} , R ² , R ⁴ , R ^{5 and X in formula (1).} In the formula (1-1), R ¹ , R ² , R ⁴ and R ⁵ are preferably hydrogen atoms.

(3,4-Dihydro-2H-pyran derivative) Another one of the specific examples of the hemiacetal ester derivative (1) is the 3,4-dihydro-2H-pyran derivative represented by the formula (1-2). Equation (1-2) should be equivalent to the case of equation (1), n=1.

In the formula ^{(1-2), R 1, R} 2, R 3, 3, R 4, R 5 , and X R ^4, R ⁵ and X are each based formula R (1) in the ^1, R ^2, R is The same meaning. In formula (1-2), it is preferable that R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} all hydrogen atoms.

(1-benzofuran derivative) Another specific example of the hemiacetal ester derivative (1) is the 1-benzofuran derivative represented by the formula (1-3). The formula (1-3) should be when n=0 in the formula (1), and R ⁴ and R ^{5 are} bonded to each other to form an aromatic carbon six-membered ring which may have a substituent.

In formula (1-3), R ¹ , R ² and X are each having the same meaning as ^{R 1} , R ² and X in formula (1). In the formula (1-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. Here, the halogen atom, the monovalent organic group, and the cyclic structure are the same as those described in the description of ^{R 1} and R ^2. In formula (1-3), R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably hydrogen atoms.

＜Polyamine(2)＞ Polyamine (2) is a compound represented by formula (2). The paste composition of the present invention may contain one type or two or more types of polyamine (2).

In the formula (2), m is an integer of 2 or more, and Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond. In formula (2), the first-stage amino group is directly bonded to a carbon atom. In an aqueous medium, the amine group (-NH ₂ ) of the polyamine (2) can also become an ammonium cation (-NH ₃ ⁺ ). The upper limit of m is not particularly limited, but 2000 is preferred, and 600 is preferred. The lower limit of m is 2, for example, 8 is preferably 8, 20 is more preferable, and 50 is more preferable.

"Organic Polyamine" In this specification, among the polyamines (2), in particular, the polyamine (2) in which Y is an m-valent organic group is referred to as an organic polyamine.

Examples of the m-valent organic group include compounds having chain hydrocarbons in the basic skeleton such as ethylene and propane; compounds having cyclic hydrocarbons in the basic skeleton such as cyclohexane; benzene, naphthalene, etc. Compounds with aromatic hydrocarbons in the basic skeleton; compounds with benzophenone skeleton such as benzophenone; compounds with diphenyl ether skeleton such as diphenyl ether; compounds with diphenyl ether skeleton, etc. Compounds with a sulfide skeleton; compounds with a biphenyl skeleton such as biphenyl; and other compounds with any m hydrogen atoms removed. However, it is not limited to these persons.

The m-valent organic group preferably does not include a group reactive with a carboxyl group. Here, as a group reactive with a carboxyl group, for example, an amino group, a hydroxyl group, a carboxyl group, a vinyloxy group, etc. can be mentioned, but it is not limited to these.

Specific examples of organic polyamines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diamine Amino diphenyl ether, 4,4′-diamino diphenyl ether, 3,3′-diamino diphenyl sulfide, 3,4′-diamino diphenyl sulfide, 4, 4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide , 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone Methane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis( 4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1, 1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminobenzene Yl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-bis(3-aminophenyl)-1-phenylethane , 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1 ,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4 -Bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(3-amino-α,α-dimethylbenzyl) Benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1, 4-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(3-amino-α,α-trifluoromethylbenzyl)benzene, 1,3- Bis(4-amino-α,α-two trifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-two trifluoromethyl benzyl)benzene, 1,4- Bis(4-amino-α,α-two trifluoromethylbenzyl)benzene, 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy) Yl)pyridine, 4,4′-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, bis[4-(3-amine Phenyloxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4 -(4-Aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl] Supplement, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether , 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [3-(3-Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)benzene Group]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4- (4-Aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(4-amine Benzyl]benzene, 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-( 4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene , 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4′-bis[4-(4-aminophenoxy)benzyl Amino]diphenyl ether, 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4′-bis[4 -(4-Amino-α,α-dimethylbenzyl)phenoxy]diphenylene, 4,4′-bis[4-(4-aminophenoxy)phenoxy]diphenyl Benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-amino) Phenoxy)-3,3,3′,3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis(4-aminophenoxy)-3, 3,3',3'-tetramethyl-1,1'-spirobiindanane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4 -Aminobutyl) tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminobutyl)polydi Methylsiloxane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[2-(aminomethoxy)ethyl ]Ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, 1,2-bis(aminomethoxy) ) Ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2 -(2-Aminoethoxy)ethoxy)ethane, ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol Bis(3-aminopropyl)ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamine Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane , 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diamine Cyclohexane, 1,4-diaminocyclohexane, 1,2-bis(2-aminoethyl)cyclohexane, 1,3-bis(2-aminoethyl)cyclohexane, 1,4-bis(2-aminoethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 2, 5-bis(aminomethyl)bicyclo[2.2.1]heptane, and dihydrazine adipate, but not limited to these.

As the organic polyamine, part or all of the hydrogen atoms on the aromatic ring of the exemplified organic polyamine can be selected from fluorine atoms, methyl groups, methoxy groups, trifluoromethyl groups, and trifluoromethoxy groups. A group of one or more substituents substituted.

In addition, as the organic polyamine, in addition to the exemplified organic polyamine, a polymer having two or more first-level amino groups (-NH ₂ ) in one molecule (removed as the first-level amino group and containing a carboxyl group) can also be used. Reactive basis). Examples of such organic polyamines include polystyrene, polyacrylic acid, polyurethane, polyamide, polyimide, polyimide imine, etc. The main chain or side chain through Modified by more than 2 first-level amine groups. Among them, at least one selected from the group consisting of polyacrylic acid, polyurethane, polyamide, and polyimide is preferred. More specifically, for example, the polymer side chain of the carboxyl group and ethyleneimine are used to graft polyethyleneimine onto the side chain of the acrylic copolymer containing the first-level amine. Base acrylic polymer; polyamide resin to extend tetracarboxylic dianhydride with excess amount of diamine or triamine; make urethane prepolymer to extend with excess amount of diamine or triamine Elongated polyurethane urea resin; modified epoxy resin to extend the epoxy resin with excess diamine or triamine.

The polymer having two or more first-stage amine groups in the above-mentioned molecule preferably does not contain groups that are reactive with carboxyl groups other than the first-stage amine group. Here, as a group having reactivity with a carboxyl group, for example, a hydroxyl group, a carboxyl group, a vinyloxy group, etc. may be mentioned, but it is not limited to these.

According to the purpose, the organic polyamine can also be used to introduce a part or all of the hydrogen atoms on the aromatic ring of the exemplified organic polyamine to introduce polyimine to form the cross-linking point during the cross-linking reaction. The choice is acetylene. One or more of the group consisting of a group, a benzocyclobutene-4'- group, a vinyl group, an allyl group, a cyano group, and an isopropenyl group as a substituent.

The organic polyamine system can be appropriately selected according to the intended physical properties. When rigid diamines such as p-phenylenediamine are used as organic polyamines, the final polyimide obtained can have a low expansion rate. Examples of rigid organic diamines include diamines (aromatic diamines) in which two amine groups are bonded to the same aromatic ring. Specific examples of such aromatic diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2 , 6-diaminonaphthalene, 2,7-diaminonaphthalene, and 1,4-diaminoanthracene. Dendrimers of polyamines can also be used.

And, as an organic polyamine, one can cite Two or more aromatic rings are bonded via a single bond, and two or more amine groups are derived from organic polyamines that are directly bonded to individual aromatic rings or bonded as part of a substituent. Specific examples of such organic polyamines include benzidine and toluidine.

Furthermore, as an organic polyamine, it can also be used Organic polyamines with substituents on the benzene ring. These substituents are monovalent organic groups, but they may also be bonded to each other. As specific examples of such organic polyamines, for example, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-trifluoromethyl-4,4'- Diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, and 3,3 '-Dimethyl-4,4'-diaminobiphenyl, dihydrazine isophthalate, etc.

As the organic polyamine other than the above, for example, an aminoethylated acrylic polymer or the like can be used. The aminoethylated acrylic polymer system includes, as a preferred aspect, an acrylic polymer in which polyethyleneimine is branched on the side link and which contains a first-stage amino group. The main chain of the aminoethylated acrylic polymer is a (meth)acrylic polymer formed from monomers containing (meth)acrylate and (meth)acrylic acid. As the aminoethylated acrylic polymer system, one having plural first-stage amino groups can be cited as one of the preferred aspects. The weight average molecular weight of the aminoethylated acrylic polymer is preferably 5,000 to 100,000.

The above-mentioned aminoethylated acrylic acid polymer series can also form hydrohalide, for example, hydrochloride, hydrobromide and other salts. As a preferred aspect of the aminoethylated acrylic polymer system, one that is water-soluble can be cited. Examples of commercially available products of aminoethylated acrylic polymers exhibiting water solubility include Polyment ^(R) NK-100PM and Polyment ^(R) NK-200PM (all manufactured by Nippon Shokubai Co., Ltd.).

"Silicone Polyamine" In this specification, among polyamine-based compounds other than hydrazine compounds, the polyamine-based compound in which Y is an m-valent organosilicon group containing a silicone bond is called a silicone-based polyamine.

As the m-valent organosilicon group containing a siloxane bond, for example, m of the hydrogen atoms of the monovalent hydrocarbon group of the organosilicon compound represented by the following formula are substituted with single bonds.

In the above formula, k is an integer greater than 1, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ and R ²² each independently represent a monovalent hydrocarbon group. When k≧2, the plural R ²¹ may be the same as each other They may be different from each other, and the plural R ²² may be the same or different from each other.

Specific examples of the silicone-based polyamine include 1,3-bis(3-aminopropyl)tetramethyldisiloxane. However, it is not limited by this.

When the silicone polyamine is used, the elastic modulus of the polyimide resin formed by curing the paste composition of the present invention can be reduced, and the glass transition temperature can be adjusted.

"Organic polyamines that can be used in combination with silicone-based polyamines" As the organic polyamine that can be used in combination with the silicone-based polyamine, from the viewpoint of heat resistance, aromatic polyamines are preferred, and aromatic diamines are preferred. One or more types of aromatic polyamines can also be used. In addition, organic polyamines other than aromatic diamines can be used in combination according to the physical properties of the purpose. As such organic polyamines, aliphatic polyamines are preferred, and aliphatic diamines are preferred. One or more types of aliphatic diamine can also be used. When an aromatic polyamine is used in combination with other organic polyamines, the usage amount of the organic polyamines other than aromatic polyamines should not exceed 60 mol% of the total amount of organic polyamines, and should not exceed The range of 40 mol% is preferable.

＜Active material for secondary battery＞ Examples of active materials for secondary batteries include positive electrode active materials and negative electrode active materials.

"Positive electrode active material" The positive electrode active material is not particularly limited, and examples thereof include composite oxides of lithium and transition metals, transition metal oxides, transition metal sulfides, and conductive polymers. Specific examples of the composite oxide of lithium and transition metal include LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiMnO ₂ and LiMn ₂ O ₄ , but they are not limited to these. Specific examples of the above-mentioned migrating metal oxide include MnO ₂ and V ₂ O ₅ , but they are not limited to these. Specific examples of the aforementioned transition metal sulfides include MoS ₂ and TiS ₂ , but they are not limited to these. Specific examples of the above-mentioned conductive polymer include polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene and polycarbazole, but are not limited to these.

"Anode Active Material" The negative electrode active material is not particularly limited, and examples thereof include graphite, amorphous carbon, fired polymer compound, coke, carbon fiber, conductive polymer, tin, silicon, and metal alloys. Specific examples of the above-mentioned polymer compound fired body include those that are fired and carbonized by phenol resin or furan resin, but are not limited to these. Specific examples of the aforementioned cokes include pitch coke, needle coke, and petroleum coke, but they are not limited to these. Specific examples of the above-mentioned conductive polymer include polyacetylene and polypyrrole, but are not limited to these. Specific examples of the aforementioned metal alloys include lithium-tin alloy, lithium-silicon alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy, but they are not limited to these.

As the negative electrode active material, in addition to graphite materials, carbonaceous materials such as amorphous hard carbon can be cited. Among them, the graphite material is preferred because it has excellent charge and discharge characteristics and exhibits high discharge capacity and potential flatness. Examples of graphite (graphite particles) used as the negative electrode active material include graphite particles such as natural graphite and artificial graphite; mesophase pitch using tar and pitch as raw materials or heat treatment of mesophase small spheres. Mesophase graphite particles or mesophase small spherical graphite particles; mesophase graphite particles or mesophase graphite fibers obtained by heat treatment after oxidizing particulate or fibrous mesophase pitch without melting; using tar, pitch Composite graphite particles obtained by heat-treating after coating natural graphite or artificial graphite; those that graphitize high crystalline needle coke, etc.

In addition, for the purpose of improving the rapid charge-discharge characteristics or cycle characteristics, the review has a combination of graphite particles and a composite conductive auxiliary agent. For example, a composite carbon material comprising a graphite material made of spherical particles and carbon fibers; a negative electrode material formed by mixing granular graphite with petroleum pitch and flake graphite to be granulated and compounded; making granular graphite A negative electrode material obtained by pulverizing flaky graphite adhered to the surface.

＜Aqueous medium＞ The aqueous medium is a medium containing water as the main component. As the water system, for example, ion-exchanged water, distilled water, deionized distilled water, RO (Reverse Osmosis; reverse osmosis) water, etc. can be used. Here, taking water as the main component means containing 60% by mass or more of water, preferably containing 75% by mass or more, and more preferably containing 90% by mass or more. The use of an aqueous medium system helps to reduce the environmental load.

For the purpose of imparting wettability to the coating surface of the paste composition (paste for electrodes) of the current collector, which is the substrate, and the anticorrosive effect of the paste composition, the aqueous medium may also contain a small environmental load and no Alcohols or ethers that adversely affect the volatility and dryness of water. Examples of alcohols include methanol, ethanol, n-propanol, 2-propanol (isopropanol), n-butanol, isobutanol, t-butanol, ethylene glycol, diethylene two Alcohol, propylene glycol, and glycerol, etc., as examples of ethers, such as butyl cellosolve, propylene glycol monomethyl ether, and 1-(2-hydroxyethyl)-2-pyrrolidone, but not limited For those. These alcohols or ethers can be used individually by 1 type, or can be used in combination of 2 or more types.

When adding alcohol to the aqueous medium, the content of alcohol in the aqueous medium relative to the total mass of the aqueous medium is preferably 1 mass% or more and 40 mass% or less, and 3 mass% or more and 25 mass% or less. Better. When the alcohol content is 1% by mass or more, the paste composition can strongly improve the wettability of the substrate, and it can inhibit the bounce of the paste composition on the substrate. When the alcohol content is 40% by mass or less, crystals do not precipitate in the paste composition, and it becomes easy to arrange the paste composition in a film form on the substrate. When the alcohol content is less than 1% by mass, the improvement effect obtained by adding alcohol may become insufficient. When the alcohol content exceeds 40% by mass, crystals may precipitate in the paste composition, and it may become difficult to arrange the paste composition in a film form on the substrate.

＜Other ingredients＞ As long as the paste composition of the present invention does not interfere with the effects of the present invention, it may contain other components other than the above-mentioned components. Examples of such other components include volatile amines, polymer components, additives, and organic solvents, but they are not limited to these.

"Volatile Amines" For the purpose of improving the stability of the paste composition of the present invention, volatile amines may also be added. The type of volatile amine that can be contained in the paste composition of the present invention is not particularly limited, and examples thereof include ammonia, trimethylamine, triethylamine, tributylamine, and N-methylmorpholine. These volatile amines may be used individually by 1 type, or may be used in combination of 2 or more types. The content of the volatile amine that can be contained in the paste composition of the present invention is not particularly limited, and preferably does not exceed the number of carboxyl moles that will not be used in the addition reaction of the cyclic unsaturated ether compound and the tetracarboxylic acid.

"Polymer Composition" As long as the paste composition of the present invention does not impair its characteristics, it may further contain polymer components other than polyimide. For example, the commonly used styrene butadiene rubber (SBR) water dispersion can be mixed and used at a ratio that does not damage its characteristics under the current technical level. When polymer components are added to the paste composition of the present invention, for example, the components can be blended by suitable mixing methods such as roll mixing, banbury mixing, screw mixing, stirring mixing, rotation and rotation mixing, etc. modulation.

"additive" When necessary, the paste composition of the present invention may further contain selected from reinforcing materials, fillers, anti-aging agents, anti-oxidants, light stabilizers, scorch inhibitors, other cross-linking retarders, plasticizers, and anti-corrosion agents. A group of more than one type of additives including additives, processing aids, lubricants, adhesives, lubricants, flame retardants, antifungal agents, antistatic agents, coloring agents, and surfactants.

"Organic solvents" The paste composition of the present invention contains substantially no organic solvents except for organic solvents such as alcohols and ethers contained in aqueous media, organic solvents contained in volatile amines, and trace organic solvents that are unavoidably mixed in. Better. Here, "substantially not containing an organic solvent" means that the content of the organic solvent in the paste composition of the present invention is 0.1% by mass or less with respect to the entire paste composition. As an organic solvent that is not substantially contained, it is preferable to include, for example, N-methyl-2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, dimethylsulfoxide, N ,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactone, acetone, γ-butyrolactone, methyl ethyl ketone and methyl isobutyl ketone Organic solvents with high environmental load.

＜Viscosity of paste composition＞ The viscosity of the paste composition of the present invention is not particularly limited. It is advisable to use a general viscometer such as a B-type viscometer, an E-type viscometer, a viscosity cup (Zahn Cup), etc. The wetness of the electric body causes obstacles to be used.

＜Preparation method of paste composition＞ The manufacturing method of the paste composition of this invention is not specifically limited, For example, the following methods can be mentioned. First, the active material for the secondary battery is put into a rotation-type mixer and set to a state where it is stirred at 30 to 500 rpm. It takes 1 to 90 minutes to mix and stir the mixture of hemiacetal ester derivative (1), polyamine (2) and aqueous medium to coat the active material for secondary battery in this state for 1 to 90 minutes. Composition. Mix the conductive additives as desired. After stirring, the temperature is raised to 50~150℃, and the pressure is reduced to 0.007~0.04MPa, and then kept for 10~150 minutes. The mixing ratio of the active material for the secondary battery and the composition for coating the active material for the secondary battery is not particularly limited. In terms of mass ratio, the active material for the secondary battery: the composition for coating the active material for the secondary battery = 1 ：0.001 ~ 1:0.1 is better.

[Electrode materials for secondary batteries] The electrode material for a secondary battery of the present invention includes a hemiacetal ester derivative (1), a polyamine (2), and an active material for a secondary battery. The hemiacetal ester derivative (1), the polyamine (2), and the active material for secondary batteries are as described above.

The electrode material for a secondary battery of the present invention is obtained by, for example, drying the paste composition of the present invention to remove the aqueous medium. When the dispersion medium is included in addition to the aqueous medium, it is also preferable to remove the dispersion medium.

[Electrode for Secondary Battery] The electrode for a secondary battery of the present invention has the electrode material for a secondary battery of the present invention. The manufacturing method of the electrode for secondary batteries of this invention is not specifically limited. For example, a coating device such as a doctor blade is used to coat the paste composition of the present invention on the current collector, and thereafter, it is dried to remove the aqueous medium, and if necessary, it is pressurized with a press. In this way, the electrode for a secondary battery of the present invention is obtained.

As the electrode for the secondary battery of the present invention, an electrode having a desired thickness by multi-layer coating can also be produced. Specifically, for the purpose of protecting the electrode for a secondary battery of the present invention from overheating on the side of the spacer, it is also possible to increase the adhesive compounding rate near the spacer. Or, for the purpose of exhibiting the protection against overheating of the secondary battery electrode of the present invention on the current collector side, it is also possible to increase the mixing ratio of the binder near the current collector. Here, the binder refers to components such as hemiacetal ester derivatives (1) and polyamines (2) after removing the active material for the secondary battery among the components constituting the electrode for the secondary battery of the present invention.

When the paste composition of the present invention contains a positive electrode active material as an active material for a secondary battery, it can obtain a positive electrode for a secondary battery, and when it contains a negative electrode active material, a negative electrode for a secondary battery can be obtained. When forming the positive electrode, various additives such as conventionally known conductive agents and binding agents can be suitably used. Examples of the conductive agent include graphitides and carbon black. Examples of binding agents include starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, tetrafluoroethylene, styrene butadiene rubber, polyethylene, and polypropylene. And other high-molecular compounds.

When forming the negative electrode, various additives such as conventionally known conductive agents and binders can be suitably used. Examples of the conductive agent include graphitides and carbon black. The binder is preferably one that exhibits chemical and electrochemical stability to the electrolyte. Examples include fluorine resin powders such as polytetrafluoroethylene and polyvinylidene fluoride; and resin powders such as polyethylene and polyvinyl alcohol. ; Carboxymethyl cellulose and so on.

[Secondary battery] The secondary battery of the present invention has the electrode for the secondary battery of the present invention. That is, the structure of the secondary battery of the present invention is the same as that of the conventional secondary battery except that the electrode for the secondary battery of the present invention is used as the positive electrode and/or the negative electrode.

The secondary battery of the present invention is obtained by combining electrodes that become opposite electrodes, storing them in a unit container together with a spacer, injecting electrolyte, and sealing the unit container. It is also possible to fabricate a bipolar electrode by forming a positive electrode on one side of the current collector and a negative electrode on the other side. The bipolar electrode and the spacer are layered and housed in a unit container and injected into the electrolysis Liquid, obtained from the sealed unit container. It is also possible that both the positive electrode and the negative electrode are the electrodes for the secondary battery of the present invention to make a secondary battery. In addition, the secondary battery of the present invention may also be an all-solid battery or an all-resin battery in which the electrolyte is reduced, or does not contain the electrolyte.

＜Spacer＞ Examples of spacers include microporous films made of polyethylene and polypropylene films; porous polyethylene films and multi-layer polypropylene films; porous polyimides, polyester fibers, and aramid ) Non-woven fabrics made of fibers, glass fibers, etc.; and those with ceramic particles such as silica, alumina, and titanium oxide attached to the surfaces.

＜Current collector＞ Examples of the current collector include copper, aluminum, titanium, stainless steel, nickel, fired carbon, conductive polymers, and conductive glass.

＜Electrolyte＞ As the electrolytic solution, an electrolytic solution containing an electrolyte and a non-aqueous solvent used in the manufacture of secondary batteries can be used.

"Electrolyte" As an electrolyte, you can use ordinary electrolytes, such as those used by users. For example, lithium salts of inorganic acids _{such as LiPF 6} , LiBF ₄ , LiSbF ₆ , LiAsF ₆ or LiClO _{4 , or LiN(CF 3} SO ₂ ) ₂ , LiN(C ₂ F ₅ SO ₂ ) ₂ or LiC(CF ₃ SO ₂ ) ₃ and other organic acid lithium salts. Among them, from the viewpoint of battery output and charge-discharge cycle characteristics, LiPF _{6 is} preferred.

"Non-aqueous solvent" As the non-aqueous solvent, ordinary electrolyte users can be used. For example, lactone compounds, cyclic or chain carbonates, chain carboxylic acid esters, cyclic or chain ethers, phosphate esters, and nitrile compounds can be used. , Amide compounds, stubborn, cyclobutane, etc. and mixtures of these. The non-aqueous solvent system may be used singly, or two or more of them may be used in combination.

Examples of lactone compounds include 5-membered ring (γ-butyrolactone, γ-valerolactone, etc.) and 6-membered ring lactone compounds (δ-valerolactone, etc.).

Examples of cyclic carbonates include propylene carbonate, ethylene carbonate, and butyl carbonate. Examples of chain carbonates include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and dicarbonate. -n-propyl ester etc.

Examples of chain carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate. Examples of cyclic ethers include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane, and the like. Examples of chain ethers include dimethoxymethane and 1,2-dimethoxyethane.

Examples of phosphoric acid esters include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, phosphoric acid Tris (trifluoromethyl ester), tris phosphate (trichloromethyl), tris phosphate (trifluoroethyl), tris phosphate (trisperfluoroethyl), 2-ethoxy-1,3, 2-Dioxaphospholan-2-one, 2-trifluoroethoxy-1,3,2-dioxaphospholan-2-one and 2-methoxyethoxy-1 ,3,2-Dioxaphospholan-2-one.

Examples of the nitrile compound include acetonitrile. As an amide compound, DMF can be mentioned, for example. As the stubborn, for example, dimethyl stubborn and diethyl stubborn are mentioned.

(Preferably non-aqueous solvent) Among the non-aqueous solvents, from the viewpoint of battery output and charge-discharge cycle characteristics, lactone compounds, cyclic carbonates, chain carbonates or phosphates are preferred, and lactone compounds, cyclic carbonates or chain carbonates are preferred. Preferably, a mixed liquid of cyclic carbonate and chain carbonate is more preferable. As a mixture of cyclic carbonate and chain carbonate, a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) is preferred. [Example]

The following describes the present invention in more detail based on the embodiments, but the present invention is not limited by these embodiments.

[Example 1] 1. Preparation of paste composition (negative electrode mixture paste) Put 1,2,4,5-benzenetetracarboxylic acid (11.1g) and water (45.9g) into a separable flask (300mL; cylinder type) equipped with a stirrer, and stir and mix for 10 minutes at 25°C. After that, 2,3-dihydrofuran (3.8g) was added, and stirring and mixing were carried out at 40°C for 90 minutes to obtain an aqueous dispersion of the dihydrofuran derivative.

Add styrene acrylic type polyamine (manufactured by Nippon Shokubai Co., Ltd., Polyment ^(R) NK-200PM; non-volatile residue 56% by mass, amine value 2.55 mmol/g-solid) to the obtained aqueous dispersion of dihydrofuran derivative ; M=60) (71.6g) and water (72.4g), stirred and mixed at 40°C for 3 hours to obtain an aqueous dispersion containing a dihydrofuran derivative and a polyamine.

The negative electrode material powder (graphite of mesophase small spheres, average particle diameter 19μm, specific surface area 2.1m ² /g) (98 parts by mass), binder (carboxymethyl cellulose) (1 part by mass), and as above The prepared aqueous dispersion containing the dihydrofuran derivative and the polyamine (the amount of the solid content removed from the aqueous medium is 1 part by mass) was put into water and stirred for 5 minutes to prepare a negative electrode mixture paste. Adjust the amount of water so that the content of the solid content (solute) in the negative electrode mixture paste becomes 50% by mass.

2. Production of the active electrode (negative electrode) The prepared negative electrode mixture paste was coated on the copper foil so as to have a uniform thickness, and the solvent was volatilized and dried at 90° C. in a vacuum to form a negative electrode mixture layer. Next, the negative electrode mixture layer was pressed by a hand press. In addition, by punching the copper foil and the negative electrode mixture layer into a circle with a diameter of 15.5 mm, a working electrode (negative electrode) that is closely adhered to the current collector made of the copper foil is produced. The electrode density is calculated from the mass and thickness of the negative electrode. Since the heating temperature is 90°C, the hemiacetal ester derivative and the polyamine do not react, and become a mixture.

3. Production of counter electrode (positive electrode) Press the lithium metal foil on the nickel mesh to make a circle shape with a diameter of 15.5mm, and make the opposite of the lithium metal foil (thickness: 0.5mm) which is closely adhered to the current collector made of the nickel mesh Electrode (positive electrode).

4. Production of the secondary battery Next, the coin-type secondary battery for evaluation shown in Figure 1 (also simply referred to as "evaluation battery") was produced. Figure 1 is a cross-sectional view showing the evaluation battery. In the evaluation battery, the peripheral portions of the outer cup 1 and the outer can 3 were caulked with the insulating gasket 6 interposed therebetween to form a sealed structure. As shown in Fig. 1, the inside of the closed structure is from the inner surface of the outer can 3 toward the inner surface of the outer cup 1, and the current collector 7a, the counter electrode 4, the spacer 5, and the working electrode (negative electrode) 2 are laminated in this order. , And current collector 7b. Such evaluation batteries were produced as follows. First, the spacer 5 impregnated with the electrolyte is sandwiched between the working electrode 2 closely adhered to the current collector 7b and the counter electrode 4 closely adhered to the current collector 7a to be laminated. After that, the working electrode 2 is housed in the exterior cup 1, and the counter electrode 4 is housed in the exterior can 3. The outer packaging cup 1 and the outer packaging can 3 are closed, and the peripheral parts of the outer packaging cup 1 and the outer packaging can 3 are caulked through the insulating gasket 6 and sealed. The electrolyte and spacer used when the battery is made are manufactured under the following conditions. •The production of electrolyte and spacer is _{to dissolve LiPF 6 in} a mixed solvent of ethylene carbonate (30% by volume) and propylene carbonate (70% by volume) to make a non-aqueous electrolyte by making LiPF 6 at a concentration of 1 mol/L. The prepared non-aqueous electrolyte was impregnated into a polypropylene porous body (thickness: 20 μm) to obtain a spacer impregnated with the electrolyte.

5. Charge and discharge test Using the produced evaluation battery, perform a charge-discharge test and evaluate various characteristics as shown below. After the circuit voltage reaches 0mV, the constant current charging of 0.9mA is carried out, and the time when the circuit voltage reaches 0mV is switched to constant voltage charging, and the charging capacity is calculated from the current value between 20μA and the current value (unit: mAh/g) ). After that, rest for 10 minutes. Next, a constant current discharge is performed at a current value of 0.9 mA until the circuit voltage reaches 1.5 V, and the discharge capacity (unit: mAh/g) is obtained from the current flow rate during this period. Let this be the first cycle. Next, let the charging current be 1C and the discharging current be 2C, and charge and discharge are performed in the same manner as in the first cycle. After that, the charge current was set to 0.5C and the discharge current was set to 2.5C, and charge and discharge were performed in the same manner as in the first cycle.

The irreversible capacity (loss of initial charge and discharge) (unit: mAh/g) is calculated from the following formula (1). Irreversible capacity = charge capacity in the first cycle-discharge capacity in the first cycle•••(1)

The 1C charging rate (unit: %) is calculated from the following formula (2). 1C charging rate=100×(the charging capacity of the CC part of the 1C current value / the discharge capacity of the first cycle)•••(2)

The 2C discharge rate (unit: %) is calculated from the following formula (3). 2C discharge rate=100×(2C current value discharge capacity / 1st cycle discharge capacity)•••(3)

In this charge-discharge test, the process of adsorbing lithium ions to the negative electrode active material is regarded as charging, and the process of separating lithium ions from the negative electrode active material is regarded as discharging. The test results are shown in Table 1 below.

6. Measurement of electrode expansion rate The evaluation battery after the charge-discharge test described above was put into a discharged state and then disassembled, and the negative electrode was recovered. Use a micrometer to measure the thickness of the recovered negative electrode. The electrode expansion rate (unit: %) was calculated according to the following formula. The results are shown in Table 1 below. Electrode expansion rate=100×{(the thickness of the recovered negative electrode)-(the thickness of the copper foil)}/{(the thickness of the negative electrode before starting the charge and discharge test)-(the thickness of the copper foil)}

7. Heat-resistant destruction test of electrode The negative electrode mixture paste prepared as described above was coated on the copper foil so as to have a uniform thickness, and the solvent was volatilized and dried at 90° C. in a vacuum to form a negative electrode mixture layer. Next, the negative electrode mixture layer was pressed by a hand press. In addition, the copper foil and the negative electrode mixture layer were cut into 5.0 cm squares to produce a negative electrode closely adhered to the current collector made of the copper foil. The negative electrode which has been made and adhered to the current collector is fixed on a glass plate with polyimide tape, preset in a furnace at 350°C, and heated for 20 minutes. Evaluate the state of the electrode (negative electrode) after the heat treatment from the viewpoint of the damage of the electrode, the damage of the current collector, and the adhesion between the electrode and the current collector. The evaluation criteria are as follows. The results are shown in Table 2 below. A: There is no damage to the electrode and current collector, and no peeling of the electrode and current collector. B: There is no damage to the electrode and current collector, and no peeling of the electrode and current collector. However, the electrode found signs of carbonization. C: There is damage to the electrode, damage to the current collector, or separation between the electrode and the current collector.

[Example 2] 1. Preparation of paste composition (negative electrode mixture paste) Put 2,3,3,4-biphenyltetracarboxylic acid (8.7g) and water (105.0g) into a separable flask (300mL; cylinder type) equipped with a stirrer, and stir and mix for 10 minutes at 25°C. After that, 2,3-benzofuran (3.0 g) was added, and the mixture was stirred and mixed at 25° C. for 45 minutes to obtain an aqueous dispersion of the benzofuran derivative.

Add styrene acrylic type polyamine (manufactured by Nippon Shokubai Co., Ltd., Polyment ^(R) NK-200PM; non-volatile residue 56 mass%, amine value 2.55 mmol/g-solid) to the obtained aqueous dispersion of benzofuran derivative ; M=60) (30.0g) and dihydrazine isophthalate (1.5g) were stirred and mixed at 25°C for 2 hours to obtain an aqueous dispersion containing a benzofuran derivative and a polyamine.

The negative electrode material powder (graphite of mesophase small spheres, average particle diameter 19μm, specific surface area 2.1m ² /g) (98 parts by mass), binder (carboxymethyl cellulose) (1 part by mass), and as above A generally prepared aqueous dispersion containing a benzofuran derivative and a polyamine (the amount of solid content after removing the aqueous medium is 1 part by mass) is put into water and stirred for 5 minutes to prepare a negative electrode mixture paste. Adjust the amount of water so that the content of the solid content (solute) in the negative electrode mixture paste becomes 50% by mass.

2. Production of secondary battery Using the prepared negative electrode mixture paste, a coin-type secondary battery (evaluation battery) was produced in the same manner as in Example 1.

3. Charge and discharge test and measurement of electrode expansion rate In the same manner as in Example 1, the charge and discharge test and the measurement of the electrode expansion rate were performed. The test results are shown in Table 1 below.

4. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 2 below.

[Example 3] 1. Preparation of paste composition (negative electrode mixture paste) Put dicyclohexylmethane 4,4′-diisocyanate (23.7g: isomer mixture) and polytetramethylene ether glycol (49.0g: average (Molecular weight 2000) and dihydroxybutyric acid (5.9g) were mixed at 90°C for 90 minutes. After that, 2-hydroxyethyl methacrylate (3.4 g) was added as a hydroxyl-containing acrylic raw material, and the mixture was further stirred for 90 minutes to obtain a urethane-based polymer. To the obtained urethane-based polymer, butyl methacrylate (18.1 g) was added to obtain a mixture of the urethane-based polymer and butyl methacrylate.

In other beakers, put triethylamine (4.2g), dihydrazine adipic acid (2.6g), 2,3,3,4-biphenyltetracarboxylic acid (2.8g), and dihydropyran ( 1.5g), add warm water pre-heated at 50°C with a funnel and stir for 90 minutes. Keep the temperature in the beaker at 50°C and keep it warm. As a result, a mixture of dihydropyran derivatives, triethylamine, and dihydrazine adipic acid was obtained by the reaction of 2,3,3,4-biphenyltetracarboxylic acid and dihydropyran.

The mixture of the above-mentioned urethane-based polymer and butyl methacrylate is mixed with the mixture of dihydropyran derivative, triethylamine and dihydrazine adipate, and warm water is added to obtain the mixture Solution. The mixed solution was prepared so that the hardening residue at the time of drying became 37% by mass. To the prepared mixed solution, 2,2′-azobis(isobutyric acid) dimethyl ester was added as a polymerization initiator, and the temperature was raised to 80° C. and stirring was continued for 120 minutes. Thereby, the urethane-based polymer, butyl methacrylate, triethylamine, and dihydrazine adipate are reacted to obtain acrylic copolymerized urethane-based polyamine (m=10 ) Aqueous solution. Dihydropyran derivatives are also dispersed in the obtained aqueous solution.

The negative electrode material powder (graphite of mesophase spheres, average particle diameter 19μm, specific surface area 2.1m ² /g) (98 parts by mass), binder (carboxymethyl cellulose) (1 part by mass), and as above The prepared acrylic copolymerized urethane-based polyamine aqueous solution (with the solid content of the aqueous medium removed is 1 part by mass) in which the dihydropyran derivative has been dispersed is placed in water and stirred for 5 minutes to prepare a negative electrode mixture Paste. The amount of water is adjusted so that the solid content (solute) in the negative electrode mixture paste becomes 50% by mass.

2. Production of secondary battery Using the prepared negative electrode mixture paste, a coin-type secondary battery (evaluation battery) was produced in the same manner as in Example 1.

3. Charge and discharge test and measurement of electrode expansion rate In the same manner as in Example 1, the charge and discharge test and the measurement of the electrode expansion rate were performed. The test results are shown in Table 1 below.

4. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 2 below.

[Comparative example 1] 1. Preparation of paste composition (negative electrode mixture paste) 98 parts by mass of negative electrode material powder (graphite of mesophase spheres, average particle diameter 19μm, specific surface area 2.1m ^{2 /g) were combined} 1 part by mass of the agent (carboxymethyl cellulose) and 1 part by mass of styrene butadiene rubber (EQ-Lib-SBR, manufactured by MTI, USA) were put into water and stirred for 5 minutes to prepare a negative electrode mixture paste. Adjust the amount of water so that the content of the solid content (solute) in the negative electrode mixture paste becomes 50% by mass.

2. Production of secondary battery Using the negative electrode mixture paste described above, in the same manner as in Example 1, a secondary battery for evaluation was produced.

3. Charge and discharge test and measurement of electrode expansion rate In the same manner as in Example 1, the charge and discharge test and the measurement of the electrode expansion rate were performed. The test results are shown in Table 1 below.

4. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 2 below.

The battery characteristics of Examples 1 to 3 and Comparative Example 1 are all good.

The electrodes (negative electrodes) of Examples 1 to 3 were not damaged even under heating at 350°C. On the other hand, the electrode of Comparative Example 1 was destroyed by heating at 350°C. Comparative Example 1 uses styrene butadiene rubber (SBR), which is widely used as a representative material for active material coating resins that can be used in an aqueous environment, but it cannot prevent electrode damage due to temperature rise.

[Example 4] 1. Preparation of paste composition (positive electrode mixture paste) Positive electrode material powder (carbon-coated LiFePO ₄ , GN-198-S manufactured by BTR Corporation, average particle diameter 4 μm, specific surface area 11 m ² /g) (97 parts by mass), and the aqueous dispersion containing dihydrofuran derivative and polyamine obtained in Example 1 (the amount of solid content removed from the aqueous medium is 3 parts by mass) was put into water, and stirred for 5 minutes to prepare a positive electrode Mixture paste. Adjust the amount of water so that the solid content (solute) in the positive electrode mixture paste becomes 50% by mass.

2. Production of positive electrode The prepared positive electrode mixture paste was coated on the aluminum foil so as to have a uniform thickness, and the solvent was volatilized and dried at 90° C. in a vacuum to form a positive electrode mixture layer. Next, press the positive electrode mixture layer with a hand press. In this way, a positive electrode adhered to a current collector made of aluminum foil was fabricated.

3. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 3 below.

[Example 5] 1. Preparation of paste composition (positive electrode mixture paste) Positive electrode material powder (carbon-coated LiFePO ₄ , GN-198-S manufactured by BTR Corporation, average particle diameter 4 μm, specific surface area 11 m ² /g) (97 parts by mass), and Example 2 to obtain an aqueous dispersion containing benzofuran derivatives and polyamine (the amount of solid content removed from the aqueous medium is 3 parts by mass), put it into water, and stir for 5 minutes to prepare a positive electrode mixture paste material. Adjust the amount of water so that the solid content (solute) in the positive electrode mixture paste becomes 50% by mass.

2. Production of positive electrode The prepared positive electrode mixture paste was coated on the aluminum foil so as to have a uniform thickness, and the solvent was volatilized and dried at 90° C. in a vacuum to form a positive electrode mixture layer. Next, press the positive electrode mixture layer with a hand press. In this way, a positive electrode adhered to a current collector made of aluminum foil was fabricated.

3. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 3 below.

[Example 6] 1. Preparation of paste composition (positive electrode mixture paste) Positive electrode material powder (carbon-coated LiFePO ₄ , GN-198-S manufactured by BTR Corporation, average particle diameter 4 μm, specific surface area 11 m ² /g) (97 parts by mass), and the dihydropyran derivative-dispersed acrylic copolymerized urethane-based polyamine aqueous solution (3 parts by mass removed from the solid content of the aqueous medium) obtained in Example 3 was put into water, The mixture was stirred for 5 minutes to prepare a positive electrode mixture paste. Adjust the amount of water so that the solid content (solute) in the positive electrode mixture paste becomes 50% by mass.

2. Production of positive electrode The prepared positive electrode mixture paste was coated on the aluminum foil so as to have a uniform thickness, and the solvent was volatilized and dried at 90° C. in a vacuum to form a positive electrode mixture layer. Next, press the positive electrode mixture layer with a hand press. In this way, a positive electrode adhered to a current collector made of aluminum foil was fabricated.

3. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 3 below.

[Comparative Example 2] 1. Preparation of paste composition (positive electrode mixture paste) Positive electrode material powder (carbon-coated LiFePO ₄ , GN-198-S manufactured by BTR Corporation, average particle diameter 4 μm, specific surface area 11 m ² /g) (97 parts by mass), and styrene butadiene rubber (EQ-Lib-SBR, manufactured by MTI, USA) (3 parts by mass) were put into water and stirred for 5 minutes to prepare a positive electrode mixture paste. Adjust the amount of water so that the solid content (solute) in the positive electrode mixture paste becomes 50% by mass.

2. Production of positive electrode The prepared positive electrode mixture paste was coated on the aluminum foil so as to have a uniform thickness, and the solvent was volatilized and dried at 90° C. in a vacuum to form a positive electrode mixture layer. Next, press the positive electrode mixture layer with a hand press. In this way, a positive electrode adhered to a current collector made of aluminum foil was fabricated.

3. Heat-resistant destruction test of electrode In the same manner as in Example 1, a heat-resistant destruction test of the electrode was performed. The test results are shown in Table 3 below.

The electrodes (positive electrodes) of Example 4 to Example 6 were not damaged even under heating at 350°C. On the other hand, the electrode of Comparative Example 2 was destroyed by heating at 350°C. Comparative Example 2 uses styrene butadiene rubber (SBR), which is widely used as a representative material for active material coating resins that can be used in an aqueous environment, but it cannot prevent electrode damage due to temperature rise.

1: Outer cup 2: Working electrode (negative electrode) 3: External cans 4: Opposite electrode 5: Spacer 6: Insulating gasket 7a: collector 7b: current collector

[Fig. 1] Fig. 1 is a schematic cross-sectional view of the battery used in the embodiment.

Claims (8)

A paste composition comprising: a hemiacetal ester derivative represented by formula (1), a polyamine represented by formula (2), an active material for secondary batteries, and an aqueous medium, the aforementioned polyamine The molar ratio of the amine relative to the hemiacetal ester derivative is 0.20~2.33;

In the aforementioned formula (1), n is 0 or 1, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and may also be formed by bonding with each other Cyclic structure, X is a tetravalent organic group. In the aforementioned formula (1), when n=0, R ² and R ⁴ or R ⁴ and R ⁵ can also be bonded to each other to form an aromatic carbon that may have substituents Six-member ring. In the aforementioned formula (2), m is an integer of 2 or more, and Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond. The paste composition of claim 1, wherein the aforementioned hemiacetal ester derivative is selected from 2,3-dihydrofuran derivatives represented by formula (1-1) and 3 represented by formula (1-2) , 4-dihydro-2H-pyran derivatives, and at least one of the group of 1-benzofuran derivatives represented by formula (1-3);

In the aforementioned formula (1-1), R ¹ , R ² , R ⁴ , R ⁵ and X have the same meaning as ^{R 1} , R ² , R ⁴ , R ⁵ and X in the aforementioned formula (1). In formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X in the aforementioned formula (1) Have the same meaning, in the aforementioned formula (1-3), R ¹ , R ² and X are each ^{having the same meaning as R 1} , R ² and X in the aforementioned formula (1). In the aforementioned formula (1-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. The paste composition of claim 1 or 2, wherein the aforementioned polyamine is at least one selected from the group consisting of polyacrylic acid, polyurethane, polyamide, and polyimide. An electrode material for a secondary battery, comprising: a hemiacetal ester derivative represented by the formula (1), a polyamine represented by the formula (2), and an active material for a secondary battery. The molar ratio of the acetal ester derivative is 0.20~2.33;

In the aforementioned formula (1), n is 0 or 1, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and may also be formed by bonding with each other Cyclic structure, X is a tetravalent organic group. In the aforementioned formula (1), when n=0, R ² and R ⁴ or R ⁴ and R ⁵ can also be bonded to each other to form an aromatic carbon that may have a substituent For a six-membered ring, in the aforementioned formula (2), m is an integer of 2 or more, and Y is an m-valent organic group or an m-valent organosilicon group containing a siloxane bond. The electrode material for a secondary battery according to claim 4, wherein the aforementioned hemiacetal ester derivative is selected from the 2,3-dihydrofuran derivative represented by the formula (1-1) and the formula (1-2) At least one of the 3,4-dihydro-2H-pyran derivatives and the 1-benzofuran derivatives represented by formula (1-3);

In the aforementioned formula (1-1), R ¹ , R ² , R ⁴ , R ⁵ and X have the same meaning as ^{R 1} , R ² , R ⁴ , R ⁵ and X in the aforementioned formula (1). In formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X in the aforementioned formula (1) Have the same meaning, in the aforementioned formula (1-3), R ¹ , R ² and X are each ^{having the same meaning as R 1} , R ² and X in the aforementioned formula (1). In the aforementioned formula (1-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. The electrode material for a secondary battery according to claim 4 or 5, wherein the polyamine is at least one selected from the group consisting of polyacrylic acid, polyurethane, polyamide, and polyimide. An electrode for a secondary battery, which has the electrode material for a secondary battery according to any one of claims 4 to 6. A secondary battery having an electrode for a secondary battery as in Claim 7.

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