JP2016139567A - Additive agent for secondary battery, electrode using the same and electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for suppressing gas generation from a nonaqueous electrolyte secondary battery and improving its charge and discharge cycle characteristics and output property.SOLUTION: Disclosed is a nonaqueous electrolyte secondary battery in which a compound (A) having at least one group selected from an urethane group, an urea group and a thiourethane group and a group represented by the following general formula (2) is added to an electrode or an electrolyte.SELECTED DRAWING: None

Description

  The present invention relates to an additive useful for a non-aqueous electrolyte secondary battery, an electrode using the additive, and an electrolyte.

  Non-aqueous electrolyte secondary batteries such as lithium ion batteries are characterized by high voltage and high energy density, so they are widely used in the field of portable information equipment, and the demand for them is rapidly expanding. A position as a standard battery for mobile information devices such as telephones and notebook computers has been established. Of course, along with the high performance and multi-functionality of portable devices, etc., even higher performance (for example, higher capacity and higher energy density) for non-aqueous electrolyte secondary batteries as its power source It has been demanded. In order to meet this demand, various methods such as higher density by improving the filling rate of electrodes, improvement of the depth of use of current active materials (especially negative electrodes), development of new high-capacity active materials, etc. have been carried out. Yes. In reality, the capacity of the non-aqueous electrolyte secondary battery is reliably increased by these methods.

Further, in order to further increase the capacity of the non-aqueous electrolyte secondary battery, improvement in the utilization rate of the positive electrode active material and development of a high voltage material are required. Among these, the improvement of the utilization depth of the positive electrode active material due to the increase in the charging voltage has attracted attention. For example, a cobalt composite oxide (LiCoO ₂ ), which is an active material of a non-aqueous electrolyte secondary battery having an operating voltage of 4.2 V class, has a charge capacity of about 155 mAh / g when charged to 4.3 V based on the current Li standard. On the other hand, when charged to 4.50 V, it is about 190 mAh / g or more. Thus, the utilization rate of a positive electrode active material becomes large by the improvement of a charging voltage.

  However, as the voltage of the battery is increased, the capacity and energy density of the battery are improved, while the charge / discharge cycle characteristics are deteriorated, and there is a problem that the gas is swollen during high-temperature storage. . Also,

  In order to solve such a problem, a technique for adding various additives is disclosed. For example, Patent Document 1 discloses a technique for adding vinylene carbonate (VC) to an electrolytic solution. Discloses a technique of adding 1,3-propane sultone to an electrolytic solution. Patent Document 3 discloses a technique for adding silicone oil to an electrolytic solution.

Japanese Patent Laid-Open No. 11-067266 JP 2000-123868 A JP 2000-294275 A

However, even if these additives are used, the effect of improving the cycle characteristics is insufficient, and further improvement has been demanded. The present invention has been made in view of this problem.
That is, the problem to be solved by the present invention is to suppress the gas generation of the nonaqueous electrolyte secondary battery and to improve the charge / discharge cycle characteristics and output characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention provides a secondary battery additive (B) comprising a group represented by the following general formula (1) and a compound (A) having a group represented by: An electrolyte solution containing the secondary battery additive (B); a lithium ion battery having at least one of the electrode and the electrolyte solution; and having at least one of the electrode and the electrolyte solution Lithium ion capacitor.

［式（１）中、Ｒは水素原子又は炭素数１〜１２の有機基である。]

[In Formula (1), R is a hydrogen atom or a C1-C12 organic group. ]

［式（２）中、Ｒ^１及びＲ^２は水素原子、ヒドロキシ基、炭素数１〜２０のアルコキシ基又は水素原子がヘテロ原子を含む官能基に置換されていてもよい炭素数１〜２０の１価の炭化水素基であり、複数個ある場合のＲ^１及びＲ^２は、それぞれ同一であっても異なっていてもよい。ｎは１〜３００の整数である。］

[In the formula (2), R ¹ and R ² are a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms or a hydrogen atom having 1 to 20 carbon atoms which may be substituted with a functional group containing a hetero atom. When there are a plurality of monovalent hydrocarbon groups, R ¹ and R ² may be the same or different. n is an integer of 1 to 300. ]

  By using the electrode or electrolyte containing the secondary battery additive of the present invention, it is possible to suppress the gas generation of the lithium ion battery or lithium ion capacitor and improve the charge / discharge cycle characteristics and output characteristics. it can.

  The additive (B) for secondary batteries of the present invention contains a compound (A) having a group represented by the general formula (1) and a group represented by the following general formula (2).

In general formula (1), R is a hydrogen atom or a monovalent organic group having 1 to 12 carbon atoms, and the monovalent organic group having 1 to 12 carbon atoms may be a monovalent fat having 1 to 12 carbon atoms. Group hydrocarbon group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group 2-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, heptyl Octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group and dodecyl group), monovalent alicyclic hydrocarbon group having 1 to 12 carbon atoms (such as cyclohexyl group and cyclopentyl group), carbon number 6 To 12 monovalent aromatic hydrocarbon groups (benzyl group, phenyl group, methylphenyl group, biphenyl group, naphthyl group, etc.) and functional groups in which these hydrogen atoms contain a hetero atom (amino group, alkylamino group, dialkyl) And monovalent groups substituted by amino groups and alkylthio groups).
Among these, from the viewpoint of battery output characteristics, R is preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrogen atom.

  The group represented by the general formula (1) is a group contained in at least one group selected from the group consisting of a urethane group, a urea group, a thiourethane group, an allophanate group, and a biuret group from the viewpoint of cycle characteristics. Preferably, it is a group contained in at least one group selected from the group consisting of a urethane group, a urea group and a thiourethane group.

  The urethane group can be obtained by the reaction of an isocyanate group and a hydroxyl group, and the urea group can be obtained by the reaction of an isocyanate group and an amino group. The thiourethane group can be obtained by the reaction of an isocyanate group and a mercapto group. Allophanate groups can be obtained by reaction of isocyanate groups and carbamate groups, and biuret groups can be obtained by reaction of isocyanate groups and carbamide groups.

In the formula (2), R ¹ and R ² are a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, or a hydrogen atom having 1 to 20 carbon atoms which may be substituted with a functional group containing a hetero atom. R ¹ and R ^{2 in the} case of plural valent hydrocarbon groups may be the same or different.
Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a butoxy group, and an octoxy group.
The monovalent hydrocarbon group which may be substituted with a functional group containing a hetero atom having 1 to 20 carbon atoms includes a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (methyl group, ethyl group, n -Propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl Group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, heptyl group, octyl group, isooctyl group Octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group and the like), monovalent alicyclic hydrocarbon group having 1 to 20 carbon atoms (such as cyclohexyl group and cyclopentyl group) and 1 having 6 to 20 carbon atoms. Valent aromatic hydrocarbon groups (benzyl group, phenyl group, methylphenyl group, biphenyl group, naphthyl group, etc.) and the like, and the functional group containing a hetero atom replacing the hydrogen atom of these groups is an amino group , Alkylamino group, dialkylamino group, alkylthio group and the like.
Of these, a methyl group is preferably used from the viewpoint of output characteristics.

  n is an integer of 1 to 300.

The compound (A) preferably has an alkyleneoxy group (c) from the viewpoint of battery output characteristics. Examples of the alkyleneoxy group (c) include alkyleneoxy groups having 2 to 4 carbon atoms (such as an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group). Among these, an ethyleneoxy group is preferable from the viewpoint of battery output characteristics.
The alkyleneoxy group (c) may be composed of one alkyleneoxy group or may be composed of two or more alkyleneoxy groups bonded in series, and from the viewpoint of battery output characteristics, It is preferable that the alkyleneoxy group or 2 to 40 alkyleneoxy groups are continuously bonded to each other, and that 3 to 30 alkyleneoxy groups are continuously bonded to each other. preferable.
When two or more alkyleneoxy groups are successively bonded, the bonded alkyleneoxy groups may be one type or two or more types. When two or more kinds of alkyleneoxy groups are continuously bonded, the bonding mode may be random, block, or a mixture thereof.

The compound (A) preferably has the alkyleneoxy group (c) as a structural unit represented by the following general formulas (3) to (5).

In Formula (3), L ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of L ^{1 s} , they may be the same or different. Specific examples of L ¹ include an ethylene group, a 1,3-propylene group, a 1,2-propylene group, and a tetramethylene group. Among these, an ethylene group is preferable from the viewpoint of battery characteristics.

L ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples of L ² include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexamethylene group. Among these, a methylene group and an ethylene group are preferable from the viewpoint of battery characteristics.

L ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms in which the hydrogen atom may be substituted with a functional group containing a hetero atom. Specific examples of L ³ include monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethyl Propyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1,2 -Trimethylpropyl group, 1-ethyl-1-methylpropyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group and dodecyl group ), Monovalent alicyclic hydrocarbon groups having 1 to 20 carbon atoms (such as cyclohexyl group and cyclopentyl group) and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms (benzyl group, phenyl group, methylphenyl group) , Biphenyl group and naphthyl group). Among these, a hydrogen atom and a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms are preferably used from the viewpoint of the cycle characteristics of the battery. R ³ is more preferably a hydrogen atom. Examples of the functional group containing a hetero atom include an amino group, an alkylamino group, a dialkylamino group, and an alkylthio group.
h is an integer of 1 to 40, preferably 3 to 30, and more preferably 5 to 20.

In formula (4), P ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of P ^{1 s} , P ¹ may be the same or different. Specific examples of P ¹ include the same as L ¹ described above, and preferable ones are also the same.
P ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, include those similar to the L ² of the specific examples of P ^2, it is preferable also the same.
i is an integer of 1 to 40, preferably 3 to 30, and more preferably 5 to 20.

In Formula (5), W ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of W ^{1 s} , they may be the same or different. W ¹ may be the same as L ¹ described above, and preferred ones are also the same. W ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the monovalent hydrocarbon group having 1 to 20 carbon atoms is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms ( Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group 1-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, heptyl group, octyl Til group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group and dodecyl group), monovalent alicyclic hydrocarbon group having 1 to 20 carbon atoms (such as cyclohexyl group and cyclopentyl group) and carbon Examples thereof include monovalent aromatic hydrocarbon groups of 6 to 20 (phenyl group, methylphenyl group, benzyl group, naphthyl group, etc.) and the like.
Among these, a hydrogen atom and a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms are preferable, and a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a 2-ethylhexyl group are more preferable. k is an integer of 1 to 40, preferably 3 to 30, and particularly preferably 5 to 20 from the viewpoint of output characteristics.

  The compound (A) preferably has a group represented by the following general formula (6) from the viewpoint of battery characteristics.

In Formula (6), Q ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of Q ^{1 s} , Q ¹ may be the same or different. Examples of Q ¹ include the same as L ¹ described above, and preferable ones are also the same.
Q ² is a divalent hydrocarbon group having 1 to 10 carbon atoms. The Q ² same can be mentioned and L ² above, it is preferable also the same.
M is a monovalent metal ion, and examples thereof include alkali metal ions such as lithium ion, sodium ion and potassium ion. Of these, lithium ions and sodium ions are preferable from the viewpoint of battery output characteristics and the like.
A is —CO ₂ ^— or —SO ₃ ^— , and —SO ₃ ^— is preferable from the viewpoint of battery output characteristics.
j is an integer of 0 to 40, preferably 3 to 30, and particularly preferably 5 to 20 from the viewpoint of output characteristics. m is 0 or 1, preferably 1.

Preferable examples of the compound (A) include those represented by the following general formula (7).

In Formula (7), R ^{3 to} R ⁷ are a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, or a 1 to 1 carbon atom that may be substituted with a functional group containing a hetero atom in the hydrogen atom. Valent hydrocarbon group. When n is 2 or more and a plurality of R ⁵ are contained, they may be the same or different.
Examples of R ^{3 to} R ⁷ include the same as R ^1, and preferred examples are also the same. Z ^{1 to} Z ³ are represented by an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a functional group containing a hetero atom, and the following general formula (8). Or a group represented by the following general formula (9), and at least one of Z ^{1 to} Z ³ is a group represented by the general formula (8) or a group represented by the general formula (9). is there. Examples of Z ^{1 to} Z ³ are the same as those described above for R ^1, and preferred are R ¹ , a group represented by general formula (8), and a group represented by general formula (9).

In Formula (8), R ⁸ is a C 1-10 divalent hydrocarbon group, R ⁹ is a C 1-20 divalent hydrocarbon group, and X is an oxygen atom, a sulfur atom or It is an imino group. F is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a group represented by the general formulas (3) to (6).

In the formula (9), R ¹⁰ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ¹¹ is a hydrocarbon group having 1 to 10 carbon atoms, and X is an oxygen atom, a sulfur atom or an imino group. is there.

Specific examples of preferable R ⁸ include divalent linear hydrocarbon groups having 1 to 10 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, dodecylene group). A divalent alicyclic hydrocarbon group having 1 to 10 carbon atoms (for example, cyclohexylene group and cyclopentylene group) and a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (for example, phenylene group, methyl group) Phenylene group, benzylene group, naphthylene group, etc.). Of these, methylene group, ethylene group and propylene group are more preferably used from the viewpoint of output characteristics.

Specific examples of preferable R ⁹ include a divalent linear hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 1 to 20 carbon atoms, and a divalent aroma having 6 to 20 carbon atoms. Group hydrocarbon group. Among these, in particular, a residue obtained by removing two isocyanate groups from hexamethylene diisocyanate, a residue obtained by removing two isocyanate groups from isophorone diisocyanate, a residue obtained by removing two isocyanate groups from dicyclohexylmethane diisocyanate, and two residues obtained from diphenylmethane diisocyanate. A residue excluding an isocyanate group is more preferably used.

X is preferably an oxygen atom from the viewpoint of the output characteristics of the battery.
Specific examples of preferable F include the monovalent linear hydrocarbon group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 1 to 20 carbon atoms, and the monovalent group having 6 to 20 carbon atoms. The aromatic hydrocarbon group of these is mentioned. Of these, methyl groups, ethyl groups, butyl groups, and groups represented by general formulas (3) to (6) are more preferably used from the viewpoint of output characteristics.

R ¹⁰ is a C 1-10 divalent hydrocarbon group, and R ¹¹ is a C 1-10 hydrocarbon group.
Specific examples of preferable R ¹⁰ include the same as R ⁸ described above, and preferable examples thereof are also the same.
Specific examples of preferable R ¹¹ include the aforementioned monovalent linear hydrocarbon group having 1 to 10 carbon atoms, monovalent alicyclic hydrocarbon group having 1 to 10 carbon atoms, and monovalent group having 6 to 10 carbon atoms. And the same aromatic hydrocarbon group. Of these, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group are preferably used from the viewpoint of output characteristics.

  The compound (A) contained in the secondary battery additive of the present invention is, for example, a compound (T1) having an isocyanate group and a compound (T2) having a siloxane bond having an active hydrogen group such as a hydroxyl group, an amino group or a mercapto group. It can be synthesized by reacting.

  As the compound (T1) having an isocyanate group, a monoisocyanate compound having 2 to 20 carbon atoms (for example, ethyl isocyanate, butyl isocyanate, octyl isocyanate and dodecyl isocyanate), a diisocyanate compound having 4 to 20 carbon atoms (for example, hexamethylene diisocyanate, isophorone) Diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate and the like) and triisocyanate compounds having 6 to 30 carbon atoms (for example, biuret-modified products of hexamethylene diisocyanate and isocyanurate-modified products of hexamethylene diisocyanate) and these And the like.

A preferable example of the compound (T2) having a siloxane bond having an active hydrogen group is a modified silicone oil. Examples of the modified silicone oil include carbinol-modified silicone oil (Shin-Etsu Chemical Co., Ltd .: KF-6000 and X-22-4039), amino-modified silicone oil (Shin-Etsu Chemical Co., Ltd .: KF-8010), and mercapto-modified silicone. Oil (Shin-Etsu Chemical Co., Ltd. product: X-22-167B) etc. are mentioned.
As the compound (T2), 1,3-bis (3-hydroxypropyl) tetramethyldisiloxane and 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane are also preferably used, and these are Wako Pure Chemical Industries, Ltd. It can be obtained from corporations.

The secondary battery additive (B) of the present invention may contain components other than the compound (A), and is an organic solvent (for example, vinylene carbonate, for example) used as an electrolyte solution for a nonaqueous solvent (H) secondary battery. Fluoroethylene carbonate, chloroethylene carbonate, ethylene sulfite, propylene sulfite, propane sultone, and α-bromo-γ-butyrolactone).
The content of the compound (A) in the secondary battery additive (B) is preferably 10 to 100% by weight, more preferably 50, based on the weight of the secondary battery additive (B). ~ 100% by weight. The compound (A) contained in the secondary battery additive (B) may be one type or two or more types.

  In the present invention, the secondary battery includes electrochemical devices such as a lithium ion battery, a lithium ion capacitor, an electric double layer capacitor, a lead storage battery, a nickel-cadmium battery, and a nickel metal hydride battery.

  The electrode of the present invention is obtained by dispersing a secondary battery additive (B), an active material (D), a binder (E) and, if necessary, a conductive additive (K) in a solvent to obtain a slurry. Can be obtained by coating on a current collector and drying the organic solvent. As the secondary battery additive (B), the active material (D), the binder (E), the solvent, and the conductive additive (K), any one or two or more of them can be used.

As the active material (D), a negative electrode for a lithium ion battery is obtained by using the negative electrode active material (D1), and a negative electrode for a lithium ion capacitor is obtained by doping lithium into the negative electrode active material (D1). Moreover, as a positive electrode active material, the positive electrode active material (D2) for lithium ion batteries and the positive electrode active material (D3) for lithium ion capacitors are mentioned.
As the negative electrode active material (D1), graphite, amorphous carbon, a polymer compound fired body (for example, those obtained by firing and carbonizing a phenol resin, a furan resin, etc.), cokes (for example, pitch coke, needle coke, and petroleum coke), Examples thereof include carbon fibers, conductive polymers (for example, polyacetylene and polypyrrole), tin, silicon, and metal alloys (for example, lithium-tin alloy, lithium-silicon alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy). .
Examples of the positive electrode active material (D2) for lithium ion batteries include composite oxides of lithium and transition metals (eg, LiCoO ₂ , LiNiO ₂ , LiMnO ₂ and LiMn ₂ O ₄ ), transition metal oxides (eg, MnO ₂ and V ₂ O). ₅ ), transition metal sulfides (eg, MoS ₂ and TiS ₂ ), and conductive polymers (eg, polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole).
Examples of the positive electrode active material (D3) for the lithium ion capacitor include activated carbon, carbon fiber, and conductive polymer (for example, polyacetylene and polypyrrole).

  Examples of the binder (E) include polymer compounds such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, and polypropylene.

  The conductive assistant (K) which is an optional component includes carbon blacks (for example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black) and metal powder (for example, aluminum powder and nickel powder) ), Conductive metal oxides (for example, zinc oxide and titanium oxide) and the like.

  Examples of the solvent used when preparing the electrode of the present invention include water, N-methylpyrrolidone, acetone and toluene.

The content of the active material (D) is preferably 70 to 98 based on the total weight of the active material (D), the binder (E), and the secondary battery additive (B) from the viewpoint of battery capacity. % By weight, more preferably 90-98% by weight.
The content of the binder (E) is preferably 0.00 based on the total weight of the active material (D), the binder (E), and the secondary battery additive (B) from the viewpoint of battery capacity. It is 5-29 weight%, More preferably, it is 1-10 weight%.
The content of the secondary battery additive (B) is selected from the viewpoints of charge / discharge cycle characteristics, battery capacity, and high-temperature storage characteristics, the active material (D), the binder (E), and the secondary battery additive (B). ), Preferably 0.01 to 10% by weight, more preferably 0.05 to 1% by weight.
The content of the conductive additive (K) is preferably 0 to 0 based on the total weight of the active material (D), the binder (E), and the secondary battery additive (B) from the viewpoint of battery output. 29% by weight, more preferably 1 to 10% by weight.

The electrolytic solution of the present invention contains a secondary battery additive (B), an electrolyte (G), and a nonaqueous solvent (H).
The electrolytic solution of the present invention can be obtained by dissolving the secondary battery additive (B) and the electrolyte (G) in a non-aqueous solvent (H).

The electrolyte (G), normal is can be used such as those used in the electrolytic solution, for _{example, LiPF 6, LiBF 4, LiSbF} 6, LiAsF 6 , and lithium salts of inorganic acids LiClO _4, etc., LiN (CF ₃ Examples include lithium salts of organic acids such as SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ and LiC (CF ₃ SO ₂ ) ₃ . Among these, LiPF ₆ is preferable from the viewpoint of battery output and charge / discharge cycle characteristics.

  As the non-aqueous solvent (H), those used in ordinary electrolytes can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphoric acid Esters, nitrile compounds, amide compounds, sulfones, sulfolanes, and the like and mixtures thereof can be used.

Of the non-aqueous solvents (H), cyclic or chain carbonates are preferred from the viewpoint of battery output and charge / discharge cycle characteristics.
Examples of the cyclic carbonate include propylene carbonate, ethylene carbonate and butylene carbonate.
Examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.

The content of the secondary battery additive (B) is determined from the viewpoints of charge / discharge cycle characteristics, battery capacity, and high-temperature storage characteristics. Secondary battery additive (B), electrolyte (G), and nonaqueous solvent (H) Is preferably 0.01 to 10% by weight, and more preferably 0.05 to 1% by weight, based on the total weight.
The content of the electrolyte (G) is preferably based on the total weight of the secondary battery additive (B), the electrolyte (G) and the nonaqueous solvent (H) from the viewpoint of battery output and charge / discharge cycle characteristics. It is 0.1-30 weight%, More preferably, it is 0.5-20 weight%.
The content of the nonaqueous solvent (H) is based on the total weight of the secondary battery additive (B), the electrolyte (G) and the nonaqueous solvent (H) from the viewpoint of battery output and charge / discharge cycle characteristics. Preferably it is 60 to 99 weight%, More preferably, it is 85 to 95 weight%.

The electrolytic solution of the present invention may further contain additives such as an overcharge inhibitor, a dehydrating agent and a capacity stabilizer.
Examples of the overcharge inhibitor include biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, aromatic compounds such as cyclohexylbenzene, t-butylbenzene, and t-amylbenzene. The amount of the overcharge inhibitor used is usually 0 to 5% by weight, preferably 0.5 to 5% based on the total weight of the secondary battery additive (B), electrolyte (G) and nonaqueous solvent (H). 3% by weight.

  Examples of the dehydrating agent include zeolite, silica gel and calcium oxide. The amount of the dehydrating agent used is usually 0 to 5% by weight, preferably 0.5 to 3% by weight, based on the total weight of the secondary battery additive (B), electrolyte (G) and non-aqueous solvent (H). %.

  Examples of the capacity stabilizer include fluoroethylene carbonate, succinic anhydride, 1-methyl-2-piperidone, heptane, and fluorobenzene. The amount of the capacity stabilizer used is usually 0 to 5% by weight, preferably 0.5 to 5%, based on the total weight of the secondary battery additive (B), electrolyte (G) and nonaqueous solvent (H). 3% by weight.

  The lithium ion battery of the present invention is a method of using the electrode of the present invention as a positive electrode or a negative electrode when an electrolyte is injected into a battery can containing a positive electrode, a negative electrode, and a separator to seal the battery can. It can be obtained by the method using the electrolytic solution of the invention and the method using these together.

  Examples of separators include microporous films made of polyethylene or polypropylene films, multilayer films of porous polyethylene films and polypropylene, non-woven fabrics made of polyester fibers, aramid fibers, glass fibers, and the like, and silica, alumina, titania, etc. on their surfaces. The thing to which ceramic fine particles were made to adhere is mentioned.

  As the battery can, metal materials such as stainless steel, iron, aluminum, and nickel-plated steel can be used, but plastic materials can also be used depending on the battery application. Further, the battery can can be formed into a cylindrical shape, a coin shape, a square shape, or any other shape depending on the application.

  The lithium ion capacitor of the present invention can be obtained by replacing the positive electrode with a positive electrode for a lithium ion capacitor and replacing the battery can with a capacitor can in the basic configuration of the lithium ion battery of the present invention. Examples of the material and shape of the capacitor can include the same as those exemplified for the battery can.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1>
A thermometer, a heating / cooling device, a stirrer and a dropping cylinder were prepared. In a pressure resistant reactor, 132 parts of lithium isethionate and 1.3 parts of potassium hydroxide were added, sealed with nitrogen, sealed and heated to 100 ° C., then decompressed to 0.5 kPa and stirred for 1 hour. Next, the temperature was raised to 150 ° C., 88 parts of ethylene oxide was added dropwise over 5 hours while adjusting the pressure to be 0.5 MPaG or less, and then aged for 3 hours at the same temperature to give an ethylene oxide 2 mol adduct of lithium isethionate. Got.

<Example 1>
Synthesis of Compound (A-1) In a flask equipped with a stirrer, a thermometer and a condenser tube, 14.6 parts of 1,3-bis (3-hydroxypropyl) tetramethyldisiloxane, 14.6 parts of cyclohexyl isocyanate, toluene 200 parts and 0.1 part of tris (2-ethylhexanoic acid) bismuth were charged and heated at 80 ° C. for 8 hours. Toluene was removed under reduced pressure (1.3 kPa) to obtain 25.3 parts of compound (A-1) represented by the following chemical formula (10). The compound (A-1) was used as the secondary battery additive (B-1).

<Example 2>
Synthesis of Compound (A-2) 14.5 parts of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were used instead of 14.6 parts of 1,3-bis (3-hydroxypropyl) tetramethyldisiloxane. Except having used, it carried out similarly to Example 1 and obtained 21.5 parts of compounds (A-2) shown by following Chemical formula (11). The compound (A-2) was used as the secondary battery additive (B-2).

<Example 3>
Synthesis of Compound (A-2) 16.5 parts of 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane was used instead of 14.6 parts of 1,3-bis (3-hydroxypropyl) tetramethyldisiloxane. Except having used, it carried out similarly to Example 1 and obtained 25.8 parts of compounds (A-3) shown by following Chemical formula (12). The compound (A-3) was used as the secondary battery additive (B-3).

<Example 4>
Synthesis of Compound (A-4) 7.3 parts of 1,3-bis (3-hydroxypropyl) tetramethyldisiloxane, 13.0 parts of isophorone diisocyanate, toluene in a flask equipped with a stirrer, thermometer and condenser 200 parts and 0.1 part of tris (2-ethylhexanoic acid) bismuth were charged and heated at 80 ° C. for 8 hours. Thereafter, 3.3 parts of propargyl alcohol was added, and the mixture was further heated at 80 ° C. for 5 hours. Toluene was removed under reduced pressure (1.3 kPa) to obtain 20.1 parts of compound (A-4) represented by the following chemical formula (13). The compound (A-4) was used as an additive (B-4) for a secondary battery.

<Example 5>
Synthesis of Compound (A-5) Compound (A-5) represented by the following chemical formula (14) was prepared in the same manner as in Example 4 except that 4.1 parts of ethylene cyanohydrin was used instead of 3.3 parts of propargyl alcohol. 19.3 parts were obtained. Compound (A-5) was used as an additive for secondary battery (B-5).

<Example 6>
Synthesis of Compound (A-6) A compound represented by the following chemical formula (15) was prepared in the same manner as in Example 4 except that 12.8 parts of triethylene glycol monomethyl ether was used instead of 3.3 parts of propargyl alcohol. -6) 25.9 parts were obtained. Compound (A-6) was used as an additive for secondary battery (B-6).

<Example 7>
Synthesis of Compound (A-7) Compound (A-7) represented by the following chemical formula (16) was prepared in the same manner as in Example 4 except that 7.7 parts of lithium isethionate was used instead of 3.3 parts of propargyl alcohol. ) 22.8 parts were obtained. The compound (A-7) was used as the secondary battery additive (B-7).

<Example 8>
Synthesis of Compound (A-8) The same procedure as in Example 4 was conducted except that 12.8 parts of ethylene oxide 2 mol adduct of lithium isethionate prepared in Preparation Example 1 was used instead of 3.3 parts of propargyl alcohol. 24.3 parts of a compound (A-8) represented by the following chemical formula (17) was obtained. Compound (A-8) was used as an additive for secondary batteries (B-8).

<Example 9>
Synthesis of Compound (A-9) Silicone oil having a side chain modified with carbinol instead of 14.6 parts of 1,3-bis (3-hydroxypropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22) 4039) Performed in the same manner as in Example 1 except that 10.0 parts of cyclohexyl isocyanate was changed to 1.2 parts. Compound (A-9) 11 having a urethane bond in the side chain and a siloxane bond in the main skeleton .2 parts were obtained. Compound (A-9) was used as an additive for secondary battery (B-9).

<Comparative Example 1>
Decamethyltetrasiloxane was used as a comparative compound (A′-1) and a comparative additive (B′-1).

<Comparative example 2>
Synthesis of Comparative Compound (A′-2) The same procedure as in Example 1 was carried out except that 4.5 parts of butanol was used instead of 3.4 parts of 2-propyn-1-ol. 11.1 parts of compound (A′-2) was obtained. The compound (A′-2) was used as a comparative additive (B′-2).

<Comparative Example 3>
Vinylene carbonate was used as a comparative compound (A′-3) as a comparative additive (B′-3).

<Comparative example 4>
1,3-propane sultone was used as a comparative compound (A′-4) and a comparative additive (B′-4).

Table 1 summarizes the secondary battery additive (B) of the example and the comparative additive (B ′) of the comparative example.
Regarding “presence / absence of alkyleneoxy group” and “presence / absence of group represented by general formula (10)”, “◯” is indicated when the compound has these groups, and “−” is indicated when the compound does not exist. Shown respectively.

<Examples 10 to 19 and Comparative Examples 5 to 9>
A lithium ion battery electrode containing the above-mentioned secondary battery additive (B) or comparative additive (B ′) in the number of parts shown in Table 2 was prepared by the following method, and the electrode was used. A lithium ion battery was produced by the following method. About the lithium ion battery using the produced electrode, the high voltage charging / discharging cycle characteristics, the output characteristics, and the gas generation characteristics were evaluated by the following methods. The results are shown in Table 2.

[Production of positive electrode for lithium ion battery]
9 parts by weight of LiCoO 2 powder, 5 parts by Ketjen Black [manufactured by Sigma-Aldrich Co., Ltd.], 5 parts by polyvinylidene fluoride [manufactured by Sigma-Aldrich Co., Ltd.] and the number of parts shown in Table 2 (B) or (B ′) After fully mixing with a mortar, 70.0 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further mixed well with a mortar to obtain a slurry. The obtained slurry was applied to one side of an aluminum electrolytic foil having a thickness of 20 μm using a wire bar in the air, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. It was dried for 2 hours and punched out to 15.95 mmφ to produce positive electrodes for lithium ion batteries of Examples 10 to 19 and Comparative Examples 5 to 9.

[Production of negative electrode for lithium ion battery]
92.5 parts of graphite powder having an average particle diameter of about 8 to 12 μm, 7.5 parts of polyvinylidene fluoride, 200 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] and the number of parts shown in Table 2 ( B) was thoroughly mixed in a mortar to obtain a slurry. The obtained slurry was applied to one side of a 20 μm-thick copper foil in the air using a wire bar, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. for 2 hours. It dried, punched to 16.15 mmphi, and made the thickness of 3 micrometers with the press machine, and produced the negative electrode for lithium ion batteries of Examples 10-19 and Comparative Examples 5-9.

[Production of lithium-ion batteries]
The positive electrode and the negative electrode of Examples 10 to 19 and Comparative Examples 5 to 9 are arranged at both ends in the 2032 type coin cell so that the coated surfaces face each other, and a separator (polypropylene non-woven fabric) is inserted between the electrodes. An ion battery cell was produced. The solution was poured and sealed in a cell in which an electrolytic solution was prepared by dissolving LiPF ₆ in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) at a ratio of 12 wt%. The results of evaluating the high voltage charge / discharge cycle characteristics by the following method are shown in Table 2.

<Evaluation of high voltage charge / discharge cycle characteristics>
Using a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.], the battery voltage is charged at 0.1 C current to a voltage of 4.5 V, and after 10 minutes of rest, the battery voltage at 0.1 C current Was discharged to 3.5 V, and this charge / discharge was repeated. At this time, the battery capacity at the first charge and the battery capacity at the 50th cycle charge were measured, and the charge / discharge cycle characteristics were calculated from the following formula. It shows that charging / discharging cycling characteristics are so favorable that a numerical value is large.
High voltage charge / discharge cycle characteristics (%) = (battery capacity at the 50th cycle charge / battery capacity at the first charge) × 100

<Evaluation of output characteristics>
Using a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.], charge to a voltage of 4.5 V with a current of 0.1 C, and after a pause of 10 minutes, apply a voltage with a current of 0.1 C The battery was discharged to 3.5 V, and the discharge capacity (hereinafter referred to as 0.1 C discharge capacity) was measured. Next, the battery was charged to a voltage of 4.5 V with a current of 0.1 C, and after 10 minutes of rest, the voltage was discharged to 3.5 V with a current of 1 C, and the capacity (hereinafter referred to as 1 C discharge capacity) was measured. The capacity retention rate during 1 C discharge was calculated and listed in Table 2 as output characteristics (%). The larger the value, the better the output characteristics.
Capacity maintenance rate during 1 C discharge (%) = (1 C discharge capacity / 0.1 C discharge capacity) × 100

<Evaluation of gas generation characteristics>
The positive electrode and the negative electrode of Examples 10 to 19 and Comparative Examples 5 to 9 were placed in a laminate cell so that the coated surfaces face each other, and a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1) 1), an electrolyte solution in which LiPF6 was dissolved at a ratio of 12% by weight was injected and sealed, the cell thickness was measured, and this value was taken as the initial thickness.
Using a charge / discharge measuring device “Battery Analyzer 1470 type” [manufactured by Toyo Technica Co., Ltd.], charge to a voltage of 4.5 V with a current of 0.1 C, and after a pause of 10 minutes, a voltage of 3 with a current of 0.1 C The cycle of discharging to 5 V was repeated three times. Further, the battery was charged to a voltage of 4.5 V with a current of 0.1 C, and stored at 60 ° C. for 7 days while maintaining the voltage. Then, the thickness of the cell was measured and set as the post-measurement thickness. Using the values of the initial thickness and the thickness after measurement, the thickness increase rate (gas generation characteristics) was obtained from the following formula. The smaller the thickness increase rate, the greater the effect of suppressing gas generation.
Thickness increase rate (%) = (Thickness after measurement / Initial thickness) × 100

<Examples 20 to 26, Comparative Examples 10 to 14>
Lithium ion battery electrolyte containing the above-mentioned secondary battery additive (B) or comparative additive (B ′) in the number of parts shown in Table 2 was prepared by the following method, and lithium was used. An ion battery was produced by the following method. About the lithium ion battery using the produced electrolyte solution, the high voltage charging / discharging cycle characteristics and the output characteristics were evaluated by the above methods, the gas generation characteristics were evaluated by the following methods, and the results are shown in Table 3.

[Preparation of electrolyte]
87.5 parts of a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) is blended with (B) or (B ′) in the number of parts shown in Table 2, and the electrolyte is 12% by weight. LiPF ₆ was dissolved, and electrolytic solutions of Examples 20 to 26 and Comparative Examples 10 to 14 were prepared.

[Production of positive electrode for lithium ion battery]
After 90.0 parts of LiCoO2 powder, 5 parts of Ketjen black [Sigma-Aldrich] and 5 parts of polyvinylidene fluoride [Sigma-Aldrich] were thoroughly mixed in a mortar, 1-methyl-2-pyrrolidone [Tokyo Chemical Industry Co., Ltd.] Made by Co., Ltd.] 70.0 parts was added, and further mixed well in a mortar to obtain a slurry. The obtained slurry was applied to one side of an aluminum electrolytic foil having a thickness of 20 μm using a wire bar in the air, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. It was dried for 2 hours and punched out to 15.95 mmφ to produce a positive electrode for a lithium ion battery.

[Production of negative electrode for lithium ion battery]
A slurry was obtained by thoroughly mixing 92.5 parts of graphite powder having an average particle size of about 8 to 12 μm, 7.5 parts of polyvinylidene fluoride and 200 parts of 1-methyl-2-pyrrolidone in a mortar. The obtained slurry was applied to one side of a 20 μm-thick copper foil in the air using a wire bar, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. for 2 hours. It was dried, punched to 16.15 mmφ, and made 3 μm thick with a press machine to produce a graphite-based negative electrode for lithium ion batteries.

[Production of lithium-ion batteries]
The above-described positive electrode and negative electrode are arranged at both ends in a 2032 type coin cell so that the respective coated surfaces face each other, and a separator (non-woven fabric made of polypropylene) is inserted between the electrodes to produce a cell for a lithium ion battery. The electrolyte solutions 20 to 26 and Comparative Examples 10 to 14 were poured into the prepared lithium ion battery cells and sealed to prepare secondary batteries.

<Evaluation of gas generation>
The positive electrode and the negative electrode are placed in the laminate cell so that the coated surfaces face each other, the electrolytes of Examples 20 to 26 and Comparative Examples 10 to 14 are injected and sealed, the cell thickness is measured, and the initial thickness Say it. Using a charge / discharge measuring device “Battery Analyzer 1470 type” [manufactured by Toyo Technica Co., Ltd.], charge to a voltage of 4.5 V with a current of 0.1 C, and after a pause of 10 minutes, a voltage of 3 with a current of 0.1 C The cycle of discharging to 0 V was repeated three times. Further, the battery was charged to a voltage of 4.5 V with a current of 0.1 C, and stored at 60 ° C. for 7 days while maintaining the voltage. Then, the thickness of the cell was measured and set as the post-measurement thickness. Using the values of the initial thickness and the thickness after measurement, the thickness increase rate (gas generation characteristics) was obtained from the following formula. The smaller the thickness increase rate, the greater the effect of suppressing gas generation.
Thickness increase rate (%) = (Thickness after measurement / Initial thickness) × 100-100

<Examples 27 to 36, Comparative Examples 15 to 19>
An electrode for a lithium ion capacitor containing the additive for secondary battery (B) or additive for comparative secondary battery (B ′) in the number of parts shown in Table 4 was prepared by the following method, and the electrode was prepared. A lithium ion capacitor was prepared by the following method. About the lithium ion capacitor using the produced electrode, the high voltage charging / discharging cycle characteristic, the output characteristic, and the gas generation characteristic were evaluated by the following methods, and the results are shown in Table 4.

[Production of positive electrode for lithium ion capacitor]
Activated carbon powder 90.0 parts, Ketjen black [Sigma-Aldrich] 5.0 parts, polyvinylidene fluoride [Sigma-Aldrich] 5.0 parts and the number of parts shown in Table 4 (B) or (B ′) After fully mixing with a mortar, 70.0 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further mixed well with a mortar to obtain a slurry. The obtained slurry was applied to one side of an aluminum electrolytic foil having a thickness of 20 μm using a wire bar in the air, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. It was dried for 2 hours and punched out to 15.95 mmφ to produce a positive electrode for a lithium ion capacitor.

[Production of negative electrode for lithium ion capacitor]
92.5 parts of graphite powder having an average particle size of about 8 to 12 μm, 7.5 parts of polyvinylidene fluoride, 200 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] and the parts shown in Table 4 ( B) was thoroughly mixed in a mortar to obtain a slurry. The obtained slurry was applied to one side of a 20 μm thick copper foil, dried at 80 ° C. for 1 hour, and further dried under reduced pressure (1.3 kPa) at 80 ° C. for 2 hours to 16.15 mmφ. Punched out and made 30 μm thick with a press. The obtained electrode and lithium metal foil are sandwiched between separators (polypropylene nonwoven fabric) and set in a beaker cell, and about 75% of the negative electrode theoretical capacity of lithium ions is occluded in the negative electrode over about 10 hours. A negative electrode was prepared.

[Production of lithium ion capacitors]
In a storage case made of an aluminum laminate film of polypropylene, the positive electrodes and negative electrodes of Examples 27 to 36 and Comparative Examples 15 to 19 are arranged so that the respective application surfaces face each other, and a separator (nonwoven fabric made of polypropylene) is placed between the electrodes. The capacitor cell was prepared by inserting. The solution was injected and sealed in a cell in which an electrolytic solution in which LiPF6 was dissolved in a proportion of 12% by weight in propylene carbonate (PC) was produced.

<Evaluation of high voltage charge / discharge cycle characteristics>
Using a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.], the battery is charged to a voltage of 3.8 V with a current of 1 C, discharged after a pause of 10 minutes to a voltage of 2.0 V with a current of 1 C. This charge / discharge was repeated. At this time, the battery capacity at the first charge and the battery capacity at the 50th cycle charge were measured, and the charge / discharge cycle characteristics were calculated from the following formula. It shows that charging / discharging cycling characteristics are so favorable that a numerical value is large.
High voltage charge / discharge cycle characteristics (%) = (battery capacity at the 50th cycle charge / battery capacity at the first charge) × 100

<Evaluation of capacitor output characteristics>
Charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.] is charged to a voltage of 3.8 V with a current of 1 C, and after a pause of 10 minutes, the voltage is increased to 1.0 V with a current of 1 C. After discharging, the discharge capacity (hereinafter referred to as 1C discharge capacity) was measured. Next, the battery is charged to a voltage of 3.8 V with a current of 1 C, and after a pause of 10 minutes, the voltage is discharged to 2.0 V with a current of 10 C, and the capacity (hereinafter referred to as 10 C discharge capacity) is measured. The capacity retention ratio at the time was calculated and listed in Table 4 as output characteristics (%). The larger the value, the better the output characteristics.
Capacity maintenance rate during 10C discharge (%) = (10C discharge capacity / 1C discharge capacity) × 100

<Evaluation of gas generation characteristics>
The thickness of the laminate cell produced by the above method was measured and used as the initial thickness. Using a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.], the battery is charged to a voltage of 3.8 V with a current of 1 C, discharged after a pause of 10 minutes to a voltage of 2.0 V with a current of 1 C. did. The battery was further charged to a voltage of 3.8 V with a current of 1 C, and stored at 60 ° C. for 7 days while maintaining the voltage. Then, the thickness of the cell was measured and set as the post-measurement thickness. Using the values of the initial thickness and the thickness after measurement, the thickness increase rate (gas generation characteristics) was obtained from the following formula. The smaller the thickness increase rate, the greater the effect of suppressing gas generation.
Thickness increase rate (%) = (Thickness after measurement / Initial thickness) × 100-100

<Examples 37 to 43, Comparative Examples 20 to 24>
An electrolyte for a lithium ion capacitor containing the above-mentioned secondary battery additive (B) or comparative additive (B ′) in the number of parts shown in Table 3 was prepared by the following method. The used lithium ion capacitor was produced by the following method. About the lithium ion capacitor using the produced electrolyte solution, the high voltage charging / discharging cycle characteristic, the output characteristic, and the gas generation characteristic were evaluated by the above-mentioned method, and the results are shown in Table 5.

[Preparation of electrolyte]
In a non-aqueous solvent consisting of 87.5 parts of propylene carbonate, the additive for secondary battery (B) was blended in the number of parts shown in Table 5, and LiPF6 as an electrolyte was dissolved therein so as to be 12% by weight, The electrolyte solutions of Examples 37 to 43 and Comparative Examples 20 to 24 were prepared.

[Production of positive electrode]
As the positive electrode active material, activated carbon having a specific surface area of about 2200 m 2 / g obtained by an alkali activation method was used. Activated carbon powder, acetylene black, and polyvinylidene fluoride are mixed in a weight ratio of 80:10:10, and this mixture is added to 1-methyl-2-pyrrolidone as a solvent and mixed by stirring. To obtain a slurry. This slurry was applied onto an aluminum foil having a thickness of 30 μm by a doctor blade method, temporarily dried, and then cut so that the electrode size was 20 mm × 30 mm. The electrode thickness was about 50 μm. Before assembling the cell, it was dried in a vacuum at 120 ° C. for 10 hours to produce a positive electrode for a lithium ion capacitor.

[Production of negative electrode]
80 parts of graphite powder having an average particle size of about 8 to 12 μm, 10 parts of acetylene black, and 10 parts of polyvinylidene fluoride are mixed, and this mixture is added to 1-methyl-2-pyrrolidone as a solvent and mixed by stirring. Got. This slurry was applied onto a copper foil having a thickness of 18 μm by a doctor blade method and temporarily dried, and then cut so that the electrode size was 20 mm × 30 mm. The electrode thickness was about 50 μm. Further, it was dried in vacuum at 120 ° C. for 5 hours. The obtained electrode and lithium metal foil are sandwiched between separators (polypropylene nonwoven fabric) and set in a beaker cell, and about 75% of the negative electrode theoretical capacity of lithium ions is occluded in the negative electrode over about 10 hours. A negative electrode was prepared.

[Assembly of capacitor cell]
A separator (polypropylene nonwoven fabric) is inserted between the positive electrode and the negative electrode, impregnated with the electrolytic solutions of Examples 37 to 43 and Comparative Examples 20 to 24, and placed in a storage case made of a polypropylene aluminum laminate film. Sealed to produce a lithium ion capacitor cell.

The lithium ion battery and lithium ion capacitor produced using the secondary battery additive (B) of the present invention are found to have excellent charge / discharge cycle performance and gas generation characteristics from the results of the above Examples and Comparative Examples. It was. Since the compound having the group and the siloxane bond (b) at the same time is superior to the compound having each independently, it is considered that these synergistic effects worked effectively (Examples 10 to 12, Comparative Examples 1 and 2). etc). It is presumed that the high polar group promoted the adsorption to the active material surface and formed a protective film having a strong bond (b) on the electrode. The effect of the compound (B-9) in which a urethane group is introduced into carbinol-modified silicone oil suggests a synergistic effect of the group and the bond (b) (Example 19).
Moreover, it turned out that what has a bond represented by an alkyleneoxy group and general formula (3)-(6) in a molecule | numerator is more excellent in cycling characteristics and output characteristics (Examples 4-8).

The electrode and electrolyte using the secondary battery additive (B) of the present invention are useful for electrochemical devices such as lithium ion batteries and thium ion capacitors, and particularly for lithium ion batteries and lithium ion capacitors for electric vehicles. Is preferred. Moreover, it is applicable also to electrochemical devices (electric double layer capacitor, nickel metal hydride battery, nickel cadmium battery, air battery, alkaline battery, etc.) other than those disclosed in the present invention.

Claims (9)

A secondary battery additive (B) containing a compound (A) having a group represented by the following general formula (1) and a group represented by the following general formula (2).

[In Formula (1), R is a hydrogen atom or a C1-C12 organic group. ]

[In the formula (2), R ¹ and R ² are a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms or a hydrogen atom having 1 to 20 carbon atoms which may be substituted with a functional group containing a hetero atom. When there are a plurality of hydrocarbon groups, R ¹ and R ² may be the same or different. n is an integer of 1 to 300. ]   The additive for secondary batteries according to claim 1, wherein the group represented by the general formula (1) is a group contained in at least one group selected from the group consisting of a urethane group, a urea group, and a thiourethane group. ).   The additive (B) for secondary batteries according to claim 1 or 2, wherein the compound (A) further has an alkyleneoxy group (c). The additive for secondary batteries according to any one of claims 1 to 3, wherein the compound (A) has the alkyleneoxy group (c) as a structural unit represented by the following general formulas (3) to (5). (B).

[In Formula (3), L ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of L ^{1 s} , L ¹ may be the same or different, and L ² is an alkylene group having 1 to 10 carbon atoms. A divalent hydrocarbon group, L ³ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a functional group containing a hetero atom, and h is an integer of 1 to 40 It is. ]

[In Formula (4), P ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of P ^{1 s} , each P ¹ may be the same or different, and P ² has 1 to 10 carbon atoms. It is a bivalent hydrocarbon group, i is an integer of 1-40. ]

[In Formula (5), W ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of W ^{1 s} , they may be the same or different, and W ² is an alkylene group having 1 to 20 carbon atoms. It is a hydrocarbon group, k is an integer of 1-40. ] The additive for secondary batteries according to any one of claims 1 to 4, wherein the compound (A) further has a group represented by the following general formula (6).

[In Formula (6), Q ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of Q ^{1 s} , Q ¹ may be the same or different, and Q ² is an alkylene group having 1 to 10 carbon atoms. A divalent hydrocarbon group, A is —CO ₂ ^— or —SO ₃ ^— , M is a monovalent metal ion, j is an integer of 0 to 40, and m is 0 or 1. . ]   The electrode containing the additive (B) for secondary batteries of any one of Claims 1-5.   The electrolyte solution containing the additive (B) for secondary batteries of any one of Claims 1-5.   A lithium ion battery comprising the electrode according to claim 6 and / or the electrolytic solution according to claim 7.   A lithium ion capacitor having the electrode according to claim 6 and / or the electrolytic solution according to claim 7.