JPWO2015163254A1 - Battery additives, electrodes, electrolytes and electrochemical devices - Google Patents

Abstract

The use of the electrode or electrolyte containing the battery additive (B) of the present invention aims to improve the cycle characteristics and output characteristics of the electrochemical device. The additive for battery (B) of the present invention is composed of 3 to 5 atoms, has 2 to 4 atoms having an electronegativity of 3 or more, and has at least one non-polymerizable double bond. It contains the compound (A) having an atomic group (X) and an ionic dissociative functional group (b) and having no polymerizable unsaturated bond.

Description

  The present invention relates to a battery additive, an electrode and an electrolytic solution containing the battery additive, and an electrochemical device having at least one of the electrode and the electrolytic solution.

  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, etc., for portable terminals such as mobile phones and notebook computers. The position as a standard battery has been established. While its uses are expanding, application to hybrid vehicles, electric vehicles, etc. in addition to conventional uses is also being studied, and some have already been put into practical use. In order to further spread these, there is a demand for higher performance of secondary batteries, and application of various technologies has been attempted.

In order to improve the performance of a lithium ion battery, a technique is known in which an additive for forming SEI (Solid Electrolyte Interface) is added to an electrolytic solution. For example, vinylene carbonate (VC), fluoroethylene carbonate (FEC), and 1,3-propane sultone (PS) are known to form SEI on the negative electrode (for example, Patent Documents 1 to 3), and vinyl ether compounds are It is known to form SEI on the positive electrode (Patent Document 4). In addition, the inventors have found that a compound having a polymerizable unsaturated bond is effective for the formation of SEI (Patent Document 5).
Since the battery characteristics greatly change due to the presence of SEI, it can be said that the control of these SEIs is a very important technique in determining the battery performance.

JP 2005-174867 A JP 2013-16517 A International Publication No. 2013/150937 JP2013-26180A International Publication No. 2014/006845

However, among the additives described in Patent Documents 1 to 3, VC and FEC form SEI at the negative electrode, but cannot form good SEI at the positive electrode, and PS is said to form good SEI at the positive electrode. However, the effect is not sufficient. In addition, the vinyl ether compound described in Patent Document 4 is cationically polymerizable, so SEI is formed at the positive electrode, but SEI with low ion conductivity is excessively formed, so that the resistance increases, resulting in output characteristics and battery characteristics at low temperatures. There was a problem of being inferior. Although the compound having a polymerizable unsaturated bond and a urethane bond described in Patent Document 5 is effective in improving the cycle characteristics, there is a problem that the output characteristics do not have an improving effect. The present invention has been made in view of these problems.
That is, an object of the present invention is to provide an additive for a battery that can form SEI excellent in ion conductivity on an electrode and can obtain an electrochemical device excellent in 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 comprises an atomic group (X) composed of 3 to 5 atoms, having 2 to 4 atoms having an electronegativity of 3 or more, and having at least one non-polymerizable double bond, and A battery additive (B) containing a compound (A) having an ion dissociative functional group (b) and having no polymerizable unsaturated bond; an electrode containing the battery additive (B); An electrolytic solution containing the battery additive (B); an electrochemical device having at least one of the electrode and the electrolytic solution.

  By using the electrode or electrolyte containing the battery additive (B) of the present invention, the cycle characteristics and output characteristics of the electrochemical device can be improved.

The additive for battery (B) of the present invention is composed of 3 to 5 atoms, has 2 to 4 atoms having an electronegativity of 3 or more, and has at least one non-polymerizable double bond. A compound (A) having an atomic group (X) and an ion dissociable functional group (b) and having no polymerizable unsaturated bond is contained.
The compound (A) may have two or more atomic groups (X) in one molecule. When the compound (A) has two or more atomic groups (X) in one molecule, they may all be the same or different. Moreover, the compound (A) may have two or more ion dissociable functional groups (b) in one molecule. When the compound (A) has two or more ion dissociable functional groups (b) in one molecule, they may all be the same or different.
1-5 are preferable and, as for the ion dissociative functional group (b) which a compound (A) has in 1 molecule, 1-3 are more preferable.

The atomic group (X) is composed of 3 to 5 atoms, has 2 to 4 atoms having an electronegativity of 3 or more, and has at least one non-polymerizable double bond.
Examples of the atoms constituting the atomic group (X) include typical elements. From the viewpoint of battery characteristics, a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a fluorine atom, a sulfur atom, a phosphorus atom, and a chlorine atom are preferable. A hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom are more preferable, and a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom are still more preferable. The atoms constituting the atomic group (X) may be one kind, two or more kinds, and preferably composed of two or more kinds of atoms.

  The number of atoms constituting the atomic group (X) is 3 to 5, but is preferably 3 from the viewpoint of battery characteristics.

  Examples of the atom having an electronegativity of 3 or more in the atomic group (X) include an oxygen atom, a nitrogen atom, a fluorine atom and a chlorine atom, and among these, an oxygen atom and a nitrogen atom are preferable from the viewpoint of cycle characteristics.

  The number of atoms having an electronegativity of 3 or more in the atomic group (X) is 2 to 4, and is preferably 2 from the viewpoint of battery characteristics and the like.

Electronegativity represents the tendency of atoms to attract electrons. In the present invention, it means the electronegativity defined by Pauling, and the value of electronegativity defined by Pauling is L.P. It is described in "The Nature of the Chemical Bond" (1960) by Pauling.
Since active materials used in electrochemical devices such as non-aqueous electrolyte secondary batteries contain highly polar atoms such as oxygen atoms, there are portions where electrons are biased. The battery additive (B) of the present invention interacts with an atom having a high electronegativity (an atom having an electronegativity of 3 or more) and an electron-biased portion of the active material. It is considered that high output characteristics and the like are manifested by adsorption of the agent (B) to the active material.

Compound (A) does not have a polymerizable unsaturated bond. This is because, when a polymerizable unsaturated bond is present, SEI is formed on the electrode, which causes a problem that the film thickness of SEI increases and the electrode resistance increases.
The polymerizable unsaturated bond in the present invention means a carbon-carbon double bond, a carbon-carbon triple bond, and a carbon-nitrogen triple bond.
Specific examples of the functional group having a polymerizable unsaturated bond include allyl group, methylallyl group, dimethylallyl group, acryloyl group, methacryloyl group, propargyl group, cyano group, and styryl group. In addition, the carbon-carbon double bond which comprises an aromatic compound among carbon-carbon double bonds is not contained in the polymerizable unsaturated bond said by this invention.

Preferable examples of the atomic group (X) include groups (bonds) represented by any of the following chemical formulas (1) to (5). In the present invention, the atomic group (X) is preferably at least one group represented by any one of the following chemical formulas (1) to (5).

The atomic group represented by the chemical formula (1) is included in an amide group, a urethane group, a urea group, an allophanate group, a biuret group, and the like.
The amide group can be generated by a dehydration condensation reaction between a carboxyl group and an amino group, the urethane group can be generated by an addition reaction between an isocyanate group and a hydroxyl group, and a urea group is a reaction between an isocyanate group and water and an isocyanate. Can be generated by the reaction of a group with an amino group or an imino group, an allophanate group can be generated by an addition reaction of an isocyanate group to a urethane group, and a biuret group can be an addition reaction of an isocyanate group to a urea group. Can be generated.

  The atomic group represented by the chemical formula (2) is contained in the ester group, and can be generated by a dehydration condensation reaction between a carboxyl group and a hydroxyl group, a ring-opening addition reaction of the hydroxyl group to an acid anhydride group, or the like.

  The atomic group represented by the chemical formula (3) can be generated by oxidizing the sulfide with an oxidizing agent.

  The atomic group represented by the chemical formula (4) can be generated by a dehydration condensation reaction between phosphoric acid and a hydroxyl group and a condensation reaction between a phosphate compound and a hydroxyl group.

  The atomic group represented by the chemical formula (5) is contained in the isocyanate group and can be generated by reacting a primary amine with phosgene.

  Each group represented by the chemical formulas (1) to (5) can be introduced into the compound (A) by, for example, the above reaction.

As the atomic group (X), the group represented by the chemical formula (1) is preferably a group introduced by a group represented by the following general formula (6). The group represented by the chemical formula (1) is preferably a group contained in the group represented by the following general formula (6). For example, the group represented by the chemical formula (1) is represented by the following general formula: It is preferable that it is a group represented by (6) or constitutes a part of a group represented by the following general formula (6).

In general formula (6), R is a hydrogen atom or a C1-C12 organic group.
Examples of the organic group having 1 to 12 carbon atoms include an aliphatic hydrocarbon group having 1 to 12 carbon atoms [chain aliphatic hydrocarbon group having 1 to 12 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, 2-ethylhexyl group Xyl group, nonyl group, decyl group, dodecyl group and the like), alicyclic hydrocarbon group having 3 to 12 carbon atoms (such as cyclohexyl group and cyclopentyl group)], and aromatic hydrocarbon group having 6 to 12 carbon atoms (benzyl group) , Phenyl groups, methylphenyl groups, biphenyl groups, naphthyl groups, etc.) and groups in which these hydrogen atoms are substituted with functional groups containing hetero atoms (amino groups, alkylamino groups, dialkylamino groups, alkylthio groups, etc.) Can be mentioned.
Among these, from the viewpoint of battery output characteristics, R is preferably a hydrogen atom and an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms. A hydrogen atom is more preferable. In the general formula (6), when R is a hydrogen atom, the group represented by the chemical formula (1) is a group represented by the general formula (6). In the general formula (6), when R is an organic group having 1 to 12 carbon atoms, the group represented by the chemical formula (1) constitutes a part of the group represented by the general formula (6). To do. As an example of a preferable embodiment of the compound (A) having the atomic group (X) and the ion dissociative functional group (b) and having no polymerizable unsaturated bond in the present invention, the compound represented by the general formula (6) is used. And a compound having an ion dissociable functional group (b) and having no polymerizable unsaturated bond.

The group represented by the general formula (6) is included in an amide group, a urethane group, a urea group, an allophanate group, a biuret group, and the like, and is selected from the group consisting of a urethane group, a urea group, an allophanate group, and a biuret group. It is preferably a group contained in at least one group, and more preferably a group contained in at least one group selected from the group consisting of a urethane group and a urea group. As the atomic group (X) in the present invention, a urethane group and a urea group are preferable.
The compound (A) preferably has at least one group selected from the group consisting of a urethane group, a urea group, an allophanate group and a biuret group, more preferably has a urethane group and / or a urea group. More preferably, it has a group or a urea group.

The ion dissociable functional group (b) of the compound (A) in the present invention is a monovalent functional group capable of dissociating into a cation and an anion in a solvent in which the compound (A) is dissolved. Preferred examples of the functional group (b) include those represented by the following general formula (7) and those in which the hydrogen atom on N in the urethane group is substituted with a monovalent metal ion. The ion dissociative functional group (b) is more preferably a group represented by the following general formula (7).

[In Formula (7), M is a monovalent metal ion, and A is —CO ₂ ^— or SO ₃ ^— . ]

In general formula (7), M is a monovalent metal ion. M is preferably an alkali metal ion such as lithium ion, sodium ion or potassium ion from the viewpoint of the output characteristics of the battery. A is —CO ₂ ^— or SO ₃ ^— .
In the urethane group in which the hydrogen atom on N is substituted with a monovalent metal ion, preferred metal ions include the same as M in the general formula (7).

  The compound (A) in the present invention preferably has 1 to 90 acceptors.

The number of acceptors is a scale representing electron acceptability, and can be evaluated by a chemical shift value of ³¹ P NMR.
The number of acceptors is triethylphosphine oxide pentachloride dissolved in 1,2-dichloroethane, with ³¹ P NMR chemical shift value of triethylphosphine oxide dissolved in nonpolar solvent such as hexane as 0. It is expressed as a relative value when the chemical shift value of ³¹ P NMR of the antimony complex is set to 100, and the larger the acceptor number, the higher the electron acceptability.
Acceptor numbers of organic solvent and water are N, N-dimethylformamide (16.0), benzonitrile (15.5), acetonitrile (18.9), dimethyl sulfoxide (19.3), nitromethane (20.5). , Chloroform (23.1), 2-propanol (33.5), ethanol (37.9), methanol (41.5) and water (54.8). Gutman (translated by Otsuki, Okada) “Donor and Acceptor” (Academic Publishing Center) provides details.
The number of acceptors of the compound (A) in the present invention is determined by the following method. Triethylphosphine oxide is dissolved in a solution obtained by dissolving the compound (A) in a nonpolar solvent such as hexane, and ³¹ P NMR is measured to record the chemical shift (δA) derived from triethylphosphine oxide. The chemical shift value of ³¹ P NMR of triethylphosphine oxide dissolved in hexane is δ0, and the chemical shift value of ³¹ P NMR of triethylphosphine oxide / antimony pentachloride complex dissolved in 1,2-dichloroethane is δ100. The number of acceptors in (A) is calculated.
Acceptor number = (δA−δ0) ÷ (δ100−δ0) × 100
The larger the number of acceptors, the higher the electron-accepting property and the greater the interaction with the active material constituting the electrode.
In the present invention, NMR measurement for determining the number of acceptors is performed using a commercially available nuclear magnetic resonance apparatus (for example, AVANCE-III, manufactured by BRUKER, etc.), and compound (A) is added to hexane at a concentration of 0.1% by weight. And a solution in which triethylphosphine oxide is dissolved so as to be 0.1% by weight can be used.

  The number of acceptors of the compound (A) is preferably 1 to 90, more preferably 2 to 80, and still more preferably 3 to 70, from the viewpoints of the adsorptivity to the active material and cycle characteristics.

The compound (A) preferably further has an alkyleneoxy group (c) from the viewpoint of the output characteristics of the battery. The alkyleneoxy group (c) is an alkyleneoxy group having 2 to 4 carbon atoms (ethyleneoxy group, 1,2-propyleneoxy group, 1,3-propyleneoxy group, 1,2-butyleneoxy group, and 1,4- 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, Of alkyleneoxy groups or 2 to 40 alkyleneoxy groups are preferably bonded together, more preferably 3 to 30 alkyleneoxy groups are bonded together. .
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 alkyleneoxy group (c) is preferably introduced into the compound (A) in the form of the general formula (8) or general formula (10) described below. That is, the compound (A) in the present invention preferably has a group represented by the following general formula (8) or a group represented by the general formula (10).

The compound (A) preferably has an atomic group (X) and an ion dissociable functional group (b) as a structural unit represented by the following general formula (8).

[In Formula (8), R ¹ is an alkylene group having 2 to 4 carbon atoms, and a plurality of R ¹ contained in the repeating unit may be the same or different. R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms. j is an integer of 0 to 20, and M and A are the same as those in the general formula (7). W represents an oxygen atom or an imino group. ]

In the general formula (8), ^{R 1} is an alkylene group having 2 to 4 carbon atoms. Specific examples thereof include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-, 2,3- or 1,3-butylene group, and tetramethylene group. Of these, particularly preferred as R ¹ are an ethylene group and a 1,2-propylene group. j is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.
R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a tetramethylene group, a hexamethylene group, and a decamethylene group. Of these, an ethylene group is preferably used. M and A in the general formula (8) are preferably the same as M and A in the general formula (7).

  The atomic group (X) of the structural unit represented by the general formula (8) is a urethane group, and the ion dissociable functional group (b) is an ion dissociable functional group represented by the general formula (7).

As the compound (A) used in the present invention, a compound represented by the following general formula (9) is preferably used.

[In Formula (9), R ³ is an (m + n) -valent residue obtained by removing an isocyanate group from an isocyanate compound, m is an integer of 1 to 4, and n is an integer of 0 to 3. When m is 1 and n is 0, Z is a group represented by the general formula (8). When m is 1 and n is an integer of 1 to 3, Z is a general formula (7). In the case where m is an integer of 2 or more, a plurality of Z's are the same or different and are each represented by the general formula (7). An ionic dissociative functional group represented by the general formula (8) or an isocyanate group, and at least one of a plurality of Zs represented by the general formula (7) It is group represented by (8). W represents an oxygen atom or an imino group, Y is a monovalent organic group, and has no polymerizable unsaturated bond. When n is an integer of 2 or more, a plurality of Ys may be the same or different. ]

In the general formula (9), R ³ is an (m + n) -valent residue obtained by removing an isocyanate group from an isocyanate compound. m is an integer of 1 to 4, and n is an integer of 0 to 3.
Specific examples of the isocyanate compound include monoisocyanate compounds having 2 to 20 carbon atoms (for example, ethyl isocyanate, butyl isocyanate, octyl isocyanate, dodecyl isocyanate, etc.), diisocyanate compounds having 4 to 20 carbon atoms (for example, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl). Methane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate and allophanate modified products of these diisocyanate compounds, triisocyanate compounds having 6 to 30 carbon atoms (for example, biuret modified products of diisocyanate compounds such as hexamethylene diisocyanate, hexamethylene diisocyanate) Isocyanurates of diisocyanate compounds such as DOO-modified, etc.) and modified products of these isocyanates compounds.

  In the general formula (9), Z is a group represented by the general formula (7), a group represented by the general formula (8), or an isocyanate group, and at least one is represented by the general formula (7) or (8). It is a group represented. When m is 1 and n is 0, Z is a group represented by the general formula (8). When m is 1 and n is an integer of 1 to 3, Z is a general formula (7). In the case where m is an integer of 2 or more, a plurality of Z's are the same or different and are each represented by the general formula (7). An ionic dissociative functional group represented by the general formula (8) or an isocyanate group, and at least one of a plurality of Zs represented by the general formula (7) It is group represented by (8). m being an integer of 2 or more means that m is an integer of 2 to 4.

  W represents an oxygen atom or an imino group. When there are a plurality of W in the compound (A), the plurality of Ws may be the same or different. As a case where there are a plurality of Ws in the compound (A), for example, when n is 2 or 3 in the above general formula (9); Z in which m is 2 or more and a plurality are represented by the general formula (8) A case where n is 1, and at least one of Z is a group represented by the general formula (8).

Y is a monovalent organic group and does not have a polymerizable unsaturated bond.
Specific examples of Y include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms (for example, a trifluoromethyl group, a perfluorocyclohexylmethyl group, and a 2,2,2-trifluoroethyl group). , 2,2,3,3-tetrafluoropropyl group and 1H, 1H, 7H-dodecafluoroheptyl group, etc.) and groups represented by the following general formula (10).
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl group). Propyl 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-dimethyl Propyl 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, 2-ethylhexyl group, nonyl group, decyl And alicyclic hydrocarbon groups having 3 to 20 carbon atoms (such as a cyclohexyl group and a cyclopentyl group).
Among these, from the viewpoint of battery characteristics, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a group represented by the following general formula (10) are preferably used, and a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms and A group represented by the following general formula (10) is more preferably used.

[In formula (10), R⁴Is an alkylene group having 2 to 4 carbon atoms and a plurality of Rs contained in the repeating unit⁴May be the same or different. k is an integer of 1 to 40, and R ⁵Is a C1-C20 hydrocarbon group or acetyl group. ]

In General Formula (10), R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, and when there are a plurality of R ^{4 s} , they may be the same or different. Examples of R ⁴ include the same ones as exemplified for the alkyleneoxy group (c), and preferred ones are also the same. Examples of R ⁴ include an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, and a 1,4-butylene group, and an ethylene group is preferable.
R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms or an acetyl group, and the hydrocarbon group having 1 to 20 carbon atoms is an aliphatic hydrocarbon group having 1 to 20 carbon atoms [chain structure having 1 to 20 carbon atoms]. Aliphatic 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-methylpro Pyryl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, 1-propylheptyl group, undecyl group, dodecyl group, etc.), alicyclic hydrocarbon group having 3 to 20 carbon atoms (Cyclohexyl group, cyclopentyl group, etc.)] and C6-C20 aromatic hydrocarbon groups (phenyl group, methylphenyl group, benzyl group, naphthyl group, etc.) and the like. Among them, R ⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, A chain aliphatic hydrocarbon group of 1 to 10 is particularly preferable, and a methyl group, an ethyl group, an isopropyl group, and a 2-ethylhexyl group are particularly preferable.
k is an integer of 1 to 40, preferably 1 to 20, more preferably 1 to 15 and particularly preferably 1 to 10 from the viewpoint of output characteristics.

Specific examples of the compound (A) include the following compounds.
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, m is 2, n Is 0, Z is a group represented by the general formula (8), R ² in the general formula (8) which is Z is a methylene group, an ethylene group or a 1,2-propylene group, and j is A compound of 0 to 20, R ¹ is an ethylene group or a 1,2-propylene group, W is an oxygen atom or an imino group, A is SO ₃ ^— , and M is a lithium ion;
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, m is 1, n 1 is a group represented by the general formula (8), Y is a group represented by the general formula (10), and R ² in the general formula (8), which is Z, is a methylene group. , Ethylene group or 1,2-propylene group, j is 0 to 20, R ¹ is ethylene group or 1,2-propylene group, and k in the general formula (10) which is Y is 1 to 20, R ⁴ is an ethylene group or a 1,2-propylene group, and R ⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms). W is an oxygen atom or imino In it, A is SO ₃ ^- and is, compound M is lithium ion;
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, m is 1, n Is Z, Z is a group represented by the general formula (8), R ² in the general formula (8) which is Z is a methylene group, an ethylene group or a 1,2-propylene group, and j is 0 to 20, R ¹ is an ethylene group or a 1,2-propylene group, Y is a fluoroalkyl group having 1 to 20 carbon atoms, W is an oxygen atom, A is SO ₃ ^— , A compound in which M is a lithium ion.

Specific examples of the compound (A) include the following compounds.
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from butyl isocyanate, m is 1, n is 0, and Z is general. R ² in the general formula (8) which is a group represented by the formula (8) and is Z is a methylene group, an ethylene group or a 1,2-propylene group, j is 0 to 20 and R ¹ Is an ethylene group or a 1,2-propylene group, W is an oxygen atom or imino group, A is —CO ₂ ^— or SO ₃ ^— , and M is a lithium ion or a sodium ion;
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from a biuret-modified product of hexamethylene diisocyanate, m is 3, and n is 0. There, Z is a group represented by the general formula (8), ^{R 2} is a methylene group, an ethylene group or a 1,2-propylene group of the general formula (8) in a Z, j is 0 to 20 A compound in which R ¹ is an ethylene group or a 1,2-propylene group, W is an oxygen atom, A is —SO ₃ ^— , and M is a lithium ion;
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from hexamethylene diisocyanate, m is 1, n is 1, and Z is R ² in the general formula (8), which is a group represented by the general formula (8), is a methylene group, an ethylene group or a 1,2-propylene group, j is 0 to 20, and R ¹ is an ethylene group or 1,2-propylene group, Y is an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms), and W is oxygen A compound that is an atom, A is SO ₃ ^— , and M is a lithium ion;
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from isophorone diisocyanate, m is 2, n is 0, and Z is general. R ² in the general formula (8) which is a group represented by the formula (8) and an isocyanate group and is Z is a methylene group, an ethylene group or a 1,2-propylene group, and j is 0 to 20 R ¹ is an ethylene group or a 1,2-propylene group, W is an oxygen atom, A is SO ₃ ^— , and M is a lithium ion.

Among these, as the compound (A) in the present invention, for example, the following compounds and the like are preferable.
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from isophorone diisocyanate, m is 2, n is 0, and there are two. Z is a group represented by the general formula (8), R ² in the general formula (8) which is Z is an ethylene group, j is 0, W is an oxygen atom or an imino group, A compound in which A is SO ₃ ^— and M is a lithium ion;
A compound represented by the general formula (9), wherein R ³ in the general formula (9) is a group obtained by removing an isocyanate group from isophorone diisocyanate, m is 1, n is 1, and Z is general. It is a group represented by the formula (8), Y is a group represented by the general formula (10), R ² in the general formula (8) which is Z is an ethylene group, and j is 0. , Y in general formula (10) is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is an ethylene group or a 1,2-propylene group, and R ⁵ is 1 to 20 carbon atoms (preferably carbon In the general formula (8) and the general formula (10), W is an oxygen atom or imino group, A is SO ₃ ^— , and M is lithium. Compounds that are ions.

Among the compounds (A) contained in the battery additive (B) of the present invention, as a method for producing a compound having a urethane group as the atomic group (X), the corresponding isocyanate compound (c1) and the general formula (7) The method of making the alcohol compound (c21) which has group represented by these react is mentioned. The reaction can be carried out by a known urethanization technique.
Among the compounds (A) contained in the battery additive (B) of the present invention, a method for producing a compound having a urea group as the atomic group (X) is represented by the general formula (7) instead of the alcohol compound (c21). And a method of reacting an amine compound (c3) having a group represented by

Examples of the isocyanate compound (c1) include a monoisocyanate compound and a polyisocyanate compound.
Specific examples of the isocyanate compound (c1) include monoisocyanate compounds having 2 to 20 carbon atoms (for example, ethyl isocyanate, butyl isocyanate, octyl isocyanate, dodecyl isocyanate, etc.), diisocyanate compounds having 4 to 20 carbon atoms (for example, hexamethylene diisocyanate and isophorone). Diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate, etc.), C 6-30 triisocyanate compounds (for example, biuret-modified products of hexamethylene diisocyanate, isocyanurate-modified products of hexamethylene diisocyanate) and the like These are modified products of isocyanate compounds.

  Specific examples of the alcohol (c21) having a group represented by the general formula (7) include alkali metal salts of hydroxycarboxylic acids having 1 to 20 carbon atoms (such as lithium glycolate and lithium lactate) or those having 1 to 20 carbon atoms. Examples include alkali metal salts of hydroxysulfonic acid (such as lithium isethionate, sodium isethionate, lithium isethionate or sodium ethylene oxide 1 to 5 mol adduct). Of these, lithium isethionate is preferably used. Specific examples of the amine (c31) having a group represented by the general formula (7) include alkali metal salts of 2-aminoethanesulfonic acid.

  In the method for producing the compound (A), other alcohol (c22) or other amine (c32) having no group represented by the general formula (7) can be used in combination. Specific examples of the other alcohol (c22) include aliphatic alcohols having 1 to 20 carbon atoms having no carboxyl group or sulfo group (for example, methanol, ethanol, propanol, butanol, octanol, dodecanol and octadecanol), carboxyl An alkylene oxide adduct of an aliphatic alcohol having 1 to 10 carbon atoms having no group or sulfo group (for example, an ethylene oxide 1 to 10 mol adduct of an alcohol such as methanol, ethanol, propanol, butanol, octanol or dodecanol); C1-C20 fluoroalcohol (for example, trifluoromethanol, perfluorocyclohexylmethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 1H, 1H, 7H-dodo Perfluoro heptanol, etc.) and (poly) glycol (such as ethylene glycol, diethylene glycol, tetraethylene glycol and their monoalkyl etherified or acetylated), and the like. Specific examples of other amines (c32) include aliphatic amines having 1 to 20 carbon atoms having no carboxyl group or sulfo group (for example, methylamine, ethylamine, butylamine, octylamine, dimethylamine, diethylamine, dibutylamine, dioctyl). Amine).

The battery additive (B) of the present invention contains the compound (A) as an essential component and can contain other compounds. Other compounds that the battery additive (B) may contain include vinylene carbonate, fluoroethylene carbonate, chloroethylene carbonate, ethylene sulfite, propylene sulfite, propane sultone, and α-bromo-γ-butyrolactone. Can be mentioned. These may be used alone or in combination of two or more.
The content of these other compounds is preferably 0 to 50% by weight, more preferably not contained, based on the weight of the battery additive (B).

  The content of the compound (A) in the battery additive (B) is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, based on the weight of the battery additive (B). Particularly preferred is 100% by weight. The compound (A) contained in the battery additive (B) may be one type or two or more types.

  In the present invention, the battery includes electrochemical devices such as secondary batteries (lead storage batteries, nickel-cadmium batteries and nickel metal hydride batteries), lithium ion capacitors and electric double layer capacitors. The battery additive (B) of the present invention is suitably used as an additive to be added to the electrode, electrolyte solution and the like of such an electrochemical device.

An electrode containing the battery additive (B) of the present invention is also included in the present invention.
The electrode of this invention is an electrode containing the said battery additive (B), for example, contains the battery additive (B), an active material (D), and a binder (E). You may contain the conductive support agent (F) as needed.
In the electrode of the present invention, a battery additive (B), an active material (D), a binder (E) and, if necessary, a conductive additive (F) are dispersed in a solvent to obtain a slurry, and the slurry is collected. It can be obtained by coating on an electric body and drying the organic solvent. The battery additive (B), active material (D), binder (E), solvent and conductive additive (F) can be used alone or in combination of two or more.

The active material (D) may be any material that can be used as an active material for a battery electrode, but a negative electrode active material and a positive electrode active material used for an electrode of a secondary battery are preferable.
As a negative electrode active material, the negative electrode active material (D1) for lithium ion batteries is more preferable. Moreover, the negative electrode for lithium ion capacitors is obtained by doping lithium into the negative electrode active material (D1) for lithium ion batteries.
Examples of the negative electrode active material (D1) for lithium ion batteries include graphite, amorphous carbon, polymer compound fired bodies (for example, those obtained by firing and carbonizing phenol resin and furan resin), cokes (for example, pitch coke, needle coke, and the like). Petroleum coke), carbon fibers, conductive polymers (eg, polyacetylene and polypyrrole), tin, silicon, and metal alloys (eg, lithium-tin alloys, lithium-silicon alloys, lithium-aluminum alloys, and lithium-aluminum-manganese alloys). Etc.
Moreover, as a preferable thing 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.
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 auxiliary agent (F) contained in the electrode of the present invention as 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 ( Examples thereof include aluminum powder and nickel powder) and conductive metal oxides (for example, zinc oxide and titanium oxide).

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

  Active material (D), binder (E), battery additive (B) based on total weight of active material (D), binder (E), battery additive (B) in electrode of the present invention And preferable content of each of conductive aid (F) is as follows.

The content of the active material (D) in the electrode of the present invention is preferably 70 to 98% by weight, more preferably 90 to 98% by weight from the viewpoint of battery capacity.
The content of the binder (E) is preferably 0.5 to 29% by weight, more preferably 1 to 10% by weight from the viewpoint of battery capacity.
The content of the battery additive (B) is preferably 0.01 to 10% by weight, more preferably 0.05 to 1% by weight, from the viewpoints of charge / discharge cycle characteristics, battery capacity, and high-temperature storage characteristics.
The content of the conductive auxiliary agent (F) is preferably 0 to 29% by weight, more preferably 1 to 10% by weight, from the viewpoint of battery output.

An electrolytic solution containing the battery additive (B) of the present invention is also encompassed by the present invention.
The electrolytic solution of the present invention is an electrolytic solution containing the battery additive (B), and preferably contains the battery additive (B), the electrolyte (G), and the nonaqueous solvent (H). The battery additive (B), the electrolyte (G) and the non-aqueous solvent (H) can be used alone or in combination of two or more.
The electrolytic solution of the present invention can be obtained, for example, by dissolving the battery additive (B) and the electrolyte (G) in a nonaqueous 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.
Specific examples of the cyclic carbonate include propylene carbonate, ethylene carbonate, butylene carbonate, and the like.
Specific 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.

  Battery additive (B), electrolyte (G) and non-aqueous solvent (H) based on the total weight of battery additive (B), electrolyte (G) and non-aqueous solvent (H) in the electrolytic solution of the present invention Each preferable content is as follows.

The content of the battery additive (B) is preferably 0.01 to 10% by weight, more preferably 0.05 to 1% by weight, from the viewpoints of charge / discharge cycle characteristics, battery capacity, and high-temperature storage characteristics.
The content of the electrolyte (G) in the electrolytic solution is preferably 0.1 to 30% by weight, and more preferably 0.5 to 20% by weight from the viewpoint of battery output and charge / discharge cycle characteristics.
The content of the non-aqueous solvent (H) is preferably 60 to 99% by weight and more preferably 85 to 95% by weight from the viewpoint of battery output and charge / discharge cycle characteristics.

  The electrolytic solution of the present invention may further contain additives such as an overcharge inhibitor, a dehydrating agent and a capacity stabilizer. The content of each of the following additive components is based on the total weight of the battery additive (B), the electrolyte (G), and the nonaqueous solvent (H).

  Examples of the overcharge inhibitor include biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, aromatic compounds such as cyclohexylbenzene, t-butylbenzene, and t-amylbenzene. The usage-amount of an overcharge inhibiting agent is 0-5 weight% normally, Preferably it is 0.5-3 weight%.

  Examples of the dehydrating agent include zeolite, silica gel and calcium oxide. The usage-amount of a dehydrating agent is 0-5 weight% normally, Preferably it is 0.5-3 weight%.

  Examples of the capacity stabilizer include fluoroethylene carbonate, succinic anhydride, 1-methyl-2-piperidone, heptane, and fluorobenzene. The usage-amount of a capacity | capacitance stabilizer is 0-5 weight% normally, Preferably it is 0.5-3 weight%.

An electrochemical device having at least one of the electrode and the electrolytic solution of the present invention is also included in the present invention. The electrochemical device of the present invention is preferably a lithium ion battery or a lithium ion capacitor.
The electrode and the electrolytic solution of the present invention are preferably used for electrochemical devices such as secondary batteries, but are particularly preferably used as electrodes and electrolytic solutions for lithium ion batteries and lithium ion capacitors.
Lithium ion batteries having the electrode and / or electrolyte of the present invention are also encompassed by the present invention. A lithium ion capacitor having the electrode and / or electrolyte of the present invention is also encompassed by the present invention.

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

  As a separator in a lithium ion battery, a microporous film made of polyethylene or polypropylene film, a multilayer film of porous polyethylene film and polypropylene, a nonwoven fabric made of polyester fiber, aramid fiber, glass fiber, etc., and silica, alumina on the surface thereof And those having ceramic fine particles such as titania attached thereto.

  As the battery can in the lithium ion battery, 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>
Into a pressure-resistant reaction vessel equipped with a thermometer, a heating / cooling device, a stirrer and a dropping cylinder, 158 parts of 4-decanol and 1.3 parts of potassium hydroxide were placed, sealed with nitrogen, sealed, heated to 100 ° C., and then 3 mmHg. And the mixture was stirred for 1 hour. Next, the temperature was raised to 150 ° C., 440 parts of ethylene oxide was added dropwise over 5 hours while adjusting the pressure to be 0.5 MPaG (gauge pressure) or less, and then aged at the same temperature for 3 hours to obtain ethylene oxide of 4-decanol. A 10 molar adduct was obtained.

<Production Example 2>
A pressure-resistant reaction vessel equipped with a thermometer, a heating / cooling device, a stirrer, and a dropping cylinder was charged with 132 parts of lithium isethionate and 1.3 parts of potassium hydroxide, sealed with nitrogen, sealed, heated to 100 ° C., and then 3 mmHg And the mixture was 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, 8.1 parts of lithium isethionate, 5.8 parts of butyl isocyanate, 100 parts of N, N-dimethylformamide (DMF) and Tris 0.1 parts of (2-ethylhexanoic acid) bismuth was charged and heated at 80 ° C. for 8 hours. DMF was removed under reduced pressure (1.3 kPa) to obtain 12.5 parts of compound (A-1) represented by the following chemical formula (11). The compound (A-1) was used as the battery additive (B-1).

<Example 2>
Synthesis of Compound (A-2) Compound (A-2) represented by the following chemical formula (12) was prepared in the same manner as in Example 1 except that 5.8 parts of butyl isocyanate was changed to 4.9 parts of hexamethylene diisocyanate. 10.0 parts were obtained. The compound (A-2) was used as the battery additive (B-2).

<Example 3>
Synthesis of Compound (A-3) A compound represented by the following chemical formula (13) was prepared in the same manner as in Example 1 except that 5.8 parts of butyl isocyanate was changed to 9.7 parts of a biuret-modified product of hexamethylene diisocyanate. A-3) 16.8 parts were obtained. The compound (A-3) was used as the battery additive (B-3).

<Example 4>
Synthesis of Compound (A-4) Compound (A-4) represented by the following chemical formula (14) was prepared in the same manner as in Example 1 except that 8.1 parts of lithium isethionate was changed to 9.1 parts of sodium isethionate. ) 13.5 parts were obtained. The compound (A-4) was used as the battery additive (B-4).

<Example 5>
Synthesis of Compound (A-5) Compound (A-5) represented by the following chemical formula (15) was prepared in the same manner as in Example 1 except that 8.1 parts of lithium isethionate was changed to 5.0 parts of lithium glycolate. ) 8.2 parts were obtained. The compound (A-5) was used as the battery additive (B-5).

<Example 6>
Synthesis of Compound (A-6) 8.1 parts of lithium isethionate was changed to 7.7 parts of lithium isethionate, 5.8 parts of butyl isocyanate was changed to 9.8 parts of hexamethylene diisocyanate, and methanol 1.9 was further changed. Except having used a part, it carried out similarly to Example 1 and obtained 16.1 parts of compounds (A-6) shown by following Chemical formula (16). The compound (A-6) was used as the battery additive (B-6).

<Example 7>
Synthesis of Compound (A-7) Compound (A-7) represented by the following chemical formula (17) was prepared in the same manner as in Example 6 except that 1.9 parts of methanol was changed to 5.8 parts of trifluoroethanol. 22.1 parts were obtained. The compound (A-7) was used as an additive for batteries (B-7).

<Example 8>
Synthesis of Compound (A-8) Compound (A-) represented by the following chemical formula (18) was prepared in the same manner as in Example 6 except that 1.9 parts of methanol was changed to 12.1 parts of tetraethylene glycol monomethyl ether. 8) 27.5 parts were obtained. The compound (A-8) was used as the battery additive (B-8).

<Example 9>
Synthesis of Compound (A-9) The reaction was carried out in the same manner as in Example 6 except that 1.9 parts of methanol was changed to 35.1 parts of 4-decanol ethylene oxide 10 mol adduct produced in Production Example 1, and the following chemical formula 50.5 parts of compound (A-9) represented by (19) was obtained. Compound (A-9) was designated as battery additive (B-9).

<Example 10>
Synthesis of Compound (A-10) Performed in the same manner as in Example 6 except that 7.7 parts of lithium isethionate was changed to 12.8 parts of ethylene oxide 2 mol adduct of lithium isethionate prepared in Production Example 2. 21.5 parts of compound (A-10) represented by the following chemical formula (20) was obtained. The compound (A-10) was used as an additive for batteries (B-10).

<Example 11>
Synthesis of Compound (A-11) Compound (A-) represented by the following chemical formula (21) was prepared in the same manner as in Example 1 except that 8.1 parts of lithium isethionate was changed to 7.6 parts of lithium salt of taurine. 11) 16.1 parts were obtained. The compound (A-11) was used as the battery additive (B-11).

<Example 12>
Synthesis of Compound (A-12) 8.1 parts of lithium isethionate was changed to 3.8 parts of lithium isethionate and 3.8 parts of lithium salt of taurine, and 4.9 parts of hexamethylene diisocyanate was 6.5 parts of isophorone diisocyanate. Except having changed into, it carried out similarly to Example 1 and obtained 13.2 parts of compounds (A-12) shown by following Chemical formula (22). The compound (A-12) was used as the battery additive (B-12).

<Example 13>
Synthesis of Compound (A-13) Example 1 except that 8.1 parts of lithium isethionate was changed to 3.9 parts of lithium isethionate and 4.9 parts of hexamethylene diisocyanate was changed to 6.5 parts of isophorone diisocyanate. In the same manner as above, 13.2 parts of a compound (A-13) represented by the following chemical formula (23) was obtained. Compound (A-13) was designated as battery additive (B-13).

<Example 14>
Synthesis of Compound (A-13) 8.1 parts of lithium isethionate was changed to 3.9 parts of lithium isethionate and 3.5 parts of diethylene glycol monomethyl ether, and 4.9 parts of hexamethylene diisocyanate was changed to 6.5 parts of isophorone diisocyanate. Except having changed, it carried out similarly to Example 1 and obtained 12.5 parts of compounds (A-14) shown by following Chemical formula (24). Compound (A-14) was designated as battery additive (B-14).

<Comparative Example 1>
Except having changed 8.1 parts of lithium isethionate to 2.0 parts of methanol, it carried out similarly to Example 1 and obtained 5.6 parts of compounds (A'-1) shown by following Chemical formula (25). Compound (A′-1) was used as comparative additive (B′-1).

<Comparative example 2>
Vinylene carbonate was used as the compound (A′-2). The compound (A′-2) was used as a comparative additive (B′-2).

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

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

  Table 1 summarizes the battery additive (B) of the example and the comparative additive (B ') of the comparative example.

<Examples 15 to 44 and Comparative Examples 5 to 13>
Evaluation of Lithium Ion Battery, Electrode and Electrolyte Solution Lithium Ion Battery Electrode or Lithium Ion Battery Electrolyte Containing the above-mentioned Battery Additive (B) or Comparative Additive (B ′) in the Number of Parts shown in Table 2 Was produced by the following method, and a lithium ion battery was produced by the following method using the electrode or the electrolytic solution.
Table 2 shows the results of evaluation of charge / discharge cycle characteristics, low temperature discharge characteristics, and output characteristics by the following methods.

[Production of positive electrode for lithium ion battery]
90.0 parts of LiCoO ₂ powder, 5 parts of Ketjen black [manufactured by Sigma Aldrich Co., Ltd.], 5 parts of polyvinylidene fluoride [manufactured by Sigma Aldrich Co., Ltd.] and the number of parts of the battery additive (B) shown in Table 2 Alternatively, after thoroughly mixing the additive for comparison (B ′) in a mortar, 70.0 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] is added, and further mixed well in a mortar. A slurry was obtained. 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 15 to 44 and Comparative Examples 5 to 13.

[Production of negative electrode for lithium ion battery]
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 number of parts shown in Table 2 The additive (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, stamped to 16.15 mmphi, and 30-micrometer-thick with the press, the negative electrodes for lithium ion batteries of Examples 15-44 and Comparative Examples 5-13 were produced.

[Preparation of electrolyte for lithium ion battery]
The battery additive (B) or comparative additive (B ′) is blended in 87.5 parts of a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) in the number of parts shown in Table 2, LiPF ₆ as an electrolyte was dissolved so as to be 12% by weight to prepare electrolyte solutions for lithium ion batteries of Examples 15 to 44 and Comparative Examples 5 to 13.

[Production of lithium-ion batteries]
The positive electrode and the negative electrode of Examples 15 to 44 and Comparative Examples 5 to 13 are arranged at both ends in the 2032 type coin cell so that the coated surfaces face each other, and a separator (polypropylene nonwoven fabric) is inserted between the electrodes, and lithium An ion battery cell was produced. The cells prepared in Examples 15 to 44 and Comparative Examples 5 to 13 were prepared by injecting and sealing the cells, and lithium ion batteries of Examples 15 to 44 and Comparative Examples 5 to 13 were produced. . The obtained lithium ion battery was evaluated for charge / discharge cycle characteristics, low temperature discharge characteristics, and output characteristics by the following methods.

<Evaluation of charge / discharge cycle characteristics>
Using a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.] at room temperature, the battery was charged to a voltage of 4.3 V with a current of 0.1 C, and after a pause of 10 minutes, 0.1 C The battery voltage was discharged to 3.0 V with the current of 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 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.
Charging / discharging cycle characteristics (%) = (battery capacity at the 50th cycle charge / battery capacity at the first charge) × 100

<Evaluation of low-temperature discharge characteristics>
Using a charge / discharge measuring device “Battery Analyzer 1470 type” [manufactured by Toyo Technica Co., Ltd.], the battery was charged to a voltage of 4.3 V with a current of 0.1 C in a thermostatic bath at 25 ° C. The battery was discharged at a current of 1 C to a voltage of 3.0 V, and this charge / discharge was repeated 5 times. The discharge capacity at the fifth time was defined as the initial discharge capacity. Furthermore, after charging to a voltage of 4.3 V with a current of 0.1 C, the battery was discharged to a voltage of 3.0 V with a current of 0.1 C in a constant temperature bath at −20 ° C., and the discharge capacity at this time was measured. Low temperature discharge characteristics were calculated from the following formula. It shows that a low-temperature discharge characteristic is so favorable that a numerical value is large.
Low temperature discharge characteristics (%) = (discharge capacity at −20 ° C./initial discharge capacity) × 100

<Evaluation of output characteristics>
Using a charge / discharge measuring device “Battery Analyzer 1470” [manufactured by Toyo Technica Co., Ltd.] at room temperature, the battery was charged to a voltage of 4.3 V with a current of 0.1 C, and after a pause of 10 minutes, 0.1 C The voltage was discharged to 3.0 V at a current of, and the discharge capacity (hereinafter referred to as 0.1 C discharge capacity) was measured. Next, the battery is charged to a voltage of 4.3 V with a current of 0.1 C, and after a pause of 10 minutes, the voltage is discharged to 3.0 V with a current of 1 C, and the capacity (hereinafter referred to as 1 C discharge capacity) is measured. The capacity retention rate during 1C discharge was calculated. The larger the value, the better the output characteristics. The capacity retention rate (%) during 1C discharge calculated from the following formula is shown in Table 2 as output characteristics (%).
Capacity maintenance rate during 1 C discharge (%) = (1 C discharge capacity / 0.1 C discharge capacity) × 100

Evaluation of Lithium Ion Capacitor and Electrolyte <Examples 45 to 58 and Comparative Examples 14 to 18>
A lithium ion capacitor using the electrolyte for a lithium ion capacitor containing the battery additive (B) or comparative additive (B ′) in the number of parts shown in Table 3 was produced by the following method. High voltage charge / discharge cycle characteristics and output characteristics were evaluated by the following methods, and the results are shown in Table 3.

[Preparation of electrolyte for lithium ion capacitor]
The battery additive (B) or the comparative additive (B ′) was blended with 87.5 parts of propylene carbonate in the number of parts shown in Table 3, and LiPF ₆ was dissolved so as to be 12% by weight, An electrolyte solution was prepared.

[Production of positive electrode for lithium ion capacitor]
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. The activated carbon powder, acetylene black, and polyvinylidene fluoride are mixed in a weight ratio of 80:10:10, and the mixture is added to 1-methyl-2-pyrrolidone as a solvent, followed by stirring and mixing. Thus, a slurry was obtained. 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 for lithium ion capacitor]
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 obtained as described above, impregnated with the above electrolytic solution, sealed in a storage case made of polypropylene aluminum laminate film, and lithium ion A capacitor cell was produced.
Similarly to the case of the lithium secondary battery, the charge / discharge cycle characteristics were evaluated by the above method, and the capacitor output characteristics were evaluated by the following method. The results are shown in Table 3.

<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 rate was calculated. The larger the value, the better the output characteristics. The capacity retention ratio (%) at the time of 10 C discharge calculated from the following formula is shown in Table 3 as output characteristics (%).
Capacity maintenance rate during 10C discharge (%) = (10C discharge capacity / 1C discharge capacity) × 100

From Examples 15 to 44 and Comparative Examples 5 to 13, the lithium ion battery including the electrode and / or the electrolyte containing the battery additive (B) of the present invention is excellent in charge / discharge cycle characteristics and output characteristics. I understood. This is considered to be because SEI having excellent lithium ion conductivity was formed due to decomposition of the additive during charge and discharge. It was found that the comparative additive (B′-1) having no sulfo group or carboxylate group was ineffective. In addition, vinylene carbonate and fluoroethylene carbonate, which have been conventionally known, have a slight effect on the cycle characteristics when the electrolyte is added, but the output characteristics are deteriorated. This is presumably because SEI having poor lithium ion conductivity was formed on the electrode surface. Further, the battery additives (B-8) to (B-10) and (B-14) having an alkylene oxide skeleton in the molecule showed particularly excellent effects in low-temperature discharge characteristics (Examples 24-26 and 30, 38-40, 44). This is presumably because the ionic conductivity at low temperature was improved due to the presence of the alkylene oxide skeleton.
Further, as is clear from Examples 45 to 58 and Comparative Examples 14 to 18, it was found that the battery additive (B) of the present invention is also effective in lithium ion capacitors.

  The electrode and electrolyte solution using the battery additive (B) of the present invention are useful for electrochemical devices such as lithium ion batteries and lithium ion capacitors, and are particularly suitable for lithium ion batteries and lithium ion capacitors for electric vehicles. is there. 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 (15)

  An atomic group (X) having 2 to 4 atoms having 3 to 5 atoms, an electronegativity of 3 or more, and having at least one non-polymerizable double bond and an ion dissociative functional group A battery additive (B) comprising a compound (A) having (b) and having no polymerizable unsaturated bond.   The battery additive (B) according to claim 1, wherein the number of acceptors of the compound (A) is 1 to 90. The battery additive (B) according to claim 1 or 2, wherein the atomic group (X) is at least one group represented by any one of the following chemical formulas (1) to (5).

The group represented by the chemical formula (1) is a group represented by the following general formula (6), or constitutes a part of the group represented by the following general formula (6). Battery additive (B).

[In general formula (6), R is a hydrogen atom or a C1-C12 organic group. ]   The battery additive (B) according to claim 4, wherein the group represented by the general formula (6) is a group contained in at least one group selected from the group consisting of a urethane group, a urea group, an allophanate group and a biuret group. ). The battery additive (B) according to any one of claims 1 to 5, wherein the ion dissociative functional group (b) is a group represented by the following general formula (7).

[In Formula (7), M is a monovalent metal ion, and A is —CO ₂ ^— or SO ₃ ^— . ]   The battery additive (B) according to any one of claims 1 to 6, wherein the compound (A) further has an alkyleneoxy group (c). The battery (1) according to any one of claims 1 to 7, wherein the compound (A) has an atomic group (X) and an ion dissociable functional group (b) as a structural unit represented by the following general formula (8). Additive (B).

[In Formula (8), R ¹ is an alkylene group having 2 to 4 carbon atoms, and a plurality of R ¹ contained in the repeating unit may be the same or different. R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms. j is an integer of 0 to 20, and M and A are the same as those in the general formula (7). W represents an oxygen atom or an imino group. ] The battery additive (B) according to any one of claims 1 to 8, wherein the compound (A) is a compound represented by the following general formula (9).

[In Formula (9), R ³ is an (m + n) -valent residue obtained by removing an isocyanate group from an isocyanate compound, m is an integer of 1 to 4, and n is an integer of 0 to 3. When m is 1 and n is 0, Z is a group represented by the general formula (8). When m is 1 and n is an integer of 1 to 3, Z is a general formula (7). In the case where m is an integer of 2 or more, a plurality of Z's are the same or different and are each represented by the general formula (7). An ionic dissociative functional group represented by the general formula (8) or an isocyanate group, and at least one of a plurality of Zs represented by the general formula (7) It is group represented by (8). W represents an oxygen atom or an imino group, Y is a monovalent organic group, and has no polymerizable unsaturated bond. When n is an integer of 2 or more, a plurality of Ys may be the same or different. ]   The Y in the general formula (9) is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a group represented by the following general formula (10). Battery additive (B).

[In formula (10), R⁴Is an alkylene group having 2 to 4 carbon atoms and a plurality of Rs contained in the repeating unit⁴May be the same or different. k is an integer of 1 to 40, and R ⁵Is a C1-C20 hydrocarbon group or acetyl group. ]   The electrode containing the battery additive (B) of any one of Claims 1-10.   The electrolyte solution containing the additive (B) for batteries of any one of Claims 1-10.   An electrochemical device having at least one of the electrode according to claim 11 and the electrolytic solution according to claim 12.   The electrochemical device according to claim 13, wherein the electrochemical device is a lithium ion battery. The electrochemical device according to claim 13, wherein the electrochemical device is a lithium ion capacitor.