CN106030874A

CN106030874A - Additive for secondary batteries, electrode and electrolyte solution each using same, lithium ion battery and lithium ion capacitor

Info

Publication number: CN106030874A
Application number: CN201580005516.8A
Authority: CN
Inventors: 田边史行; 高田顺子
Original assignee: Sanyo Chemical Industries Ltd
Current assignee: Sanyo Chemical Industries Ltd
Priority date: 2014-01-24
Filing date: 2015-01-21
Publication date: 2016-10-12
Also published as: KR20160113598A; WO2015111612A1; JPWO2015111612A1

Abstract

This additive for secondary batteries is characterized by containing a compound (A) which has a triple bond (b) and an atomic group (X) that is configured of 3-5 atoms and contains 2-4 atoms having an electronegativity of 3 or more, while having at least one double bond.

Description

Secondary cell additive, the electrode employing this additive and electrolyte, lithium ion Battery and lithium-ion capacitor

Technical field

The present invention relates to additive, the electrode that employ this additive and the electricity useful for nonaqueous electrolytic solution secondary battery Solve liquid, lithium ion battery and lithium-ion capacitor.

Background technology

The nonaqueous electrolytic solution secondary batteries such as lithium ion battery have high voltage, a such feature of high-energy-density, thus quilt Being widely used in portable information device field etc., its demand expands the most rapidly, at present, has been established for as with mobile electricity Words, subnotebook PC are the status of the mobile information equipment normal cell of representative.Certainly, along with portable equipment Deng high performance and multifunction, for also requiring that further high-performance as the nonaqueous electrolytic solution secondary battery of its power supply Change (such as, high capacity and high-energy-density).In order to tackle this requirement, implementing various method, such as by improving Electrode filling rate and realize densification, improve utilizing the degree of depth, developing novel Gao Rong of existing active substance (especially negative pole) Amount active substance etc..Further, reality has utilized these methods make nonaqueous electrolytic solution secondary battery high capacity effectively.

It addition, for the further high capacity realizing nonaqueous electrolytic solution secondary battery, it is desirable to the profit of positive active material With raising and the exploitation of high voltage material of rate.Wherein, the positive active material that the rising of particularly charging voltage is brought The raising utilizing the degree of depth receives publicity.Such as, for the work as the nonaqueous electrolytic solution secondary battery that running voltage is 4.2V level Cobalt composite oxide (the LiCoO of property material₂For), in terms of present Li benchmark, charge to charging capacity during 4.3V be about 155mAh/g, on the other hand, when charging to 4.50V, charging capacity is about more than 190mAh/g.So, by improving charged electrical Pressure, the utilization rate of positive active material increases.

But, along with the Towards Higher Voltage of battery, although the capacity of battery, energy density improve, and but then, exist and fill Discharge cycles characteristic reduces, expands such problem when high-temperature storage because producing gas.It addition, positive active material Become unstable, decompose when high temperature and easily cause oxygen evolution, therefore, leading because external short circuit, internal short-circuit etc. are abnormal Send a telegraph pond overheated in the case of, there is also the problem that the safety such as breaking out of fire accident reduces.

Produce as gas when solving the reduction of charge/discharge cycle characteristics of nonaqueous electrolytic solution secondary battery, high-temperature storage With the exception of battery heat caused by the method for the problem such as fire incident, disclose and with silane coupler, battery material entered The technology (referenced patent document 1) of row process, the technology (referenced patent document 2 and 3) of interpolation ether based compound, interpolation have three The technology (referenced patent document 4) of the sulfone based compound of key and use phosphate ester as technology (the referenced patent literary composition of electrolyte Offer 5 and 6).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2012-169249 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2008-077950 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2007-311217 publication

Patent documentation 4: International Publication the 2008/133112nd

Patent documentation 5: Japanese Unexamined Patent Publication 2007-258067 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2012-248311 publication

Summary of the invention

Invent problem to be solved

But, when using the silane coupler described in patent documentation 1, although there is certain gas and produce suppression effect Really, but its effect is insufficient, there is also the problem that cycle characteristics is deteriorated.Add in the electrolytic solution described in patent documentation 2 and 3 During sulfone based compound described in ether based compound or patent documentation 4, there is the problem that cycle characteristics is deteriorated.Make in the electrolytic solution During with phosphate ester described in patent documentation 5 and 6, although safety improves, but have that ionic conductance reduces, output characteristics becomes The problem of difference.

The present invention completes in view of the above problems.

Problem the most to be solved by this invention is that the gas of suppression nonaqueous electrolytic solution secondary battery produces and improves charge and discharge The cycle characteristics of electricity and output characteristics.

Means for solving the above

The present inventor conducts in-depth research to solve the problems referred to above, and result achieves the present invention.That is, the present invention is: A kind of secondary cell additive, it contains compound (A), and described compound (A) has atomic group (X) and three keys (b), described Atomic group (X) by 3～5 atomic buildings, there are 2～4 electronegativity be the atom of more than 3 and there is at least 1 double bond；Contain There is the electrode of above-mentioned secondary cell additive；Electrolyte containing above-mentioned secondary cell additive；Have above-mentioned electrode and/ Or the lithium ion battery of this electrolyte；There is above-mentioned electrode and/or the lithium-ion capacitor of above-mentioned electrolyte.

Invention effect

By using electrode or the electrolyte of the secondary cell additive containing the present invention, it is possible to suppression lithium ion battery Or the gas of lithium-ion capacitor produces, and cycle characteristics and the output characteristics of discharge and recharge can be improved.It addition, by suppression The heating that the abnormal response occurred when lithium ion battery reaches a high temperature is caused, it is possible to improve safety.

Detailed description of the invention

Hereinafter, also the secondary cell additive of the present invention is referred to as the secondary cell additive (B) of the present invention.

The secondary cell of the present invention is with additive (B) containing compound (A), and this compound (A) has atomic group (X) and three Key (b), described atomic group (X) by 3～5 atomic buildings, there are 2～4 electronegativity be the atom of more than 3 and have at least 1 Individual double bond.

Compound (A) can have the atomic group (X) of more than 2 in 1 molecule.Compound (A) has in 1 molecule In the case of having more than 2 atomic groups (X), these atomic groups (X) can the most identical, can also be different.

It addition, compound (A) can have three keys (b) of more than 2 in 1 molecule.Compound (A) is at 1 molecule In there are more than 2 three keys (b) in the case of, these three keys (b) can the most identical, can also be different.1 molecular compound (A) three keys (b) being had are preferably 1～4, more preferably 1～3.

Atomic group (X) is by 3～5 atomic buildings, and having 2～4 electronegativity is the atom of more than 3, and has at least 1 Double bond.

As the atom of constituting atom group (X), typical element can be enumerated, from the viewpoint of battery behavior, preferably hydrogen Atom, carbon atom, oxygen atom, nitrogen-atoms, fluorine atom, sulphur atom, phosphorus atoms and chlorine atom, more preferably hydrogen atom, carbon atom, oxygen Atom, nitrogen-atoms, sulphur atom and phosphorus atoms, further preferred hydrogen atom, carbon atom, oxygen atom and nitrogen-atoms.Constituting atom group (X) atom can be a kind, can also be two or more.

The atom of constituting atom group (X) is usually 3～5, is preferably 3 from the viewpoint of battery behavior.

As the atom that electronegativity is more than 3 in atomic group (X), oxygen atom, nitrogen-atoms, fluorine atom and chlorine can be enumerated Atom, among these, from the viewpoint of cycle characteristics, preferably oxygen atom and nitrogen-atoms.

Electronegativity is that the quantity of the atom of more than 3 is usually 2～4, from viewpoints such as battery behaviors, and preferably 2.

It should be noted that electronegativity represents that atom attracts the tendency of electronics, therefore, in the present invention, refer to by Pauling (Pauling) electronegativity defined, Pauling the value of the electronegativity defined is recorded in Linus karr Pauling (L.Pauling) in " essence (The Nature of the Chemical Bond) of chemical bond " (1960) that write.

Containing the atom that oxygen atom isopolarity is high in the active substance that nonaqueous electrolytic solution secondary battery is used, therefore deposit In the part biased with the presence of electronics.Think compound (A) institute by containing in the secondary cell additive (B) of the present invention The part generation phase interaction that the electronics of the big atom (electronegativity is the atom of more than 3) of the electronegativity that has and active substance biases With, the secondary cell additive (B) of the present invention is adsorbed in active substance, thus shows high gas and produces inhibition Deng.

As the double bond contained in atomic group (X), carbon-to-carbon double bond, carbon-oxygen double bond, carbon-to-nitrogen double bond, sulfur-oxygen can be enumerated Double bond and phosphorus-oxygen double bond etc., as preferred double bond, can enumerate carbon-oxygen double bond, phosphorus-oxygen double bond and sulfur-oxygen double bond, more excellent Select carbon-oxygen double bond.

As preferred atomic group (X), such as, can enumerate any one represented base in following chemical formula (1)～(5) Group's (key).

[changing 1]

[changing 2]

[changing 3]

[changing 4]

[changing 5]

Atomic group represented by chemical formula (1) be included in amide groups, carbamate groups, urea groups, allophanate group and In biuret groups etc..

Amide groups can be generated by the dehydration condensation of carboxyl with amino, and carbamate groups can pass through isocyanide Perester radical generates with the additive reaction of hydroxyl, urea groups can by the reaction of NCO and water and NCO with The reaction of amino or imino group generates, and allophanate group can be entered with carbamate groups further by NCO Row additive reaction generates, and biuret groups can carry out additive reaction with urea groups further by NCO and generate.

Atomic group represented by chemical formula (2) is included in such as ester group, can be by the dehydrating condensation of carboxyl with hydroxyl Reaction and hydroxyl opening etc. in anhydride group generate.

Atomic group represented by chemical formula (3) can make sulfide generation oxidation reaction generate by utilizing oxidant.

Atomic group represented by chemical formula (4) can be by phosphoric acid and the dehydration condensation of hydroxyl and by phosphatization Thing and hydroxyl carry out condensation reaction and generate.

Atomic group represented by chemical formula (5) can generate with phosgene reaction by making primary amine.

Each group represented by chemical formula (1)～(5) such as can be directed in compound (A) by above-mentioned reaction.

As the atomic group (X) in the present invention, the most such as group represented by chemical formula (1).As in the present invention Compound (A), the most such as there is the group represented by least 1 chemical formula (1) and there is the chemical combination of three keys (b) Thing.

Group represented by above-mentioned chemical formula (1) is preferably the group represented by following formula (6).

[changing 6]

In formula (6), R is hydrogen atom or organic group that carbon number is 1～12.

As the organic group that carbon number is 1～12, can enumerate: carbon number is the aliphatic alkyl (first of 1～12 Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl-propyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, 1-methyl fourth Base, 2-methyl butyl, 1,1-dimethyl propyl, 2,2-dimethyl propyl, 1,2-dimethyl propyl, 1-ethyl propyl, n-hexyl, Isohesyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1,1,2- Thmethylpropyl, 1-ethyl-1-methyl-propyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, nonyl, decyl and dodecyl Deng), carbon number be 1～12 ester ring type alkyl (cyclohexyl and cyclopenta etc.), carbon number be 6～12 aromatic hydrocarbyl (benzyl, phenyl, aminomethyl phenyl, xenyl and naphthyl etc.) and their hydrogen atom are by containing heteroatomic functional group (ammonia Base, alkyl amino, dialkyl amido and alkyl sulfenyl etc.) substituted group etc..

Among these, from the viewpoint of battery output characteristics, it is 1～12 as R, preferably hydrogen atom and carbon number Aliphatic alkyl, further preferred hydrogen atom.

Group represented by formula (6) is included in amide groups, carbamate groups, urea groups, allophanate group and contracting two In urea groups etc., wherein it is preferably selected from the group being made up of carbamate groups, urea groups, allophanate group and biuret groups Group included at least one group, more preferably selects free carbamate groups (-OCONH-) and urea groups (-NHCONH-) The group included at least one group in the group of composition.Compound (A) in the present invention preferably has and selects free amino group first At least one in the group of perester radical, urea groups, allophanate group and biuret groups composition, more preferably has carbamate groups Or urea groups.

Three keys (b) being had as compound (A), from the viewpoint of cycle characteristics and gas produce suppression, preferably Carbon-to-carbon triple bond and/or carbon-to-nitrogen three key.

From the viewpoint of the output characteristics of battery, compound (A) preferably has alkylidene epoxide (d).As above-mentioned Asia Alkyl oxy (d), can enumerate alkylidene epoxide (ethyleneoxy group, propylidene epoxide and butylidene that carbon number is 2～4 Epoxide etc.).Wherein, from the viewpoint of battery output characteristics, preferably ethyleneoxy group.

The alkylidene epoxide that alkylidene epoxide (d) can be made up of, can also be more than 21 alkylidene epoxide is continuous Being bonded and constitute, from the viewpoint of battery output characteristics, preferably 1 alkylidene epoxide or 2～40 alkylidene epoxides are continuous Being bonded and constitute, more preferably 3～30 alkylidene epoxides are bonded continuously and constitute.

In the case of more than 2 alkylidene epoxides are bonded continuously, the alkylidene epoxide being bonded mutually can be a kind, can also For two or more.In the case of alkylidene epoxide of more than two kinds is bonded continuously, bonding pattern can be random, block or its mixing In any one.

Compound (A) preferably has three keys (b) and Asia with the form of the construction unit represented by following formula (7) or (8) Alkyl oxy (d).

[changing 7]

In formula (7), R¹Be carbon number be the alkylidene of 2～4, there is multiple R¹In the case of, R¹Each can identical also Can be different.As R¹, ethylidene, trimethylene, propylene and tetramethylene etc. can be enumerated.Among these, from From the viewpoint of battery behavior, preferably ethylidene.

R²Be carbon number be the bivalent hydrocarbon radical of 1～10, as R², methylene, ethylidene, propylidene, Aden can be enumerated Base and hexa-methylene etc..Among these, from the viewpoint of battery behavior, preferably methylene and ethylidene.

R³It is hydrogen atom or the hydrocarbon that carbon number is 1～20 that hydrogen atom can be replaced containing heteroatomic functional group Base, as R³, can enumerate aliphatic alkyl that carbon number is 1～20 (methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl-propyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, 1-methyl butyl, 2-methyl butyl, 1,1-dimethyl propyl, 2,2-dimethyl propyl, 1,2-dimethyl propyl, 1-ethyl propyl, n-hexyl, isohesyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1,1,2-thmethylpropyl, 1-ethyl-1-methyl-propyl, Heptyl, octyl group, iso-octyl, 2-ethylhexyl, nonyl, decyl and dodecyl etc.), carbon number be 1～20 ester ring type hydrocarbon Base (cyclohexyl and cyclopenta etc.) and aromatic hydrocarbyl (benzyl, phenyl, aminomethyl phenyl, biphenyl that carbon number is 6～20 Base and naphthyl etc.) etc..Among these, from the viewpoint of the cycle characteristics of battery, hydrogen atom is preferably used and carbon number is 1 ～the aliphatic alkyl of 20.R³More preferably hydrogen atom.It should be noted that as containing heteroatomic functional group, Ke Yiju Go out amino, alkyl amino, dialkyl amido and alkyl sulfenyl etc..

H is the integer of 1～40, preferably 3～30, more preferably 5～20.

[changing 8]

In formula (8), P¹Be carbon number be the alkylidene of 2～4, there is multiple P¹In the case of, P¹Each can identical also Can be different.As P¹, can enumerate and above-mentioned R¹Identical group, preferred group is the most identical.

P²Be carbon number be the bivalent hydrocarbon radical of 1～10, as P², can enumerate and above-mentioned R²Identical group, preferably Group is the most identical.

I is the integer of 1～40, preferably 3～30, more preferably 5～20.

From the viewpoint of battery output characteristics, compound (A) is preferably with the construction unit represented by following formula (9) Form has above-mentioned alkylidene epoxide (d).

[changing 9]

In formula (9), W¹Be carbon number be the alkylidene of 2～4, there is multiple W¹In the case of, W¹Each can identical also Can be different.As W¹, can enumerate and above-mentioned R¹Identical group, preferred group is the most identical.W²Be carbon number be 1～ The alkyl of 20, as W², can enumerate aliphatic alkyl that carbon number is 1～20 (methyl, ethyl, n-pro-pyl, isopropyl, Normal-butyl, 1-methyl-propyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, 1-methyl butyl, 2-methyl butyl, 1,1-diformazan Base propyl group, 2,2-dimethyl propyl, 1,2-dimethyl propyl, 1-ethyl propyl, n-hexyl, isohesyl, 3-methyl amyl, 2-first Base amyl group, 1-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1,1,2-thmethylpropyl, 1-ethyl-1-first Base propyl group, heptyl, octyl group, iso-octyl, 2-ethylhexyl, nonyl, decyl, undecyl and dodecyl etc.), carbon number be The ester ring type alkyl (cyclohexyl and cyclopenta etc.) of 1～20 and aromatic hydrocarbyl (phenyl, methyl that carbon number is 6～20 Phenyl, benzyl and naphthyl etc.) etc., wherein preferably carbon number is the aliphatic alkyl of 1～20, more preferably methyl, ethyl, different Propyl group and 2-ethylhexyl.K is the integer of 1～40, from the viewpoint of output characteristics, and preferably 3～30, particularly preferably 5 ～20.

Compound (A) preferably has the group represented by following formula (10).

[changing 10]

In formula (10), Q¹Be carbon number be the alkylidene of 2～4, there is multiple Q¹In the case of, Q¹Each can be identical Can also be different.As Q¹, can enumerate and above-mentioned R¹Identical group, preferred group is the most identical.

Q²Be carbon number be the bivalent hydrocarbon radical of 1～10.As Q², can enumerate and above-mentioned R²Identical group, preferably Group is the most identical.

M is monovalent metallic ion, can enumerate the alkali metal ions etc. such as lithium ion, sodium ion and potassium ion.Among these, From viewpoints, preferably lithium ion and sodium ion such as battery output characteristics.

A is-CO₂ ^-Or-SO₃ ^-, from the viewpoint of battery output characteristics, preferably-SO₃ ^-。

J is the integer of 0～40, from the viewpoint of output characteristics, and preferably 3～30, particularly preferably 5～20.M is 0 Or 1, preferably 1.

As the preference of compound (A), the compound represented by following formula (11)～(16) can be enumerated.Following logical Each compound represented by formula (11)～(16) as the group having represented by above-mentioned chemical formula (1) as atomic group (X) Compound is applicable.

[changing 11]

In formula (11), R⁴It it is the alkyl that carbon number is 1～20 with carbon-to-carbon triple bond or carbon-to-nitrogen three key.R⁵It is that carbon is former Subnumber is the alkyl of 1～20.X¹Represent oxygen atom or imino group.

[changing 12]

In formula (12), R⁶And R⁸Be independently of one another carbon number be the alkyl of 1～20, R⁶And R⁸In at least 1 have Carbon-to-carbon triple bond or carbon-to-nitrogen three key.R⁷Be carbon number be the bivalent hydrocarbon radical of 1～20.X²And X³Represent oxygen atom independently of one another Or imino group.

[changing 13]

In formula (13), R⁹And R¹⁵Be independently of one another carbon number be the alkyl of 1～20.R¹⁰～R¹⁴It is independently of one another Carbon number is the bivalent hydrocarbon radical of 1～20, R⁹、R¹¹、R¹³And R¹⁵In at least 1 there is carbon-to-carbon triple bond or carbon-to-nitrogen three key.n It it is the integer of 0～20.X⁴、X⁵、X⁶、X⁷、X⁸And X⁹Represent oxygen atom or imino group independently of one another.Containing multiple X in molecule⁵With X⁶In the case of, X⁵Each can be the same or different, X⁶Each can be the same or different.

[changing 14]

In formula (14), R¹⁶、R¹⁸And R²⁰Be independently of one another carbon number be the alkyl of 1～20.R¹⁷And R¹⁹The most independent Ground be carbon number be the bivalent hydrocarbon radical of 1～20, R¹⁶、R¹⁸And R²⁰In at least 1 there is carbon-to-carbon triple bond or carbon-to-nitrogen three key. X¹⁰、X¹¹And X¹²Represent oxygen atom or imino group independently of one another.

[changing 15]

In formula (15), R²¹、R²⁴And R²⁶Be independently of one another carbon number be the alkyl of 1～20.R²²、R²³And R²⁵The most solely Be on the spot carbon number be the bivalent hydrocarbon radical of 1～20, R²¹、R²⁴And R²⁶In at least 1 there is carbon-to-carbon triple bond or carbon-to-nitrogen three Key.X¹³、X¹⁴And X¹⁵Represent oxygen atom or imino group independently of one another.

[changing 16]

In formula (16), R²⁷It it is the group removing the m+g valency after NCO from polyisocyanate compounds.Y is carbon Atomic number is the alkyl of 1～20, and at least one is the hydrocarbon that carbon number is 1～20 with carbon-to-carbon triple bond or carbon-to-nitrogen three key Base.Containing in the case of multiple Y in molecule, Y each can be the same or different.M is the integer of 1～7, g be 0～6 whole Number.X¹⁶Represent oxygen atom or imino group.Containing multiple X in molecule¹⁶In the case of, X¹⁶Each can be the same or different.

In formula (11)～(15), as R⁴Preferred concrete example, can enumerate 2-propynyl, 3-hexin base, 4-oneself Group represented by alkynyl, 2-phenyl-2-propynyl, 3-phenyl-2-propynyl, 2-cyano ethyl, formula (7) and formula (8) Represented group etc..

In formula (11)～(15), as R⁶、R⁸、R⁹、R¹⁵、R¹⁶、R¹⁸、R²⁰、R²¹、R²⁴And R²⁶Preferred concrete example, can To enumerate methyl, propyl group, butyl, cyclohexyl, 2-propynyl, 3-hexin base, 4-hexin base, 2-phenyl-2-propynyl, 3-benzene Group represented by base-2-propynyl, 2-cyano ethyl, formula (7), the group represented by formula (8), formula (9) are represented Group, group etc. represented by formula (10).As R⁵Preferred concrete example, can enumerate carbon number is 1～10 Straight-chain alkyl (such as, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, dodecyl), carbon number are 1～10 Ester ring type alkyl (such as, cyclohexyl and cyclopenta) and aromatic hydrocarbyl (such as, phenyl, the first that carbon number is 6～10 Base phenyl, benzyl and naphthyl etc.).

As R⁷、R¹⁰、R¹²、R¹⁴、R¹⁷、R¹⁹、R²²、R²³And R²⁵In preferred concrete example, can enumerate carbon number is 1 ～bivalence ester ring type alkyl that the divalent straight alkyl of 20, carbon number are 1～20 and divalent aromatic that carbon number is 6～20 Race's alkyl.Among these, particularly preferably use the residue after removing 2 NCOs from hexamethylene diisocyanate, From isophorone diisocyanate, remove the residue after 2 NCOs, remove from dicyclohexyl methyl hydride diisocyanate Go the residue after 2 NCOs and remove after 2 NCOs from methyl diphenylene diisocyanate residual Base.

As R¹¹And R¹³In preferred concrete example, divalent straight alkyl, carbon that carbon number is 1～20 can be enumerated Atomic number is the bivalence ester ring type alkyl of 1～20 and aromatic hydrocarbyl that carbon number is 6～20.Among these, particularly preferably After using the residue after removing 2 hydroxyls from 2-butyne-1,4-glycol and removing 2 hydroxyls from 3-hexin-1,6-glycol Residue.

As R⁵In preferred concrete example, can enumerate from the monoisocyanate compound that atomic number is 2～20 (such as Ethyl isocyanate, butyl isocyanate, octyl isocyanate, Carbimide. dodecyl ester etc.) in remove the group after NCO.

In formula (16), as R²⁷In preferred concrete example, can enumerate from the diisocyanate that carbon number is 4～20 Compound (such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexichol Dicyclohexylmethane diisocyanate, XDI, toluene di-isocyanate(TDI) etc.), carbon number be 6～30 three different Cyanate esters (the biuret modified thing of such as hexamethylene diisocyanate, the isocyanide urea of hexamethylene diisocyanate Acid esters modifier etc.) and the modifier of these polyisocyanate compounds in remove the group after NCO.

As the preferred concrete example of Y, can enumerate such as: methyl, propyl group, butyl, cyclohexyl, 2-propynyl, 3-are own Group represented by alkynyl, 4-hexin base, 2-phenyl-2-propynyl, 3-phenyl-2-propynyl, 2-cyano ethyl, formula (7), Group represented by group represented by formula (8), the group represented by formula (9), formula (10).

As the concrete example of compound (A), following compound can be enumerated.

R in formula (11)⁴For 2-propynyl, 2-cyano ethyl, 3-hexin base, 3-phenyl-2-propynyl, 2-phenyl-2- Group represented by propinyl, above-mentioned formula (7) or the group represented by formula (8), X¹For oxygen atom or imino group (preferably X¹ For oxygen atom), R⁵For butyl or the compound of the combination of cyclohexyl；

R in formula (12)⁶And R⁸It is each independently represented by 2-propynyl, 2-cyano ethyl, 3-hexin base, formula (9) Group or formula (10) represented by group and R⁶And R⁸In at least 1 be 2-propynyl, 2-cyano ethyl or 3-hexin Base, R⁷For the residue after 2 NCOs of removing from hexamethylene diisocyanate, from isophorone diisocyanate Remove the residue after 2 NCOs or remove after 2 NCOs from dicyclohexyl methyl hydride diisocyanate residual Base, X²And X³Compound for the combination of oxygen atom；

R in formula (13)⁹And R¹⁵For methyl, 2-propynyl, 2-cyano ethyl, 3-hexin base, 3-phenyl-2-propynyl or 2-phenyl-2-propynyl, R¹⁰、R¹²And R¹⁴For remove from hexamethylene diisocyanate the residue after 2 NCOs, From isophorone diisocyanate, remove the residue after 2 NCOs or remove from dicyclohexyl methyl hydride diisocyanate Remove the residue after 2 NCOs, R¹¹And R¹³For the residue after 2 hydroxyls of removing from 2-butyne-1,4-glycol or from 3- Hexin-1, removes the residue after 2 hydroxyls, X in 6-glycol⁴、X⁵、X⁶、X⁷、X⁸And X⁹Compound for the combination of oxygen atom；

R in formula (14)¹⁶And R²⁰For 2-propynyl, 2-cyano ethyl, 3-hexin base, 3-phenyl-2-propynyl or 2-benzene Base-2-propynyl, R¹⁸For propyl group (preferably isopropyl), 2-propynyl, 2-cyano ethyl, 3-hexin base, 3-phenyl-2-propine Base or 2-phenyl-2-propynyl, R¹⁷And R¹⁹For remove from hexamethylene diisocyanate the residue after 2 NCOs, From isophorone diisocyanate, remove the residue after 2 NCOs or remove from dicyclohexyl methyl hydride diisocyanate Remove the residue after 2 NCOs, X¹⁰、X¹¹And X¹²Compound for the combination of oxygen atom；

R in formula (15)²¹、R²⁴And R²⁶For 2-propynyl, 3-hexin base, 2-cyano ethyl, 3-phenyl-2-propynyl or 2-phenyl-2-propynyl, R²²、R²³And R²⁵For remove from hexamethylene diisocyanate the residue after 2 NCOs, From isophorone diisocyanate, remove the residue after 2 NCOs or remove from dicyclohexyl methyl hydride diisocyanate Remove the residue after 2 NCOs, X¹³、X¹⁴And X¹⁵Compound for the combination of oxygen atom；

R in formula (16)²⁷For the residue after 2 NCOs of removing from isophorone diisocyanate or from bicyclo- Removing the residue after 2 NCOs in hexyl methane diisocyanate, Y is 2-propynyl or 2-cyano ethyl, X¹⁶For oxygen Atom, g is 0～1, and m is the compound etc. of the combination of 1～2.

The secondary cell of the present invention is with in the compound (A) contained by additive (B), and atomic group (X) is chemical formula (1) institute The compound (A1) of the group represented can be by making the compound (T1) with NCO and the activity containing three keys (b) The method etc. that hydrogen compound (Z1) reacts manufactures.

As having the compound (T1) of NCO, the monoisocyanates that carbon number is 2～20 can be enumerated Compound (such as ethyl isocyanate, butyl isocyanate, NSC 87419, octyl isocyanate, Carbimide. dodecyl ester etc.), carbon Atomic number be 4～20 diisocyanate cpd (such as hexamethylene diisocyanate, isophorone diisocyanate, two Diphenylmethane diisocyanate, methyl diphenylene diisocyanate, XDI, toluene di-isocyanate(TDI) Deng) and tri-isocyanate compound that carbon number is 6～30 (such as hexamethylene diisocyanate biuret modified Thing, the isocyanurate-modified thing of hexamethylene diisocyanate, the allophanate-modified thing of hexamethylene diisocyanate Deng) etc..

As having the active dydrogen compounds (Z1) of three keys (b), can enumerate: 2-propine-1-alcohol, 2-propine-1-amine, 3- Phenyl-1-propine-1-amine, 3-phenyl-2-propine-1-amine, 3-butyne-2-alcohol, 4-diethylamino-2-butyne-1-alcohol, 3-fourth Alkynes-2-amine, 3-butyne-1-ol, 3-butine-1-amine, 4-pentyne-1-alcohol, 3-pentyne-1-alcohol, 5-hexin-1-alcohol, 4-hexin-1- Alcohol, 3-hexin-1-alcohol, 2-butyne-1,4-glycol, 3-hexin-1,6-glycol, 3-hexin-2,5-glycol, 2-propargyl propane- 1,3-glycol, 2-cyanoethanol, cyanamide and 2-hydroxyl-2-phenylacetonitrile.

The secondary cell of the present invention is with in the compound (A) contained by additive (B), and atomic group (X) is chemical formula (2) institute The compound (A2) of the group represented can be by making chloroacetic chloride or phosgene anti-with the active dydrogen compounds (Z1) containing three keys (b) Should wait and manufacture.

The secondary cell of the present invention is with in the compound (A) contained by additive (B), and atomic group (X) is chemical formula (3) institute The compound (A3) of the group represented can react with the active dydrogen compounds (Z1) containing three keys (b) by making haloalkylsulfone Etc. manufacturing.

The secondary cell of the present invention is with in the compound (A) contained by additive (B), and atomic group (X) is chemical formula (4) institute The compound (A4) of the group represented can come with active dydrogen compounds (Z1) reaction containing three keys (b) etc. by making phosphoryl chloride phosphorus oxychloride Manufacture.

The secondary cell of the present invention is with in the compound (A) contained by additive (B), and atomic group (X) is chemical formula (5) institute The compound (A5) of the group represented can be by making the compound with the group represented by above-mentioned formula (5) of more than 2 (T5) react with the active dydrogen compounds (Z1) containing three keys (b) and manufacture.

As the concrete example of the compound (T5) of the group having represented by the above-mentioned chemical formula (5) of more than 2, Ke Yiju Go out the diisocyanate cpd that above-mentioned carbon number is 4～20 and the tri-isocyanate compound etc. that carbon number is 6～30.

The secondary cell of the present invention, with in the compound (A) contained by additive (B), has alkylidene epoxide further Compound (A6) can manufacture by using the compound with alkylidene epoxide when manufacturing above-mentioned (A1)～(A5), permissible Enumerate the method etc. importing alkylidene epoxide in the active dydrogen compounds (Z1) containing three keys (b).Use such containing Asia During active dydrogen compounds (Z1) of alkyl oxy and three keys (b), it is possible to obtain the compound (A) with alkylidene epoxide.As Active dydrogen compounds (Z1) containing alkylidene epoxide and three keys (b), can enumerate such as: 2-(2-(2-(2-propine-1-oxygen Base) ethyoxyl) ethyoxyl) ethanol, 3-(2-(2-(2-hydroxyl-oxethyl) ethyoxyl) ethyoxyl) propionitrile etc..

In the present invention, manufacture compound (A) time, can as required with the active dydrogen compounds containing three keys (b) (Z1) it is used together the active dydrogen compounds without three keys (b).For example, it is possible to there is alkylidene epoxide by use and do not have The active dydrogen compounds (Z2) of three keys, imports alkylidene epoxide in compound (A).

The secondary cell additive (B) of the present invention can contain the composition beyond compound (A), can be sub-containing carbonic acid Vinyl acetate, fluoroethylene carbonate, chlorocarbonic acid ethyl, glycol sulfite, sulfurous acid Asia propyl ester, propane sultone and α- Bromo-gamma-butyrolacton etc..

About the secondary cell content of the compound (A) in additive (B), with the secondary cell weight of additive (B) On the basis of amount, preferably 10～100 weight %, more preferably 50～100 weight %.Secondary cell additive (B) contains Compound (A) can be a kind, can also be for two or more.

In the present invention, secondary cell include lithium ion battery, lithium-ion capacitor, double layer capacitor, lead battery, The electrochemical device such as nickel-cadmium cell and Ni-MH battery.The secondary cell additive (B) of the present invention is suitable as being added on so The electrode of secondary cell, additive in electrolyte etc..

The electrode of the secondary cell additive containing the present invention is also contained in the present invention.The electrode of the present invention such as may be used With by making secondary cell additive (B), active substance (D) and binding agent (E) and conductive auxiliary agent (F) as required point Dissipate in a solvent and after obtaining slurry, on the current collector and make organic solvent be dried to obtain by slurry coating.Secondary cell is used Additive (B), active substance (D), binding agent (E), solvent and conductive auxiliary agent (F) all can use one kind or two or more.

As active substance (D), as long as the material that can use as the active substance of the electrode of secondary cell, Negative electrode active material (D1), positive active material can be enumerated.By using negative electrode active material (D1), lithium ion can be obtained The negative pole of battery, by elements doped lithium in negative electrode active material (D1), can obtain lithium-ion capacitor negative pole.It addition, As positive active material, positive electrode active material for lithium ion battery (D2) and lithium-ion capacitor positive-active can be enumerated Material (D3).

As negative electrode active material (D1), graphite, amorphous carbon, macromolecular compound fired body (such as general can be enumerated Phenolic resin and furane resins etc. are fired, carbonization and the material that obtains), coke class (such as pitch coke, needle coke and oil Coke), carbon fiber, electroconductive polymer (such as polyacetylene and polypyrrole), stannum, silicon and metal alloy (such as lithium-ashbury metal, Lithium-silicon alloy, lithium-aluminium alloy and lithium-aluminum-manganese alloy etc.) etc..

As positive electrode active material for lithium ion battery (D2), the composite oxides (example of lithium and transition metal can be enumerated Such as LiCoO₂、LiNiO₂、LiMnO₂And LiMn₂O₄), transition metal oxide (such as MnO₂And V₂O₅), transient metal sulfide (such as MoS₂And TiS₂) and electroconductive polymer (such as polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, poly-second Alkynes, poly and polycarbazole) etc..

As lithium-ion capacitor with positive active material (D3), activated carbon, carbon fiber and electric conductivity high score can be enumerated Son (such as polyacetylene and polypyrrole) etc..

As binding agent (E), starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyethylene can be enumerated The macromolecular compounds such as ketopyrrolidine, tetrafluoroethene, polyethylene and polypropylene.

The optionally conductive auxiliary agent (F) of composition, can enumerate white carbon black class (such as white carbon black, acetylene black, Ketjen black, channel process White carbon black, furnace black, dim and thermals) and metal dust (such as aluminium powder and nikel powder), conductive metal oxide (such as oxygen Change zinc and titanium dioxide) etc..

As the solvent that the uses during electrode of the preparation present invention, water, N-Methyl pyrrolidone (1-methyl-2-can be enumerated Ketopyrrolidine), acetone and toluene etc..

From the viewpoint of battery capacity, based on active substance (D), binding agent (E) and secondary cell additive (B) Gross weight, the content of the active substance (D) in electrode is preferably 70～98 weight %, more preferably 90～98 weight %.

From the viewpoint of battery capacity, based on active substance (D), binding agent (E) and secondary cell additive (B) Gross weight, the content of binding agent (E) is preferably 0.5～29 weight %, more preferably 1～10 weight %.

From the viewpoint of charge/discharge cycle characteristics, battery capacity and high-temperature storage characteristics, based on active substance (D), glue Knot agent (E) and the secondary cell gross weight of additive (B), the content of secondary cell additive (B) is preferably 0.01～10 Weight %, more preferably 0.05～1 weight %.

From the viewpoint of battery exports, based on active substance (D), binding agent (E) and secondary cell additive (B) Gross weight, the content of conductive auxiliary agent (F) is preferably 0～29 weight %, more preferably 1～10 weight %.

The electrolyte of the secondary cell additive containing the present invention is also contained in the present invention.The electrolyte of the present invention is excellent Choosing is containing secondary cell additive (B), electrolyte (G) and nonaqueous solvent (H).Secondary cell additive (B), electrolyte And nonaqueous solvent (H) all can use one kind or two or more (G).

The electrolyte of the present invention such as can be dissolved in non-aqueous by making secondary cell additive (B) and electrolyte (G) Solvent (H) obtains.

As electrolyte (G), it is possible to use electrolyte etc. used in common electrolyte, such as, can enumerate LiPF₆、 LiBF₄、LiSbF₆、LiAsF₆And LiClO₄Lithium salts Deng mineral acid；LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂With LiC (CF₃SO₂)₃ Lithium salts Deng organic acid.Among these, from the viewpoint of battery output and charge/discharge cycle characteristics, preferably LiPF₆。

As nonaqueous solvent (H), it is possible to use nonaqueous solvent etc. used in common electrolyte, such as in can using Ester compounds, ring-type or linear carbonate, chain carboxylate, ring-type or chain ether, phosphate ester, nitrile compound, amide compound, Sulfone, sulfolane etc. and their mixture.

In nonaqueous solvent (H), from the viewpoint of battery output and charge/discharge cycle characteristics, the most ring-type or chain carbon Acid esters.

As cyclic carbonate, propylene carbonate, ethylene carbonate and butylene carbonate etc. can be enumerated.

As linear carbonate, dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate, methyl positive third can be enumerated Base ester, carbonic acid ethyl n-pro-pyl ester and carbonic acid di-n-propyl ester etc..

From the viewpoint of charge/discharge cycle characteristics, battery capacity and high-temperature storage characteristics, add based on secondary cell Agent (B), electrolyte (G) and the gross weight of nonaqueous solvent (H), the content of secondary cell additive (B) is preferably 0.01～10 Weight %, more preferably 0.05～1 weight %.

From the viewpoint of battery output and charge/discharge cycle characteristics, based on secondary cell additive (B), electrolyte (G) and the gross weight of nonaqueous solvent (H), the content of electrolyte (G) is preferably 0.1～30 weight %, more preferably 0.5～20 weights Amount %.

From the viewpoint of battery output and charge/discharge cycle characteristics, based on secondary cell additive (B), electrolyte (G) and the gross weight of nonaqueous solvent (H), the content of nonaqueous solvent (H) is preferably 60～99 weight %, more preferably 85～95 weights Amount %.

The electrolyte of the present invention can contain the additives such as overcharge preventing agent, dehydrant and capacity stabilizer further.

As overcharge preventing agent, biphenyl, alkyl biphenyl, terphenyl, the part hydride of terphenyl, hexamethylene can be enumerated The aromatic compounds etc. such as base benzene, tert-butyl benzene and tert-amyl benzene.Based on secondary cell additive (B), electrolyte (G) and non- The gross weight of aqueous solvent (H), the usage amount of overcharge preventing agent is usually 0～5 weight %, preferably 0.5～3 weight %.

As dehydrant, zeolite, silica gel and calcium oxide etc. can be enumerated.Based on secondary cell additive (B), electrolyte (G) and the gross weight of nonaqueous solvent (H), the usage amount of dehydrant is usually 0～5 weight %, preferably 0.5～3 weight %.

As capacity stabilizer, can enumerate fluoroethylene carbonate, succinic anhydrides, 1-methyl-2-piperidones, heptane and Fluorobenzene etc..Based on secondary cell additive (B), electrolyte (G) and the gross weight of nonaqueous solvent (H), making of capacity stabilizer Consumption is usually 0～5 weight %, preferably 0.5～3 weight %.

Electrode and the electrolyte of the present invention are suitable for secondary cell, wherein, are suitable as lithium ion battery and lithium ion The electrode of capacitor and electrolyte.

The lithium ion battery of the electrode and/or electrolyte with the present invention is also contained in the present invention.Have the present invention's The lithium-ion capacitor of electrode and/or electrolyte is also contained in the present invention.

The lithium ion battery of the present invention can be by injecting electrolyte in the battery can being accommodated with positive pole, negative pole and dividing plate And use the electrode method as negative or positive electrode of the present invention during sealed cell tank, use the electrolyte of the present invention as electrolysis The method of liquid and share their method and obtain.

As dividing plate, polyethylene or the micro-porous film of polypropylene masking, porous polyethylene film and poly-third can be enumerated The multilayer film of alkene, the non-woven fabrics being made up of polyester fiber, aramid fibre and glass fibre etc. and the surface at them It is attached with the material of the ceramic particles such as silicon dioxide, aluminium oxide and titanium dioxide.

As battery can, it is possible to use the metal materials such as rustless steel, ferrum, aluminum and nickel-plated steel, it is also possible to according to battery use Use plastic material.It addition, battery can make cylinder type, coin shape, square or other arbitrary shape according to purposes.

The lithium-ion capacitor of the present invention is by being replaced by positive pole in the basic composition of the lithium ion battery of the present invention The positive pole of lithium-ion capacitor, battery can is replaced by capacitor tank and obtains.As material and the shape of capacitor tank, can With enumerate illustrated with battery can as material and shape.

Embodiment

Below, by embodiment, the present invention will be described further, but the present invention is not limited to these embodiments.Under Wen Zhong, as long as no being particularly limited to, % represents that weight %, part represent weight portion.

The number-average molecular weight of compound (A-7) uses GPC to be measured under the following conditions.

Device (example): TOSOH Co., Ltd manufactures HLC-8120

Post (example): TSK GEL GMH6 2 [TOSOH Co., Ltd's manufacture]

Mensuration temperature: 40 DEG C

Sample solution: the THF solution of 0.25 weight %

Solution injection rate: 100 μ L

Detection device: RI-detector

Primary standard substance: 5 kinds of (Mw of TOSOH Co., Ltd's manufacturer's standard polystyrene (TSKstandard POLY STYRENE) 500、1050、2800、5970、9100)

Ethoxy sulphur is put in the pressure-resistant reaction vessel possessing thermometer, heating-cooling device, blender and dropping tank Acid lithium 132 parts and potassium hydroxide 1.3 parts, airtight and be warming up to 100 DEG C after nitrogen displacement, then it is decompressed to 0.5kPa and stirs 1 Hour.Then, being warming up to 150 DEG C, with pressure as 0.5MPaG, (gauge pressure) mode below is adjusted, and 5 hours used times dripped simultaneously Add 88 parts of oxirane, the most at such a temperature ripening 3 hours, obtain 2 moles of addition products of oxirane of hydroxyethylsulfonic acid. lithium.

The synthesis of compound (A-1)

2-propine-1-alcohol 3.4 parts, Carbimide. hexamethylene is put in the flask being provided with blender, thermometer and cooling tube Ester 7.3 parts, toluene 200 parts and three (2 ethyl hexanoic acid) bismuth 0.1 part, heat 8 hours at 80 DEG C.Remove under decompression (1.3kPa) Toluene, obtains the compound (A-1) 10.1 parts represented by following chemical formula (17).Compound (A-1) is used as secondary cell Additive (B-1).

[changing 17]

The synthesis of compound (A-2)

2-propine-1-alcohol 3.4 parts is changed to 3-hexin-1-alcohol 7.1 parts, carries out the most similarly to Example 1, Obtain the compound (A-2) 13.5 parts represented by following chemical formula (18).Using compound (A-2) as secondary cell additive (B-2)。

[changing 18]

The synthesis of compound (A-3)

2-propine-1-alcohol 3.4 parts is changed to 2-cyanoethanol 4.4 parts, carries out the most similarly to Example 1, Obtain the compound (A-3) 10.2 parts represented by following chemical formula (19).Using compound (A-3) as secondary cell additive (B-3)。

[changing 19]

The synthesis of compound (A-4)

2-propine-1-alcohol 3.4 parts is changed to 3-phenyl-2-propine-1-amine 8.0 parts, the most similarly to Example 1 Ground is carried out, and obtains the compound (A-4) 14.1 parts represented by following chemical formula (20).Using compound (A-4) as secondary cell With additive (B-4).

[changing 20]

The synthesis of compound (A-5)

2-propine-1-alcohol 3.4 parts is changed to 6.5 parts, NSC 87419 7.3 parts is changed to DURANATE (registration Trade mark) A201H (allophanate-modified hexamethylene diisocyanate) [Asahi Kasei Corporation's manufacture] 22.5 parts, except this with Carry out similarly to Example 1 outward, obtain the compound (A-5) 25.7 parts represented by following chemical formula (21).By compound (A- 5) as secondary cell with additive (B-5).

[changing 21]

The synthesis of compound (A-6)

2-propine-1-alcohol 3.4 parts is changed to 9.8 parts, NSC 87419 7.3 parts is changed to DURANATE24A- 100 (biuret modified hexamethylene diisocyanates) [Asahi Kasei Corporation's manufacture] 29.4 parts, in addition with embodiment 1 Similarly carry out, obtain the compound (A-6) 37.1 parts represented by following chemical formula (22).Using compound (A-6) as secondary Battery is with additive (B-6).

[changing 22]

2-butyne-1,4-glycol 5.0 parts, six methylenes are put in the flask being provided with blender, thermometer and cooling tube Group diisocyanate 11.8 parts, toluene 200 parts and three (2 ethyl hexanoic acid) bismuth 0.1 part, heat 8 hours at 80 DEG C.Then put into Methanol 3 parts, further heating 4 hours.Under decompression (1.3kPa), remove toluene, obtain the change represented by following chemical formula (23) Compound (A-7) 16.2 parts.Using compound (A-7) as secondary cell with additive (B-7).The equal molecule of number of compound (A-7) Amount is 1600.In formula (23), n is about 4.

[changing 23]

2-propine-1-alcohol 3.4 parts is changed to 2-(2-(2-(2-propine-1-epoxide) ethyoxyl) ethyoxyl) ethanol 11.5 Part, carry out the most similarly to Example 1, obtain the compound (A-8) 17.3 parts represented by following chemical formula (24).Will Compound (A-8) as secondary cell with additive (B-8).

[changing 24]

2-propine-1-alcohol 3.4 parts is changed to 3-(2-(2-(2-hydroxyl-oxethyl) ethyoxyl) ethyoxyl) propionitrile 12.4 Part, carry out the most similarly to Example 1, obtain the compound (A-9) 18.5 parts represented by following chemical formula (25).Will Compound (A-9) as secondary cell with additive (B-9).

[changing 25]

NSC 87419 7.3 parts is changed to hexamethylene diisocyanate 9.8 parts, by the 3.4 parts of changes of 2-propine-1-alcohol More 2-propine-1-alcohol 3.3 parts and hydroxyethylsulfonic acid. lithium 7.7 parts, carry out the most similarly to Example 1, obtain following Compound (A-10) 19.2 parts represented by chemical formula (26).Using compound (A-10) as secondary cell additive (B- 10)。

[changing 26]

NSC 87419 7.3 parts is changed to hexamethylene diisocyanate 9.8 parts, by the 3.4 parts of changes of 2-propine-1-alcohol The 2 moles of addition products of oxirane 12.8 parts of the hydroxyethylsulfonic acid. lithium manufactured in more 2-propine-1-alcohol 3.3 parts and manufacture example 1, Carry out the most similarly to Example 1, obtain the compound (A-11) 23.5 parts represented by following chemical formula (27).Generalization Compound (A-11) as secondary cell with additive (B-11).

[changing 27]

2-(2-(2-(2-propine-1-epoxide) ethoxy is put in the flask being provided with blender, thermometer and cooling tube Base) ethyoxyl) ethanol 11.0 parts, chloroacetic chloride 4.6 parts, triethyl ammonium 5.8 parts and oxolane 100 parts, little 60 DEG C of reactions 8 Time.Then, under reduced pressure remove oxolane, utilize silica gel column chromatography to be purified, thus obtain following chemical formula (28) institute The compound (A-12) 4.6 parts represented.Using compound (A-12) as secondary cell with additive (B-12).

[changing 28]

2-(2-(2-(2-propine-1-epoxide) ethoxy is put in the flask being provided with blender, thermometer and cooling tube Base) ethyoxyl) ethanol 11.0 parts, 2-bromoethyl methyl sulfone 10.7 parts, sodium hydroxide 2.3 parts and oxolane 100 parts, at 60 DEG C React 8 hours.Then, under reduced pressure remove oxolane, utilize silica gel column chromatography to be purified, thus obtain following chemical formula (29) compound (A-13) 8.6 parts represented by.Using compound (A-13) as secondary cell with additive (B-13).

[changing 29]

2-(2-(2-(2-propine-1-epoxide) ethoxy is put in the flask being provided with blender, thermometer and cooling tube Base) ethyoxyl) ethanol 11.0 parts, phosphoryl chloride phosphorus oxychloride 2.9 parts, triethylamine 5.8 parts and oxolane 100 parts, react 8 hours at 60 DEG C. Then, under reduced pressure remove oxolane, utilize silica gel column chromatography to be purified, thus obtain following chemical formula (30) represented Compound (A-14) 4.5 parts.Using compound (A-14) as secondary cell with additive (B-14).

[changing 30]

Isophorone diisocyanate 13.0 parts, 2-is added in the flask being provided with blender, thermometer and cooling tube Cyanoethanol 4.1 parts, dibutyl tin laurate 0.1 part and toluene 100 parts, react 6 hours at 80 DEG C.The most under reduced pressure remove Toluene, obtains the compound (A-15) 17.0 parts represented by following chemical formula (31).Using compound (A-15) as secondary cell With additive (B-15).Compound (A-15) has the group represented by above-mentioned chemical formula (1) and the base represented by chemical formula (5) Group.

[changing 31]

Hexamethylene diisocyanate 9.8 parts, 2-third is added in the flask being provided with blender, thermometer and cooling tube Alkynes-1-alcohol 3.3 parts, 5 moles of addition products of EO 14.7 parts, dibutyl tin laurate 0.1 part and the toluene 100 parts of methanol, at 80 DEG C React 6 hours.The most under reduced pressure remove toluene, obtain the compound (A-16) 17.0 parts represented by following chemical formula (32). Using compound (A-16) as secondary cell with additive (B-16).

[changing 32]

Relatively with the synthesis of compound (A '-1)

2-propine-1-alcohol 3.4 parts is changed to 4.5 parts of butanol, carries out the most similarly to Example 1, under obtaining State the compound (A '-1) 11.1 parts represented by chemical formula (33).Using compound (A '-1) as comparing with additive (B '-1).

[changing 33]

By 1,9-decadinene is as comparing with compound (A '-2), as comparing with additive (B '-2).

Using ethyl acetate as comparing with compound (A '-3), as comparing with additive (B '-3).

Using dimethyl sulfoxide as comparing with compound (A '-4), as comparing with additive (B '-4).

Using tributyl phosphate as comparing with compound (A '-5), as comparing with additive (B '-5).

Using hexamethylene diisocyanate as comparing with compound (A '-6), as comparing with additive (B '-6).

The comparison additive of the secondary cell additive (B) of embodiment and comparative example (B ') is summarized in table 1.Close In " presence or absence of alkylidene epoxide " and " presence or absence of the group represented by formula (10) ", there is at compound the situation of these groups Under be shown as "○", be shown as "-" in the case of not having.

[table 1]

Lithium ion battery and the evaluation of electrode

Made by following method and contain above-mentioned secondary cell additive (B) with the cooperation number shown in table 2 or compare With the lithium ion battery electrode of additive (B '), this electrode is used to make lithium ion battery by following method.

For the lithium ion battery made, gentle to high voltage charge/discharge cycle characteristics, output characteristics by following method Body produces characteristic and is evaluated, and shows the result in table 2.

[making of lithium ion battery positive pole]

By LiCoO₂90.0 parts of powder, Ketjen black [manufacture of SIGMA-ALDRICH Co., Ltd.] 5 parts, polyvinylidene fluoride The secondary cell additive (B) of number shown in [manufacture of SIGMA-ALDRICH Co., Ltd.] 5 parts and table 2 or compare with adding Agent (B ') it is sufficiently mixed in mortar, then add 1-Methyl-2-Pyrrolidone [Tokyo HuaCheng Industry Co., Ltd's manufacture] 70.0 parts, it is sufficiently mixed in mortar further, obtains slurry.By bar, obtained slurry is applied to thickness in an atmosphere Being the one side on the aluminium electroloysis paper tinsel of 20 μm, be dried 1 hour at 80 DEG C, the most under reduced pressure (1.3kPa) is dried in 80 DEG C 2 hours, it is die-cut intoProduce embodiment 17～33 and the lithium ion battery positive pole of comparative example 7～13.

[making of negative electrode for lithium ion battery]

By the powdered graphite 92.5 parts of mean diameter about 8～12 μm, polyvinylidene fluoride 7.5 parts, 1-methyl-2-pyrrolidine Shown in ketone [Tokyo HuaCheng Industry Co., Ltd's manufacture] 200 parts and table 2, the secondary cell additive (B) of number fills in mortar Divide mixing, obtain slurry.By bar, obtained slurry is applied to the one side of the Copper Foil that thickness is 20 μm in an atmosphere, 80 DEG C be dried 1 hour, the most under reduced pressure (1.3kPa) in 80 DEG C be dried 2 hours, be die-cut intoUse forcing press Making thickness is 3 μm, produces embodiment 17～33 and the negative electrode for lithium ion battery of comparative example 7～13.

[making of lithium ion battery]

Two ends in 2032 type button cells, by embodiment 17～33 and the positive pole of comparative example 7～13 and negative pole according to Respective coated face mode in opposite directions configures, and inserts dividing plate (polypropylene-made nonwoven cloth), produce lithium ion battery between electrode Use unit.Will be with 12 weight % in the ethylene carbonate (EC) mixed solvent (volume ratio 1:1) with diethyl carbonate (DEC) Ratio be dissolved with LiPF₆Electrolyte be injected in made unit and seal.By following method to high voltage charge and discharge Electricity cycle characteristics is evaluated, and shows the result in table 2.

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by obtained Lithium ion battery charges to voltage as 4.5V with the electric current of 0.1C, after suspending 10 minutes, with the current discharge of 0.1C to battery electricity Pressure is 3.5V, repeats this discharge and recharge.When battery capacity when measuring primary charging now circulates with charging the 50th Battery capacity, is calculated charge/discharge cycle characteristics by following formula.Numerical value is the biggest, represents that charge/discharge cycle characteristics is the best.

High voltage charge/discharge cycle characteristics (%)=(charge the 50th circulation time battery capacity/primary charging time electricity Tankage) × 100

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Pond charges to voltage as 4.5V with the electric current of 0.1C, after suspending 10 minutes, with the current discharge of 0.1C to voltage as 3.5V, measures Discharge capacity (is designated as 0.1C discharge capacity) below.Then the electric current with 0.1C charges to voltage as 4.5V, after suspending 10 minutes, With the current discharge of 1C to voltage as 3.5V, measure capacity (being designated as 1C discharge capacity below), following formula when calculating 1C electric discharge Capacity dimension holdup.Numerical value is the biggest, represents that output characteristics is the best.

Capacity dimension holdup (%)=(1C discharge capacity/0.1C discharge capacity) × 100 during 1C electric discharge

Capacity dimension holdup (%) when being discharged by 1C is shown in table 2 and table 3 with the form of output characteristics (%).

By embodiment 17～33 and the positive pole of comparative example 7～13 and negative pole configure according to respective coated face mode in opposite directions In lamination unit, be infused in the mixed solvent (volume ratio 1:1) of ethylene carbonate (EC) and diethyl carbonate (DEC) with The ratio of 12 weight % is dissolved with LiPF₆Electrolyte and seal, produce lithium ion battery, measure the thickness of its unit (just Beginning thickness).

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Pond charges to voltage as 4.5V with the electric current of 0.1C, after suspending 10 minutes, with the current discharge of 0.1C to voltage as 3.5V, repeats Carry out 3 above-mentioned circulations.Electric current with 0.1C charges to voltage as 4.5V further, when maintaining voltage 60 DEG C of guarantors Deposit 7 days.Then, the thickness (thickness after mensuration) of determination unit.Thickness increment rate (gas generation characteristic) is obtained according to following formula.Thick Degree increment rate is the least, represents that gas produces inhibition the biggest.

Thickness increment rate (%)=(thickness/original depth after mensuration) × 100

[table 2]

Lithium ion battery and the evaluation of electrolyte

Make to employ by following method and contain above-mentioned secondary cell additive (B) with the cooperation number shown in table 3 Or compare the lithium ion battery of electrolyte for lithium ion battery with additive (B ').

With the situation of electrode similarly, for the lithium ion battery made, evaluate high voltage discharge and recharge by said method Cycle characteristics and output characteristics, evaluate gas by following method and produce, show the result in table 3.

[preparation of electrolyte]

With the part shown in table 3 in the ethylene carbonate mixed solvent (volume ratio 1:1) 87.5 parts with diethyl carbonate Number coordinates secondary cell additive (B) or compares with additive (B '), makes the LiPF as electrolyte₆To reach 12 weight % Mode be dissolved in wherein, prepare embodiment 34～48 and the electrolyte of comparative example 14～20.

[making of lithium ion battery positive pole]

By LiCoO₂90.0 parts of powder, Ketjen black [manufacture of SIGMA-ALDRICH company] 5 parts and polyvinylidene fluoride [manufacture of SIGMA-ALDRICH company] 5 parts is sufficiently mixed in mortar, and [Tokyo is melted into then to add 1-Methyl-2-Pyrrolidone Industrial Co., Ltd manufactures] 70.0 parts, it is sufficiently mixed in mortar further, obtains slurry.In an atmosphere by bar by gained To slurry be applied to the one side on the aluminium electroloysis paper tinsel that thickness is 20 μm, 80 DEG C be dried 1 hour, the most under reduced pressure (1.3kPa) it is dried 2 hours in 80 DEG C, is die-cut intoProduce lithium ion battery positive pole.

[making of negative electrode for lithium ion battery]

By the powdered graphite 92.5 parts of mean diameter about 8～12 μm, 7.5 parts and 1-methyl-2-pyrroles of polyvinylidene fluoride Alkanone 200 parts is sufficiently mixed in mortar, obtains slurry.By bar, obtained slurry being applied to thickness in an atmosphere is 20 The one side of the Copper Foil of μm, is dried 1 hour at 80 DEG C, and the most under reduced pressure (1.3kPa) is dried 2 hours in 80 DEG C, die-cut BecomeMake thickness be 3 μm with forcing press, produce lithium ion battery graphite system negative pole.

[making of lithium ion battery]

Two ends in 2032 type button cells, join above-mentioned positive pole and negative pole according to respective coated face mode in opposite directions Put, between electrode, insert dividing plate (polypropylene-made nonwoven cloth), produce lithium ion battery unit.

By embodiment 34～48 and the electrolyte of comparative example 14～20 be injected in made lithium ion battery unit Rear sealing, produces secondary cell (lithium ion battery).

Above-mentioned positive pole and negative pole are arranged in lamination unit according to respective coated face mode in opposite directions, inject embodiment 34～48 and the electrolyte of comparative example 14～20 sealing, produce lithium ion battery, the thickness measuring its unit is (initially thick Degree).

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Pond charges to voltage as 4.5V with the electric current of 0.1C, after suspending 10 minutes, with the current discharge of 0.1C to voltage as 3.0V, repeats Carry out 3 above-mentioned circulations.Electric current with 0.1C charges to voltage as 4.5V further, when maintaining voltage 60 DEG C of guarantors Deposit 7 days.Then, the thickness (thickness after mensuration) of determination unit.Thickness increment rate is obtained according to following formula.Thickness increment rate is the least, Represent that gas produces inhibition the biggest.

Thickness increment rate (%)=(thickness/original depth after mensuration) × 100-100

[table 3]

Lithium-ion capacitor and the evaluation of electrode

Made by following method and contain above-mentioned secondary cell additive (B) with the cooperation number shown in table 4 or compare With the lithium-ion capacitor electrode of additive (B '), this electrode is used to produce lithium-ion capacitor by following method.

By the following method high voltage charge/discharge cycle characteristics, output characteristics and gas are produced characteristic to be evaluated, will Result is shown in Table 4.

[making of lithium-ion capacitor positive pole]

By active carbon powder 90.0 parts, Ketjen black [manufacture of SIGMA-ALDRICH company] 5.0 parts, polyvinylidene fluoride The secondary cell additive (B) of number shown in [manufacture of SIGMA-ALDRICH company] 5.0 parts and table 4 or compare and use additive (B ') it is sufficiently mixed in mortar, then add 1-Methyl-2-Pyrrolidone [Tokyo HuaCheng Industry Co., Ltd's manufacture] 70.0 Part, it is sufficiently mixed in mortar further, obtains slurry.By bar, obtained slurry being applied to thickness in an atmosphere is 20 One side on the aluminium electroloysis paper tinsel of μm, is dried 1 hour at 80 DEG C, and the most under reduced pressure (1.3kPa) is dried 2 little in 80 DEG C Time, it is die-cut intoProduce lithium-ion capacitor positive pole.

[making of lithium-ion capacitor negative pole]

By the powdered graphite 92.5 parts of mean diameter about 8～12 μm, polyvinylidene fluoride 7.5 parts, 1-methyl-2-pyrrolidine Shown in ketone [Tokyo HuaCheng Industry Co., Ltd's manufacture] 200 parts and table 4, the secondary cell additive (B) of number fills in mortar Divide mixing, obtain slurry.Obtained slurry is applied to the one side of the Copper Foil that thickness is 20 μm, 80 DEG C be dried 1 hour, so After the most under reduced pressure (1.3kPa) in 80 DEG C be dried 2 hours, be die-cut intoForcing press is utilized to make thickness be 30 μ m.Obtained electrode and lithium metal foil dividing plate (polypropylene-made nonwoven cloth) are clipped and be arranged in cup type unit, the used time about 10 Hour make negative pole contains about negative pole theoretical capacity 75% lithium ion, produce lithium-ion capacitor negative pole.

[making of lithium-ion capacitor]

By embodiment 49～65 and the positive pole of comparative example 21～27 in the containing box being made up of polyacrylic aluminum stacked film Configure according to respective coated face mode in opposite directions with negative pole, between electrode, insert dividing plate (polypropylene-made nonwoven cloth), produce Capacitor unit.LiPF will be dissolved with the ratio of 12 weight % in propylene carbonate (PC)₆Electrolyte be injected into system Make unit in and seal, produce lithium-ion capacitor.

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Container charges to voltage as 3.8V with the electric current of 1C, after suspending 10 minutes, with the current discharge of 1C to voltage as 2.0V, repeat into This discharge and recharge of row.Battery capacity when measuring primary charging now and battery capacity when circulating of charging the 50th, by following formula Calculate charge/discharge cycle characteristics.Numerical value is the biggest, represents that charge/discharge cycle characteristics is the best.

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Container charges to voltage as 3.8V with the electric current of 1C, and after suspending 10 minutes, with the current discharge of 1C to voltage as 1.0V, mensuration is put Capacitance (is designated as 1C discharge capacity) below.Then the electric current with 1C charges to voltage as 3.8V, after suspending 10 minutes, with 10C Current discharge to voltage be 2.0V, measure capacity (being designated as 10C discharge capacity below), by following formula calculate 10C electric discharge time appearance Amount sustainment rate.Numerical value is the biggest, represents that output characteristics is the best.

Capacity dimension holdup (%)=(10C discharge capacity/1C discharge capacity) × 100 during 10C electric discharge

Capacity dimension holdup (%) when being discharged by 10C is shown in table 4 and 5 with the form of output characteristics (%).

Measure the thickness (original depth) of the lamination unit (lithium-ion capacitor) made by said method.

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Container charges to voltage as 3.8V with the electric current of 1C, after suspending 10 minutes, with the current discharge of 1C to voltage as 2.0V, measures and holds Amount (first battery capacity).Electric current with 1C charges to voltage as 3.8V further, when maintaining voltage 60 DEG C of guarantors Deposit 7 days.Then, the thickness (thickness after mensuration) of determination unit.Thickness increment rate is obtained according to following formula.Thickness increment rate is the least, Represent that gas produces inhibition the biggest.

[table 4]

Lithium-ion capacitor and the evaluation of electrolyte

Make to employ by following method and contain above-mentioned secondary cell additive (B) with the cooperation number shown in table 5 Or compare the lithium-ion capacitor of lithium-ion capacitor electrolyte with additive (B ').In the same manner as the situation of electrode, logical Cross said method and evaluate high voltage charge/discharge cycle characteristics, output characteristics and gas generation characteristic, show the result in table 5.

[preparation of electrolyte]

Adding with secondary cell with the number shown in table 5 in 87.5 parts of nonaqueous solvents constituted of propylene carbonate Agent (B) or compare with additive (B '), makes the LiPF as electrolyte₆It is dissolved in wherein in the way of reaching 12 weight %, system Standby go out embodiment 66～80 and the electrolyte of comparative example 28～34.

[making of positive pole]

As positive active material, the specific surface area obtained by alkali activation method is used to be about 2200m²The activated carbon of/g. Active carbon powder, acetylene black and polyvinylidene fluoride are mixed according to the mode of the ratio that respective weight ratio is 80:10:10, will This mixture adds to as in the 1-Methyl-2-Pyrrolidone of solvent, and stirring mixes, and obtains slurry.Utilize the doctor blade method should Slurry is applied on the aluminium foil that thickness is 30 μm, predrying after, cut according to the mode that electrode size is 20mm × 30mm. The thickness of electrode is about 50 μm.Before module units, by electrode in a vacuum in 120 DEG C be dried 10 hours, produce lithium from The positive pole of sub-capacitor.

[making of negative pole]

By the powdered graphite 80 parts of mean diameter about 8～12 μm, acetylene black 10 parts and polyvinylidene fluoride 10 parts mixing, will This mixture adds to as in the 1-Methyl-2-Pyrrolidone of solvent, and stirring mixes, and obtains slurry.Utilize the doctor blade method should Slurry is applied on the Copper Foil that thickness is 18 μm, predrying after, cut according to the mode that electrode size is 20mm × 30mm. The thickness of electrode is about 50 μm.It is dried 5 hours in 120 DEG C the most in a vacuum.Obtained electrode and lithium metal foil are used Dividing plate (polypropylene-made nonwoven cloth) clips and is arranged in cup type unit, and it is theoretical that about 10 hours used times made to contain in negative pole about negative pole The lithium ion of the 75% of capacity, produces lithium-ion capacitor negative pole.

[assembling of capacitor unit]

Dividing plate (polypropylene-made nonwoven cloth) is inserted so that it is middle infiltration embodiment 66～80 He between above-mentioned positive pole and negative pole The electrolyte of comparative example 28～34, puts in the containing box being made up of polyacrylic aluminum stacked film and seals, producing lithium ion Capacitor unit.

[table 5]

The safety evaluatio of lithium ion battery

[making of lithium ion battery]

Above-mentioned secondary cell additive (B) or compare is changed to shown in table 6 with the number that coordinates of additive (B ') Coordinate number, make lithium ion battery electricity consumption by the method as embodiment 17～33 and comparative example 7～13 in addition Pole, uses this electrode fabrication lithium ion battery.

For the lithium ion battery made, by following method, caloric value and exothermal peak temperature are evaluated, by result It is shown in Table 6.Caloric value is the lowest, exothermal peak temperature is the highest, then safety more improves.

Utilize discharge and recharge determinator " battery analysis device 1470 type " [TOYO Corporation manufacture], by lithium-ion electric Pond charges to voltage as 4.3V with the electric current of 0.1C, after suspending 10 minutes, with the current discharge of 0.1C to cell voltage as 3.0V, Repeating 3 these discharge and recharges, then the electric current with 0.1C charges to voltage as 4.3V.This battery is divided under an argon atmosphere Solving, take out positive pole, utilize diethyl carbonate to be carried out, under reduced pressure (1.3kPa) is dried 2 hours.Then, in argon gas atmosphere Under in LVC dish (resistance to platen), put into above-mentioned positive pole about 3mg and the mixing at ethylene carbonate (EC) Yu diethyl carbonate (DEC) Solvent (volume ratio 1:1) is dissolved with LiPF with the ratio of 12 weight %₆Electrolyte about 2mg, produce test sample.

Use differential scanning calorimeter (DSC) [Perkin Elmer company manufacture], from 25 DEG C with the speed of 5 DEG C/min It is warmed up to 320 DEG C, measures caloric value and exothermal peak temperature.

[table 6]

Result according to above-described embodiment and comparative example is judged, uses secondary cell additive (B) institute of the present invention The lithium ion battery made and the charge-discharge performance of lithium-ion capacitor and gas produce excellent, but also have and send out Hot inhibition.The reason improved as charge-discharge performance, it is believed that be because having the former of the atom that electronegativity is more than 3 The absorption of son group is at active material surface, it is suppressed that the decomposition reaction of electrolyte.It addition, as can effectively suppress gas to produce Reason, it is believed that be because three keys and active substance and there occurs reaction.It addition, it is represented to have above-mentioned chemical formula (2) in molecule Group or the compound (embodiment 8,9,11～14 and 16) of alkylidene epoxide (d) demonstrate the most excellent in terms of output characteristics Different effect.It is thought that because the lithium ion conductivity of these additives is high.About heating inhibition, detailed mechanism is the most not Clear, but considering is absorption work from the oxygen of active material surface releasing when the additive of positive electrode surface inhibits at high temperature With.

Industrial applicability

Employ the electrode of the secondary cell additive (B) of the present invention and electrolyte at lithium ion battery and lithium-ion electric In the electrochemical device purposes such as container useful, be particularly suitable for lithium ion battery used for electric vehicle and lithium-ion capacitor.It addition, For electrochemical device (double layer capacitor, Ni-MH battery, nickel-cadmium cell, the air electricity beyond disclosed in the present invention Pond, alkaline cell etc.) it also is able to application.

Claims

1. a secondary cell additive, it contains compound (A), and described compound (A) has atomic group (X) and three keys (b), described atomic group (X) by 3～5 atomic buildings, there are 2～4 electronegativity be the atom of more than 3 and there is at least 1 Double bond.

2. secondary cell additive as claimed in claim 1, wherein, atomic group (X) is in following chemical formula (1)～(5) Any one represented at least one group,

[changing 1]

[changing 2]

[changing 3]

[changing 4]

[changing 5]

-N=C=O (5).

3. secondary cell additive as claimed in claim 2, wherein, the group represented by chemical formula (1) is following formula (6) group represented by,

[changing 6]

4. secondary cell additive as claimed in claim 3, wherein, the group represented by formula (6) is for selecting free amino group first The group included at least one group in the group of perester radical, urea groups, allophanate group and biuret groups composition.

5. the secondary cell additive as according to any one of Claims 1 to 4, wherein, three keys (b) be carbon-to-carbon triple bond and/ Or carbon-to-nitrogen three key.

6. the secondary cell additive as according to any one of Claims 1 to 5, wherein, compound (A) has Asia further Alkyl oxy (d).

7. secondary cell additive as claimed in claim 6, wherein, compound (A) is with following formula (7) or (8) institute table The form of the construction unit shown has three keys (b) and described alkylidene epoxide (d),

[changing 7]

In formula (7), R¹Be carbon number be the alkylidene of 2～4, there is multiple R¹In the case of, R¹The most identical or different, R²It is Carbon number is the bivalent hydrocarbon radical of 1～10, R³Be hydrogen atom or carbon number that hydrogen atom can be exchanged for heteroatoms be 1～ The alkyl of 20, h is the integer of 1～40,

[changing 8]

In formula (8), P¹Be carbon number be the alkylidene of 2～4, there is multiple P¹In the case of, P¹The most identical or different, P²It is Carbon number is the bivalent hydrocarbon radical of 1～10, and i is the integer of 1～40.

8. secondary cell additive as claimed in claim 6, wherein, compound (A) is with the knot represented by following formula (9) The form of structure unit has alkylidene epoxide (d),

[changing 9]

In formula (9), W¹Be carbon number be the alkylidene of 2～4, there is multiple W¹In the case of, W¹The most identical or different, W²It is Carbon number is the alkyl of 1～20, and k is the integer of 1～40.

9. the secondary cell additive as according to any one of claim 1～8, wherein, under compound (A) has further State the group represented by formula (10),

[changing 10]

In formula (10), Q¹Be carbon number be the alkylidene of 2～4, there is multiple Q¹In the case of, Q¹The most identical or different, Q² Be carbon number be the bivalent hydrocarbon radical of 1～10, A is-CO₂ ^-Or-SO₃ ^-, M is monovalent metallic ion, and j is the integer of 0～40, and m is 0 or 1.

10. an electrode, it contains the secondary cell additive according to any one of claim 1～9.

11. 1 kinds of electrolyte, it contains the secondary cell additive according to any one of claim 1～9.

12. 1 kinds of lithium ion batteries, it has the electrode described in claim 10 and/or the electrolyte described in claim 11.

13. 1 kinds of lithium-ion capacitors, it has the electrode described in claim 10 and/or the electrolysis described in claim 11 Liquid.