* NOTICE *
`
`dPO and INPIT are not responsitie far any damages caused by the use of this teansiation.
`
`1. This document has been translated by computer. Se the transigtion may nat sefiect ine original precisely.
`
`2°" shows a word which cannot be transiated,
`
`3, in the drawings, any words are not franstated,
`
`Publication Number
`
`JIP2018 1494494,
`
`Bibliography
`
`(19) [Publication country] JP
`
`(12) [Kind of official gazette] A
`
`(17) [Publication number} 2016743449
`
`(43) [Date of publication of application] 20760808
`
`(54) [Tite of the invention] NONAQUEOUS. TYPE ELECTROLYTIC SOLUTION AND
`
`NONAQUEOQUS TYPE ELECTROLYTIC SOLUTION SECONDARYBATTERY USING
`
`THE SAME
`
`(51) finternational Patent Classification]
`
`(2010043
`
`(2010.04)
`
`{2010.04}
`
`HOIM «10/0867
`
`HOIM 10/0825
`
`HOIM 10/054
`
`[Fl]
`HOIM 10/0567
`
`HOIM 10/0525
`
`HOIM 10/054
`
`(21) [Application number} 2015015877
`
`(22) fFiling date] 20750729
`
`(71) [Applicant]
`
`iName] MITSUBISHI CHEMICALS CORP
`
`(72) [inventor]
`iFull name} OHASHI YOICHI
`
`fFull name} FUUN TAKASHI
`
`Themecode (reference)]
`5HO2S
`
`{F-term (referance) J
`
`

`

`SHO294 02
`
`SHOZIAJOS
`
`SHOZSAIO?
`
`BHOZSAKOS
`
`SHOZSAL07
`
`SHOZSAMOS
`
`SHOZSAMO?
`
`SHO2ZSBJO4
`
`SHOZSBII2
`
`SHOZEC02
`
`SHOZ9CIO3
`
`SHOZSCTSOS
`
`SHOZSCI13
`
`SHO29CJ22
`
`SHO2ZSDIO9
`
`SHOZSE S11
`
`SHOZGHIO2
`
`SHOZSHIIO
`
`Abstract
`
`(57) [Oveniew)
`PROBLEM TO BE SOLVED: To provitle nonaqueaus type electrolytic salution that can
`
`suppress occurrence of gas under a high temperature condition, enhance the cycle
`
`characteristic and enhance a high efficiency discharge characteristic, and a nonaqueous
`
`type electrolytic liquki secondary battery using the same.
`
`SOLUTION: Nonaqueous type electrolytic solution used for @ nonaqueous type
`
`electrolytic solution secondary batfery contains a positive electrode having a positive
`
`electrode active material capable of occlucing/discharging metal jons, and a negative
`
`electrode having a negative electrode active material capable of occluding/discharging
`
`metal ions. The nonaqueous type electrolytic sohution contains cyclic carbonate having
`
`unsaturated bonds, cyclic carbonate having halogen atoms, at
`
`least one kind of
`
`compounds selected from a sultone compound and a nitryl compound, a compound
`having isocyanate group (N=C=O group}, and at least one kind of compounds selected
`
`fram a compound represented by the formula (1) and a compound having twe or more
`acrylic groups or methacryl groups in a molecule, these compounds being contained in
`
`respective specific amount ranges.
`
`

`

`SELECTED DRAWING: None
`
`Claim
`
`[Patent Claims]
`{Claim 4]
`
`It
`
`is a nonaqueous efectolyte used for a nonaqueous slectrolytic solution secondary
`
`battery provided with the pasitive electrade which has the pasitive active material which
`
`may occlude and emit metal ion, and the anode which has the negative electrode active
`
`material which may occlude and emit metal jon,
`
`The content of a cyclic carbonate having an unsaturated bond is X (mass%).
`The content of a cyclic carbonate having a halogen atomis Y (mass%)}.
`
`The content of at least 1 kinds of compounds selected from a sultone cormpound and a
`
`nitride compound is Z (mass%4}.
`
`tis A (mass %) about the contained arnount of al least 1 or more type of compounds
`
`chosen fram the compound which has an isocyanate group (N=C=O group), and the
`
`compound which has the compound and acrylic group, or methacrylic group denoted by
`
`a following formula (1) in f two or more | a molecule,
`
`{Chemical formula 1]
`
`{R 1, R 2, and R 3 each independently represents an organic group, and at least one of
`
`Ri, R 2, and KR 3 represents an organic group having an unsaturated bond.)
`
`The nonaqueous electrolyte solution is characterized by satisfying all of the following
`
`expressions.
`
`g<s%s0.5
`
`058Y¥<8.0
`
`0.86s266.0
`
`08sAs5.0
`
`However, fhe above content refers to the ratio (mase%} of each compound to the total
`
`weight of the nonaqueous electrolyte solution, and when 2 armore of each compound is
`
`contained, X, Y, Z, and A represent the total amount thereof.
`iClaim 2]
`
`The content of the sultane compound is Z (nass%).
`408 254.0
`
`The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous
`
`

`

`electratytic solution contains no vinylene carbonate and no vinylene carbonate.
`
`iClaim 3]
`
`The contert of the dinitrie compound is represented by 2 (> by mass}.
`
`TOsZs4.0
`
`The nonaquecus electrolytic solution according to claim 1, wherein the nonaqueous
`
`electrolytic solution contains no vinylene carbonate arid no vinylene carbonate.
`
`Claim 4]
`
`is @ nonaqueous electrolytic solution secondary battery provided with ihe positive
`electrode which hasthe positive active material which mayocclude and emit metal jon,
`
`and the anode which has the negative electrode active material which may occlude and
`
`emt metal ion,
`
`Nonaqueous electrolytic solution using a nonaqueous electrofytic solution according to
`
`any one of claims 7 to 3
`
`““ rechargeable battery.
`
`Description
`
`[Detailed description of the invention}
`
`fTechnical flelc]
`
`foo0T}
`
`The present invention relates to a nonaqueous electrolytic solution and a nonaqueous
`
`electrolytic solution 2 battery using the same.
`
`fBackground of the invention]
`
`(002)
`
`With rapid progress of electronic equipment, there has been an increasing demand for
`
`higher capacity for secondary batteries, and a nonaqueous electrolyte battery such as a
`
`lithium ion secondary battery having a high energy density has been widely used and
`
`has been actively stuciac as well as a 2 battery having a high capacity for a 2 battery.
`
`Anelectrolytic solution used in a nonaqueous electrolyte battery generally comprises an
`
`électrolyie and a nonaqueous solvent. As an electrolytic salution of a Hihiun ion
`
`secondary battery, a nonaqueous electrolytic solution in which an electrolyte such as
`
`LIPF 2 is dissolved in a mixed solvent of a high dielectric canstant solvent such as a
`
`cyole carbonate and a low viscosity solvent such as @ chain carbonate is used as the
`
`electrolyte of the INhium ian secondary battery 6.
`{0003}
`
`in a lithium jon secondary battery, when charging and discharging are repested, an
`
`

`

`electratyte decomposes on an electrade, and deterioration of a material constituting a
`
`battery occurs, and thus a capacity of a battery is reducedin the battery 2. In some cases,
`
`there is @ possibilty that the safety against swelling, ignition, explosion, explosion, and
`
`the like is reduced.
`
`The method of improving the battery characteristic of a rechargeabie lithium-ion battery
`
`is proposed by making a specific additive agent cantain into nonaqueous siectrolyte until
`
`now. For example, in Patent Document 1, a positive electrode is a material containing a
`
`lithium composite oxide, a negative electrode is a material containing graphite, and a
`
`nonaqueous solvent is mainly a cyclic carbonate and a linear carbonate. It has been
`
`reported that by using an electrolytic solution containing 0.1 wis or more and 4 wi% or
`less of 1,3-propanoic sultone and / or 1,4-butane sultone in a nonaqueous solvent, the
`
`capacity retention ratio after 50 cycles at
`
`room temperature is improved. Patent
`
`Document 2: A 2 anion of the 7 anion represented by [B (CiH 2 (i- 2) 4) (CJM 2 & - 25434]
`
`~ where | and j are integers of 2 or more} and anionaf the 7 anion ;
`
`It has been reported that by using an electrolyte containing an anion,
`
`the cycle
`
`characteristics and the low-temperature characteristics at - 20° C. in an environment of
`
`4.2 V and 25 ° C. are improved. Ata Patent docurnent 3, it is Cu affinity.
`
`AS a sex compound, a diniirile compound having 2 nitiie groups, a trinttrile compound
`
`having 3 nitrile groups, and a trinitrile compound having one nitrie group are provided. If
`
`has been reported that an over-discharge property is improved by using an electrolytic
`
`solution containing 2 nitrile groups and containing 1 or 2 or more of thiodialkyinitrile
`
`compounds having a thio Ether group in the molecule.
`
`iPrior art reference]
`
`iPatent document]
`
`{0004}
`
`iPatent document 1]JP 2000-0037244
`
`{Patent document 2)LUP 2005-228565A
`
`[Patent document SP 2006-73513A4
`
`fSummary of the invention]
`
`iProblem to be solved by the invention]
`
`{0005}
`
`The present invention makes if problem toprovide the nonaqueous efectolyte which can
`
`manufacture the cell which there waslittle generation af gas on high temperature service,
`
`was excellent in the cycle characteristic, ancl excellent also in the high rate discharging
`characteristic, and the nonaqueous electrolytic solution secondary battery swerved and
`
`usedin a nonaqueous electrolytic solution secondary battery.
`
`

`

`iMeans for solving the problen]
`
`(O008)
`
`Patent Documents 1 fo 3 certainly contribute tea improvement of various characteristics,
`
`but in particular, the gas generation whichis important for the safety of a battery is not
`
`scived, and a high temperature cycle cycie is important in battery characteristics.
`
`It has not been demonstrated that
`
`the lucharacteristics and high-rate discharge
`
`characteristics are improved.
`
`As a result of carrying out various studies in order to solve the above problems, the
`
`present inventors have found that the above problems can be solved when a specific
`
`compound is combined in a predetermined amount, and has completed ihe present
`INVENT,
`
`fO007}
`
`Namely, the summaryof the present invention,
`
`<|>
`
`Non-water system used for a nonaqueous electrolytic salution secondary battery
`
`provided with the positive electrode which has the positive active material which may
`
`occlude and emit metal ion, and the anoce which has the negative electrode active
`
`material which may occlude and emit metal ion
`
`The electrolyte is an electrolyte.
`
`The content of a cyclic carbonate having an unsaturated bond is X (mass%).
`
`The content of a cyclic carbonate having a halogen atom is Y¥ (mass).
`
`The content of at least 1 kinds of compounds selected from a sultone compound and a
`
`nitrde compound is Z (mass).
`
`A imass%s) is a content of at least one compound selected from a compound having an
`isocyanate group ( C = O = O group), a compound represented by formula (1), anda
`
`compound having 2 or more acryl or methacryl groups in the molecule : and A (1)
`
`{0008}
`
`{Chemical formula 7]
`
`{0009}
`
`{R 1, R 2, and R 3 each independently represents an organic group, and at least one of
`
`R1,R2, and R 3 represents an organic group having an unsaturated bond}
`The nonaqueous electrolyte solution is characterized by satisfying all of the following
`
`expressions,
`
`

`

`OsXs0.5
`
`O5¢¥<s8.0
`
`C8<s£s6.0
`
`O&8sA65.0
`
`However, the above content refers io the ratio (mass36) of each compound to the total
`
`weight of the nonaqueous electrolyte solution, and when 2 of more of each compound is
`
`conlained, x, ¥, 2, and A represent the ictal amount thereof,
`
`2> The content of the sultorie compound is represented by 2 (> by mass).
`10<254.0
`
`The nonaqueous electrolytic solution according to (1), wherein the nonaqueous
`electrolytic solution cortains winylene carbonate and daes not contain vinylene
`
`carbonate.
`
`(3) The Z (mass%) is a content of a dinitrile compound :
`
`10<254.0
`
`The nonaqueous electrolytic solution according to (1), wherein the nonaqueous
`
`electrolytic solution contains vinylene carbonate and dees not contain vinylene
`
`carbonate.
`
`<A>
`
`it is a nonaqueous electroiytic solution secondary battery orovided with the
`
`positive elactrode which has the positive active material which may occlude and emit
`
`metal ion, and the anode which has the negative electrode active material which may
`
`occlude and emit metalion,
`
`A nonaqueous electrolytic solution secondary battery using the nonaqueous electrolytic
`
`solution according to any one of (1) ta (3). 2.
`
`fEHect of the Invention]
`
`{0070}
`
`According to the present invention, there is ittle generation of gas and it can obtain the
`
`nonaqueous electrolytic solution secondary battery excellent in the cycle characteristic
`
`and the high rate discharging characteristic.
`
`fMode for carrying out the invention)
`
`{004 7]
`
`Hereinafter, embodiments of the present invention will be described in detail, However,
`
`the folowing description is an example of an embodiment of the present invention
`
`(representative example), and the present invention is not limited to these contents
`
`unless the gist of the appended claims is exceeded.
`{0042}
`
`[i. Nonaqueous Electrolyte salution]
`
`

`

`The nonaqueous electrolytic solution accarding to the present invention is similar to a
`
`general nonaqueous electrolytic solution of the present invention.
`
`The composition contains @ nonaqueous solvent.
`
`The content of a cyclic carbonate having an unsaturated bond is X (mass%).
`
`The content of a cyclic carbonate having a halogen atom is Y (mass%s).
`
`The content of at least 1 kinds of compounds selected from a sultone campound and a
`
`nitrie compound is Z (mass4).
`
`A (mass%s)is a content of at least one compound selected from a compound having an
`
`isocyanate group & C = O = O group), a compound represented by formula (1), and a
`compound having 2 or more acryl or methacryl graups in the molecule ; and A (7)
`
`[0043]
`
`[Chemical formula 2]
`
`jod44}
`
`(R 1,R 2, and R 3 each independently represents an organic group, and at least one of
`
`R1,R2, and R 3 reoresents an organic group having an unsaturated bond.)
`
`In this case, the following equation is satisfied.
`
`O5xXs0.5
`
`O58¥<8.9
`
`C847<6.0
`
`O8sAs5.0
`
`However, the above content refers to the ratio (mass%) of each compound ta the total
`
`weight of the nonaqueous electrolyte solution, and when 2 or more of each compound is
`
`contained, X, ¥, Z, and A represent the total amount thereof.
`
`[O04 5}
`
`(1-4) A cyclic carbonate having an unsaturated bond ;
`
`Examples of the unsaturated cyclic carbonate having an unsaturated band include, but
`
`are not limited to, the following.
`
`For example, vinylene carbonate (VC), methyl vinylene carbonate, ethyl vinylene
`
`carbonate, 1,2-dimethylvinyiene carbonate, 1,2-diethylvinylene carbonate, Vinylene
`
`carbonate compounds such as fluarovinylene carbonate and trifluoromethyl vinylene
`carbonate ; vii ethylene carbonate,
`t-methyl-2-vinylethyiene carbonate,
`jJ-ethyl-2-
`
`vinylethylene carbonate, and 1-n-propyl-2-vinylethylene carbonate ; Examoles thereof
`
`

`

`include vinyl ethylene carbonate compounds
`
`such as
`
`t-methyl-2-vinylethylene
`
`carbonate, 1,1-divinylethylene carbonate and 1,2-divinylethylene carbonate ; methylene
`
`ethylene carbonate compounds such as 1, 1-dirnethyl-2-methyleneethyiene carbonate
`
`and 1,1-diphenyl-2-methyleneethylene carbonate ; and ***°""eteeee*
`
`fO0716}
`
`They are virryiene carbonaie, vinyl ethylene carbonate, and ethynyl *** among these.
`
`The ******* is preferred from the viewpoint of improving the cycle characteristics and ihe
`
`capacity retention characteristics after storage at high temperature, more preferably
`
`vinylene carbonate or vinyl ethylene carbonate, and particularly preferably vinylene
`
`carbonate. These may be used alone ar in combination of 2 or more. When 2 or more of
`
`therm are used in combination, vinylene carbonate and vinyl ethylene carbonate are
`
`preferably used in combination.
`
`{0047]
`
`The content of the cycle carbonate having an unsaturated bond is represented by X (%
`
`by mass} based on the weight of the whole qonaqueous electrolytic solution.
`
`O<X<0.5
`
`“*** In particular, the upperlimit of the content X is preferably 0.3 or less, more preferably
`
`0.2 of fess. Under such conditions,
`
`in combination with other additives, generation of
`
`high-temperature storage gas can be suppressed, and increase in resistance is
`
`suppressed, sa that high temperature cycle characteristics and high-rate discharge
`
`characteristics can be improved.
`
`{9078}
`
`(1-2) a cyclic carbonate having a halogen aiom ;
`
`The cyclic carbonate having a halogen atorn as claimed in the claims is not particularly
`
`limited, and exarnpies thereof inchude the following.
`
`Examples of the halogen atom of a cyclic carbonate having a halogen atom include a
`
`fluorine atom, a chiorine atom, a bromine atorn and a ladine atom, and amang these, a
`
`fluorine atom and a chiofine atom are preferred, and a fuarine atom is particularly
`
`preferred,
`
`{0079}
`
`As cyclic carbonate which has a fluorine atom, they are fluaro ethylene carbonate, 1,2-
`
`difluoroethyiene
`
`ester
`
`carbonate,
`
`1.1-difluoroethylene
`
`ester
`
`carbonate,
`
`1,1,2-
`
`1~-fluoro-
`trifuoroethylene carbonate, and tetrafluarc ethylene carbonate, for example,
`Z-methylethyiené ester carbonate, 1-fluore-i-methylethylene ester carbonate, 1,2-
`
`difluoro-t-methylethyiene
`
`ester
`
`carbonate,
`
`1,1,2-trifluoro-2-methylethyiene
`
`ester
`
`

`

`carbonate, trifluaro rnethyl ethylene carbanate, etc. are mentioned.
`
`(0020)
`
`Of these, fluoroethylene carbonate, 1,2-difluoroethyiene ester carbonate and 1-fluore-2-
`
`methylethylene ester carbonate are preferred from the viewpoint of improving cycle
`
`characteristics and improving high-temperature storage characteristics. These may be
`used alone or in combination of 2 or more.
`
`The content of a cyclic carbonate having a halogen atom is represented by Y (mass%)
`
`based on the weight of the whole nonaqueous electrolyte.
`GC5<¥s38.0
`
`wee* In particular, the upper limit of the content Y is preferably 7.0 orless, more preferably
`6.0 of less, and particularly preferably 5.0 or less. The lowerlimit af the content Y is mare
`
`preferably 0.8 or more, and further preferably 1.0 or more. Under such conditions, in
`
`combination with other additives, generation of high-temperature storage gas can be
`
`suppressed and high-temperature cycle characteristics can be improved.
`
`[0027]
`
`f4-3. A sultone compound and a nitrile cornpound}.
`
`The sultone compound and the nitrile compound described in the claims are not
`
`particularly limited, and examples thereof include the following.
`
`AS a sulfone compound -- for example
`
`1,3-propandic sultone, 14-butane sultone, 1,3-propenaic sultone, and 1,4-buten sultone
`
`are mentioned. Among these, 1,3-propansic sultone, 1,4-butane sultone and 7,3-
`
`propenoic sultone are preferred, and 1,3-propancic sultone and 1,3-propendic sultone
`
`are particularly preferred for obtaining excellant cycle charactenstics. These may be
`
`usedalone or in combination of 2 or more.
`
`{0022}
`
`As a nitryl compound -- for example
`Acetonitrile,
`propionitrile,
`butyronitile,
`
`valeraniinie,
`
`hexanenitrile,
`
`hepstanenitnile,
`
`octanenitnle, nonornitrile, decanenitrile,
`
`lauronitrile, tridecanenitrile,
`
`tetradecanenitrile,
`
`hexadecanenitrile,
`
`pentadecanenitrile,
`
`heptadecanenitrie
`
`Qctadecanonitrie,
`
`nanadecanenitrile, icosanonitrie, crotononitrile Monanitries such as methacryionitrile,
`
`acrylonitrile, methoxyacryioniirile, and the like ; malono nitrile, succinonitrile, glutaronitrle,
`
`adiponitrile, pimeloonitriia, subeelonitrie, azelaonitrile, *'**, and the like ;
`
`Ethyl malona nitrile,
`Li, undecanedinitrile, dodecanedinitrile, methyimaiononitrile,
`isoprapyl maiono nitrile, te r Cbutyimalononitrile, *°°****""",, 2. 2-dimethylsuccinaninie,
`f
`2,d-dimethyisuccinonitrie,
`imethylsuccinonitrile,
`tetramethyisuccinanitle, 3,3 |
`~
`
`

`

`weeded
`
` - thiedipropionitrile, 3,3 “
`Dinitries, such as propionitrile, 3.3 °
`tereeees 33°"
`- (athylenedithio) dipropionitrile, 1.
`
` - (ethylenediaxy}
`
`Mention may be made of
`
`irnitrles
`
`such as 2,3-propanetricarbonittie, 1,3,5-
`
`pentanetnicarbonitrile, 1,2,3-tris(2-cyanoethoxyjpropanoic, tris(2-cyanoethyl esterjamine
`and the like.
`
`{0023}
`
`Among these, preferred are valeronitrile, octanenitrde, decanenitrile,
`
`lauronitria,
`
`succinonitrile, glutaronitrie, adiponitrie, pimeloonitrile, suberonitriie, and crotonanitdie,
`
`it is preferred that ocilanenitrile, decanenitrile,
`among which valeronitriie is preferred.
`lauronitrde, succinonitrie, aciponitrde, pimenitie, and sbeelonitrie have a large effect of
`
`suppressing gas generation inside the battery. These may be used alone or in
`
`combination of 2 or rere,
`
`[0024]
`
`The content of at least 1 kinds of compounds selected frarn a sultone compound and-a
`
`niiriie compound is represented by 2 dmassds) based on the weight of the whole
`
`nonaqueous electrolyte solution.
`
`0.8s226.0
`
`“«** In particular, the upper limit of the content 2 is preferably 5.5 or less, more preferably
`
`5.0 orless. The lower limit of the content Z is more preferably 1.0 or more. Whenit is
`
`within this range, an increase in the resistance of the battery is not excessively large,
`
`and a gas generation suppressing effect can be sufficiently obtained.
`
`{9025}
`When the content of the sultone compound is Z (S$), 1.0 = 2 {5} & 4.0, and more
`preferably 1.0 =: Z(S) & 3.8. Also dinitrile
`
`When the content of the compound is 2 (), 1.0 & 20 % 4.0, and more preferably 1.0
`
`& 24) & 3.8.
`
`(1-4) A compound having an isocyanate group (= C =O group), a compound represented
`
`by formula (1), and a compound having 2 or more acryl or methacryl groups in the
`
`molecule ;
`
`Examples of the compound having an isocyanato group C = O group), a campound
`
`represented by Formula (7), and a compound having 2 or more acry! or methacryl groups
`
`in the molecule are not particularly imited, and examples thereof include the fallowing.
`
`fO026)
`AS a compound having an isocyanato group @ C = © group},
`
`for example,
`
`isacyanatomethans, isocyanatoethana, 1-isocyanatopropane, and the like are described,
`
`

`

`j-socyanatobutane, 1-isocyanatopentane, {-isocyanatohexane, j-isocyanato heptanaic,
`
`y-4socyanatoactane,
`
`T-isocyanalo
`
`nonanoic,
`
`j-isocyanato
`
`Gecanoic,
`
`isocyanatocyciohexane, and the hke.
`
`see Ethoxycarbonyl fsocyanate, ANTHERS seeeenenneeeeessnteereeee
`Cyanate, rr esteetinis scoosmmmeeareiine mmannineesniEmiEREEREND MEER
`
`} A-diisocyanate butanoic, 1,5-diisocyanato pentanoic, 1,6-diisocyanato hexanoic, 1,7-
`
`disocyanato heptanoic, 1.8-diisocyanaio octanoic, 1,9-diisocyanato nonanoic, 1,10-
`
`diisocyanato decancic,
`
`1,3-disocyanate propensic, 1 4-dlisocyanalo-2-buten, 1,4-dlisocyanato-2-fluorobutane,
`
`4 ,4-diisocyanato-2,3-difluorobutane, 1,5-diisocyanato-2-penten, 1,5 - dlisocyanato-5-
`mathyipen 2
`
`A tongue, 17,6-clisecyanato-2-hexen, 1,6-diisocyanato-3-hexen, 1,6-diisecyanato-3-
`
`fluorchexane, 1,0-diisocyanato-3,4-difluorohexane,
`
`Toluene
`
`diisocyanate,
`
`xylenedisocyanate,
`
`olyiene
`
` disacyanate,
`
`bisisocyanatomethylicyciohexan,
`
`1,3-bistisocyanatomethyljcyclohexan,
`
`te.
`
`14
`
`cyclohexan,
`i,2-diisocyanate
`bisisocyanatomethyjcyciohexan,
`cyclohexan, 1.4-diisacyanato cyclohexan, dicyclohexyimethane 1.1’
`
` 1,3-dilsacyanate
`- diisocyanate,
`
`aeeeenase 22 -
`
`diisocyanate,
`
`dicyclohexyimethane
`
`-
`
`3,3'
`
`-
`
`diisocyanate,
`
`dicyclohexyimethane - 4,4' - diisocyanate, isaphorone
`
`Diisocyanates, 1,6,]1-triisocyanato undecanoic, 4-isacyanatomethyl- 1 ,8-actamethylene
`
`ester disocyanate, 1,3,6 - trisocyanate methyibenzene, bicycle [2.2. Theptandic-2,5-
`
`diyibis(methy! = isocyanate], bicyclo [2.2. Theptancic-2,6-diylbis(methyl = isocyanate].
`
`Examples thereof include 1,3,5- tris (6 - "rr'** - 1 - yw) - 1,35 - Wagine-2 (1h. 3h, 5
`
`hh} - trione, 2,4 4-trimethylhexamethylene metinyibenzene, 2.2,4-rimethyilhexamethylens
`
`methylbenzene,, 4-(isocyanatomethyloctamethylene aster, and the like. 2.4.6.
`
`[027]
`
`They are t-butylisocyanate and tetramethyiene di-isocyanate among these, Preferred
`
`is
`
`pentamethyienedi
`
`isocyanate,
`
`hexamethylene
`
`diisocyanate,
`
`bisGsocyanatomethylicyclohexan,
`
`1,3-bissocyanatomethylicyciohexan,
`
`and
`
`1,2-
`
` 1,4-
`
`bis(isocyanatomethyljcyciohexan, and mere preferred is hexamethylene diisocyanate
`
`and 1,3-bis(isocyanatomethyljcyciohexan. These are preferred from the viewpoint of
`
`improving cycle characteristics and improving high-temperature storage characteristics.
`These may be used alone or in combination of 2 or more.
`
`Examples of the compound represented by ihe following formula (7) include the following
`
`

`

`compounds.
`
`{0028}
`
`[Chemical formula 3]
`
`{5029}
`
`(R 1, R 2, and R 3 each independently represents an organic greup, and atleast one of
`R1,R 2, and R 3 represents an organic group having an unsaturated bond.)
`
`For example, bird vinyl
`isocyanurate,
`timethallyl
`
`Triallyl
`isocyanurate and tri(1-propenyl}isocyanurate,
`socyanurale, methyldiallyl
`isocyanurate, *"*****ere**,
`
`WASSERAPRSCREES | RRMWHELASHEStel (Oroparayl) isocyanurate, iris (2 - acrylate}
`
`Mention may be made of alkoxymethy]) isocyanurate, tris (2 - acryloxyethy!) isocyanurate,
`
`tris(2-methacryloxy methylisecyanurate,
`
`tris(2-methacryloxy ethylsocyanurate,
`
`& -
`
`caprolactane-modified tris - (2 - acryloxyethyl) isocyanurate and the like.
`
`[O030}
`
`Among these,
`
`tiallyl
`
`isocyanurate,
`
`trimethally! isocyanurate,
`
`tris (2 - acryloxyethy)
`
`isocyanurate, tis(2-methacrylony ethyl Nsocyanurate,. epsilon.
`
`- caprolactone modified
`
`tris ~ (2 - acryloxyethyl) isocyanurate, andthe like wit be described.
`
`Preferably,
`
`tnallyi
`
`isocyanurate, tis (2 - acryloxyethyl)
`
`isocyanurate is particularly
`
`preferred because of its high effect of improving cycle characteristics. These may be
`
`usedalone or in combination of 2 or more.
`
`{0037}
`
`The compound having 2 or more acry! groups or methacryl groupsin its molecule is not
`
`particularly limited, and examples thereof include the following.
`
`For exampie, 2 - hydroxy - 3 - ***8888ereereseeestetracthylene
`
`Glycol diacrylate, nonaethylene glycol diacrylate, Propoxylated ethoxylated bisphenol
`
`A diacryiate,
`
`propoxylated
`
`ethoxylated
`
`bisphenol A diacrylate,
`
`9,9-bis[4-(2-
`
`acryloyloxyethoxyjphenylifiuorene,
`
`ftricycis decanedimethanol
`
`diacrylate,
`
`1,10
`
`-
`
`decanediol diacrylate, 1,6 - glycidy!
`
`Sun Diol diacrylate, 1,9-nonane diol di acrylate, dipropyiene glycol diacrylate,
`
`tripropyiene glycol diacrylate, pentaerythritol tiacrylate, rimethyloipropane triacrylate,
`
`Ditrimethyicl
`peniaeryihritol
`
`ethoxylated
`tetraacrylate,
`propane
`tetraacrylate,
` dipentaerythritol
`
`pentaerythritol
`hexaacrylate,
`
`tetraacrylate,
` dipentaerythnitol
`
`peniaacrylate, dipentaeryihritol hexamethacryiate, and dipentaerythrito!l hexaacrfate.
`
`

`

`tHeeanerereaeeetett tatrasthylene glycol dimsthacrylate, “****«" propoxylated
`
`ethoxylated bisphenol A dimethacrylate Propoxylated ethoxylated bisphenol A
`
`dimethacrylate,
`
`9,9-bis[4-(2-acryioyloxyethoxyjphenyiifiuerens,
`
`tricyclodecane
`
`dimethanol dimethacryiate, 7,70 - decanaciol dimethacrylate, 1,G-hexanedial
`
`Dimethacrylate, 1,9-nonane diol di methacrylate, diprapylene glyco! dimethacrylate,
`
`Tripropylene
`
`qiycol
`
`dimethacrylate,
`
`pentaerythritol
`
`trimethacrylate,
`
`trirmethylciprapanetrimethacrylate,
`
`ditrimethylalnrapane
`
`tetra
`
`methacrylate,
`
`Ethoxylation pentaerythritol
`
`tetra methacrylate, pentaerythritel
`
`tetra methacrylate,
`
`Exampies
`
`thereof
`
`include
`
`dipentaerythritol
`
`hexamethacrylate,
`
`dipentaerythritel
`
`dipantaerythritol
`pentamethacrylate,
`teiramethyloimethane tetraacrylate.
`
`fOg32]
`
`hexamethacrylate, “Tseand
`
`Of these,
`
`tetraethylene glyco! diacrylate, pentaerythritol
`
`triacrylate. cipentaeryihrite!
`
`hexaacrylate, dipentaerythritol pentaacrylate, anc tetramethylalmethane tetraacrylate
`
`are preferred because they have a large effect of improving the cycle characteristics and
`
`suppressing the gas.
`
`The compound which has an isocyanate group (N=G=O group), the compound denoted
`
`by a following formula (1), And when the contained amount of at least 1 or more type of
`
`compounds chosen from the compound which has an acrylic group or an methacrylic
`
`group in f two or more ] a molecule sets contained amount to the weight of the whole
`
`nonaqueous electrolyte to A (mass %)},
`08s A55.0
`
`““s* in particular, the upper limit of the content A is preferably 4.0 or less, more preferably
`3.0 of less. The lowerlimit of the content A is mere preferably 1.0 er more. On such
`
`conditions
`
`In addition, in combination with other additives, since the effect of improving the cycle
`
`characteristics is large and the increase of the resistance is suppressed, the high-rate
`
`discharge characteristics are also excellent.
`
`[O03]
`
`In adelition, when each compound contains 2 or more kinds of aach campound, x, Y, 2
`
`and A represent the total amount thereof.
`
`According to the presentinvention, it is possible to obtain a battery of a balanced nature
`
`which can not be achieved either alone or when using an amount deviating fram a
`
`particular range by combining a particular compound in a particular amount and adding
`to an electrolyte. Detallecl Description of the Present Invention
`
`

`

`Although # is not known,
`
`it is considered as follows.
`
`in other words,
`
`in the present
`
`invention, the amount of the cyclic carbonate having an unsaturated bond is limited to 4
`
`fixed amount or less, and by using a cycke carbonate having a halogen atom, the
`
`resistance of a film formed an the surface of the negative electrode is suppressed. At
`
`1 cr more type of compounds chosen from a sultone campound and a nitry!
`least
`compound,
`the compound which has an isocyanate group (N=C=O group),
`the
`
`compound denoted by a following formula (1), When at least 2 or mare compounds
`
`selected from compounds having 1 or more acrylic or methacrylic groups in the molecule
`
`are present in a certain amount, the stability of a film formed on a surface of a negative
`
`electrode is improved, and as a result, various battery characteristics such as cycie
`characteristics and storage characterstics are improved.
`
`fOgS4]
`
`{7-5. electrolyte}
`
`There is no limitation on the electrolyte used in the nonaqueouselectrolyte of the present
`
`invention, and any known electroiyie may be employed as lang as it is used as an
`
`electrolyte in a desired nonaqueous electrolyte secondary battery 2.
`
`In using the
`
`nonaqueous electoalyte of the present invention for a lithium secondary battery, it usually
`
`uses lithium salt as an electrolyte.
`
`[O03 5}
`
`As ithium=salf,an electrolytic example, it is inorganic such as
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`LiGiO4d LiASFS LIPFO, LIBF4 LiSbF6 LISOSFLIN(FSO2) 2;
`LIiCF3SO3,LIN (FSO 2) (CF 3 SO 2), LIN (CF 3 SO 2) 2, LIN (C 2 F 5 SO 2) 2, lithium
`
`cyclic 13 - “esses Hthigm cyclic 1,2 - tetrafluoroethanedisulfonyl imide, LIN
`
`(OF 3 SO 2) {0 4F 9 SO 2). LIACF3ISO2) 3, LIPF4 (CF3) Fluorine-containing organicity
`lithium salt,
`such as
`2, LIPF4(C2F532, LIPF4(CF3SO2}2. LIPFA(C2F5SO02)2,
`
`LIBF2(CF 332, LIBF2(C2F532, LiBF2(CF3SO2}2, and LIBFA(C2F5S02}2:
`
`Examples thereof include a dicarboxylic acid complex lithium salt such as ithium bis
`
`{oxalate} borate, lithium difkiorooxalatoborate, lithum tis (oxalate) phosphate, lithium
`
`difiuorobis (oxalato) phosphate, and “****°?* foxalate) phosphate.
`
`{0036}
`
`OF these, LIPFG,LIBF4 LISOSFLIN (SO 2) 2, LIN (FSO 2} (CF 3 SO 2), LIN (CF 3 SO
`
`2) 2, LIN {C 2 F & SO 32} 2. lithium bis (oxalats} borate, and LIN (C 2 F & SO) are obtained
`
`from the viewpoint of solubility / dissociation degree in nonaqueous solvent and electric
`
`conductivity. Preference is given to lithium difluorocxalatoborate, lithium tris foxalato)
`phosphate,
`lithium difluorobis (oxalate) phosphate, *"""'""** (oxalato} phosphate,
`
`especially LIPFG LIBF4.
`
`

`

`[O037}
`
`In addition, 1 kinds of electrolytes may be used alone, or 2 or mare kinds of electrolytes
`
`may be used in combination in any combination and ratio. Among these, itis preferable
`
`fo use a combination of 2 kinds of specific inorganic lithlurn salts or a combination of an
`
`inorganic lithium sali and a fluorine-containing organic fithium sait, because gas
`
`generation during trickle charging is suppressed and deterioration after storage at high
`
`In particular, a combination of LIPF @ and LIBF 4. an
`temperature is suppressed.
`inorganic iithiurn salt such as LIPFS,LIBF4, and LICF3503,LIN (CF) :It is preferred to use
`a fluorine-containing organic lithium salt such as 3 SO 2) 2 and LIN (C 2 F & SO 2) 2 in
`
`combination.
`
`{O038}
`
`When using LIPFFS and LISF4 together, itis preferable that LIBF4 is usually contained ta
`
`the whole electrolyte by the ratio more than the 0.01 mass % and below the 50 mass 5s.
`
`The ratio is preferably 0.05% by weight or more, more preferably 0.1%by weight or mare,
`
`and is preferably 20% by weight or less, more preferably 10% by weight or less,
`
`particularly preferably 5% by weight or less, and most preferably 3% by weight or less.
`
`When the ratio is within the above range, desired effects are obtained.
`
`ht becomes easy to obtain, and the lowering of the resistance of the elactralytic solution
`
`is suppressed due to the low dissociation degree of LIGF 4.
`
`{0039}
`On the other hand, Inorganic ithium salt, such as LIPFG,LIBF4, Inorganic lithium salt,
`
`such as LISOSP, LIN(FSO2} 2, and LICFSSO03 LIN(CF3S02) 2, LIN(C2F5S02)2, lithium
`
`
`
`
`ring-like Lithium=cyclic1,3-hexafluoropropanedisulfonylimide, 12 -
`
`tetrafluoroethanedisulfonylimide, LIN (CF 3 50 2) (C 4 F 9 SO 2}, LIC (CF 3 SO 2} 3,
`
`LIPF 4 {CF 3) 2, a fluorine-containing orgaric lithium salt such as LIPF 4 (C 2 F 5} 2,
`LIPF 4 (CF 350 2)2,UPF4(C 2F 4590 2) 2, LIBF 2 (CF 3) 2, LIBF 2(C 2 F 832, IBF
`
`2 (CF 3 SO 2) 2, and LiB 2 (C 2 F 5 SO 2}2; Lithium bis foxalate) borate, lithium ir