TW201203678A

TW201203678A - Electrode protective film-forming agent and electrolyte

Info

Publication number: TW201203678A
Application number: TW100109542A
Authority: TW
Inventors: Bunpei Yoshida
Original assignee: Sanyo Chemical Ind Ltd
Priority date: 2010-04-12
Filing date: 2011-03-21
Publication date: 2012-01-16
Also published as: WO2011129053A1; JPWO2011129053A1

Abstract

Provided is an electrolyte used in a lithium ion secondary battery or a lithium ion capacitor with high valtage, high capacity, excellent charge-discharge cycle performance and high-temperature storage characteristics. The invention provides an electrode protective film-forming agent (F) comprising at least one compound (A) or compound (B), which is selected from a group consisting of the following (A1), (A2), (A3), (B1), and (B2). (A1) is an aliphatic hydrocarbon having alkenyloxy (a) of specific structure; (A2) is a polyhydric alcohol ether having alkenyloxy (a); (A3) is a polyoxyalkylene ether having alkenyloxy (a); (B1) is a polyhydric alcohol ether having at least one substituent (b) selected from the group consisting of a substituent represented by general formula (2), a substituent represented by general formula (3), (meth)acryloyloxyalkyl and (meth)acryloylalkyl; (B2) is a polyoxyalkylene having a substituent (b) of specific structure.

Description

201203678 六、發明說明：【發明所屬之技術領域】離子電容本發明是有關於一種尤其對裡二次電池或鍾器有用的電極保護膜形成劑以及電解液。【先前技術】201203678 VI. Description of the Invention: [Technical Field] The present invention relates to an electrode protective film forming agent and an electrolytic solution which are useful particularly for a secondary secondary battery or a clock. [Prior Art]

經二次電池等非水電站、波-士 φ a丄丄· 高能量密度之類的特徵，領域等，且其需要急速擴大，目前，作為以行動電話衣2 記型個人電腦為代表的行動資訊裝置用的標準電池的地位已確立。當然，隨著可攜式裝置等的高性能化及多功能化，對作為其電源的非水電解液二次電池亦謀求進一步的高性用匕化（例如尚容量化及高能量密度化）。正在開發用以應對該要求的各種方法，例如藉由提高電極填充率的高密度化、新穎高容量的活性物質等。而且，現實中非水電解液一次電池藉由該些方法而確實地高容量化。另外’為了實現非水電解液二次電池的進一步高容量化，而謀求正極活性物質的利用率的提高或高電壓材料的開發。其中，尤其受到關注的是由於充電電壓的上升而提高正極活性物質的利用深度。例如，作為工作電壓為4 2 v 級的非水電解液二次電池的活性物質的鈷複合氧化物 (LiCo〇2)若以目前的U基準充電至4 3v為止，則充電谷量約為155 mAh/g，相對於此，若充電至4 5 v，則約為 190 mAh/g以上。如此，藉由充電電壓的提高，正極活性物質的利用率變大。 4 201203678 但疋，隨著電池的高電壓化，電池的容量或能量密产 =2:方面’產生充放電循環特性的降低、或在高溫儲藏時的膨脹等問題。的’已提出有解決電池的充放電循環的降低或電池二脹相題的各種技術。例如於專利文獻丨及專利文獻二提出有於電解液中添加硫化合物作為添加劑。雖記些硫化合物吸附於正極表面而抑制電解液的氧溫:藏特該些硫化合物，充放電循環特性或高 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平7_32〇779號公報 [專利文獻2]日本專利特開平1〇_64591號公報 I發明内容】本發明的目的在於提供高電壓、古，形成劑的電解液(尤其是鐘二次：二：容ς器用），以及制該些電解液_二次電池或鐘離子電本發明者為了達成上述目的而進行積極研究，成本發明。即，本發明是一種 70 有選自由下述〇u)、⑽=護膜形成劑⑺，含成組群中的至少1種化人物/Δ、、（Β1)及（Β2)所組们主少1種化合物（Α)或化合物⑻。 ⑷）：具有下述通式⑴所表示的稀氧基⑷的 201203678r ^ f I I *^/«Γ 脂肪族烴； (A2):具有烯氧基（a)的多元醇的越； (A3).具有稀氧基（a)的聚氧伸烧基謎 (polyoxyalkylene ether)； (B1 ):具有選自由下述通式（2)所表示的取代基、下述通式（3)所表示的取代基、（曱基)丙烯醯氧基烷基、及（甲基）丙稀醯基烧基所組成組群中的至少〗種取代基（b) 的多元醇的喊； (B2):具有取代基（b)的聚氧伸烷基醚； [化1] 一 Ο —C = C —τ3 II ⑴ *1*1 丁2 [τ、T2及τ3為氫原子或碳數1〜3的院基] [化2] —R2—c=c一Q3 [式中，R2為碳數1〜3的伸燒基，Qi、Q2及Q3分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數1 6 201203678 或2的氟烷基、苯基、氰基、羧基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基] [化3] Q4 Q5 Q6It is a non-hydroelectric power station such as a secondary battery, a wave-study, a high-energy density, and the like, and it needs to be rapidly expanded. Currently, it is a mobile information representative of a mobile phone 2 type personal computer. The status of standard batteries for devices has been established. Of course, with the increase in the performance and the versatility of the portable device, the non-aqueous electrolyte secondary battery as the power source is further improved (for example, capacity is increased and energy density is increased). . Various methods for coping with this demand are being developed, for example, by increasing the density of the electrode filling rate, creating a novel high-capacity active material, and the like. Further, in reality, the non-aqueous electrolyte primary battery is surely increased in capacity by these methods. In addition, in order to further increase the capacity of the nonaqueous electrolyte secondary battery, the utilization of the positive electrode active material is improved or the development of a high voltage material is sought. Among them, particular attention is paid to an increase in the utilization depth of the positive electrode active material due to an increase in the charging voltage. For example, when the cobalt composite oxide (LiCo〇2) which is an active material of a nonaqueous electrolyte secondary battery having a working voltage of 4 2 v is charged to 4 3v on the current U basis, the charge amount is about 155. mAh/g, on the other hand, is about 190 mAh/g or more when charged to 4 5 v. As a result, the utilization rate of the positive electrode active material becomes large by the increase in the charging voltage. 4 201203678 However, with the increase in the voltage of the battery, the capacity or energy density of the battery is in the range of =2: the occurrence of a decrease in the charge/discharge cycle characteristics or the expansion at the time of high-temperature storage. The various techniques have been proposed to address the reduction of the charge and discharge cycle of the battery or the battery expansion. For example, in the patent document 专利 and the patent document 2, it is proposed to add a sulfur compound as an additive to the electrolyte. Although some sulfur compounds are adsorbed on the surface of the positive electrode to suppress the oxygen temperature of the electrolyte: the sulfur compounds are contained, and the charge/discharge cycle characteristics are high. [Prior Art Document] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 7-32 SUMMARY OF THE INVENTION The object of the present invention is to provide an electrolyte solution of a high voltage, ancient, and forming agent (especially a clock twice: two: ς ς ς ς ς 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 In order to achieve the above object, the inventors of the present invention have made active research on the above-mentioned electrolytes. That is, the present invention is a group of 70 selected from the group consisting of 〇u) and (10) = film forming agent (7), and at least one type of person/Δ, (Β1), and (Β2) in a group. One less compound (Α) or compound (8). (4)): 201203678r ^ f II *^/«Γ aliphatic hydrocarbon having a dilute oxy group (4) represented by the following formula (1); (A2): the more the polyol having an alkenyloxy group (a); (A3) a polyoxyalkylene ether having a dilute oxy group (a); (B1) having a substituent represented by the following formula (2), represented by the following formula (3) a polyol of at least one substituent (b) in a group consisting of a substituent, a (decyl) acryloxyalkyl group, and a (meth) propyl sulfhydryl group; (B2): having Substituent (b) polyoxyalkylene ether; [Chemical 1] a Ο - C = C - τ3 II (1) *1 * 1 butyl 2 [τ, T2 and τ3 are hydrogen atoms or a carbon number of 1 to 3 Base] [Chemical 2] - R2 - c = c - Q3 [wherein R2 is a stretching group having a carbon number of 1 to 3, and Qi, Q2 and Q3 are each independently a hydrogen atom, a halogen atom, and a carbon number of 1 to 4; Alkyl group, carbon number 1 6 201203678 or 2 fluoroalkyl group, phenyl group, cyano group, carboxyl group, alkoxy group having 1 to 3 carbon atoms or alkoxycarbonyl group having 1 to 4 carbon atoms] [Chemical 3] Q4 Q5 Q6

[式中’ R3為碳數1〜3的伸烷基，Q4為氫原子或鹵素原子’ Q5、Q6及Q7分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數i或2的氟烷基、苯基、氰基、羧基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基]。另外’本發明是含有該電極保護膜形成劑（F)的電解液、含有該電解液的鋰二次電池或鋰離子電容器、以及具有由該電極保護膜形成劑（F)所包覆的電極活性物質的鋰二次電池或鋰離子電容器。 [發明的效果] 本發明的電極保護膜形成劑（F)可抑制高電壓下的面的轉㈣分解，提高級錢職性及高溫儲解液藉t使用合有本發明的電極保護卿成劑⑺的電解液’尤其可獲得高電壓、高容量_二次電池或鐘離子 201203678 電容器，並且可提高該些鋰二次電池或鋰離子電容器的高電壓下的充放電循環性能及高溫儲藏特性。【實施方式】本發明的電極保護膜形成劑（F)是含有於電解而使用，此外亦可以現合於電極中、直接塗佈於專方法來使用。本發明的電極保護膜形成劑（F)含有選自由下述 (A1)、（A2)、（A3)、（B1)及（B2)所組成組群中的至少1種化合物（A)或化合物（B)。（Α1)·具有通式⑴所表示的烯氧基（a)的脂肪族烴； (A2).具有烯氧基（a)的多元醇的醚； (A3) ·具有烯氧基（a)的聚氧伸烷基醚； (B1)」具有選自由通式⑺所表示的取代基通式表示的取代基、（曱基)丙稀酿氧基烧基、及（曱基） ^酿基絲顺成組群巾的至少i種取代多元醇的喊； (B2) ·具有取代基⑻的聚氧伸烧基鱗。人物t、物（A)發揮作為正極保護膜形成劑的功能，化 :m 2發揮作為負極保護卿成義魏。即，化合 m *、化合物（B)在初次充電時，分別於正極及負極極^制溶劑分解的保護膜。該保制抑制高電壓下的電面的電解液的分解’提高充放電循環特性。匕δ物（A)及化合物⑻中，較佳為化合物（A)。 8 201203678 ---__ 作為化合物（A)的（A1)〜（A3)具有通式（1) 所表示的烯氧基（a)。通式（1)中，τι、护及τ3為氫原子或碳數1〜3的烷基。具體而言，上述烯氧基（a)可列舉乙烯氧基 (vinyloxy)、1-丙烯氧基（^ρ^ρ^γίοχγ)、丄-丁稀氧基 (Ι-butenyloxy)及 1·曱基丙稀氧基（i_methyi pr〇penyi〇Xy) 等。該些烯氧基中，較佳為乙烯氧基及丨_丙烯氧基。 [化4] 一 Ο—C = C——τ3 I I ⑴ Τ1 τ2 (Α1)中的脂肪族烴可列舉：碳數2〜2〇的直鏈或分支的烧烴（乙烧、丙烧、丁烧H己烧、辛院、癸燒、十二烷、十三烷、十四烷、十五烷、十八烷及二十烷等）以及碳數2〜20的直鏈或分支的烯烴（乙稀、丙烯、丁稀、戊稀、己稀、辛烯、癸烯、十—稀、十二稀、十三稀、十四烯、十五烯、十八烯及二十烯等）。 _ (Α1)可列舉自上述烷烴或者烯烴中丨個以上的氫原子經烯氧基（a)[較佳為乙烯氧基及丨丙烯氧基]所取代的化合物。 ^(A2)中的多元醇可列舉2元〜6元的多元醇，具體而《為.乙二醇（）、二乙二醇[In the formula, R3 is an alkylene group having 1 to 3 carbon atoms, and Q4 is a hydrogen atom or a halogen atom. Q5, Q6 and Q7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number. Ii or a fluoroalkyl group, a phenyl group, a cyano group, a carboxyl group, an alkoxy group having 1 to 3 carbon atoms or an alkoxycarbonyl group having 1 to 4 carbon atoms]. Further, the present invention relates to an electrolytic solution containing the electrode protective film forming agent (F), a lithium secondary battery or a lithium ion capacitor containing the electrolytic solution, and an electrode coated with the electrode protective film forming agent (F). A lithium secondary battery or a lithium ion capacitor of an active material. [Effects of the Invention] The electrode protective film forming agent (F) of the present invention can suppress the transition of the surface (4) at a high voltage, improve the grade and the high-temperature storage solution, and use the electrode protection of the present invention. The electrolyte of the agent (7) can obtain, in particular, a high voltage, a high capacity _ secondary battery or a clock ion 201203678 capacitor, and can improve the charge and discharge cycle performance and high temperature storage characteristics of the lithium secondary battery or the lithium ion capacitor at a high voltage. . [Embodiment] The electrode protective film forming agent (F) of the present invention is used by being used for electrolysis, or may be used in an electrode and directly applied to a specific method. The electrode protective film forming agent (F) of the present invention contains at least one compound (A) or compound selected from the group consisting of the following (A1), (A2), (A3), (B1) and (B2). (B). (Α1) an aliphatic hydrocarbon having an alkenyloxy group (a) represented by the general formula (1); (A2) an ether of a polyhydric alcohol having an alkenyloxy group (a); (A3) having an alkenyloxy group (a) a polyoxyalkylene ether; (B1)" having a substituent represented by a substituent represented by the formula (7), a (fluorenyl) propylene oxide alkyl group, and a (fluorenyl) aryl group At least i kinds of substituted polyols of the group of silk stalks; (B2) - polyoxyalkylene scaly scales having a substituent (8). The person t and the object (A) function as a positive electrode protective film forming agent, and m 2 functions as a negative electrode protection. That is, when the compound m* and the compound (B) are charged for the first time, a solvolysis protective film is formed on the positive electrode and the negative electrode, respectively. This protection suppresses the decomposition of the electrolytic solution on the electric surface at a high voltage, and improves the charge and discharge cycle characteristics. Among the 匕δ (A) and the compound (8), the compound (A) is preferred. 8 201203678 ---__ (A1) to (A3) as the compound (A) have an alkenyloxy group (a) represented by the formula (1). In the formula (1), τι, 护和τ3 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Specifically, the above-mentioned alkenyloxy group (a) may, for example, be a vinyloxy group, a 1-propenyloxy group (^ρ^ρ^γίοχγ), a 丄-butenyloxy group, and a fluorenyl group. Propyloxy (i_methyi pr〇penyi〇Xy) and the like. Among these alkenyloxy groups, a vinyloxy group and a rhodium-propyleneoxy group are preferable.化 Ο C C C C C C C C C C C C C C C 脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪脂肪Burn H-burn, Xinyuan, Shaohao, dodecane, tridecane, tetradecane, pentadecane, octadecane and eicosane, etc.) and linear or branched olefins with a carbon number of 2 to 20 ( Ethylene, propylene, butadiene, pentane, hexene, octene, decene, deuterium, diuret, thirteen, tetradecene, pentadecene, octadecene and hexadecene, etc.). _ (Α1) A compound in which one or more hydrogen atoms from the above alkane or olefin are substituted with an alkenyloxy group (a) [preferably a vinyloxy group and a fluorenyloxy group] can be mentioned. The polyhydric alcohol in (A2) may be a polyhydric alcohol of 2 to 6 yuan, specifically, "ethylene glycol (), diethylene glycol

201203678 */ / / / -r^r*X (diethyleneglycol)、三乙二醇（triethyleneglycol)、丙二醇（propyleneglycol)、二丙二醇（dipropyleneglycol)、三丙二醇（tripropyleneglycol)、1，3,丁二醇（l，3-butanediol)、 1,4-丁二醇（l，4-butanediol)、甘油（glycerin)、三經甲基乙烧（trimethylolethane )、三經曱基丙燒 (trimethylolpropane )、2-曱基甘油（2-methylglycerin )、二甘油（diglycerin )、三甘油（triglycerin )、四甘油 (tetraglycerin )、季戊四醇（pentaerythritol)、二季戊四醇 (dipentaerythritol)及山梨糖醇（sorbitol)等。較佳為乙二醇、二乙二醇及三乙二醇。 (A2)可列舉由上述多元醇及具有烯氧基（a)[較佳為乙稀氧基及1-丙烯氧基]的化合物所衍生的喊。 (A3)是由具有烯氧基（a)[較佳為乙烯氧基及丨_丙烯氧基]的化合物所衍生的聚氧伸烷基醚。 (A3)是於具有烯氧基（a)的化合物上加成環氧烷 (alkylene oxide，以下簡記為A〇 )而獲得。凡所加成的AO較佳為碳數為2〜4的AO，具體而古可列舉：環氧乙烧（ethylene oxide，以下簡記為E〇)、環丙烷（propylene oxide，以下簡記為p〇)、丨，2環氧丁俨 (l，2-bmylene oxide)、2,3_環氧丁烷、丨，3·環氧丁烷或者二 A ^ T ^ (isobutylene oxide tetrahydrofUran ^ 及該些AO的2種以上的併用。）、該些AO +，較佳為E0。A〇的加成莫耳數較佳莫耳〜10莫耳，尤佳為丨莫耳〜5莫耳。為1 201203678 化合物（A)中，就充放電循環特性的觀點而言，較佳為通式（4)所表示的化合物、通< ⑴所表示的化合物及具有2個以上乙烯氧基或μ烯氧基的環己烧衍生物。 R4-CH=CH-0-(CH2)p-0-CH=CH-R5 [式中，R4及R5分別獨立地為氫原子或甲基，p為丄〜10的整數。]201203678 */ / / / -r^r*X (diethyleneglycol), triethyleneglycol, propyleneglycol, dipropyleneglycol, tripropyleneglycol, 1,3, butanediol (l , 3-butanediol), 1,4-butanediol, glycerin, trimethylolethane, trimethylolpropane, 2-mercapto 2-methylglycerin, diglycerin, triglycerin, tetraglycerin, pentaerythritol, dipentaerythritol, and sorbitol. Preferred are ethylene glycol, diethylene glycol and triethylene glycol. (A2) exemplified by the above polyol and a compound having an alkenyloxy group (a) [preferably an ethyleneoxy group and a 1-propenyloxy group]. (A3) is a polyoxyalkylene ether derived from a compound having an alkenyloxy group (a) [preferably a vinyloxy group and a fluorene-propenyloxy group]. (A3) is obtained by adding an alkylene oxide (hereinafter abbreviated as A〇) to a compound having an alkenyloxy group (a). The AO to be added is preferably AO having a carbon number of 2 to 4, and specific examples include: ethylene oxide (hereinafter abbreviated as E〇) and propylene oxide (hereinafter abbreviated as p〇). ), 丨, 2, l-butylene oxide, 2,3-butylene oxide, hydrazine, 3·butylene oxide or di-A ^ T ^ (isobutylene oxide tetrahydrofUran ^ and these AO The combination of two or more types is used.), the AO +, preferably E0. The addition of a mole of A〇 is better. Moer ~ 10 Mo, especially good for Mo Mo ~ 5 Mo. In the case of the compound (A), it is preferably a compound represented by the formula (4), a compound represented by the formula (1), and having two or more ethyleneoxy groups or μ. a cyclohexane derivative of an alkenyloxy group. R4-CH=CH-0-(CH2)p-0-CH=CH-R5 [wherein R4 and R5 are each independently a hydrogen atom or a methyl group, and p is an integer of 丄10. ]

xly 5 /IV R6-CH=CH-0-(C2H40)q-CH=CH-R7 [式中’ R及R分別獨立地為氮原子或曱基，q為1 〜5的整數。] 通式（4)所表示的化合物的具體例可列舉：ι，4_丁二醇二乙稀喊（1,4-butanedioldivinylether)、1，5-戊二醇二乙稀趟（l，5-pentanediol divinylether)、1,6-己二醇二乙稀鱗 (1,6-hexanediol divinylether )、1，7-庚二醇二乙稀謎 (l，7-heptanediol divinylether )、1，8-辛二醇二乙烯趟 (l，8-octanediol divinylether )、1，9-壬二醇二乙稀 _ (l，9-nonanediol divinylether )、1，10-癸二醇二乙稀 _ (l，10-decanedioldivinylether)、1，4-丁二醇（1-丙烯基）乙烯醚（l，4_butanediol(l-propenyl)divinylether)、1，5-戊二醇(1-丙稀基）乙烯鱗（l,5-pentanediol(l-propenyl)divinylether)、 201203678 1，6- 己二醇（1- 丙烯基）乙烯醚 (l，6-hexanediol(l-propenyl)divinylet;her)、1，7-庚二醇（1-丙稀基）乙稀醚（1，7-heptanediol( 1-propenyl)divinylether )、 1，8- 辛二醇（1- 丙烯基）乙烯醚 (l，8-octanediol(l-propenyl)divinylether)、1，9-壬二醇（1-丙婦基）乙稀驗（l，9-nonanediol(l-propenyl)divinylet;her )、 1，10- 癸二醇（1- 丙烯基）乙烯醚 (l，10-decanediol(l-propenyl)divinylether)、1，4-丁二醇二 (1-丙稀基)騎（l，4-butanediol di(l-propenyl)ether)、1,5-戊二醇二（1-丙婦基）趟（1,5-pentanediol di(l-propenyl)ether )、1，6-己二醇二（1-丙烯基）醚 (l，6-hexanediol di(l-propenyl)ether)、1，7-庚二醇二(1-丙稀基)喊（l，7-heptanediol di(l-propenyl)ether)、1，8-辛二醇一（1-丙稀基）謎（l，8-octanediol di(l-propenyl)ether)、1，9-壬一醇一（1_丙稀基)越（l，9-nonanediol di(l-propenyl)ether) 及 1，10-癸·一醇一（1-丙稀基）峻（l，l〇-decanediol di(l-propenyl)ether)。該些化合物可由市售品獲得。該些化合物中，就充放電循環特性的觀點而言，較佳為R4及R5分別為氫原子且p為6〜8的化合物。通式（5)所表示的化合物的具體例可列舉：乙二醇二乙婦醚、二乙二醇二乙婦域、三乙二醇二乙婦_、四乙二醇二乙烯醚、五乙二醇二乙烯醚、乙二醇(丨_丙烯基）乙烯醚、二乙二醇(1·丙烯基）乙烯醚、三乙二醇(丨·丙烯基）乙烯醚、四乙二醇(1-丙烯基）乙烯醚、五乙二醇(丨_丙烯基）乙烯 12 201203678 醚、乙二醇二(1-丙烯基)醚、二乙二醇二(1_丙烯基)醚、三乙二醇二(1-丙烯基)醚、四乙二醇二(1_丙烯基)醚及五乙二醇一(1-丙烯基)醚等。該些化合物可由市售品獲得。该些化合物中，就充放電循環特性的觀點而言，較佳為R6及R7為氫原子且q為2或3的化合物。 .具有2個以上乙烯氧基或1_丙烯氧基的環己烷衍生物的具體例可列舉：1，2_雙（1-丙烯氧基曱基）環己烷 (l，2-bis(l-pr〇penoxymertiyl)cycl〇hexane)、1，3·雙（1-丙烯氧基曱基)環己烷、1，4-雙(1-丙烯氧基曱基)環己烷、13,5_ 二（1-丙稀氧基曱基）環己烧、1，2·雙（乙稀氧基曱基）環己烧、1,3-雙（乙稀氧基甲基)環己烧、1，4_雙（乙稀氧基曱基) 環己烧及1，3,5-三（乙烯氧基曱基)環己烧等。該些化合物可由市售品獲得。化合物（B)可列舉（B1)及（B2)。 (B1):具有選自由上述通式（2)所表示的取代基、上述通式（3)所表示的取代基、（甲基)丙烯醯氧基烷基、及（甲基)丙烯醯基貌基所組成組群中的至少1種取代基（b) 的多元醇的趟； (B2):具有取代基（b)的聚氧伸烷基醚。 (B1)及（B2)具有選自由通式（2)所表示的取代基、通式（3)所表示的取代基、（甲基)丙烯醯氧基烷基、及（甲基）丙烯醯基烧基所組成組群中的至少1種取代基 (b)。取代基（b)中，就負極保護膜的形成容易度的觀點而 13 201203678f j / / / *rpit 言，較佳為通式（2)所表示的取代基、通式（3) 一的取代基及（曱基)丙烯醯氧基烷基。不 [化5] —R2—C=C—·Q3 (2)Xly 5 /IV R6-CH=CH-0-(C2H40)q-CH=CH-R7 [wherein R and R are each independently a nitrogen atom or a fluorenyl group, and q is an integer of 1 to 5. Specific examples of the compound represented by the formula (4) include: iota, 4-butanediol divinyl sulfonate (1,4-butanedioldivinylether), 1,5-pentanediol diethylene sulfonate (l, 5) -pentanediol divinylether), 1,6-hexanediol divinylether, 1,7-heptanediol divinylether, 1,8-octane 1,8-octanediol divinylether, 1,9-nonanediol divinylether, 1,10-nonanediol diethylene _ (l,10- Decanedioldivinylether), 1, 4-butanediol (l-propenyl) vinyl ether, 1,5-pentanediol (1-propanyl) vinyl scale (l, 5 -pentanediol(l-propenyl)divinylether), 201203678 1,6-hexanediol (1-propenyl)divinylet;her), 1,7-heptanediol 1-, 1-Heptanediol (1-propenyl) divinylether, 1,8-octanediol (1-propenyl) vinyl ether (1,8-octanediol (l-propenyl)divinylether ), 1,9-nonanediol (1-propanyl) ethylene test (l 9-nonanediol(l-propenyl)divinylet;her ), 1,10-decanediol (l-propenyl) vinyl ether, 1,4-butanediol II (1-propanyl) di(l-propenyl)ether, 1,5-pentanediol di(1-propanyl) oxime (1,5-pentanediol di (l-propenyl) ), 1,6-hexanediol di(l-propenyl)ether, 1,7-heptanediol di(1-propanyl) (1,8-heptanediol di(l-propenyl)ether), 1,8-octanediol di(l-propenyl)ether, 1,9- (1,9-nonanediol di(l-propenyl)ether) and 1,10-癸-ol-ol- 1-propylidene (l,l〇- Decanediol di (l-propenyl) ether). These compounds are available from commercial products. Among these compounds, from the viewpoint of charge and discharge cycle characteristics, a compound in which R4 and R5 are each a hydrogen atom and p is 6 to 8 is preferable. Specific examples of the compound represented by the formula (5) include ethylene glycol dieththyl ether, diethylene glycol diethylene glycol, triethylene glycol diethylene glycol, tetraethylene glycol divinyl ether, and five. Ethylene glycol divinyl ether, ethylene glycol (丨-propenyl) vinyl ether, diethylene glycol (1·propenyl) vinyl ether, triethylene glycol (丨·propylene) vinyl ether, tetraethylene glycol ( 1-propenyl) vinyl ether, pentaethylene glycol (丨-propenyl) ethylene 12 201203678 ether, ethylene glycol bis(1-propenyl) ether, diethylene glycol bis(1-propenyl) ether, triethyl Diol bis(1-propenyl)ether, tetraethylene glycol bis(1-propenyl)ether, pentaethylene glycol mono(1-propenyl)ether, and the like. These compounds are available from commercial products. Among these compounds, from the viewpoint of charge-discharge cycle characteristics, a compound wherein R6 and R7 are a hydrogen atom and q is 2 or 3 is preferred. Specific examples of the cyclohexane derivative having two or more ethyleneoxy groups or 1-propyleneoxy groups include 1,2-bis(1-propenyloxyindenyl)cyclohexane (1,2-bis ( L-pr〇penoxymertiyl)cycl〇hexane), 1,3·bis(1-propenyloxyfluorenyl)cyclohexane, 1,4-bis(1-propoxyoxyindenyl)cyclohexane, 13,5_ Bis(1-propoxyoxyindenyl)cyclohexene, 1,2·bis(ethyloxyindenyl)cyclohexane, 1,3-bis(ethyleneoxymethyl)cyclohexane, 1 4_bis(ethyloxyindenyl) cyclohexane and 1,3,5-tris(ethyleneoxyfluorenyl)cyclohexene. These compounds are available from commercial products. Examples of the compound (B) include (B1) and (B2). (B1): having a substituent represented by the above formula (2), a substituent represented by the above formula (3), a (meth) acryloxyalkyl group, and a (meth) acrylonitrile group a hydrazine of a polyol of at least one substituent (b) in a group consisting of a phenotype; (B2): a polyoxyalkylene ether having a substituent (b). (B1) and (B2) have a substituent represented by the formula (2), a substituent represented by the formula (3), a (meth) propylene decyloxyalkyl group, and a (meth) propylene oxime. At least one substituent (b) in the group consisting of ketone groups. In the substituent (b), from the viewpoint of easiness of formation of the negative electrode protective film, 13 201203678f j / / / *rpit, a substituent represented by the formula (2) and a substitution of the formula (3) are preferred. And (mercapto) acryloxyalkyl. Not [Chemical 5] —R2—C=C—·Q3 (2)

I I Q1 Q2 通式（2)中的R2為碳數1〜3的伸燒基i 2 Q3分別獨立地為氫原子、鹵素原子、碳數1〜4 及石反數1〜2的敗烧基、苯基、氰基、羧基、碳數1 氧基或碳數1〜4的烷氧基羰基。的規碳數1〜3的伸烧基可列舉亞曱基、伸乙基、基及1，3-伸丙基。該些伸烧基中，就充放電生= 點而言，較佳為亞甲基。的觀碳數1〜4的烷基可列舉甲基、乙基、正丁基及第三T基等。丙基、 «原子可列舉氟原子、氣原子、漠原子碳數1〜2的氟烧基可列舉將甲基或乙 1丄氣乙基、四的nintr基，可列舉= 一氣甲基、二氟甲基、氟乙基、二氟乙義、氟乙基及五氟乙基等。土' 正丙碳數1〜3的烧氧基例如可列舉甲氣義一氧基及異丙氧基。土、乙氧基、 201203678 碳數1〜4的烷氧基羰基例如可列舉曱氧基羰基、乙氧基羰基、正丙氧基羰基及異丙氧基羰基等。 ^、(^、(^及以的較佳組合可列舉以下的㈠）〜“）。 (1 ) R2=亞曱基’ Q1=氫原子，Q2=氫原子，q3=苯基； (2) R2=亞曱基’ QL氫原子，Q2=氫原子，qU烷氧基羰基； (3) R2=亞曱基’ Qk苯基’ Q2=氩原子，q3=笨基； (4) R2=亞曱基’ Qk笨基’ Q2=氫原子，q3=烧氧基II Q1 Q2 R2 in the general formula (2) is a calcining group i 2 Q3 having a carbon number of 1 to 3, and each independently is a hydrogen atom, a halogen atom, a carbon number of 1 to 4, and a pyrene group of 1 to 2 A phenyl group, a cyano group, a carboxyl group, a carbon number 1 oxy group or an alkoxycarbonyl group having 1 to 4 carbon atoms. The alkylene group having a carbon number of 1 to 3 may, for example, be an anthracene group, an exoethyl group, a benzyl group or a 1,3-propanyl group. Among these stretching bases, a methylene group is preferred in terms of charge and discharge. The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, an n-butyl group or a third T group. Examples of the propyl group and the atom include a fluorine atom, a gas atom, and a fluoroalkyl group having a carbon number of 1 to 2, and examples thereof include a methyl group or an ethyl group of an ethylene group and a nintr group of four, and examples thereof include a gas methyl group and a second group. Fluoromethyl, fluoroethyl, difluoroethylene, fluoroethyl and pentafluoroethyl. Soil 'n-propyl" The alkoxy group having 1 to 3 carbon atoms is exemplified by a gas-like monooxy group and an isopropoxy group. Soil, ethoxy group, 201203678 The alkoxycarbonyl group having 1 to 4 carbon atoms may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group or an isopropoxycarbonyl group. ^, (^, (^) and the preferred combination can be exemplified by the following (a)) ~ "). (1) R2 = anthracene group 'Q1 = hydrogen atom, Q2 = hydrogen atom, q3 = phenyl; (2) R2 = anthracenylene 'QL hydrogen atom, Q2 = hydrogen atom, qU alkoxycarbonyl group; (3) R2 = anthracene group 'Qk phenyl group' Q2 = argon atom, q3 = stupid group; (4) R2 = sub曱基' Qk基基' Q2=hydrogen atom, q3=alkoxy

ViU 甘· 叛基， (5 ) R =亞曱基’ Q1=烧氧基羰基，q2=氫原子，q3= 苯基； (6) R2=亞甲基，Qk烷氧基羰基，（^氫原子，q3= 烧氧基裁基。該些組合中，尤佳為（2)的組合。 [化6]ViU 甘· 叛基, (5) R = fluorenylene 'Q1 = alkoxycarbonyl, q2 = hydrogen atom, q3 = phenyl; (6) R2 = methylene, Qk alkoxycarbonyl, (hydrogen) Atom, q3 = alkoxy groups. Among these combinations, a combination of (2) is preferred.

Q4 Q5 QQ4 Q5 Q

、通式（3)中的R3為碳數1〜3的伸烷基，q4為氫原子或_素原子，Q5、Q6及Q7分觸立地為氫原子^素原子、碳數1〜4的烷基、碳數1或2的氟烷基君千、鹵素、苯基、氰 15 201203678R3 in the general formula (3) is an alkylene group having 1 to 3 carbon atoms, q4 is a hydrogen atom or a _ atom, and Q5, Q6 and Q7 are in a hydrogen atom, and have a carbon number of 1 to 4. Alkyl, fluoroalkyl group with a carbon number of 1 or 2, halogen, phenyl, cyanide 15 201203678

L 基、羧基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基。通式（3)中的碳數1〜3的伸烷基、鹵素原子、碳數 1〜4的烷基、碳數1或2的氟烷基、碳數1〜3的烷氧基及碳數1〜4的烷氧基羰基的具體例可列舉與通式（2)中例示的例子相同的例子。就負極保護膜的形成容易度及通式（3)所表示的取代基的穩定性的觀點而言，Q4較佳為氫原子、氣原子及氣原子，尤佳為氫原子。就負極保護膜的形成容易度的觀點而言，Q5較佳為氫原子、碳數1〜4的絲及㈣原子，尤佳為氫原子及碳數 1〜4的烧基’特佳為氫原子。就負極保護膜的形成容易度的觀點而言，及佳為氫原子、碳數1〜4的絲及函素原^尤佳 ^ 〜（⑴Q Q、Q Q的較佳組合可列舉以下的⑴ 子、子，Q5如，Q6=氫原子，二叫 (3 ) R3=亞曱基，（^二氮子，Q7=氫原子；氣原子原子f氫原 (4)R3=亞曱基，Qk氫原子，q5 Q7=lL^-f ； V虱原子，Q=甲基， 201203678 (5) R3=亞甲基，Q4=氟原子，Q5=氫原子，q6=曱基， Q7=氫原子； (6) R3=亞曱基，Q4=氣原子，Q5=氫原子，q6=甲基， Q7=氫原子； (7) R3=亞曱基，Q4=氫原子，Q5=氫原子，q6=氫原子，Q7=甲基； (8) R3=亞曱基，Q4=氟原子’ Q5=氫原子，q6=氫原子，Q7=曱基； (9) R3=亞曱基，Q4=氯原子，Q5=氫原子，Q6=氫原子，Q7=曱基； (10) R3=亞甲基，Q4=氫原子，Q5=氫原子，q6=曱基， Q7=甲基； (11) R3=亞曱基’ Q4=氟原子，Q5=氫原子，q6=甲基， Q7=甲基； (12 ) R3=亞曱基’ Q4=氣原子’ Q5=氮原子，q6=曱基， Q7=甲基。該些組合中，尤佳為（1)的組合。 (曱基）丙烯醯氧基烷基較佳為丙烯醯氧基甲基、丙稀醯氧基乙基、曱基丙烯醯氧基曱基及曱基丙烯醯氧基乙基等烷基的碳數為1〜2的（曱基)丙烯醯氧基烷基。 (曱基)丙烯醯基烷基較佳為丙烯醯基甲基、丙烯醯基乙基、甲基丙烯醯基甲基及曱基丙烯醯基乙基等烷基的碳數為1〜2的（曱基)丙烯醯基烷基。 (B1)中的多元醇可列舉與（A2)中例示的多元醇相 17 201203678 fj t t I 同的多元醇。較佳為乙二醇、二乙二醇及三乙二醇。 (B1)是由多元醇及具有上述取代基（b)的化合物所衍生的喊。較佳為通式（6)所表示的化合物。 (6)L group, carboxyl group, alkoxy group having 1 to 3 carbon atoms or alkoxycarbonyl group having 1 to 4 carbon atoms. The alkylene group having 1 to 3 carbon atoms, the halogen atom, the alkyl group having 1 to 4 carbon atoms, the fluoroalkyl group having 1 or 2 carbon atoms, the alkoxy group having 1 to 3 carbon atoms, and carbon in the formula (3) Specific examples of the alkoxycarbonyl group having 1 to 4 may be the same as those exemplified in the formula (2). From the viewpoint of easiness of formation of the negative electrode protective film and stability of the substituent represented by the formula (3), Q4 is preferably a hydrogen atom, a gas atom or a gas atom, and particularly preferably a hydrogen atom. From the viewpoint of easiness of formation of the negative electrode protective film, Q5 is preferably a hydrogen atom, a carbon number of 1 to 4, and a (iv) atom, and particularly preferably a hydrogen atom and a carbon number of 1 to 4 are particularly preferably hydrogen. atom. From the viewpoint of the ease of formation of the negative electrode protective film, and preferably a hydrogen atom, a filament having a carbon number of 1 to 4, and a preferred element of the element (or) ((1)Q Q, QQ, the following (1) , sub, Q5, Q6 = hydrogen atom, two called (3) R3 = sulfhydryl, (^ diazide, Q7 = hydrogen atom; gas atom atom f hydrogenogen (4) R3 = fluorene, Qk hydrogen Atom, q5 Q7=lL^-f ; V虱 atom, Q=methyl, 201203678 (5) R3=methylene, Q4=fluorine, Q5=hydrogen atom, q6=fluorenyl, Q7=hydrogen atom; 6) R3 = fluorenylene, Q4 = gas atom, Q5 = hydrogen atom, q6 = methyl group, Q7 = hydrogen atom; (7) R3 = fluorene group, Q4 = hydrogen atom, Q5 = hydrogen atom, q6 = hydrogen Atom, Q7 = methyl; (8) R3 = fluorenylene, Q4 = fluorine atom 'Q5 = hydrogen atom, q6 = hydrogen atom, Q7 = fluorenyl; (9) R3 = fluorenylene, Q4 = chlorine atom, Q5=hydrogen atom, Q6=hydrogen atom, Q7=mercapto group; (10) R3=methylene group, Q4=hydrogen atom, Q5=hydrogen atom, q6=mercapto group, Q7=methyl group; (11) R3=亚Sulfhydryl group Q4 = fluorine atom, Q5 = hydrogen atom, q6 = methyl group, Q7 = methyl group; (12) R3 = fluorene group 'Q4 = gas atom' Q5 = nitrogen atom, q6 = sulfhydryl group, Q7 = A Base. In the combination, a combination of (1) is particularly preferred. The (fluorenyl) propylene methoxyalkyl group is preferably an acryloxymethyl group, an acryloxyethyl group, a decyl propylene fluorenyl group and an anthracene. The alkyl group having a carbon number of 1 to 2 such as an alkyl propylene oxyethyl group is preferably a fluorenylmethyl group or a propylene group. a (mercapto)propenylalkyl group having 1 to 2 carbon atoms of an alkyl group such as an ethyl group, a methacryloylmethyl group or a mercaptopropenylethyl group. The polyhydric alcohol in (B1) may be exemplified by ( The polyol phase exemplified in A2) is the same polyol, preferably ethylene glycol, diethylene glycol and triethylene glycol. (B1) is a polyol and has the above substituent (b) The compound derived from the compound is preferably a compound represented by the formula (6).

X-(0-RV〇-Y 通式（6)中的X及Y分別獨立地為通式（2)所表示的取代基、通式（3)所表示的取代基、（甲基)丙烯醯氧基烷基或（曱基)丙烯醯基烷基。通式（6)中的R1為碳數1〜3的伸烷基，可列舉亞甲基、伸乙基、1，2-伸丙基及1，3-伸丙基。該些伸烧基中，就輸出特性的觀點而言，較佳為伸乙基。通式（6)中的r為1〜5的整數，就充放電循環特性的觀點而言，較佳為1〜4的整數，尤佳為2。 (B1)的具體例可列舉：乙二醇二(2-丁烯酸曱酯）醚 (ethyleneglycol di(2-butenoic acid methyl)ether)、二乙二醇二(2-丁烯酸曱酯）醚、三乙二醇二(2-丁烯酸甲酯）醚、四乙二醇二(2-丁烯酸甲酯）醚、五乙二醇二(2_丁烯酸曱酯）趟、乙一醇二肉桂峻（ethyleneglycol dicinnamyl ether)、二乙二醇二肉桂醚、三乙二醇二肉桂醚、四乙二醇二肉桂越、五乙二醇二肉桂醚、乙二醇二(4_乙烯基苄基）醚 (ethyleneglycol di(4-vinylbenzyl)ether)、二乙二醇二(4_ 乙稀基苄基)醚、三乙二醇二(4-乙烯基苄基)醚、四乙二醇二 201203678 (4-乙稀基苄基)醚、五乙二醇二(4-乙烯基苄基)醚、乙二醇二（1-丙婦酿氧基乙基)鍵（ethyleneglycol di(l-acryloyloxy ethyl)ether)、二乙二醇二(1-丙烯醯氧基乙基)醚、三乙二醇二(1-丙烯醢氧基乙基)醚、四乙二醇二(1_丙烯醯氧基乙基) 醚、五乙二醇二(1-丙烯醯氧基乙基)蜮、二乙二醇(2_戊烯酸乙酉日）_( diethyleneglycol (2-pentenoic acid ethyl)ether)、三乙二醇(2-戊烯酸乙酯)醚等。 s亥些化合物可由市售品獲得，或者以公知的方法合成。 (B2)為具有取代基（b)的聚氧伸烷基醚，是於具有取代基（b)的化合物上加成環氧烷（以下簡記為A〇) 而獲得。所加成的AO可列舉與（A3)中例示的A〇相同的 A0。較佳為E0。AO的加成莫耳數較佳為i莫耳〜1〇莫耳，尤佳為1莫耳〜5莫耳。、本發明的電極保護膜形成劑（F)含有選自由上述 (ad'uu'wwbd及（B2)所組成組群中的至少1種化合物（A)或化合物（B)。本發明的電解液含有電解質（G)、非水溶劑（h)及電極保護膜形成劑（F)作為必需成分。藉由使電極保護膜形成劑（F)刀含有於電極或電解液加電壓，而使電極保護膜形成劑(二性物質表面聚合形成被膜而成為保護膜。，_二次電池絲離子電容;|的錄或電解質中含有電極保護膜形成劑（F)的情況，於初次充電時形成上 201203678 述保護膜，但亦可使用另行於電極表面（活性物質表面）形成有電極保護膜（F)的聚合被膜的電極來作為鋰二次電池或鋰離子電容器的電極。電解質（G)可使用通常的電解液中使用的電解質，例如可列舉：LiPF6、LiBF4、LiSbF6、LiAsF6 及 LiC104 等無機酸的鋰鹽；LiN(CF3S02)2、LiN(C2F5S02)2、 LiC(CF3S02)3等有機酸的鋰鹽。該些電解質中，就電池輸出及充放電循環特性的觀點而言，較佳為LiPF6。非水溶劑（H)可使用通常的電解液中使用的溶劑，例如可使用：内醋（lactone)化合物、環狀或键狀碳酸醋、鏈狀羧酸酯、環狀或鏈狀醚、磷酸酯、腈（nitrile)化合物、酿胺（amide)化合物、颯（sulfone)、環丁礙（sulfolane) 等以及該些化合物的混合物。内酯化合物可列舉5員環（γ- 丁内酯（γ-butyrolactone ) 及γ-戊内S旨（γ-valerolactone)等）及6員環的内醋化合物 (δ-戊内酯等）等。環狀碳酸酯可列舉：碳酸丙二酯（pr〇pylene carbonate)、碳酸乙二 S旨（ethylene carbonate)及碳酸丁一醋(butylene carbonate)等0 鏈狀碳酸酯可列舉：碳酸二甲酯（dimethylX-(0-RV〇-Y X and Y in the formula (6) are each independently a substituent represented by the formula (2), a substituent represented by the formula (3), or a (meth) propylene group. a decyloxyalkyl group or a (fluorenyl)propenylalkyl group. R1 in the formula (6) is an alkylene group having 1 to 3 carbon atoms, and examples thereof include a methylene group, an exoethyl group, and a 1,2-extension. The propyl group and the 1,3-propanyl group. Among these stretching groups, from the viewpoint of output characteristics, it is preferably an ethyl group. In the formula (6), r is an integer of 1 to 5, and is charged. From the viewpoint of discharge cycle characteristics, it is preferably an integer of 1 to 4, and particularly preferably 2. (B1) Specific examples thereof include ethylene glycol bis(2-butenoate) ether (ethyleneglycol di (2) -butenoic acid methyl)ether), diethylene glycol bis(2-butenoate) ether, triethylene glycol bis(2-butenoate)ether, tetraethylene glycol bis(2-butene) Methyl ester) ether, pentaethylene glycol bis(2-butenoate) oxime, ethyleneglycol dicinnamyl ether, diethylene glycol dicinnamyl ether, triethylene glycol dicinnamate, four Ethylene glycol di-cinnabar, pentaethylene glycol dicinnamyl ether, ethylene glycol bis(4-vinylbenzyl) ether (ethyleneglycol di(4-vinylbenzyl)ether), diethylene glycol bis(4-ethethylenebenzyl)ether, triethylene glycol bis(4-vinylbenzyl)ether, tetraethylene glycol II 201203678 (4- Ethylene benzyl)ether, pentaethylene glycol bis(4-vinylbenzyl)ether, ethyleneglycol di(l-acryloyloxyethyletherether) , diethylene glycol bis(1-propenyloxyethyl)ether, triethylene glycol bis(1-propenyloxyethyl)ether, tetraethylene glycol bis(1-propyleneoxyethyl) Ether, pentaethylene glycol bis(1-propenyloxyethyl) hydrazine, diethyleneglycol (2-pentenoic acid ethylether), triethylene glycol (diethyleneglycol (2-pentenoic acid ethyl ether)) Ethyl 2-pentenoate) Ether, etc. These compounds are commercially available or can be synthesized by a known method. (B2) is a polyoxyalkylene ether having a substituent (b), which is substituted. The compound of the group (b) is obtained by adding an alkylene oxide (hereinafter abbreviated as A〇). The AO to be added may be the same A0 as the one shown in (A3). It is preferably E0. The molar number is preferably i-mole~1〇m, especially preferably 1m~5m The electrode protective film forming agent (F) of the present invention contains at least one compound (A) or compound (B) selected from the group consisting of the above (ad'uu'wwbd and (B2). The liquid contains an electrolyte (G), a nonaqueous solvent (h), and an electrode protective film forming agent (F) as essential components. When the electrode protective film forming agent (F) blade is applied to the electrode or the electrolyte to apply a voltage, the electrode protective film forming agent (the surface of the amphoteric substance is polymerized to form a film to form a protective film. _ secondary battery wire ion capacitor; In the case where the recording or electrolyte contains the electrode protective film forming agent (F), the protective film of 201203678 is formed at the time of initial charging, but an electrode protective film (F) may be formed separately from the electrode surface (active material surface). The electrode of the polymer film is used as an electrode of a lithium secondary battery or a lithium ion capacitor. The electrolyte (G) may be an electrolyte used in a usual electrolyte solution, and examples thereof include inorganic acids such as LiPF6, LiBF4, LiSbF6, LiAsF6, and LiC104. Lithium salt; lithium salt of an organic acid such as LiN (CF3S02) 2, LiN (C2F5S02) 2, and LiC (CF3S02) 3. Among these electrolytes, LiPF6 is preferred from the viewpoint of battery output and charge/discharge cycle characteristics. As the nonaqueous solvent (H), a solvent used in a usual electrolytic solution can be used, for example, a lactone compound, a cyclic or key carbonate, a chain carboxylate, a cyclic or chain ether, and phosphorus can be used. An ester, a nitrile compound, an amide compound, a sulfone, a sulfolane, etc., and a mixture of the compounds. The lactone compound may be a 5-membered ring (γ-butyrolactone (γ) -butyrolactone), γ-valerolactone, etc., and a 6-membered ring internal vinegar compound (δ-valerolactone, etc.). The cyclic carbonate can be exemplified by propylene carbonate (pr〇pylene). Carbonate, ethylene carbonate, and butylene carbonate, etc., may be exemplified by dimethyl carbonate (dimethyl carbonate).

carbonate)、碳酸曱基乙醋（methyl ethyl carbonate)、石厌I 二乙酿（diethyl carbonate )、碳酸曱基·正丙西曰 (methyl-n-propyl carbonate )、碳酸乙基-正丙西曰 (ethyl-n-propyl carbonate)及碳酸二-正丙醋（di_n-Pr〇Pyl 20 201203678 ^ * * * 'tr“ carbonate)等。鏈狀羧酸酯可列舉：乙酸甲酯（methyl acetate)、乙酸乙酯（ethyl acetate )、乙酸丙酯（propyl acetate )及丙酸曱酯（methyl propionate )等。環狀醚可列舉：四氫呋喃、四氫吡喃 (tetrahydropyran)、1,3-二氧戊環（l，3-dioxolane)及 1,4-二°惡烧（l，4-dioxane)等。鏈狀趟可列舉：二甲氧基曱炫（dimethoxy methane) 及 1，2-二曱氧基乙烧（i,2-dimethoxyethane)等。填酸酯可列舉：鱗酸三甲酯（trimethyl phosphate )、磷酸三乙酯、磷酸乙基二甲酯、磷酸二乙基甲酯、磷酸三丙酯、磷酸三丁酯、磷酸三（三氟曱基）酯 (tri(trifluoromethyl)phosphate)、磷酸三(三氣曱基)酯、磷酸三(三氟乙基)酿、磷酸三(三全氟乙基)g旨、2-乙氧基二氧磷雜環戊 -2- _ (2-ethoxy-1，3，2-dioxaphospholan-2-one )、2·三氟乙氧美 -1，3,2-二氧磷雜環戊_2_酮、2-甲氧基乙氧基-i，3,2_二氧填雜環戊-2·酮等。 ’ 腈化合物可列舉乙腈（acetonitrile)等。醯胺化合物可列舉二甲基甲酿胺（dimethylformamide)等。非水溶劑（H)可單獨使用，亦可併用2種以上。非水溶劑（H)中，就電池輸出及充放電循環特性的觀點而言，較佳為内酯化合物、鏈狀碳酸酯、鏈狀碳酸酯及磷酸酯，尤佳為内酯化合物及鏈狀碳酸酯，特佳為内= 21 201203678 一，* .r*i 化合物，最佳為5員環或6員環的内酯化合物，特佳員環的内酯化合物。 ~ 内酯化合物由於與碳酸酯化合物相比電位窗狹窄，故而無法用作先前鋰電池用途中的非水溶劑。然而，本發明的電解液由於存在由電極保護膜形成劑（F)形成的保護膜，故而内酯化合物亦可用作非水溶劑，與碳酸酯化合物相比較耐熱保存穩定性優異，因此可使高溫儲藏特性提高。本發明的電解液較佳為更含有路易斯鹼（c)。上述具有烯氧基（a)的化合物（a)的反應性高，容易與例如電解液中微量混合存在的水分和LiPF6等電解質鹽反應產生的HF等酸性化合物進行反應。藉由在電解液中添加路易斯鹼（C)，可增加化合物（A)於電解液中的穩定性。另外，於路易斯驗（c)為後述的氮雜冠趟（azacrownether) 衍生物（Cl)的情況，由於氮雜冠醚衍生物（C1)形成負極保護膜，故而可使充放電循環特性進一步提高。路易斯鹼（C)可列舉氮雜冠醚衍生物（C1)及*** (triazole)竹生物（C2)等。該些化合物中，就循環特性的觀點而言，較佳為氮雜冠趟衍生物（Ci)。氮雜冠醚衍生物（C1)具有包含1個〜4個氮原子的 9員環〜24員環的冠醚骨架，較佳為於該骨架的氮原子的 1個以上鍵結有具有聚合性不飽和雙鍵的取代基的化合物0 具有1個〜4個氮原子的9員環〜24員環的冠醚骨架可列舉：氮雜-9-冠-3-喊（4-氣雜-9-冠_3_謎及4,7-二氮雜-9- 22 201203678 冠各謎等）、氮雜、12·冠_4,（4-氮雜·12·冠·4,及41〇二氮，-12_冠，等）、氮雜孙冠领（4•氮雜_14_冠_4_ 謎及4，他—轉_14•冠4__)、氮雜_15.冠相（ Τ^ιΐιΤ^^ ，，一氮雜-15-冠-5-醚等）、氮雜·18•冠冰醚雜-18-冠-6-趟备；鼠 18 Μ 6 MU ^ 雜驗及⑽，1卜三氮雜 -18-冠-6-醚專)、氮雜_21•冠领(4氮雜必二氮雜-21-冠-7-醚及4 1η 16 一备铋μ q， ,1U" 麴,，，，氮雜冠_7,等〕以及氮 ’、 -一C -氮雜-24_冠-8-_、4，1〇-二氮雜·24_冠·8_ 醚及4，10，16_三氮雜_24-冠_8，等）等。架中，就與鋰離子的配位力的觀點而言，幸义佳為氮雜-12-冠_4_喊、氮雜·14_冠_4, 氮雜-i2-冠-4-鱗味氮雜_15_冠_5_趟及4，1〇_二氮雜七-冠= 就對鐘離子的配位力的觀點而言，氮雜冠喊骨架氮原子數較佳為1個〜3個，尤佳^個或2個。”、氮雜冠驗衍生物（C1)所具有的具有聚合性不飽和雙鍵的取代基例如可列舉：上料式⑴所麵的取代基、通式（3)所表示的取代基、（甲基）丙烯醯氧基烷基及^甲基)丙稀醯基院基等，較佳的取代基亦相同。氮雜冠醚衍生物（C1)的具體例可列舉：N_(2_丁烯酸甲酉曰）-4-氮雜-12-冠 _4_ 趟(N-(2-butenoic acid methyl)-4-aza-12-crown-4-ether )、N,N_ 二-(2- 丁稀酸甲 23 201203678 酯)-4，l〇-二氮雜_12_冠_4_醚、N_(2_丁烯酸曱酯)_4_氮雜-Μ 冠HN，N-二-(2-丁烯酸曱醋M，l〇-二氮雜-15·冠 N-(肉桂基氮雜_12_冠_4，、取-二(肉桂基)4抓二氣雜-I2-冠、N_(肉桂基)冬氮雜七冠_5醚、N，N-二(肉桂基)-4，1〇-二氮雜_15_冠·5•醚、N_(4乙烯基苄基)_4 -12-冠-4-醚、N，Nc_(4_乙烯基节基)·4，1〇二氮雜·12_冠< 醚、Ν-(4-乙烯基苄基)_4_氮雜-15-冠_5·醚、Ν，Ν-二-(4-乙烯基苄基)-4，1〇-二氮雜_15·冠_5_醚、ν，Ν-:-(1-丙烯醯氧基乙基)-4，10_二氮雜-Ι5-冠_5_醚、N-(l-丙烯醯氧基乙基X氮雜 -14-冠-4-趟、ν_(2_戊烯酸乙酯)冰氮雜·18_冠_6_醚及ν，ν· 二-(2-戊烯酸曱酯)_4，14-二氮雜-18-冠-6-醚等。本發明中的氮雜冠醚衍生物（C1)可以通常的方法製造。例如可列舉如下方法：於有機溶劑中，在無觸媒或者觸媒的存在下’使未經取代的氮雜冠醚與具有聚合性不飽和雙鍵的齒化烷基進行反應。有機溶劑例如可列舉：腈系有機溶劑（乙腈、丙腈 (propionitrile )及苯曱腈（benzonitrile )等）、酮系有機溶劑（丙綱（acetone )及曱基乙基嗣（methyl ethyl ketone ) 等）、醯胺系有機溶劑（曱醯胺、乙醯胺、二甲基曱醯胺及二曱基乙醯胺等）、醚系有機溶劑（二曱醚、四氫呋喃及二噁烷等）、酯系有機溶劑（乙酸乙酯及順丁烯二酸二乙酯等）、含硫有機溶劑（二曱基亞颯（dimethyl sulfoxide)及環丁颯等）、鹵化烴（氣仿及二氣曱烷等）、烴（己烷、庚烷、曱苯及二曱苯等）以及該些溶劑的兩種以上的混合物。 24 201203678 觸媒可列舉：驗金屬氮氧化物（例如氫氧化鐘、氫氧化納及氫氧化卸等）、驗金屬碳酸鹽（碳酸氫鈉、碳酸氫钟、碳酸鋼及碳酸钟等）及鹼金屬氫化物（氫化鈉及氫化钾等）等。反應溫度通常為1〇。(：〜150°C，反應時間通常為0.5 小時〜24小時。反應結束後，可視需要中和觸媒，以吸附劑進行處理而將觸媒去除，加以純化。具有聚合性不飽和雙鍵的鹵化烧基例如可列舉：4-漠 -2-丁稀酸曱醋（4_bromo-2-butenoic acid methyl ester)、4- 氯-2- 丁烯酸曱酯、1-溴-4-氰基-2- 丁晞 (l-bromo-4-cyano-2-butene)、1-氣-4-氰基-2-丁烯、丙稀酸氯曱酯（chloromethyl acrylate )、丙稀酸演甲g旨、丙稀酸 -2-氯乙酯、丙烯酸_2_溴乙酯、曱基丙烯酸氣曱酯、甲基丙烯酸溴曱酯、甲基丙烯酸-2-氣乙酯、甲基丙稀酸溴乙酯、肉桂基氯（cinnamyl chloride)、肉桂基溴、4-(氯曱基) 苯乙烯（4-(chloromethyl)styrene)及4-(溴曱基)苯乙烯。 ***衍生物（C2 )可列舉：ι，2,3-苯幷*** (l，2,3-benzotriazole)、5-甲基-l，2,3-苯幷***、5,6-二曱基 -1，2,3-苯幷***、1，2,4-***、3-胺基-1，2,4-***、3,5-二胺基-1，2,4·***、3-胺基-5_甲基_ι，2,4·***、3_胺基·5_乙基 -1，2,4-二唑、3-胺基-5-丙基_ι，2,4·***及3-胺基_5_丁基 -1，2,4-***等。該些***衍生物可獲得市售品。該些*** 衍生物中，就充放電循環特性的觀點而言，較佳為^胺基 -1，2,4-三〇坐。本發明的祕料更含有化合物⑷及化合物⑻ 25 201203678 -- A- i 以外的負極保護膜形成劑（D)。藉由電解液含有負極保護膜形成劑（D)，負極保護膜的穩定性進一步提高，可使充放電循環特性進一步提高。負極保護膜形成劑（D )可列舉：碳酸亞乙烯酯 (vinylene carbonate)、碳酸氟乙二酯、碳酸氣乙二酯、亞硫酸乙二酯（ethylene sulfite)、亞硫酸丙二酯及…溴个丁内酯等。該些化合物中，就循環特性的觀點而言，較佳為碳酸亞乙烯酯。本發明的電解液中的電極保護膜形成劑（F)、路易斯驗（C)、負極保護膜形成劑（d)、非水溶劑（H)及電解質（G)的各較佳含量或濃度為如下所述。就充放電循環特性、電池容量及高儲藏特性的觀點而 έ ’作為電極保護膜形成劑（F)的化合物（a)的含量基於電解液的重量，較佳為〇.〇1重量百分比（wt%)〜1〇 wt% ’ 尤佳為〇〇5 wt%〜1 wt0/〇。就電池容量、電池輸出及充放電循環特性的觀點而言’作為電極保護膜形成劑（F)的化合物（B)的含量基於電解液的重量，較佳為0.01 wt%〜1〇 wt%，尤佳為〇〇1 wt% 〜1 wt%。就電池容量、電池輸出及充放電循環特性的觀點而言’路易斯鹼（C)的含量基於電解液的重量，較佳為〇wt% 〜10 wt% ’更佳為0.01 wt%〜10 wt% ’尤佳為0·〇5 wt%〜 1 wt%。就電池容量、電池輸出及充放電循環特性的觀點而 26 201203678 -· ·【-- 言’負極保護膜形成劑（D)的含量基於電解液的重量，較佳為0 wt%〜5 wt%，更佳為〇 01 wt%〜5 wt%，尤佳為 0.01 wt%〜3 wt%。就電池輸出及充放電循環特性的觀點而言，非水溶劑 (H)的含量基於電解液的重量，較佳為7〇 wt%〜99 wt°/〇，尤佳為93 wt%〜99 wt%。Carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propylpropionate (ethyl-n-propyl carbonate) and di-n-propyl acrylate (di_n-Pr〇Pyl 20 201203678 ^ * * * 'tr" carbonate), etc. The chain carboxylic acid esters may be exemplified by methyl acetate. Ethyl acetate (ethyl acetate), propyl acetate, methyl propionate, etc. Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane. (l,3-dioxolane) and 1,4-dioxane, etc. Chain-like oxime can be exemplified by dimethoxy methane and 1,2-dimethoxy group. I, 2-dimethoxyethane, etc. Examples of the acid esters include: trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, and tripropyl phosphate. , tributyl phosphate, tri(trifluoromethyl)phosphate, tris(trimethylsulfonyl) phosphate, phosphoric acid Tris(trifluoroethyl) brewing, tris(trifluoroethyl)phosphoric acid, 2-ethoxydioxolan-2-(2-ethoxy-1,3,2-dioxaphospholan-2 -one ), 2 · trifluoroethoxymethan-1,3,2-dioxaphosphol-2-one, 2-methoxyethoxy-i, 3,2-dioxane -2. A ketone or the like. The acetonitrile compound may, for example, be acetonitrile. The guanamine compound may be dimethylformamide or the like. The nonaqueous solvent (H) may be used singly or in combination of two or more. In the nonaqueous solvent (H), from the viewpoint of battery output and charge/discharge cycle characteristics, a lactone compound, a chain carbonate, a chain carbonate, and a phosphate are preferable, and a lactone compound and a chain are preferable. Carbonate, especially good for inner = 21 201203678 one, * .r*i compound, preferably a 5-membered or 6-membered lactone compound, a lactone compound of a special ring. ~ a lactone compound due to carbonic acid Since the ester compound is narrower than the potential window, it cannot be used as a nonaqueous solvent in the prior lithium battery use. However, the electrolyte of the present invention is protected by the electrode protective film forming agent (F). , And therefore the lactone compound can also be used a non-aqueous solvent, as compared with a carbonate compound is excellent in heat-resistant storage stability, high temperature storage characteristics can be improved. The electrolyte of the present invention preferably further contains a Lewis base (c). The compound (a) having an alkenyloxy group (a) has high reactivity, and is easily reacted with, for example, an acidic compound such as HF which is produced by a reaction between a water which is slightly mixed in an electrolytic solution and an electrolyte salt such as LiPF6. The stability of the compound (A) in the electrolyte can be increased by adding the Lewis base (C) to the electrolyte. Further, in the case where the Lewis test (c) is an azacrownether derivative (Cl) to be described later, since the azacrown ether derivative (C1) forms a negative electrode protective film, the charge and discharge cycle characteristics can be further improved. . The Lewis base (C) may, for example, be an azacrown ether derivative (C1) or a triazole bamboo organism (C2). Among these compounds, from the viewpoint of cycle characteristics, an azacrown derivative (Ci) is preferred. The azacrown ether derivative (C1) has a crown ether skeleton of a 9-membered ring to a 24-membered ring containing 1 to 4 nitrogen atoms, preferably one or more bonds of a nitrogen atom of the skeleton are polymerizable. Compound 0 of the substituent of the unsaturated double bond The crown ether skeleton of the 9-membered ring to 24 ring member having 1 to 4 nitrogen atoms can be enumerated: aza-9-crown-3-cry (4-gas-9) - crown _3_ mystery and 4,7-diaza-9- 22 201203678 crowns, etc.), aza, 12·crown _4, (4-aza·12·crown 4, and 41〇2 Nitrogen, -12_ crown, etc.), aza-sun crown (4 • aza _14_ crown _4_ mystery and 4, he-turn _14 • crown 4__), aza _15. crown phase ( Τ ^ ΐΐιΤ^^ ,, aza-hetero-15-crown-5-ether, etc.), aza·18•crown ether ether-18-crown-6-prepared; mouse 18 Μ 6 MU ^ abundance and (10),1 Bu triaza-18-crown-6-ether special), aza-21• crown collar (4 aza-bidiazepine-21-crown-7-ether and 4 1η 16 a 铋μq, ,1U&quot ; 麴,,,, aza crown _7, etc.] and nitrogen ', -C-aza-24_crown-8-_, 4,1〇-diaza·24_crown·8_ ether and 4 , 10, 16_ triaza-24-crown _8, etc.). In the framework, from the viewpoint of the coordination force with lithium ions, Xingyi Jia is aza-12-crown_4_ shouting, aza·14_crown_4, aza-i2-crown-4-scale Aza nitrogen _15_ crown _5_趟 and 4,1〇_diazepine seven-crown = from the viewpoint of the coordination force of the bell ion, the number of nitrogen atoms in the aza-crown skeleton is preferably one ~3, especially good ^ or 2. The substituent having a polymerizable unsaturated double bond which the aza crown derivative (C1) has, for example, a substituent represented by the above formula (1), a substituent represented by the formula (3), The methyl group is a propylene methoxyalkyl group and a methyl group propyl thiol group, and the preferred substituents are also the same. Specific examples of the azacrown ether derivative (C1) include: N_(2_丁N-(2-butenoic acid methyl)-4-aza-12-crown-4-ether ), N,N_ di-(2-) Butyric acid A 23 201203678 Ester)-4,l〇-diazepine_12_crown_4_ether, N_(2-butenoate) _4_aza-Μ Crown HN,N-di-( 2-butenoic acid vinegar vinegar M, l〇-diazepine-15·crown N-(cinnamyl aza _12_crown _4, taken-two (cinnamyl) 4 grasped two gas-I2-crown , N_(cinnamyl), azapine, seven crowns, _5 ether, N,N-di(cinnamyl)-4,1〇-diaza-15_crown·5•ether, N_(4vinylbenzyl) _4 -12-crown-4-ether, N,Nc_(4_vinyl nodal)·4,1 diazepine·12_crown<ether, Ν-(4-vinylbenzyl)_4_nitrogen Hetero-15-crown_5·ether, anthracene, fluorene-di-(4-vinylbenzyl)-4,1〇-diaza-15·crown_5_ether, ν, -:-(1-Propyloxyethyl)-4,10-diaza-indole-5-crown-5-ether, N-(l-acryloxyethylethylaza-14-crown-4 -趟, ν_(2-pentenoate ethyl ester) ice aza·18_crown_6_ether and ν,ν·bis-(2-pentenoate) _4,14-diaza--18- Crown-6-ether, etc. The azacrown ether derivative (C1) in the present invention can be produced by a usual method, and examples thereof include the following methods: in an organic solvent, in the absence of a catalyst or a catalyst, The substituted azacrown ether is reacted with a dentate alkyl group having a polymerizable unsaturated double bond. Examples of the organic solvent include a nitrile-based organic solvent (acetonitrile, propionitrile, benzonitrile, etc.). , ketone organic solvents (acetone and methyl ethyl ketone, etc.), amide amine organic solvents (guanamine, acetamide, dimethyl decylamine and dimethyl hydrazine) Amines, etc., ether-based organic solvents (dimethyl ether, tetrahydrofuran, dioxane, etc.), ester-based organic solvents (ethyl acetate and diethyl maleate, etc.), sulfur-containing organic solvents (dithiopyrene) Dimethyl sulfoxide and Cyclohexane, etc.), halogenated hydrocarbons (such as gas and dioxane), hydrocarbons (hexane, heptane, toluene, diphenylbenzene, etc.) and mixtures of two or more of these solvents. 24 201203678 Catalyst For example, metal oxynitrides (such as hydrazine hydroxide, sodium hydroxide, and hydrazine), metal carbonates (sodium bicarbonate, hydrogencarbonate, carbonic acid, carbonic acid, etc.) and alkali metal hydrides ( Sodium hydride, potassium hydride, etc.). The reaction temperature is usually 1 Torr. (: ~150 ° C, the reaction time is usually 0.5 hours to 24 hours. After the reaction is completed, the catalyst can be neutralized as needed, treated with an adsorbent to remove the catalyst and purified. Polymerizable unsaturated double bonds Examples of the halogenated alkyl group include 4-bromo-2-butenoic acid methyl ester, 4-chloro-2-butenoic acid ester, and 1-bromo-4-cyano- 2-butyl group (l-bromo-4-cyano-2-butene), 1-gas-4-cyano-2-butene, chloromethyl acrylate, and acrylic acid ,-2-chloroethyl acrylate, _2_bromoethyl acrylate, decyl decyl acrylate, bromo methacrylate, 2-ethyl methacrylate, bromoethyl methacrylate Ester, cinnamyl chloride, cinnamyl bromide, 4-(chloromethyl)styrene and 4-(bromomethyl)styrene. Triazole derivative (C2) Listed: i, 2,3-benzotriazole, 5-methyl-l,2,3-benzotriazole, 5,6-dimercapto-1,2, 3-benzotriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4.triazole, 3- 5--5-methyl_ι,2,4·triazole, 3-amino-5·ethyl-1,2,4-diazole, 3-amino-5-propyl_ι, 2,4 Triazole and 3-amino-5-butyl-1,2,4-triazole, etc. These triazole derivatives are commercially available. Among these triazole derivatives, charge and discharge cycle characteristics In view of the above, the amine compound-1,2,4-trisole is preferred. The secret material of the present invention further contains the compound (4) and the compound (8) 25 201203678 -- A negative electrode protective film forming agent other than A- i (D) By containing the negative electrode protective film forming agent (D) in the electrolytic solution, the stability of the negative electrode protective film is further improved, and the charge/discharge cycle characteristics can be further improved. The negative electrode protective film forming agent (D) can be exemplified by vinylene carbonate (vinylene). Carbonate, fluoroethylenedicarbonate, ethylene carbonate, ethylene sulfite, propylene sulfite, brominated butyrolactone, etc. Among these compounds, from the viewpoint of cycle characteristics In other words, the electrode protective film forming agent (F), the Lewis test (C), the negative electrode protective film forming agent (d), the nonaqueous solvent (H), and the electrolysis in the electrolytic solution of the present invention. The preferred content or concentration of (G) is as follows. The content of the compound (a) as the electrode protective film forming agent (F) is based on the viewpoint of charge and discharge cycle characteristics, battery capacity, and high storage characteristics. The weight of the liquid is preferably 〇.〇1 by weight (wt%)~1〇wt% ' More preferably 〇〇5 wt%~1 wt0/〇. The content of the compound (B) as the electrode protective film forming agent (F) is preferably 0.01% by weight to 1% by weight based on the weight of the electrolytic solution, from the viewpoints of battery capacity, battery output, and charge and discharge cycle characteristics. It is especially good for 〇〇1 wt% ~1 wt%. The content of the Lewis base (C) is preferably from 〇wt% to 10 wt%, more preferably from 0.01 wt% to 10 wt%, from the viewpoints of battery capacity, battery output, and charge and discharge cycle characteristics. 'Youjia is 0·〇5 wt%~ 1 wt%. From the viewpoints of battery capacity, battery output, and charge and discharge cycle characteristics, the content of the negative electrode protective film forming agent (D) is preferably 0 wt% to 5 wt% based on the weight of the electrolytic solution. More preferably, it is wt01 wt%~5 wt%, and particularly preferably 0.01 wt%~3 wt%. The content of the nonaqueous solvent (H) is preferably from 7 〇 wt% to 99 wt ° / 〇, particularly preferably from 93 wt% to 99 wt%, based on the weight of the battery and the charge and discharge cycle characteristics. %.

就電池輸出及充放電循環特性的觀點而言，電解液中的電解質（G)的濃度基於電解液的體積，較佳為0.01 mol/L 〜3 mol/L ’ 尤佳為 0.05 mol/L〜1.5 mol/L。本發明的電解液可更含有過量充電防止劑、脫水劑及谷量穩定劑等添加劑。過量充電防止劑可列舉：聯苯（biphenyl)、烷基聯笨 (alkyl biphenyl )、聯三笨（te卬henyl )、聯三苯的部分氫化物、環己基苯（cyclohexyl benzene)、第三丁基苯及第三戊基苯等芳香族化合物等。過量充電防止劑的使用量基於電解液的總重量，通常為〇wt%〜5 wt% ’較佳為〇wt%〜 3 wt%。脫水劑可列舉沸石（zeolite)、矽膠（silica gel)及氧化舞等。基於鐘二次電池用電解液的總重量，脫水劑的使用里通常為〇 wt%〜5 wt%，較佳為0 wt%〜3 wt% 〇容量穩定劑可列舉：碳酸氟乙二酯、琥珀酸酐、甲基底咬酮（l-methyl-2-piperidone)、庚烧及氟苯等。基於電解液的總重量，容量穩定劑的使用量通常為0 wt%〜5 wt% ’ 較佳為〇 wt%〜3 wt%。 27 201203678 ……*r— 本發明的電解液尤其作為鐘二次電池用的電解液而有用。使用本發明的電解液的鐘二次電池是藉由在收納有正極、負極及分隔片的電池罐内注入本發明的電解液，將電池罐密封而獲得。鐘二次電池中的正極可使用以棒式塗佈機等塗佈裝置，將使正極活性物質、導電劑及黏合劑分散於溶劑中而衆料化者塗佈於正極用集電體上，加以乾燥而去除溶劑，視需要利用壓製機進行壓製而成的正極等。正極活性物質可列舉：鋰與過渡金屬的複合氧化物（例如 LiCo02、LiNi02、LiMn02 及 LiMn204 等）、過渡金屬氧化物（例如Mn〇2及V2〇5等）、過渡金屬硫化物（例如m〇S2 及TiS2等）、以及導電性高分子（例如聚苯胺 (polyaniline)、聚偏二氟乙稀（p〇iyvinyHdene f|uoride)、聚吡咯（polypyrrole)、聚噻吩（；p〇1ythi〇phene)、聚乙炔 (polyacetylene)' 聚對亞苯基（p〇iy_p_phenyiene)及聚口卡唑（polycarbazole)等）等。導電劑可列舉：石墨（例如天然石墨及人工石墨等）、碳黑（carbon black)類（例如碳黑、乙炔黑（acetylene black)、柯琴黑（Ketjen black)、槽黑（channel black)、爐黑（furnace black)、燈黑（iamp black)及熱黑（thermal black) 等）、金屬粉末（例如is粉及鎳粉等）、導電性金屬氧化物 (例如氧化鋅及氧化鈦等）等。黏合劑例如可列舉：澱粉、聚偏二氟乙烯、聚乙烯醇 28 201203678 (polyvinyl alcohol )、叛甲基纖維素（carb〇xymethyl cellulose)、聚乙稀基。比 π各 π定酮（p〇iyVinyipyrr〇ud〇ne)、四氟乙烯（tetrafluoroethylene)、聚乙烯及聚丙烯等高分子化合物。溶劑例如可列舉：1-曱基_2_吡咯啶酮、曱基乙基酮、二曱基曱醯胺、二甲基乙醯胺、N，N_二曱基胺基丙基胺及四氫吱喃等。正極用集電體可列舉：鋁、鈦、不鏽鋼、鎳、碳極（b aked carbon)、導電性高分子及導電性玻璃等。鋰二次電池中，基於正極總重量的正極活性物質、導電劑及黏合劑的各較佳含量為如下所述。正極活性物質的含量較佳為7〇 wt%〜98 wt%，尤佳為 9〇Wt%〜98wt%。導電劑的含量較佳為丨wt%〜29wt% : 尤佳為1 wt%〜1〇 wt%。黏合劑的含量較佳為1糾％〜29 wt%，尤佳為 1 wt%〜10 wt〇/。。、基於正極活性物質、導電劑及黏合劑的總重量，正極活性物質、導電劑及黏合劑㈣料化時的溶劑使用量較佳為 20 wt%〜70 Wt%，尤佳為 30 wt%〜6〇 wt〇/〇。鐘一次電池中的負極可使用以棒式塗佈機等塗佈装置，將使負極活性物質、導電劑及黏合劑分散於溶劑中而裝料化者塗佈於負極用集電體上，加以乾燥而去除溶劑，視需要以壓製機進行壓製而成的負極等。負極活性物質可列舉：石墨、高分子化合物锻燒體如將盼樹月曰及吱嚼樹脂等炮燒碳化而成的般燒體）、焦炭類 29 201203678 l. (例如遞青焦炭（Pitch coke)、針狀焦炭（needle c〇ke)及石油焦炭等）、碳纖維、導電性高分子（例如聚乙炔及聚吡咯等）、金屬合金（例如鋰-鋁合金、鋰-鋁-錳合金等）等。導電劑、黏合劑及溶劑可使用與製造正極時所使用的材料相同的材料。負極用集電體可列舉：銅、不鏽鋼、鎳、鋁、鈦、碳極、導電性向分子、導電性玻璃及鋁-鎘合金等。鐘二次電池中，基於負極總重量的負極活性物質、導電劑及黏合劑的各較佳含量馬如下所述。負極活性物質的含量較佳為70 wt%〜98 wt%，尤佳為 90 wt%〜98 wt%。導電劑及黏合劑的含量與正極的情況相同。 θ負極活性物質、導電劑及黏合劑的漿料化時的溶劑使用量與正極活性物質、導電劑及黏合劑的漿料化時的溶劑使用量相同。鐘二次電池中的分隔片可列舉：聚乙烯、聚丙烯製膜 1微多孔膜；多孔性聚乙稀膜與聚丙烯的多層膜；包含聚面a纖維、芳族聚醯胺纖維（aramid行ber)、玻璃纖維等的不織布，以及於其等的表面附著有二氧化梦、氧化鋁、氧化鈦等陶瓷微粒子的分隔片。 M二次電池中的電池罐可使用不鏽鋼（stainless steel)’鑛有鐵、铭及鎳的鋼等金屬材料，亦可根據電池用途而使用歸材料。另外，電池罐可根據肢而形成圓筒型、硬幣型、方型、其他任意的形狀。 201203678 本發明的電解液尤其作為鋰離子電容器用的電解液亦有用。使用本發明的電解液的鋰離子電容器是藉由在收納有正極、負極及分隔片的電容器罐内注入本發明的電解液，將電容器罐密封而獲得。鋰離子電容器中的正極可使用以棒式塗佈機等塗佈裝置，將使活性碳（正極活性物質）、導電劑及黏合劑分散於溶劑中而漿料化者塗佈於正極用集t體上，加以乾燥而去除溶劑，視需要利用壓製機進行壓製而成的正極等。導電劑、黏合劑、溶劑及正極用集電體可列舉與鋰二次電池的情況相同者。 ' 鐘離子電谷器中，基於正極總重量的正極活性物質、導電劑及黏合劑的各較佳含量為如下所述。正極活性物質的含量較佳為70 wt%〜98 wt%，尤佳為 9〇 Wt%〜98 wt%。導電劑的含量較佳為1 wt%〜29 wt〇/0，尤佳為1 wt%〜10 wt%。黏合劑的含量較佳為i wt%〜^ wt% ’ 尤佳為 1 wt%〜1〇 wt%。基於正極活性物質、導電劑及黏合劑的總重量，正極活性物質、導電劑及黏合劑的漿料化時的溶劑使用量較佳為 20 wt%〜7〇 wt%，尤佳為 3〇 wt%〜6〇 wt〇/〇。鐘離子電谷器中的負極可使用以棒式塗佈機等塗佈裝置，將使負極活性物質、導電劑及黏合劑分散於溶劑中而漿料化者塗佈於負極㈣f體上，加以乾燥而去除溶劑，視需要利用壓製機進行壓製而成的負極等。 201203678 負極活1*生物質可列舉··非晶碳（am〇rph〇us carb〇n)、石墨（graphite)、錫及其合金、矽及其合金等。導電劑、黏合劑及溶劑可使用與製造正極時所使用的材料相同的材料。 . 負極用集電體可列舉：銅、不鏽鋼、鎳、紹、鈦、碳極、導電性高分子、導電性朗域，合金等。鋰離子電容器中’基於負極總重量的負極活性物質、導電劑及黏合劑的各較佳含量為如下所述。負極活性物質的含量較佳為70 wt%〜98 wt%，尤佳為 90 wt%〜98 Wt%。導電劑雜合劑的含量與正極的情況相同。負極活性物質、導電劑及黏合劑的漿料化時的溶劑使用量與正極雜物質、導電劑及黏合獅料化時的溶使用量相同。鋰離子電容器中的分隔片可列舉：聚乙烯、聚丙烯靠膜的微多孔膜；多孔性聚乙烯膜與聚丙烯的多層膜；包$ 聚酯纖維、芳族聚醯胺纖維、玻璃纖維等的不織布；以^ 於其等的表續著有二氧化♦、氧她、氧化鈦等粒子的分隔片。 1 鋰離子電容器中的電池罐可使用不鏽鋼，鍍有鐵、金及鎳的鋼等金屬材料，亦可根據電池用途而使用塑膠和料。另外，電池罐可根據用途而形成圓筒型、硬、卞型、其他任意的形狀。本發明的電極保護膜形成劑（F)可添加、含有於齒 32 201203678 --人電池或轉子電容㈣正極及/或貞極巾而使用。眺ΐ加於正Μ的料刊舉如下妓等：於使正極、、壬 ^亟保護膜形成劑(F)，以棒式塗佈機等塗佈裝置二機上，加以乾燥而去除溶劑，視需要利用壓製添加於負極中的方法可列舉如性物質、導電劑及黏合劑分散於溶劑中而活負極用集電體ί ▲式塗佈機等塗佈裝置塗佈於機進行壓製。乾燥而去除溶劑，視需要利用壓製就充放電循環特性、電池言，添加於正性的觀點而加量基於正_性物質，齡為（U wt%lT (。以的添為〇·5 wt%〜5 wt°/〇。 0 1〇 wt/〇，尤佳就充放電循環特性、電池言，添加於負極中的情況的電極保f 性的觀點而加量基於負極活性物質，較佳為〇T:t。添為 0.5 wt%〜5 wt%。 · wt/°〜10 wt%，尤佳 [實例] 以下，利用實例對本發明進一牛並不限定於該些實例。以下，朗，但本發明 [路易斯驗（C)的合成]π里份。〈製造例1〉 33 201203678 ^ 1 N，N-二-(2- 丁烯酸曱酯）_4，i〇_ 二氮雜·ΐ5_ 冠 _5·醚 (ΑΖ-1 )的合成：於安裝有攪拌機、溫度計及冷卻管的燒瓶中，加入 4，10_二氮雜-15-冠-5-醚[東京化成工業（股）製造]061份 (2.8 mmol份）、4-溴-2-丁烯酸甲酯[東京化成工業（股）製造]1份（5.6 mmol份）及乙腈1〇份，一邊攪拌一邊使其均勻溶解，然後於攪拌下在室溫下反應24小時。於減壓 (10 mmHg)下去除乙腈後’利用以丙酮為溶劑的氧化鋁管柱[150 mesh，Brockman 1，標準級，Aldrich (股）製造] 將反應物純化，獲得N，N-二-(2-丁烯酸曱酯)_4，1〇-二氮雜 -15-冠-5-趟（AZ-1) 0.85 份（2.0 mmol 份）（產率 71%)。 (AZ-1)是通式（2)中，R2為亞曱基，Qi及q2為氫原子， Q3為曱氧基羰基且具有聚合性不飽和雙鍵的取代基鍵結於氮原子上的二氮雜冠醚化合物。〈製造例2〉 N，N-j^-(1_丙烯醯氧基乙基)_4，1〇_二氮雜_15冠-5•醚 (AZ-2)的合成：除了代替4-溴-2-丁烯酸曱酯1份而使用丙烯酸_2_氣乙酯[東京化成工業（股）製造]0.76份（5.6 mmol份）以外，以與製造例i相同的方式獲得N，N-二_(卜丙烯醯氧基乙基)-4，1〇-二氮雜_15_冠_5·醚（az-2) 〇.6〇份（1.9 mmol 份）（產率68%)。此外，當將4-溴-2-丁烯酸曱酯1份變更為丙烯酸_2· 氣乙酯0.76份時，以反應成分的莫耳比及非反應成分（溶 34 201203678 劑等）的重量比成為與製造例1的情況同等的方式調整各原料的量而進行操作。對以下的製造例3亦同樣進行。 (ΑΖ-2)是丙烯醯氧基乙基作為具有聚合性不飽和雙鍵的取代基而鍵結於氮原子上的二氮雜冠醚化合物。〈製造例3〉 ^_，队二肉桂基-4，10-二氮雜-15-冠-5-喊（八2-3)的合成：除了代替4-溴-2-丁烯酸曱酯1份而使用肉桂基氯[東京化成工業（股）製造]0.85份（5.6 mmol份）以外，以與製造例1相同的方式獲得N，N-二肉桂基-4,10-二氮雜-15- 冠-5-醚（C1-3 )0_92 份（2.0 mmol 份）（產率 73%)。（ AZ-3 ) 是通式（2)中，R2為亞曱基，Q1及Q2為氫原子，q3為苯基且具有聚合性不飽和雙鍵的取代基鍵結於氮原子上的一氮雜冠趟化合物。〈實例1〉二乙二醇二(2-丁烯酸曱酯）醚（B-1)的合成：於安裝有攪拌機、溫度計及冷卻管的燒瓶中，加入二乙二醇[東京化成工業（股）製造]7.26份（68.4 mmol份）、 4_溴-2-丁烯酸曱酯[東京化成工業（股）製造]26.9份（15〇 3 mmol份）、氫氧化鈉6.00份（150 mmol份）及甲苯1〇〇份，一邊攪拌一邊使其均勻溶解後，於室溫下攪拌15分鐘，然後添加四丁基溴化銨1·32份（4.1 mmol份）。升溫至65°C後，攪拌4小時，進行醚化反應。放置冷卻後，添加水200份，分離水層。進而將有機層以水2〇〇份加以清洗。藉由減壓（10 mmHg)而去除曱苯後，利用以己烧為 35 201203678 溶劑的氧化铭管柱[150 mesh，Brockman 1，標準級，Aldrich (股）製造]將反應物純化，獲得二乙二醇二(2-丁烯酸曱西旨）謎（B-1 ) 15.5 份（51·3 mmol 份）（產率 75%) 〈實例2〉 —乙.一碎·一(4_乙稀基卞基)謎（B-2)的合成. 除了代替4-溴-2-丁烯酸甲酯26.9份（150.3 mmol份）而使用4-乙烯基苄基氣[東京化成工業（股）製造]22.9份 (150.3 mmol份）以外，以與實例1相同的方式獲得二乙二醇二(4_乙烯基节基)_( B-2 ) 16.9份（49.9 mmol份）（產率 73%)。〈實例3〉 1，4-雙(1-丙烯氧基曱基)環己烷（A-1)的合成：於安裝有攪拌機、溫度計及冷卻管的燒瓶中，加入1,4-環己烷二曱醇[東京化成工業（股）製造]9.86份（68.4 mmol 份）、氯丙烯[東京化成工業（股）製造]11.51份（150.3 mmol 份）、氳氧化鈉6.00份（150 mmol份）及曱苯1〇〇份，一邊攪拌一邊使其均勻溶解後，於室溫下攪拌15分鐘，然後添加四丁基溴化敍1.32份（4.1 mmol份）。以2小時升溫至65°C，進而攪拌4小時，進行醚化反應及重排反應。放置冷卻後，添加水200份，分離水層。進而將有機層以水 200份加以清洗。藉由減壓（10 mmHg)而去除曱苯後，利用以己烧為溶劑的氧化銘管柱[150 mesh，Brockman 1，標準級，Aldrich (股）製造]將反應物純化，獲得ι，4-雙(ι_ 丙婦氧基甲基)環己烧（八-1)10_9份（48.6 111111〇1份）（產 36 201203678 率 71%) 〇此外’表1〜表3中記載的化合物（a)中的ι，4-雙（乙烯氧基甲基)環已烷、1,4-丁二醇二乙烯醚及三乙二醇二乙稀_是使用束售品[Nippon Carbide Industries (股）製造]。 [電解液的製備] 〈實例4〜實例35〉以表1〜表3所示的重量比例來調配化合物（a)、化合物（B)、路易斯鹼（C)、負極保護膜形成劑（D)及非水溶劑（H) ’於其中以成為1 mol/L的濃度的方式溶解 LiPF0來調整實例4〜實例35的電解液。〈比較例1> 於碳酸乙二酯與碳酸二乙酯的混合溶劑（體積比率 3 : 7)中，使LiPF6以1 mol/L的比例溶解後，以2 wt%的比例混合碳酸亞乙烯酯，來調整比較例1的電解液。〈比較例2〉於碳酸乙二酯與碳酸二曱酯的混合溶劑（體積比率 1 : 2)中，使LiPF6以1 m〇i/L的比例溶解後，以成為0.1 mol/L的方式混合二甲基礙，來調整比較例2的電解液。〈比較例3〉於碳酸乙二酯與碳酸二曱酯的混合溶劑（體積比率 1 : 1)中’使LiPF6以1 mol/L的比例溶解後，以5 wt%的比例混合1，3-丙烷磺内酯，來調整比較例3的電解液。 37 201203678 J-a寸α 卜 ε 【1<】實例13 1 d 1 1 1 S 〇 (N 〇 1 1 1 1 1 1 實例12 没 d 1 1 1 S 〇〇 1 1 I 1 實例11 1 1 1 〇〇 CN d 1 1 (N 1 實例10 s ο 1 1 1 S 〇 tN d 1 1 (N 1 1實例9 s d 1 < f S d f 1 1 (N 1 實例8 1 1 1 1 S 〇 CN 〇 1 1 CS 1 例7」 1 1 1 S 〇 S 〇 (N 〇 1 1 (S 1 實例6 1 1 S 〇 1 〇 d <N 〇 1 1 CN 1 實例5 1 S d 1 1 ο d (N d 1 1 (N 1 [實例4 s d 1 1 1 s d (N 〇 1 1 CN 1 化合物名 1，‘雙(1-丙烯氧基甲基)環己烧 Μ-雙(1-乙烯氧基甲基)環己烷 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基节基)醚 (AZ-l) (AZ-2) (AZ-3) 3-胺基-1,2,4-*** 3,5-二胺基-1,2,4-*** 3-胺基-5-曱基-1，2,4-*** 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1,2,4-*** 3-胺基-5-丁基-1,2,4-*** 碳酸亞乙烯酯 γ-丁内酯 γ-戊内酯化合物（A) (份）化合物（B) (份）路易斯鹼（c) (份）負極保護膜形成劑（D) (份） *πχν °°ε 201203678 47.73 1 47.73 1 46.78 1 47.75 1 47.93 1 47.78 1 47.73 1 47.73 • 47.73 1 47.73 1 δ-戊内酯碳酸乙二酯碳酸二乙酯碳酸二甲酯碳酸乙基曱酯 LiPF6 電解質（mol/L) 201203678 玄寸卜卜卜ε t(N<〕 S d 1 1 S 〇 1 (Ν 〇 1 I 1 1 1 1 ^Τ) ο ο 1 1 S 〇 1 CN 〇 1 1 1 1 1 1 實例 22 s d 1 1 S 〇 <Ν d 1 〇 1 1 1 1 1 rN 實例 21 s o 1 1 S 〇 1 1 1 1 1 1 1 rs 没 o 1 I S 〇 1 1 1 t 1 1 1 (N 實例| J9_ s d 1 1 S 〇 1 <N d 1 1 1 1 1 1 CN 實例| 18___ s o 1 1 S 〇 CN Ο 1 1 1 1 1 1 1 (N 實例 17 s d 1 1 S d cs ο 1 1 1 1 1 1 1 <N 實例； J6__ s o 1 1 S d <Ν| ο 1 1 1 1 1 1 1 <N 實例 J5_ s o 1 1 s ο CN Ο 1 1 1 t 1 1 1 (N 拉2； s d 1 1 s d cs d 1 1 1 1 1 1 1 iN 化合物名 1 1，4-雙(1-丙烯氧基甲基)環1 己院 1，4-雙(1-乙烯氧基甲基)環| 己烧 i 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2· 丁烯酸曱酯）醚二乙二醇二(4-乙烯基苄基） |醚 (AZ-l) (AZ-2) (AZ-3) 3-胺基-1,2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-曱基-1，2,4-*** 1 3-胺基-5-乙基-1，2,4-*** 3-胺基-5-丙基-1,2,4-*** 3-胺基-5-丁基-1,2,4-*** 碳酸亞乙烯酯成分 |ί 化合物（Β) (份）路易斯鹼（c) (份）負極保護膜形成劑 (D) (份） 0寸 201203678 1 I 47.63 1 r—Η 1 ! 47.63 1 1 47.63 1 1 47.83 1 1 47.83 1 1 47.73 1 97.73 1 1 1 97.73 1 1 1 〇 1 1 69.73 〇 1 67.73 1 〇 67.73 1 1 γ-丁内酯 γ-戊内酯 δ-戊内酯碳酸乙二酯碳酸二乙酯碳酸二甲酯碳酸乙基甲酯 LiPF6 ML· \^y 電解質（mol/L) 201203678 J'a寸α 卜 ε 【ε^】駟ίί! S 〇 1 1 1 1 S 〇 tN d 1 1 1 1 1 1 1 1 S 〇 1 1 1 CN 〇〇 1 CN d 1 1 1 1 1 ^ 5λ S 〇 1 1 1 <N 〇 1 <N 〇 1 1 1 (S ? 駟Ρ! 〇〇 1 1 1 t 1 <N d 1 1 1 CS S d 1 1 1 ( S 〇 fN 〇 1 1 1 (N s d 1 1 1 s d 1 1 1 1 ίΝ s o 1 1 1 s d 1 1 1 1 駟？3 s o 1 1 1 s d 1 s o 1 1 1 CN s d 1 1 1 S d 1 CN 〇 1 1 (S s d 1 1 1 s d 1 (N 〇 I 1 1 CS 革 s d 1 1 s d 1 d 1 1 d 1 1 CN 化合物名 1，4-雙(1-丙烯氧基甲基)環己烧 1,4-雙(1-乙烯氧基甲基)環己烷 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯）謎二乙二醇二(4-乙烯基苄基）謎 (AZ-l) (AZ-2) (AZ-3) 3-胺基-1,2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1，2,4-*** 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1，2,4-*** 3-胺基-5-丁基-1,2,4-*** 1 碳酸亞乙烯酯成分 1 化合物（A) (份）化合物（B) (份）路易斯鹼（C) (份）被5 S^ 201203678 J-a寸αζ,ε 1 1 1 49.73 1 1 1 1 49.73 1 1 1 1 47.55 1 1 1 1 47.75 1 ««Η 1 1 1 47.73 1 1 1 1 46.93 1 1 1 1 47.83 1 1 1 1 47.88 1 1 1 1 47.63 1 1 1 1 47.63 1 1 1 1 47.63 1 γ-丁内酯 γ_戊内酯 δ-戊内酯碳酸乙二酯碳酸二乙酯碳酸二甲酯碳酸乙基曱酯 1 LiPF6 電解 (mol/L)The concentration of the electrolyte (G) in the electrolyte is preferably 0.01 mol/L to 3 mol/L', and particularly preferably 0.05 mol/L, from the viewpoint of battery output and charge and discharge cycle characteristics. 1.5 mol/L. The electrolytic solution of the present invention may further contain an additive such as an excessive charge preventing agent, a dehydrating agent, and a bar stabilizer. Examples of the overcharge preventing agent include biphenyl, alkyl biphenyl, te卬henyl, a partial hydride of diphenyl, cyclohexyl benzene, and third butyl. An aromatic compound such as benzene or tripentylbenzene. The amount of the overcharge preventing agent used is usually 〇wt% to 5 wt%', preferably 〇wt% to 3 wt%, based on the total weight of the electrolyte. Examples of the dehydrating agent include zeolite, silica gel, and oxidative dance. The dehydrating agent is usually used in an amount of from 〇wt% to 5 wt%, preferably from 0 wt% to 3 wt%, based on the total weight of the electrolyte for the secondary battery, and may be exemplified by fluoroethylene glycol ester, Succinic anhydride, l-methyl-2-piperidone, heptane and fluorobenzene. The capacity stabilizer is usually used in an amount of from 0 wt% to 5 wt%, based on the total weight of the electrolyte, preferably from 〇 wt% to 3 wt%. 27 201203678 ......*r The electrolytic solution of the present invention is useful particularly as an electrolytic solution for a clock secondary battery. The clock secondary battery using the electrolytic solution of the present invention is obtained by injecting the electrolytic solution of the present invention into a battery can containing a positive electrode, a negative electrode, and a separator to seal the battery can. The positive electrode in the secondary battery can be applied to a positive electrode current collector by dispersing a positive electrode active material, a conductive agent, and a binder in a solvent, using a coating device such as a bar coater. The positive electrode obtained by drying and removing the solvent, if necessary, is pressed by a press. Examples of the positive electrode active material include composite oxides of lithium and transition metals (for example, LiCoO 2 , LiNi 2 , LiMn 2 , and LiMn 204), transition metal oxides (for example, Mn 〇 2 and V 2 〇 5, etc.), and transition metal sulfides (for example, m 〇). S2 and TiS2, etc., and conductive polymers (such as polyaniline, polyvinylidene fluoride (p〇iyviny Hdene f|uoride), polypyrrole, polythiophene (; p〇1ythi〇phene) , polyacetylene (polyphenylene) (p〇iy_p_phenyiene) and polycarbazole (polycarbazole), etc. Examples of the conductive agent include graphite (for example, natural graphite and artificial graphite) and carbon black (for example, carbon black, acetylene black, Ketjen black, channel black, and the like). Furnace black, iamp black, and thermal black, metal powder (such as is powder and nickel powder), conductive metal oxide (such as zinc oxide and titanium oxide), etc. . Examples of the binder include starch, polyvinylidene fluoride, polyvinyl alcohol 28 201203678 (polyvinyl alcohol), carb〇xymethyl cellulose, and polyethylene. A polymer compound such as π π hexanone (p〇iyVinyipyrr〇ud〇ne), tetrafluoroethylene, polyethylene, or polypropylene. Examples of the solvent include 1-mercapto-2-pyrrolidinone, mercaptoethyl ketone, decyl decylamine, dimethylacetamide, N,N-didecylaminopropylamine, and four. Hydrogen oxime and so on. Examples of the current collector for the positive electrode include aluminum, titanium, stainless steel, nickel, carbonized carbon, conductive polymer, and conductive glass. In the lithium secondary battery, preferred contents of the positive electrode active material, the conductive agent and the binder based on the total weight of the positive electrode are as follows. The content of the positive electrode active material is preferably from 7 〇 wt% to 98 wt%, particularly preferably from 9 〇 Wt% to 98 wt%. The content of the conductive agent is preferably 丨wt% to 29% by weight: more preferably 1% by weight to 1% by weight. The content of the binder is preferably from 1% to 29% by weight, particularly preferably from 1% by weight to 10% by weight. . Based on the total weight of the positive electrode active material, the conductive agent and the binder, the positive electrode active material, the conductive agent and the binder (4) are preferably used in an amount of 20 wt% to 70 Wt%, more preferably 30 wt%. 6〇wt〇/〇. In the negative electrode in the primary battery, a coating device such as a bar coater can be used, and the negative electrode active material, the conductive agent, and the binder are dispersed in a solvent, and the charge is applied to the current collector for the negative electrode. The anode is dried by removing the solvent, and if necessary, pressing it by a press. Examples of the negative electrode active material include graphite and a polymer compound calcined body, such as a calcined carbon obtained by calcination of a mixture of a mixture of a mixture of a mixture of a mixture of a mixture and a resin, and a coke. 29 201203678 l. (for example, Pitch coke) ), needle coke (needle c〇ke) and petroleum coke, etc., carbon fiber, conductive polymer (such as polyacetylene and polypyrrole), metal alloy (such as lithium-aluminum alloy, lithium-aluminum-manganese alloy, etc.) Wait. As the conductive agent, the binder, and the solvent, the same materials as those used in the production of the positive electrode can be used. Examples of the current collector for the negative electrode include copper, stainless steel, nickel, aluminum, titanium, carbon, conductive molecular, conductive glass, and aluminum-cadmium alloy. In the secondary battery, the preferred content of the negative electrode active material, the conductive agent and the binder based on the total weight of the negative electrode is as follows. The content of the negative electrode active material is preferably from 70 wt% to 98 wt%, particularly preferably from 90 wt% to 98 wt%. The content of the conductive agent and the binder is the same as that of the positive electrode. The solvent used in the slurrying of the θ negative electrode active material, the conductive agent, and the binder is the same as the solvent used in the slurrying of the positive electrode active material, the conductive agent, and the binder. The separator in the secondary battery can be exemplified by a film of a polyethylene, a polypropylene film, a microporous film, a multilayer film of a porous polyethylene film and a polypropylene, and a polyaluminum fiber, an aramid fiber (aramid). A non-woven fabric such as ber) or glass fiber, and a separator having ceramic fine particles such as oxidized dream, alumina, or titanium oxide adhered to the surface thereof. The battery can in the secondary battery of M can be made of stainless steel (stainless steel), metal materials such as iron, nickel, and nickel, and can be used depending on the battery. Further, the battery can can be formed into a cylindrical shape, a coin shape, a square shape, or any other shape depending on the limb. 201203678 The electrolyte of the present invention is also useful as an electrolyte for lithium ion capacitors. The lithium ion capacitor using the electrolytic solution of the present invention is obtained by injecting the electrolytic solution of the present invention into a capacitor can containing a positive electrode, a negative electrode, and a separator to seal the capacitor can. In the positive electrode of the lithium ion capacitor, a coating device such as a bar coater can be used, and the activated carbon (positive electrode active material), the conductive agent, and the binder are dispersed in a solvent, and the slurry is applied to the positive electrode set. The body is dried, and the solvent is removed, and a positive electrode or the like which is pressed by a press as needed is used. The conductive agent, the binder, the solvent, and the current collector for the positive electrode are the same as those in the case of the lithium secondary battery. In the bell ion grid, the preferred content of the positive electrode active material, the conductive agent and the binder based on the total weight of the positive electrode is as follows. The content of the positive electrode active material is preferably from 70 wt% to 98 wt%, particularly preferably from 9 〇 Wt% to 98 wt%. The content of the conductive agent is preferably from 1 wt% to 29 wt〇/0, particularly preferably from 1 wt% to 10 wt%. The content of the binder is preferably i wt% to ^ wt% ', particularly preferably 1 wt% to 1 〇 wt%. The solvent used in the slurrying of the positive electrode active material, the conductive agent, and the binder is preferably 20 wt% to 7 wt%, more preferably 3 wt%, based on the total weight of the positive electrode active material, the conductive agent, and the binder. %~6〇wt〇/〇. The negative electrode in the ion-electric grid can be applied to a negative electrode (four) body by using a coating device such as a bar coater, and the negative electrode active material, the conductive agent, and the binder are dispersed in a solvent. The anode is dried by removing the solvent, and if necessary, pressing it by a press. 201203678 Negative activity 1* biomass can be exemplified by amorphous carbon (am〇rph〇us carb〇n), graphite (graphite), tin and its alloys, niobium and its alloys. As the conductive agent, the binder, and the solvent, the same materials as those used in the production of the positive electrode can be used. Examples of the current collector for the negative electrode include copper, stainless steel, nickel, samarium, titanium, carbon, conductive polymer, conductive domain, and alloy. In the lithium ion capacitor, the preferred contents of the negative electrode active material, the conductive agent and the binder based on the total weight of the negative electrode are as follows. The content of the negative electrode active material is preferably from 70 wt% to 98 wt%, particularly preferably from 90 wt% to 98 wt%. The content of the conductive agent hybrid is the same as that of the positive electrode. The amount of the solvent used in the slurrying of the negative electrode active material, the conductive agent, and the binder is the same as that of the positive electrode dopant, the conductive agent, and the binder. Examples of the separator in the lithium ion capacitor include a microporous film of polyethylene and polypropylene, a multilayer film of a porous polyethylene film and polypropylene, and a polyester fiber, an aromatic polyamide fiber, a glass fiber, and the like. Non-woven fabric; a sheet containing particles such as oxidized x, oxygen, titanium oxide, etc., continued to be used. 1 The battery can in the lithium ion capacitor can be made of stainless steel, metal such as iron, gold, or nickel, or plastic or plastic depending on the battery. Further, the battery can can be formed into a cylindrical shape, a hard shape, a 卞 type, or any other shape depending on the application. The electrode protective film forming agent (F) of the present invention can be added and contained in the tooth 32 201203678 - a human battery or a rotor capacitor (four) positive electrode and/or a blemish. The material to be added to the main product is as follows: the positive electrode, the protective film forming agent (F), and the coating device such as a bar coater are dried and the solvent is removed. The method of adding the negative electrode to the negative electrode as needed may be, for example, a chemical substance, a conductive agent, and a binder dispersed in a solvent, and a live negative electrode is applied to a machine by a coating device such as a current collector or a ▲ coater. Drying and removing the solvent, if necessary, using charging to charge and discharge cycle characteristics, the battery is added to the positive point of view and the amount is based on the positive-positive substance, and the age is (U wt% lT (. The addition is 〇·5 wt %1~5 wt°/〇. 0 1〇wt/〇, particularly preferably, the charge/discharge cycle characteristics and the battery are added to the negative electrode active material, and the amount is based on the negative electrode active material. 〇T: t. The addition is 0.5 wt% to 5 wt%. · wt/° to 10 wt%, especially good [Examples] Hereinafter, the present invention is not limited to these examples by way of example. The present invention [synthesis of Lewis test (C)] π aliquot. <Production Example 1> 33 201203678 ^ 1 N,N-di-(2-decyl decanoate) _4, i〇_ diazepine ΐ 5_ crown Synthesis of _5·ether (ΑΖ-1): 4,10-diaza-15-crown-5-ether was added to a flask equipped with a stirrer, a thermometer and a cooling tube [manufactured by Tokyo Chemical Industry Co., Ltd.] 061 parts (2.8 mmol parts), methyl 4-bromo-2-butenoate [manufactured by Tokyo Chemical Industry Co., Ltd.] 1 part (5.6 mmol part) and 1 part acetonitrile, and uniformly dissolved while stirring Then, it was reacted under stirring for 24 hours at room temperature. After removing acetonitrile under reduced pressure (10 mmHg), 'Using acetone as a solvent for alumina column [150 mesh, Brockman 1, standard grade, manufactured by Aldrich) The reaction was purified to obtain N,N-di-(2-butenoate)- 4,1 〇-diaza-15-crown-5-oxime (AZ-1) 0.85 parts (2.0 mmol) ( Yield 71%). (AZ-1) is a substituent bond of the formula (2) wherein R2 is a fluorenylene group, Qi and q2 are a hydrogen atom, and Q3 is a fluorenyloxycarbonyl group and has a polymerizable unsaturated double bond. A diazacrown ether compound attached to a nitrogen atom. <Production Example 2> N, Nj^-(1_acryloxyethyl)_4,1〇_diaza--15 crown-5•ether (AZ Synthesis of -2): In place of 1 part of 4-bromo-2-butenoic acid ester, 0.76 parts (5.6 mmol parts) of 2-ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in addition to In the same manner as in Production Example i, N,N-di-(dipropenyloxyethyl)-4,1〇-diaza-15_crown-5 ether (az-2) 〇.6 〇 (( 1.9 mmol part) (yield 68%). In addition, when 1 part of 4-bromo-2-butenoate was changed to acrylic acid ········· In the case of 6 parts, the weight ratio of the molar ratio of the reaction component and the non-reactive component (solvent 34 201203678, etc.) was adjusted to adjust the amount of each raw material in the same manner as in the case of Production Example 1. The following Production Example 3 was carried out. The same goes for it. (ΑΖ-2) is a diazepane ether compound in which an acryloxyethyl group is bonded to a nitrogen atom as a substituent having a polymerizable unsaturated double bond. <Manufacturing Example 3> ^_, the synthesis of the group 2 cinnamyl-4,10-diaza-15-crown-5- shouting (eight 2-3): except for the substitution of 4-bromo-2-butenoate N,N-dicinnamyl-4,10-diaza- was obtained in the same manner as in Production Example 1, except that 0.8 parts (5.6 mmol) of cinnamyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. 15-crown-5-ether (C1-3) 0-92 parts (2.0 mmol) (yield: 73%). (AZ-3) is a nitrogen in the formula (2) wherein R2 is a fluorenylene group, Q1 and Q2 are a hydrogen atom, q3 is a phenyl group, and a substituent having a polymerizable unsaturated double bond is bonded to a nitrogen atom. Mixed crown compound. <Example 1> Synthesis of diethylene glycol bis(2-butenoate) ether (B-1): Diethylene glycol was added to a flask equipped with a stirrer, a thermometer, and a cooling tube [Tokyo Chemical Industry Co., Ltd. ( Manufacture] 7.26 parts (68.4 mmol parts), 4-bromo-2-butenoate (manufactured by Tokyo Chemical Industry Co., Ltd.) 26.9 parts (15〇3 mmol), sodium hydroxide 6.00 parts (150 mmol) The mixture and 1 part of toluene were uniformly dissolved while stirring, and then stirred at room temperature for 15 minutes, and then 1.32 parts (4.1 mmol) of tetrabutylammonium bromide was added. After raising the temperature to 65 ° C, the mixture was stirred for 4 hours to carry out an etherification reaction. After standing to cool, 200 parts of water was added and the aqueous layer was separated. Further, the organic layer was washed with 2 parts of water. After the benzene was removed by decompression (10 mmHg), the reaction was purified by oxidizing the column [150 mesh, Brockman 1, standard grade, manufactured by Aldrich) with a solvent of 35 201203678. Ethylene glycol bis(2-butene citrate) mystery (B-1) 15.5 parts (51·3 mmol) (yield 75%) <Example 2> - B. One broken · One (4_B Synthesis of the dilute thiol) mystery (B-2). In addition to 26.9 parts (150.3 mmol) of methyl 4-bromo-2-butenoate, 4-vinylbenzyl gas was used [Tokyo Chemical Industry Co., Ltd.) In the same manner as in Example 1, except that 22.9 parts (150.3 mmol parts), diethylene glycol bis(4-vinylphenyl)-(B-2) 16.9 parts (49.9 mmol parts) was obtained (yield 73%) ). <Example 3> Synthesis of 1,4-bis(1-propenyloxyindenyl)cyclohexane (A-1): In a flask equipped with a stirrer, a thermometer and a cooling tube, 1,4-cyclohexane was added. Didecyl alcohol [manufactured by Tokyo Chemical Industry Co., Ltd.] 9.86 parts (68.4 mmol parts), chloropropene [manufactured by Tokyo Chemical Industry Co., Ltd.] 11.51 parts (150.3 mmol parts), sodium bismuth oxide 6.00 parts (150 mmol parts) and 1 part of toluene was dissolved in a homogeneous manner while stirring, and then stirred at room temperature for 15 minutes, and then 1.32 parts (4.1 mmol) of tetrabutyl bromide was added. The temperature was raised to 65 ° C over 2 hours, and further stirred for 4 hours to carry out an etherification reaction and a rearrangement reaction. After the cooling was allowed to stand, 200 parts of water was added, and the aqueous layer was separated. Further, the organic layer was washed with 200 parts of water. After the benzene was removed by decompression (10 mmHg), the reaction was purified by oxidizing the column [150 mesh, Brockman 1, standard grade, manufactured by Aldrich) using hexane as a solvent to obtain ι, 4 - bis (ι_ propyl ethoxymethyl) cyclohexan (8-1) 10_9 parts (48.6 111111 〇 1 part) (production 36 201203678 rate 71%) 〇 In addition to the compounds described in Table 1 to Table 3 (a i,4-bis(vinyloxymethyl)cyclohexane, 1,4-butanediol divinyl ether and triethylene glycol diethylene in the use of bundles [Nippon Carbide Industries (shares) Manufacturing]. [Preparation of Electrolyte Solution] <Example 4 to Example 35> The compound (a), the compound (B), the Lewis base (C), and the negative electrode protective film forming agent (D) were blended in the weight ratios shown in Tables 1 to 3. The electrolyte solution of Example 4 to Example 35 was adjusted by dissolving LiPF0 in a non-aqueous solvent (H)' at a concentration of 1 mol/L. <Comparative Example 1> In a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 3:7), LiPF6 was dissolved at a ratio of 1 mol/L, and then vinylene carbonate was mixed at a ratio of 2 wt%. The electrolytic solution of Comparative Example 1 was adjusted. <Comparative Example 2> In a mixed solvent of ethylene carbonate and dinonyl carbonate (volume ratio: 1:1), LiPF6 was dissolved at a ratio of 1 m〇i/L, and then mixed at 0.1 mol/L. The electrolyte of Comparative Example 2 was adjusted by dimethyl group. <Comparative Example 3> In a mixed solvent of ethylene carbonate and dinonyl carbonate (volume ratio 1:1), 'LiPF6 was dissolved at a ratio of 1 mol/L, and then mixed at a ratio of 5 wt%. Propane sultone was used to adjust the electrolytic solution of Comparative Example 3. 37 201203678 Ja inch α 卜 ε [1<] Example 13 1 d 1 1 1 S 〇(N 〇1 1 1 1 1 1 Example 12 no d 1 1 1 S 〇〇1 1 I 1 Example 11 1 1 1 〇〇 CN d 1 1 (N 1 instance 10 s ο 1 1 1 S 〇tN d 1 1 (N 1 1 instance 9 sd 1 < f S df 1 1 (N 1 instance 8 1 1 1 1 S 〇CN 〇1 1 CS 1 Example 7" 1 1 1 S 〇S 〇 (N 〇1 1 (S 1 Example 6 1 1 S 〇1 〇d <N 〇1 1 CN 1 Example 5 1 S d 1 1 ο d (N d 1 1 (N 1 [Example 4 sd 1 1 1 sd (N 〇1 1 CN 1 compound name 1, 'bis(1-propenyloxymethyl)cyclohexanium bismuth-bis(1-vinyloxymethyl) ring) Hexane 1,4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol bis(2-butenoic acid methyl ester) ether diethylene glycol bis(4-vinyl benzyl) ether (AZ -l) (AZ-2) (AZ-3) 3-Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-oxime 1,2-,4-triazole 3-amino-5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 3-amino -5-butyl-1,2,4-triazole vinylene carbonate γ-butyrolactone γ-valerolactone (A) (part) Compound (B) (part) Lewis base (c) (part) Negative electrode protective film forming agent (D) (part) *πχν °° ε 201203678 47.73 1 47.73 1 46.78 1 47.75 1 47.93 1 47.78 1 47.73 1 47.73 • 47.73 1 47.73 1 δ-valerolactone ethylene carbonate diethyl carbonate diethyl carbonate dimethyl carbonate ethyl phthalate LiPF6 electrolyte (mol/L) 201203678 玄卜卜卜 ε t(N< d 1 1 S 〇1 (Ν I1 I 1 1 1 1 ^Τ) ο ο 1 1 S 〇1 CN 〇1 1 1 1 1 1 Example 22 sd 1 1 S 〇<Ν d 1 〇1 1 1 1 1 rN Example 21 so 1 1 S 〇1 1 1 1 1 1 1 rs no o 1 IS 〇1 1 1 t 1 1 1 (N instance | J9_ sd 1 1 S 〇1 <N d 1 1 1 1 1 1 CN instance | 18___ so 1 1 S 〇CN Ο 1 1 1 1 1 1 1 (N instance 17 sd 1 1 S d cs ο 1 1 1 1 1 1 1 <N instance; J6__ so 1 1 S d <Ν | ο 1 1 1 1 1 1 1 <N Example J5_ so 1 1 s ο CN Ο 1 1 1 t 1 1 1 (N pull 2; sd 1 1 sd cs d 1 1 1 1 1 1 1 iN Compound name 1 1,4-bis(1-propenyloxymethyl) )) Ring 1 1,4- 1,4-bis(1-vinyloxymethyl) ring | hexene i 1,4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol di(2· Ethyl crotonate) Ether diethylene glycol bis(4-vinylbenzyl) | Ether (AZ-l) (AZ-2) (AZ-3) 3-Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-mercapto-1,2,4-triazole 1 3-amino-5-ethyl-1,2,4 - Triazole 3-Amino-5-propyl-1,2,4-triazole 3-Amino-5-butyl-1,2,4-triazole vinylene carbonate component | ί Compound (Β) (Part) Lewis base (c) (part) Negative electrode protective film forming agent (D) (part) 0 inch 201203678 1 I 47.63 1 r-Η 1 ! 47.63 1 1 47.63 1 1 47.83 1 1 47.83 1 1 47.73 1 97.73 1 1 1 97.73 1 1 1 〇1 1 69.73 〇1 67.73 1 〇67.73 1 1 γ-butyrolactone γ-valerolactone δ-valerolactone ethylene carbonate diethyl ester diethyl carbonate dimethyl carbonate ethyl methyl carbonate LiPF6 ML· \^y Electrolyte (mol/L) 201203678 J'a inch α Bu ε [ε^] 驷ίί! S 〇1 1 1 1 S 〇tN d 1 1 1 1 1 1 1 1 S 〇1 1 1 CN 〇〇1 CN d 1 1 1 1 1 ^ 5λ S 〇1 1 1 <N 〇1 <N 〇1 1 1 (S ? 驷Ρ! 〇〇1 1 1 t 1 <N d 1 1 1 CS S d 1 1 1 ( S 〇fN 〇1 1 1 (N sd 1 1 1 sd 1 1 1 1 ίΝ so 1 1 1 sd 1 1 1 1 驷? 3 so 1 1 1 sd 1 so 1 1 1 CN sd 1 1 1 S d 1 CN 〇1 1 (S sd 1 1 1 sd 1 (N 〇I 1 1 CS leather sd 1 1 sd 1 d 1 1 d 1 1 CN Compound name 1,4-bis(1-propenyloxymethyl)cyclohexene 1,4-bis(1-vinyloxymethyl)cyclohexane 1,4-butanediol divinyl ether triethylene Alcohol Divinyl Ether Diethylene Glycol Di(2-Methyl Butyrate) Enigmatic Diethylene Glycol Di(4-vinylbenzyl) Enigma (AZ-l) (AZ-2) (AZ-3) 3- Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-methyl-1,2,4-triazole 3-amino group- 5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 3-amino-5-butyl-1,2,4-triazole 1 Vinylene carbonate component 1 Compound (A) (part) Compound (B) (part) Lewis base (C) (part) by 5 S^ 201203678 Ja inch αζ, ε 1 1 1 49.73 1 1 1 1 49.73 1 1 1 1 47.55 1 1 1 1 47.75 1 ««Η 1 1 1 47.73 1 1 1 1 46.93 1 1 1 1 47.83 1 1 1 1 47.88 1 1 1 1 47.63 1 1 1 1 47.63 1 1 1 1 47.63 1 γ-丁内Ester γ-valerolactone δ-valerolactone ethylene carbonate diethyl carbonate carbonate Yue carbonate, ethyl carbonate ester 1 LiPF6 electrolyte (mol / L)

201203678 ^ L201203678 ^ L

[鋰離子電池用正極的製作] 基於表4〜表7所示的配方’利用以下方法製成添加有電極保護膜形成劑（F)的正極。將LiCo〇2粉末90.0份、柯琴黑[Aldrich公司製造]5 份、聚偏二氟乙烯[Aldrich公司製造]5份、及表4〜表7 所示重量的電極保護膜形成劑（F)於研缽中充分混合後，添加1-曱基-2-β比略咬酮[東京化成工業（股）製造]〇份，進而於研缽中充分混合而獲得漿料。將所得的漿料於大氣中使用線棒來塗佈於厚度20 μιη的紹電解箱上的單面，於 100°C下乾燥15分鐘後，進而於減壓下（1〇mmHg)在8(rc 下乾燥5分鐘，衝壓為15.95 mm(p，製作實例36〜實例67 的鋰離子電池用正極。 [鋰離子電池用負極的製作] 基於表4〜表7所示的配方，利用以下方法製成添加有電極保護膜形成劑（F)的負極。將平均粒徑約8 μιη〜12 μιη的石墨粉末92.5份、聚偏二氟乙稀7.5份、1·甲基_2_0比咯啶酮[東京化成工業（股）製造]200份及表4〜表7所示重量的電極保護膜形成劑（ρ) 於研缽中充分混合而獲得漿料。將所得的漿料塗佈於厚度 20卜111的鋼箔的單面，於1〇〇。(：下乾燥15分鐘而使溶劑蒸發後’衝壓為16.15 mmcp，利用壓製機形成厚度30 ，製作實例36〜實例67的鋰離子電池用負極。 [鋰離子電容器用正極的製作] 基於表7所示的配方，利用以下方法製成添加有電極 44 201203678 保護膜形成劑（F)的正極。將活性碳粉末90.0份、柯琴黑[Aldrich公司製造]5.0 份、聚偏二氟乙浠[Aldrich公司製造]5.0份、及表4〜表7 所示重量的電極保護膜形成劑（F)於研缽中充分混合後，添加1-甲基-2-吡咯啶酮[東京化成工業（股）製造]7〇〇份，進而於研蛛中充分混合而獲得漿料。將所得的漿料於大氣中使用線棒來塗佈於厚度2〇 μιη的铭電解箔上的單面，於 100C下乾燥15分鐘後，進而減壓下（1〇 mmHg)在8〇。〇下乾燥5分鐘，衝壓為15.95 mmcp ’製作實例68〜實例71 的鋰離子電容器用正極。 [鋰離子電容器用負極的製作] 基於表7所示的配方，利用以下方法製成添加有電極保護膜形成劑（F)的負極。將平均粒徑約8 μιη〜12 μιη的石墨粉末92.5份、聚偏二氟乙烯7.5份、1-曱基_2·吡咯啶酮[東京化成工業（股）製造]200份及表4〜表7所示重量的電極保護膜形成劑（F) 於研缽中充分混合而獲得漿料。將所得的漿料塗佈於厚度 2〇从111的銅箔的單面，於1〇〇。〇下乾燥15分鐘而使溶劑^ 發後，衝壓為16.15 mnup，利用壓製機形成厚度3〇 μιη。、將所得的電極、及鋰金屬箔以分隔片（聚丙烯製不織布）失持而設置於燒杯單元，使負極理論容量的約75%的鋰離子以約10小時吸藏於負極中，製作實例68〜實例71的鋰離子電容器用負極。 ^ 〈比較例4〉 45 201203678 除了代替電極保護膜形成劑（F)而添加曱基颯1.5份以外’以與實例36〜實例67相同的方法製成比較例4的鋰離子電池用正極。除了不添加電極保護膜形成劑（F)以外，以與實例 36〜實例67相同的方法製成比較例4的鋰離子電池用負極0 〈比較例5〉除了代替電極保護膜形成劑（F)而添加1，3-丙烷磺内醋1.5份以外’以與實例36〜實例67相同的方法製成比較例5的鋰離子電池用正極。除了不添加電極保護膜形成劑（F)以外，以與實例 36〜實例67相同的方法製成比較例5的鋰離子電池用負極。〈比較例6〉除了代替電極保護膜形成劑（F)而添加二曱基颯1.5 份以外，以與實例68〜實例71相同的方法製成比較例6 的鐘離子電容器用正極。除了不添加電極保護膜形成劑（F)以外，以與實例 68〜實例71相同的方法製成比較例6的鋰離子電容器用負〇〈比較例7〉除了代替電極保護膜形成劑（F)而添加1,3-丙烷磺内醋15份以外，以與實例68〜實例71相同的方法製成比較例7的鋰離子電容器用正極。 46 201203678 除了不添加電極保護膜形成劑（F)以外，以與實例 68〜實例71相同的方法製成比較例7的鋰離子電容器用負極0 47 201203678 J-a寸卜卜卜ε 【寸<】實例44 1 1 1 1 1 1 1 1 1 in 1 1 1 1 1 1 實例43 1 1 1 1 1 1 1 yn 1 1 1 1 1 1 實例42 狐想 1 1 1 1 1 1 1 Ό 1 1 1 1 1 1 實例41 卿（想 1 1 1 1 1 1 t 1 1 1 1 1 1 實例40 1 »〇 1 1 1 1 1 1 in 1 1 in 1 1 1 1 1 實例39 柳C璁 1 *〇 1 1 1 1 1 1 1 1 1 1 1 1 1 1 實例38 ζ缌 1 V) 1 1 1 1 t 1 1 ΙΓ) 1 1 1 1 1 1 1 實例37 1 1 1 1 1 1 1 1 v-j > 1 1 I 1 1 1 實例36 卿：缌 1 1 1 1 1 1 1 Μ璁 W-ϊ 1 1 1 1 1 1 1 化合物名電極 1，4-雙(1-丙烯氧基甲基）環己烷 1,4-雙(1-乙烯氧基甲基）環己烷 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲醋)謎二乙二醇二(4-乙烯基苄基)醚 (ΑΖ-1) (AZ-2) 1 (AZ-3) 3-胺基-1，2,4**** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1，2,4-*** 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1,2,4-*** 3-胺基-5-丁基-1，2,4-*** 成分化合物（A) (份）化合物（B) (份）路易斯鹼 (c) (份） 8寸 201203678 J-a寸卜卜l>e 實例53 1 1 in 1 1 1 1 Η想 1 1 1 1 t 實例52 棚C邀 1 IT) 1 1 1 1 1 1 1 1 1 實例51 1 1 1 1 1 1 1 1 1 1 1 實例50 郷ζ璁 1 »—Η 1 1 1 1 1 irj 1 1 1 1 1 實例49 ζ鸡 1 1 1 1 1 1 … 1 1 1 實例48 C锶 1 1 1 1 1 <i^ 1 r Η 1 1 1 實例47 1 1 1 1 1 1 in 1 1 1 實例46 1 1 1 1 1 Μ缌 1 1 1 1 實例45 m. ig 1 1 1 1 1 1 1 1 1 1 化合物名想鮮1 1,4-雙(1-丙烯氧基甲基）環己烷 1,4-雙(1-乙烯氧基甲基）環己烷 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)醚 (AZ-1) (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1,2,4-*** 3-胺基-5-曱基-1,2,4-*** 3-胺基-5-乙基-1，2,4-*** 3-胺基-5-丙基-1，2,4-二α坐 3-胺基-5-丁基-1,2,4-*** 成分化合物（A) (份）化合物（Β) (份）路易斯鹼 (C) (份） 6寸 201203678 J-a寸卜/,卜rn 【9<】實例62 1 1 1 1 d 1 1 1 I 1 1 1 1 1 Θ想 1 1 1 1 1 1 1 1 1 1 1 1 實例61 C想 1 1 1 1 1 1 VO 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1實例60 1 棚C邀 1 1 1 ( 1 1 ( 1 1 1 1 in 1 1 1 1 1 1 1 1 1 1 1 實例59 <5Κ ^ 1 1 1 1 1 1 1 1 1 1 1 1 i〇 1 1 1 1 1 1 1 1 1 1 1 實例58 ζ锶 1 1 1 1 1 1 1 1 1 1 1 ^Ti 1 1 1 1 1 1 1 1 1 1 1 實例57 1 1 1 1 1 1 1 1 1 1 1 *rj 1 1 1 1 1 1 1 1 1 1 1 實例56 卿；埵 1 1 1 1 1 1 1 1 1 1 1 V) 1 1 1 1 1 1 1 1 1 1 1 實例55 1 1 1 1 1 1 1 1 1 1 1 1 Η璁 1 1 1 1 1 1 1 1 1 I 1 實例54 職璁 1 1 1 1 1 1 1 1 1 1 1 1 4璁 in 1 1 1 1 1 1 1 1 1 1 1 I 化合物名電極 1，4-雙(1-丙烯氧基甲基）環己烷 1 1,4-雙(1-乙烯氧基甲基）環己烷 1，4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)醚 (AZ-1) (AZ-2) (AZ-3) 丨3-胺基-1,2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1，2,4-*** 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1,2,4·*** 3-胺基-5-丁基-1,2,4·*** 成分化合物（A) (份）化合物（B) (份）路易斯鹼 (C) (份）[Production of Positive Electrode for Lithium Ion Battery] The positive electrode to which the electrode protective film forming agent (F) was added was produced by the following method based on the formulation shown in Tables 4 to 7. 90.0 parts of LiCo〇2 powder, 5 parts of Keqin black [manufactured by Aldrich], polyvinylidene fluoride [manufactured by Aldrich] 5 parts, and electrode protective film forming agent (F) shown in Tables 4 to 7 After thoroughly mixing in a mortar, a 1-mercapto-2-β ketone ketone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further mixed in a mortar to obtain a slurry. The obtained slurry was applied to a single surface of a 20 μm thick electrolysis box in the atmosphere using a wire bar, and dried at 100 ° C for 15 minutes, and further under reduced pressure (1 〇 mmHg) at 8 ( The rc was dried for 5 minutes and punched to 15.95 mm (p, the positive electrode for the lithium ion battery of Example 36 to Example 67. [Production of negative electrode for lithium ion battery] Based on the formulations shown in Tables 4 to 7, the following method was used. A negative electrode to which an electrode protective film forming agent (F) is added. 92.5 parts of graphite powder having an average particle diameter of about 8 μm to 12 μm, 7.5 parts of polyvinylidene fluoride, and 1·methyl-2_0-pyrrolidone [ Manufactured by Tokyo Chemical Industry Co., Ltd.] 200 parts and the electrode protective film forming agent (ρ) having the weights shown in Tables 4 to 7 were thoroughly mixed in a mortar to obtain a slurry. The obtained slurry was applied to a thickness of 20 One side of the steel foil of 111 was placed at 1 Torr. (: After drying for 15 minutes to evaporate the solvent, 'pressing was 16.15 mmcp, and a thickness of 30 was formed by a press machine, and a negative electrode for a lithium ion battery of Examples 36 to 67 was produced. [Preparation of positive electrode for lithium ion capacitor] Based on the formulation shown in Table 7, the following method was used. Electrode 44 201203678 The positive electrode of the protective film forming agent (F) was added. 90.0 parts of activated carbon powder, 5.0 parts of Keqin black [manufactured by Aldrich], polyvinylidene fluoride (made by Aldrich) 5.0 parts, and a table After the electrode protective film forming agent (F) having the weight shown in Table 7 and Table 7 was sufficiently mixed in a mortar, 7 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further The slurry was thoroughly mixed with a spider to obtain a slurry, and the obtained slurry was applied to a single surface of an electrolytic foil having a thickness of 2 μm by using a wire rod in the air, dried at 100 C for 15 minutes, and then decompressed. The lower (1〇mmHg) was dried at 8 〇. The underside was dried for 5 minutes and punched to 15.95 mmcp. The positive electrode for the lithium ion capacitor of Example 68 to Example 71 was fabricated. [Production of Negative Electrode for Lithium Ion Capacitor] Based on the formulation shown in Table 7. A negative electrode to which the electrode protective film forming agent (F) was added was produced by the following method: 92.5 parts of graphite powder having an average particle diameter of about 8 μm to 12 μm, 7.5 parts of polyvinylidene fluoride, and 1-mercapto-2. Pyrrolidone [Made in Tokyo Chemical Industry Co., Ltd.] 200 parts and Table 4 to Table 7 The electrode protective film forming agent (F) was thoroughly mixed in a mortar to obtain a slurry, and the obtained slurry was applied to one side of a copper foil having a thickness of 2 Å from 111 to 1 Torr. After the solvent was applied, it was punched to 16.15 mnup, and a thickness of 3 μm was formed by a press machine. The obtained electrode and the lithium metal foil were placed in a beaker unit with a separator (polypropylene non-woven fabric), and the negative electrode was placed. About 75% of the theoretical capacity of lithium ions was absorbed in the negative electrode for about 10 hours, and the negative electrode for lithium ion capacitors of Examples 68 to 71 was produced. <Comparative Example 4> 45 201203678 A positive electrode for a lithium ion battery of Comparative Example 4 was produced in the same manner as in Example 36 to Example 67 except that 1.5 parts of fluorenyl hydrazine was added instead of the electrode protective film forming agent (F). A negative electrode for a lithium ion battery of Comparative Example 4 was produced in the same manner as in Examples 36 to 67 except that the electrode protective film forming agent (F) was not added. <Comparative Example 5> In place of the electrode protective film forming agent (F) Further, a positive electrode for a lithium ion battery of Comparative Example 5 was produced in the same manner as in Example 36 to Example 67 except that 1.5 parts of 1,3-propane sulphuric acid was added. The negative electrode for a lithium ion battery of Comparative Example 5 was produced in the same manner as in Example 36 to Example 67 except that the electrode protective film forming agent (F) was not added. <Comparative Example 6> A positive electrode for a bell ion capacitor of Comparative Example 6 was produced in the same manner as in Example 68 to Example 71 except that 1.5 parts of a fluorenyl hydrazine was added instead of the electrode protective film forming agent (F). A negative electrode for a lithium ion capacitor of Comparative Example 6 was prepared in the same manner as in Examples 68 to 71 except that the electrode protective film forming agent (F) was not added. <Comparative Example 7> In place of the electrode protective film forming agent (F) A positive electrode for a lithium ion capacitor of Comparative Example 7 was produced in the same manner as in Example 68 to Example 71 except that 15 parts of 1,3-propane sulphuric acid was added. 46 201203678 A negative electrode for a lithium ion capacitor of Comparative Example 7 was produced in the same manner as in Example 68 to Example 71 except that the electrode protective film forming agent (F) was not added. 0 47 201203678 Ja inch Bub ε [inch < Example 44 1 1 1 1 1 1 1 1 1 in 1 1 1 1 1 1 Example 43 1 1 1 1 1 1 1 yn 1 1 1 1 1 1 Example 42 Fox 1 1 1 1 1 1 1 Ό 1 1 1 1 1 1 Example 41 Qing (Think 1 1 1 1 1 1 t 1 1 1 1 1 1 Example 40 1 »〇1 1 1 1 1 1 in 1 1 in 1 1 1 1 1 Example 39 Liu C璁1 *〇1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 38 ζ缌1 V) 1 1 1 1 t 1 1 ΙΓ) 1 1 1 1 1 1 1 Example 37 1 1 1 1 1 1 1 1 vj > 1 1 I 1 1 1 Example 36 Qing: 缌1 1 1 1 1 1 1 Μ璁W-ϊ 1 1 1 1 1 1 1 Compound name electrode 1,4-bis(1-propenyloxymethyl)cyclohexane 1, 4-bis(1-vinyloxymethyl)cyclohexane 1,4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol di(2-butenoic acid methyl vinegar) enigma two alcohol Bis(4-vinylbenzyl)ether (ΑΖ-1) (AZ-2) 1 (AZ-3) 3-Amino-1,2,4*triazole 3,5-diamino-1,2 ,4-triazole 3-amino-5-methyl-1,2,4-triazole 3-amino-5-ethyl-1,2,4-triazole 3-amino-5-propyl -1,2,4-triazole 3-amino-5-butyl-1,2,4-triazole component compound (A) (part) Compound (B) (part) Lewis base (c) (part) 8 inch 201203678 Ja inch Bu Bu l>e Example 53 1 1 in 1 1 1 1 Η想1 1 1 1 t Example 52 shed C invite 1 IT) 1 1 1 1 1 1 1 1 1 Example 51 1 1 1 1 1 1 1 1 1 1 1 Example 50 郷ζ璁1 »—Η 1 1 1 1 1 irj 1 1 1 1 1 Example 49 ζ chicken 1 1 1 1 1 1 ... 1 1 1 Example 48 C锶1 1 1 1 1 &lt ;i^ 1 r Η 1 1 1 Example 47 1 1 1 1 1 1 in 1 1 1 Example 46 1 1 1 1 1 Μ缌1 1 1 1 Example 45 m. ig 1 1 1 1 1 1 1 1 1 1 Compound 1 1,4-bis(1-propenyloxymethyl)cyclohexane 1,4-bis(1-vinyloxymethyl)cyclohexane 1, 4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol bis(2-methylbutenoate) ether diethylene glycol bis(4-vinylbenzyl) ether (AZ-1) ( AZ-2) (AZ-3) 3-amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-mercapto-1, 2,4-triazole 3-amino-5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-di-α-sodium 3-amino-5- Butyl-1,2,4-triazole component compound (A) (part) Compound (Β) (part) Lewis base (C) (part) 6 inch 201203678 Ja inch / / rn [9 <] Example 62 1 1 1 1 d 1 1 1 I 1 1 1 1 1 1想1 1 1 1 1 1 1 1 1 1 1 1 Example 61 C想1 1 1 1 1 1 VO 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 60 1 Shed C invites 1 1 1 ( 1 1 ( 1 1 1 1 in 1 1 1 1 1 1 1 1 1 1 1 Example 59 < 5Κ ^ 1 1 1 1 1 1 1 1 1 1 1 1 i〇1 1 1 1 1 1 1 1 1 1 1 Example 58 ζ锶1 1 1 1 1 1 1 1 1 1 1 ^Ti 1 1 1 1 1 1 1 1 1 1 1 Example 57 1 1 1 1 1 1 1 1 1 1 1 *rj 1 1 1 1 1 1 1 1 1 1 1 Example 56 埵;埵1 1 1 1 1 1 1 1 1 1 1 V) 1 1 1 1 1 1 1 1 1 1 1 Example 55 1 1 1 1 1 1 1 1 1 1 1 1 Η璁1 1 1 1 1 1 1 1 1 I 1 Example 54 Job 1 1 1 1 1 1 1 1 1 1 1 1 4璁in 1 1 1 1 1 1 1 1 1 1 1 I Compound name Electrode 1,4-bis(1-propenyloxymethyl)cyclohexane 1 1,4-bis(1-vinyloxymethyl)cyclohexane 1,4-butanediol divinyl ether triethylene glycol Divinyl ether diethylene glycol bis(2-methylbutanoate) ether diethylene glycol bis(4-vinylbenzyl)ether (AZ-1) (AZ-2) (AZ-3) 丨3- Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-methyl-1,2,4-triazole 3-amino group- 5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4·triazole 3-amino-5-butyl-1,2,4·triazole Compound (A) (part) Compound (B) (part) Lewis base (C) (part)

OS 201203678 【卜d JU寸卜卜卜ε 1實例71 1 ΙΓ1 1 1 1 1 1 1 1 Η缉 ir> 1 1 to 1 1 1 1 1 實例70 鄉ζ邀 1 υ-ϊ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 實例69 邀 1 1 1 1 1 1 1 1 i〇 1 1 V) 1 1 1 1 1 實例68 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 實例67 I 1 1 1 1 1 1 1 in 1 1 1 < 1 1 1 1 實例66 卿；頌 1 1 1 1 1 1 1 1 W-) 1 1 1 1 1 1 1 < 實例65 ζ邀 1 vn 1 1 1 1 1 1 1 iri 1 1 1 1 1 1 1 1 實例64 <DBC 總 1 1 1 1 1 1 1 1 Θ缌 yn 1 1 1 1 1 1 1 1 實例63 C埤 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 化合物名電極 1，4-雙(1-丙烯氧基甲基）環己烷 1,4-雙(1-乙烯氧基甲基）環己烷 1，4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)醚 (AZ-1) (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1,2,4-*** 3-胺基-5-甲基-1,2,4-*** 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1,2,4-*** 3-胺基-5-丁基-1,2,4-*** 成分化合物（A) (份）化合物（B) (份）路易斯鹼 (C) (份） 201203678.OS 201203678 [Bu d JU inch Bub ε 1 instance 71 1 ΙΓ 1 1 1 1 1 1 1 1 Η缉ir> 1 1 to 1 1 1 1 1 Example 70 Township invitation 1 υ-ϊ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 69 Invite 1 1 1 1 1 1 1 1 i〇1 1 V) 1 1 1 1 1 Example 68 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 67 I 1 1 1 1 1 1 1 in 1 1 1 < 1 1 1 1 Example 66 Qing;颂1 1 1 1 1 1 1 1 W-) 1 1 1 1 1 1 1 < Example 65 ζ invitation 1 vn 1 1 1 1 1 1 1 iri 1 1 1 1 1 1 1 1 Example 64 <DBC Total 1 1 1 1 1 1 1 1 Θ缌yn 1 1 1 1 1 1 1 1 Example 63 C埤1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Compound name electrode 1,4-bis(1-propenyloxymethyl)cyclohexane 1,4-bis(1-vinyloxymethyl)cyclohexane Alkane 1,4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol bis(2-butenoic acid methyl ester) ether diethylene glycol bis(4-vinylbenzyl) ether (AZ- 1) (AZ-2) (AZ-3) 3-Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-methyl -1,2,4-three 3-amino-5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 3-amino-5-butyl-1,2, 4-triazole component compound (A) (part) Compound (B) (part) Lewis base (C) (part) 201203678.

[鋰離子電池、鋰離子電容器的製作] (1) 鐘離子電池的製作 (1-1)正極的製作將LiCo〇2粉末9.0份、村琴黑[Aldrich公司製造]〇 5 份及聚偏二氟乙烯[Aldrich公司製造]〇5份於研缽中充分混合後，添加1-曱基-2-n比咯咬酮[東京化成工業（股）製造]7.0份，進而於研缽中充分混合而獲得漿料。將所得的漿料於大氣中使用線棒來塗佈於厚度2〇 μιη的鋁電解箔上的單面，於l〇〇C下乾燥15分鐘後，進而於減壓下（1〇 mmHg)在80 C下乾燥5分鐘，衝壓為15 95 mrmp，製作膜厚30 μιη的鋰離子電池用的正極。 U-2)負極的製作將平均粒徑約8 μιη〜12 μιη的石墨粉末92.5份、聚偏二氟乙烯7.5份及1-曱基_2_吡咯啶酮[東京化成工業（股）製造]200份於研缽中充分混合而獲得漿料。將所得的漿料塗佈於厚度20 μιη的銅箔的單面，於1〇〇。〇下乾燥15分鐘而使〉谷劑蒸發後，衝壓為16.15 mm(p，利用壓製機形成厚度30 μιη ’製作鋰離子電池用的負極。 (1-3)二次電池用單元的製作於2032型硬幣單元内的兩端，將上述正極及負極以各自的塗佈面相對的方式配置而製作二次電池用單元。 (2) 鋰離子電容器的製作 (2-1)正極的製作使用利用鹼活化法而獲得的比表面積約為22〇〇 m2/g 52 201203678 的活性碳作為正極活性物質。將活性碳粉末、聚偏二氟乙稀分別以重量比成為8〇: 1〇:⑺的比例=及混合，將該混合物添加於料_彳的_ A轉伽式攪拌混合而獲得聚料。將該聚料以刮刀‘二中，叫的減上，暫時乾燥後，以電極尺寸成為20_= 30 二取。電極的厚度約為5〇 μιη mm ，製成•電容器匕 (2-2)負極的製作將平均粒徑約8 μιη〜12 μ 黑10份、及聚偏二氟乙稀10份混八j末80伤、乙炔作為溶劑的N_甲基t各姻中_;字=合物添加於漿料以刮刀法塗佈於厚产18 * D，獲付漿料。將該以電極尺寸成為2。mm:3。m:二=暫時乾燥後，約為5〇帅。於單桃喊前，電極的厚度小時，製成鐘離子電容器用的負^真工中以咖乾燥5 (2-3)於負極中的鋰的摻雜於以上述方式獲得的負極中。雜量為負極理論容量=7=、時吸藏於負極 U-4)電容器單元的組裝於以上述方式獲得的正極鱼丙職颂朴使(收聚 53 201203678 納箱中並密封，製成鋰離子電容器。 [評價] 電解液的評價將實例4〜實例35以及比較例1〜比較例3中調整的電解液分別注入上述二次電池用單元中後密封，以下述方法來評價高電壓充放電循環特性及高溫保存特性，廿入電容器單元中後密封，以下述方法來評價高電且注循環特性及高溫保存特性，將上述兩種評價妹壓充玫電中。示於表8 54 201203678 [表8] 裡離子電池鋰離子電容器項目高電壓循環特性（％) 高溫保存特性 (%) 高電壓循環特性 (%) 高溫保存特性 (%) 實例4 92.0 96.7 88.5 94.2 實例5 89.3 94.9 86.6 93.0 實例6 89.0 94.7 88.2 90.3 實例7 89.6 94.3 86.1 92.0 實例8 87.1 93.6 86.1 90.9 實例9 91.5 94.6 89.0 89.6 實例10 87.9 92.6 83.7 87.7 實例11 90.5 95.6 86.3 90.6 實例12 87.8 92.5 83.2 88.0 實例13 86.9 91.1 85.4 91.0 實例14 90.6 85.4 86.2 83.8 實例15 89.7 84.2 85.1 83.7 實例16 89.4 84.4 87.3 80.0 實例17 88.8 93.6 83.9 89.0 實例18 87.8 92.2 85.5 88.0 實例19 87.7 92.5 83.1 91.8 實例20 86.8 91.2 83.0 89.8 實例21 86.9 91.7 83.1 90.6 實例22 90.8 96.2 90.3 95.4 實例23 90.1 96.5 85.9 91.9 實例24 90.2 96.2 89.9 93.4 實例25 90.1 96.3 85.6 95.3 實例26 90.3 96.1 88.3 93.0 實例27 90.2 96.4 87.2 94.3 實例28 86.9 86.5 83.2 85.8 實例29 86.9 91.8 84.9 88.9 實例30 86.9 91.1 84.2 90.3 實例31 89.4 94.2 85.7 90.9 實例32 89.7 94.7 85.5 93.2 實例33 90.1 95.4 88.9 93.6 實例34 89.5 93.2 88.2 89.1 實例35 88.9 91.9 84.4 89.8 比較例1 50.2 55.9 46.2 53.6 比較例2 71.3 76.7 67.8 75.6 比較例3 76.3 81.6 72.1 78.9 電極的評價 55 201203678 J / / / -τριί (1 )裡二次電池的製作於2032型硬幣單元内的兩端，將實例36〜實例67以及比較例4、比較例5的正極及負極以各自的塗佈面相對的方式配置而製作二次電池用單元。將於碳酸乙二酯與碳酸二甲酯的混合溶劑（體積比率1:1)中使LiPF6以1 mol/L 的比例溶解而成的電解液注入至所製成的單元中並密封，將利用以下方法評價高電壓充放電循環特性及高溫保存特性的結果示於表9中。 (2)鋰離子電容器的製作於包含層壓膜的收納箱中，將實例68〜實例71以及比較例6、比較例7的正極及負極以各自的塗佈面相對的方式配置而製作電容器用單元。將於碳酸乙二酯與碳酸二曱酯的混合溶劑（體積比率1 : 1)中使LiPF6以1 m〇i/L 的比例溶解而成的電解液注入至所製成的單元中並密封，將利用以下方法評價高電壓充放電循環特性及高溫保存特性的結果示於表9中。 56 201203678 [表9] 正極單元的種類※ 高電壓循環特性（％) 高溫保存特性（％) 實例36 LIB 88.9 91.5 實例37 LIB 88.2 91.1 實例38 LIB 89.6 92.9 實例39 LIB 89.2 91.5 實例40 LIB 88.4 92.2 實例41 LIB 88.6 91.5 實例42 LIB 89.5 91.5 實例43 LIB 89.3 91.4 實例44 LIB 89.3 91.6 實例45 LIB 88.9 91.2 實例46 LIB 83.3 89.7 實例47 LIB 84.7 88.8 實例48 LIB 84.1 90.0 實例49 LIB 84.7 88.9 實例50 LIB 89.0 92.0 實例51 LIB 88.7 92.9 實例52 LIB 89.3 91.5 實例53 LIB 88.1 91.6 實例54 LIB 88.0 92.8 實例55 LIB 89.4 91.4 實例56 LIB 88.5 91.3 實例57 LIB 88.1 91.8 實例58 LIB 89.2 91.6 實例59 LIB 88.9 91.1 實例60 LIB 89.0 92.9 實例61 LIB 91.1 93.2 實例62 LIB 84.1 89.2 實例63 LIB 83.4 88.4 實例64 LIB 84.5 89.8 實例65 LIB 83.3 88.8 實例66 LIB 84.9 89.7 實例67 LIB 83.9 89.0 實例68 LIC 88.8 91.4 實例69 LIC 87.2 90.0 實例70 LIC 83.2 89.5 實例71 LIC 83.8 89.9 比較例4 LIB 49.3 55.1 比較例5 LIB 70.9 76.0 比較例6 LIC 45.4 53.1 比較例7 LIC 46.0 53.2 ※：LIB (鋰離子電池），LIC (鋰離子電容器） 57 201203678 ^ / / /*tpif 〈高電壓紐電循環軸使用充放電測定裝置「[Production of Lithium Ion Battery and Lithium Ion Capacitor] (1) Preparation of a Clock Ion Battery (1-1) Preparation of a positive electrode 9.0 parts of LiCo〇2 powder, 5 parts of Murakami [made by Aldrich], and 2 pieces of polyethylene 5 parts of fluoroethylene [manufactured by Aldrich Co., Ltd.] was thoroughly mixed in a mortar, and then 7.0 parts of 1-mercapto-2-n ratio ketamine [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further mixed in a mortar. And the slurry is obtained. The obtained slurry was applied to a single surface of an aluminum electrolytic foil having a thickness of 2 μm by using a wire bar in the air, dried at 10 ° C for 15 minutes, and further under reduced pressure (1 〇 mmHg). It was dried at 80 C for 5 minutes, and punched into 15 95 mrmp to prepare a positive electrode for a lithium ion battery having a film thickness of 30 μm. U-2) Preparation of a negative electrode 92.5 parts of graphite powder having an average particle diameter of about 8 μm to 12 μm, 7.5 parts of polyvinylidene fluoride, and 1-mercapto-2-pyrrolidinone [Made in Tokyo Chemical Industry Co., Ltd.] 200 parts were thoroughly mixed in a mortar to obtain a slurry. The obtained slurry was applied to one side of a copper foil having a thickness of 20 μm at 1 Torr. After drying under the arm for 15 minutes, the varnish was evaporated, and the film was punched to 16.15 mm (p, and a thickness of 30 μm was formed by a press to prepare a negative electrode for a lithium ion battery. (1-3) Production of a secondary battery unit at 2032 In the both ends of the coin unit, the positive electrode and the negative electrode are disposed so that the respective coated surfaces face each other to form a secondary battery unit. (2) Production of a lithium ion capacitor (2-1) Preparation of a positive electrode using a base The activated carbon obtained by the activation method has a specific surface area of about 22 〇〇m 2 /g 52 201203678 as a positive electrode active material. The activated carbon powder and polyvinylidene fluoride are respectively made into a weight ratio of 8 〇: 1 〇: (7) Proportion = and mixing, the mixture is added to the _ A gamma-type stirring mixing of the material _ 而 to obtain a granule. The granule is reduced by the squeegee 'two, the temporary drying, and the electrode size becomes 20 _ = 30. The thickness of the electrode is about 5 〇μιη mm, and the negative electrode made of capacitor 匕(2-2) has an average particle size of about 8 μm~12 μ black, 10 parts, and polyvinylidene fluoride. Part of the mixed eight j end 80 wounds, acetylene as a solvent N_methyl t in each marriage _; word = combined The material was added to the slurry and applied to a thick product of 18 * D by a doctor blade method to obtain a slurry. The electrode size was 2. mm: 3. m: two = after temporary drying, it was about 5 〇 handsome. Before the peach screams, the thickness of the electrode is small, and the negative electrode is made into a negative electrode for the plasma ion capacitor to dry 5 (2-3) the lithium in the negative electrode to be doped in the negative electrode obtained in the above manner. The theoretical capacity of the negative electrode = 7 =, when occluded in the negative electrode U-4) The assembly of the capacitor unit was carried out in the above-described manner, and the positive electrode was prepared in a container of 2012-03678 and sealed to form a lithium ion capacitor. [Evaluation] Evaluation of the electrolytic solution The electrolytic solutions adjusted in the example 4 to the example 35 and the comparative example 1 to the comparative example 3 were respectively injected into the secondary battery unit, and then sealed, and the high voltage charge and discharge cycle characteristics and the following were evaluated by the following method. The high-temperature storage characteristics are sealed into the capacitor unit and sealed. The high-voltage and cycle-charging characteristics and high-temperature storage characteristics are evaluated by the following methods. The above two evaluations are charged in the furnace. Table 8 54 201203678 [Table 8] Lithium battery lithium ion capacitor project high voltage cycle Ring characteristics (%) High temperature storage characteristics (%) High voltage cycle characteristics (%) High temperature storage characteristics (%) Example 4 92.0 96.7 88.5 94.2 Example 5 89.3 94.9 86.6 93.0 Example 6 89.0 94.7 88.2 90.3 Example 7 89.6 94.3 86.1 92.0 Example 8 87.1 93.6 86.1 90.9 Example 9 91.5 94.6 89.0 89.6 Example 10 87.9 92.6 83.7 87.7 Example 11 90.5 95.6 86.3 90.6 Example 12 87.8 92.5 83.2 88.0 Example 13 86.9 91.1 85.4 91.0 Example 14 90.6 85.4 86.2 83.8 Example 15 89.7 84.2 85.1 83.7 Example 16 89.4 84.4 87.3 80.0 Example 17 88.8 93.6 83.9 89.0 Example 18 87.8 92.2 85.5 88.0 Example 19 87.7 92.5 83.1 91.8 Example 20 86.8 91.2 83.0 89.8 Example 21 86.9 91.7 83.1 90.6 Example 22 90.8 96.2 90.3 95.4 Example 23 90.1 96.5 85.9 91.9 Example 24 90.2 96.2 89.9 93.4 Example 25 90.1 96.3 85.6 95.3 Example 26 90.3 96.1 88.3 93.0 Example 27 90.2 96.4 87.2 94.3 Example 28 86.9 86.5 83.2 85.8 Example 29 86.9 91.8 84.9 88.9 Example 30 86.9 91.1 84.2 90.3 Example 31 89.4 94.2 85.7 90.9 Example 32 89.7 94.7 85.5 93.2 Example 33 90.1 95.4 88.9 93.6 Example 34 89.5 93 .2 88.2 89.1 Example 35 88.9 91.9 84.4 89.8 Comparative Example 1 50.2 55.9 46.2 53.6 Comparative Example 2 71.3 76.7 67.8 75.6 Comparative Example 3 76.3 81.6 72.1 78.9 Electrode Evaluation 55 201203678 J / / / -τριί (1 ) The positive electrode and the negative electrode of Examples 36 to 67 and Comparative Example 4 and Comparative Example 5 were placed at opposite ends of the 2032 type coin unit, and the secondary battery cells were produced by arranging the positive electrode and the negative electrode facing each other. An electrolyte obtained by dissolving LiPF6 in a ratio of 1 mol/L in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio 1:1) is injected into the produced unit and sealed, and will be utilized. The results of the evaluation of the high voltage charge and discharge cycle characteristics and the high temperature storage characteristics by the following methods are shown in Table 9. (2) Preparation of Lithium Ion Capacitor In the storage case including the laminate film, the positive electrode and the negative electrode of Examples 68 to 71 and Comparative Example 6 and Comparative Example 7 were placed so as to face each other with the coated surface thereof to prepare a capacitor. unit. An electrolyte obtained by dissolving LiPF6 in a ratio of 1 m〇i/L in a mixed solvent of ethylene carbonate and dinonyl carbonate (volume ratio of 1:1) is injected into the prepared unit and sealed. The results of evaluating the high voltage charge and discharge cycle characteristics and the high temperature storage characteristics by the following methods are shown in Table 9. 56 201203678 [Table 9] Types of positive electrode unit ※ High voltage cycle characteristics (%) High temperature storage characteristics (%) Example 36 LIB 88.9 91.5 Example 37 LIB 88.2 91.1 Example 38 LIB 89.6 92.9 Example 39 LIB 89.2 91.5 Example 40 LIB 88.4 92.2 Example 41 LIB 88.6 91.5 Example 42 LIB 89.5 91.5 Example 43 LIB 89.3 91.4 Example 44 LIB 89.3 91.6 Example 45 LIB 88.9 91.2 Example 46 LIB 83.3 89.7 Example 47 LIB 84.7 88.8 Example 48 LIB 84.1 90.0 Example 49 LIB 84.7 88.9 Example 50 LIB 89.0 92.0 Example 51 LIB 88.7 92.9 Example 52 LIB 89.3 91.5 Example 53 LIB 88.1 91.6 Example 54 LIB 88.0 92.8 Example 55 LIB 89.4 91.4 Example 56 LIB 88.5 91.3 Example 57 LIB 88.1 91.8 Example 58 LIB 89.2 91.6 Example 59 LIB 88.9 91.1 Example 60 LIB 89.0 92.9 Example 61 LIB 91.1 93.2 Example 62 LIB 84.1 89.2 Example 63 LIB 83.4 88.4 Example 64 LIB 84.5 89.8 Example 65 LIB 83.3 88.8 Example 66 LIB 84.9 89.7 Example 67 LIB 83.9 89.0 Example 68 LIC 88.8 91.4 Example 69 LIC 87.2 90.0 Example 70 LIC 83.2 89.5 Example 71 LIC 83.8 89.9 Comparative Example 4 LIB 49.3 55.1 Comparison 5 LIB 70.9 76.0 Comparative Example 6 LIC 45.4 53.1 Comparative Example 7 LIC 46.0 53.2 ※: LIB (Lithium Ion Battery), LIC (Lithium Ion Capacitor) 57 201203678 ^ / / /*tpif <High Voltage New Cycle Cycling Shaft Using Charge and Discharge Measurement Device

Tedmica (股）製造]，以^池为析儀1470型」[T〇y〇停頓10分鐘後，以（U c的.，電流充電至電壓4·5 V，反覆進行該充放電1定此^將電池電壓放電至3.5 V，第50循環充電時的電缝、^次充電時的電池容量及性。數值越大，表示充放電:述式算出充放電循環特电痛％特性越良好。高電壓充放電循環特性（電池容量/初次充電時的電池容量）X1QG衣充電時的〈向‘保存特性的評價〉Tedmica (manufacturing)], using ^池 as the analyzer type 1470"[T〇y〇 pause for 10 minutes, then (U c., current is charged to voltage 4·5 V, repeat the charge and discharge 1 ^The battery voltage is discharged to 3.5 V, the electrical gap at the 50th cycle charge, and the battery capacity and the charge at the time of charge. The larger the value, the more the charge and discharge are: the formula calculates the charge/discharge cycle. High-voltage charge-discharge cycle characteristics (battery capacity/battery capacity at the time of initial charge) Evaluation of the "to-memory characteristics" of X1QG clothes during charging

Tech^=_絲置「電池分㈣1·型」[Toyo Techmca (股）劁 w，，” Λ ^ 土」wyo 容量（初次電池容量）谁而^電至電壓3.5V，測定 ^於坑下^量7)日1而以.1〇的電流充電至電壓“ V，w 存後，以0.1 C的電流進行放電至3.5 •^伴)拉^各4 (高溫保存後電池容量）。由下述式算出 ^皿保存特性。數值越大，表示高溫保存特性越良好。池容量）2特性⑻=(高溫保存後電池容量/初次電 f產業上之可利用性】 58 201203678 使用本發明的電極保護膜形成劑（F)的電解液由於高電壓下的循環特性及高溫儲藏穩定性優異，故而尤其作為鋰二次電池用電解液或鋰離子電容器用電解液而有用，適合用於電動汽車。【圖式簡單說明】無。【主要元件符號說明】無0 59Tech^=_Wire set "Battery sub (4) 1 type" [Toyo Techmca (share) 劁 w,," Λ ^ soil" wyo capacity (first battery capacity) who ^ electricity to voltage 3.5V, measured ^ under the pit ^ Quantity 7) Day 1 and charge with a current of .1〇 to the voltage “V, w, then discharge to a current of 0.1 C to 3.5 • ^ with) pull each 4 (battery capacity after high temperature storage). The formula is used to calculate the storage characteristics of the dish. The larger the value, the better the high-temperature storage characteristics. Pool capacity) 2 characteristics (8) = (the battery capacity after high-temperature storage / the initial availability of the industry f) 58 201203678 Using the electrode protection of the present invention Since the electrolyte solution of the film forming agent (F) is excellent in cycle characteristics at high voltage and high-temperature storage stability, it is particularly useful as an electrolyte solution for a lithium secondary battery or an electrolyte solution for a lithium ion capacitor, and is suitable for use in an electric vehicle. Simple description of the schema] None. [Key component symbol description] None 0 59

Claims

201203678, -? / / /τριί 七、申請專利範圍： 1· 一種電極保護膜形成劑（F)，含有選自由下述 (Α1)、（Α2)、（Α3)、（Β1)及（Β2)所組成組群中的至少1種化合物（Α)或化合物（Β): (Α1):具有下述通式（1)所表示的烯氧基（&)的脂肪族烴； (A2).具有稀氧基（a)的多元醇的謎； (A3).具有稀氧基（a)的聚氧伸烧基_ ; (B1).具有選自由下述通式（2)所表示的取代基、下述通式（3)所表示的取代基、（曱基)丙烯醢氧基烷基、及（曱基）丙烯醯基燒基所組成組群中的至少i種取代基（b) 的多元醇的喊； (B2):具有取代基（b)的聚氧伸烷基醚； [化1]201203678, -? / / /τριί VII. Patent application scope: 1. An electrode protective film forming agent (F) containing one selected from the group consisting of (Α1), (Α2), (Α3), (Β1) and (Β2) At least one compound (Α) or compound (Β) in the group consisting of: (Α1): an aliphatic hydrocarbon having an alkenyloxy group (&) represented by the following formula (1); (A2). The mystery of a polyol having a dilute oxy group (a); (A3). a polyoxyalkylene group having a dilute oxy group (a); (B1) having a substitution selected from the group consisting of the following formula (2) a group, at least one substituent (b) of a group represented by the following formula (3), a (fluorenyl) acryloxyalkyl group, and a (fluorenyl) acrylonitrile group; (2) a polyoxyalkylene ether having a substituent (b);

τ1 τ2 [Τ、Τ2及Τ3為氫原子或碳數1〜3的烷基] [化2] (2)201203678 R2—CΤ1 τ2 [Τ, Τ2 and Τ3 are hydrogen atoms or alkyl groups having a carbon number of 1 to 3] [Chemical 2] (2) 201203678 R2—C

:C—Q3 I Q2 [式中，R2為碳數1〜3的伸烷基’ Q1、Q2及Q3分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數1 或2的氟烷基、苯基、氰基、羧基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基] [化3]:C—Q3 I Q2 [wherein R 2 is an alkylene group having 1 to 3 carbon atoms” Q1, Q2 and Q3 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon number of 1 or a fluoroalkyl group, a phenyl group, a cyano group, a carboxyl group, an alkoxy group having 1 to 3 carbon atoms or an alkoxycarbonyl group having 1 to 4 carbon atoms] [Chemical 3]

[式中’ R3為碳數1〜3的伸炫t基’ Q4為氫原子或鹵素原子’ Q5、Q6及Q7分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數1或2的氟烷基、苯基、氰基、羧基、碳數1〜3的烷氧基或碳數丨〜4的烷氧基羰基]。 2.如申請專利範圍第1項所述之電極保護膜形成劑 (F)，其中上述烯氧基（a)為乙烯氧基或丨_丙烯氧基。料^㈣專利範圍第1項或第2項所述之電極保護膜夕()’其巾上述電極保護鄉成劑（F)是含有選 201203678 —^ / i / 自由（A1 )、（ A2 )及（A3 )所組成組群中的至少1種化合物（A)而成，上述化合物（A)為通式（4)所表示的化合物、通式（5)所表示的化合物或者具有2個以上乙稀氧基或1-丙烯氧基的環己烷衍生物： R4-CH=CH-0-(CH2)p-0-CH=CH-R5 ( 4 ) [式中，R4及R5分別獨立地為氫原子或曱基，p為1 〜10的整數] R6-CH=CH-0-(C2H40)q-CH=CH-R7 (5) [式中，R6及R7分別獨立地為氫原子或甲基，q為i 〜5的整數]。 4. 一種電解液’含有如申請專利範圍第1項至第3項中任一項所述之電極保護膜形成劑（F)。 5. 如申請專利範圍第4項所述之電解液，其中更包含路易斯鹼（C)。 6. 如申請專利範圍第5項所述之電解液，其中上述路易斯驗（C)為氮雜冠醚衍生物（ci)及/或***衍生物 (C2)〇 7. 如申請專利範圍第6項所述之電解液，其中上述氮雜冠越衍生物（C1)是在氮雜冠醚環中的氮原子的1個以上鍵結具有聚合性不飽和雙鍵的取代基而成的衍生物 62 201203678 8. 如申請專利範圍第7項所述之電解液，其中上述具有聚合性不飽和雙鍵的取代基為取代基（b)。 9. 如申請專利範圍第6項至第8項中任一項所述之電解液’其中上述氮雜冠醚衍生物（C1)的氮雜冠醚骨架為氮雜-12-冠-4-醚、氮雜-14-冠-4-醚、氮雜-15-冠-5-醚或者氣雜-18-冠-6-趟。 10. 如申請專利範圍第6項所述之電解液，其中上述二嗤竹生物（C2)為3-胺基-1，2,4-三嗅、3,5-二胺基-1，2,4_ ***、3-胺基-5-曱基·1，2,4-***、3-胺基-5-乙基-1,2,4-三 11 坐、3-胺基-5_丙基-1，2,4-三唾或者3-胺基-5-丁基-1，2,4-三〇坐。 11·如申請專利範圍第4項至第1〇項中任一項所述之電解液，其_更包含5員環或6員環的内酯化合物作為溶劑。 12.如申請專利範圍第4項至第η項中任一項所述之電解液，其用於鋰二次電池或鋰離子電容器。 13· —種鋰二次電池或鋰離子電容器，包含如申請專利範圍第12項所述之電解液。 14. 一種鋰二次電池或鋰離子電容器，具有由如申請專利範圍第1項至第3項中任一項所述之電極保護膜形成劑（F)反應而形成的膜（f)所包覆的電極活性物質。 15. —種鋰二次電池或鋰離子電容器，其於正極及/戈負極含有如申請專利範圍第1項至第3項中任一項所述之電極保護膜形成劑（F)。 ' 63 201203678 A. 16. —種電極保護膜形成方法，其藉由對含有電極保護膜形成劑（F)的電解液進行充電而於電極表面形成膜，上述電極保護膜形成劑（F)含有選自由下述（A1)、（A2)、 (A3)、（B1)及（B2)所組成組群中的至少1種化合物 (A)或化合物（B): (A1):具有下述通式（1)所表示的烯氧基（a)的脂肪族烴； (A2):具有稀氧基（a)的多元醇的醚； (A3):具有烯氧基（a)的聚氧伸烷基醚； (B1):具有選自由下述通式（2)所表示的取代基、下述通式（3)所表示的取代基、（曱基）丙烯醯氧基烷基、及（甲基)丙烯醯基烧基所組成組群中的至少丨種取代基（b) 的多元醇的喊； (B2):具有取代基的聚氧伸烷基醚； [化4] —〇—c = c—T3 I I ⑴ T1 T2 [τ、T及τ3為氫原子或碳數丨〜3的烧基] [化5] 64 (2) (2)201203678 一 R2C=C —Q3 I I Q1 Q2 [式中，R2為碳數1〜3的伸烷基，Q1、Q2及Q3分別獨立地為氫原子、鹵素原子、碳數1〜4的烧基、碳數1 f 2的敗烧基、笨基、氰基、羧基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基] [化6][In the formula, R3 is a condensing t group having a carbon number of 1 to 3, and Q4 is a hydrogen atom or a halogen atom. 'Q5, Q6 and Q7 are each independently a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 4, and carbon. A fluoroalkyl group having 1 or 2, a phenyl group, a cyano group, a carboxyl group, an alkoxy group having 1 to 3 carbon atoms or an alkoxycarbonyl group having a carbon number of 丨4. 2. The electrode protective film forming agent (F) according to claim 1, wherein the above alkenyloxy group (a) is a vinyloxy group or a fluorene-propyleneoxy group. Material ^ (4) The electrode protective film described in item 1 or 2 of the patent scope 夕()' The above-mentioned electrode protection agent (F) of the towel contains the selected 201203678 - ^ / i / free (A1), (A2) And at least one compound (A) in the group consisting of (A3), wherein the compound (A) is a compound represented by the formula (4), a compound represented by the formula (5), or two or more a cyclohexane derivative of ethyleneoxy or 1-propenyloxy: R4-CH=CH-0-(CH2)p-0-CH=CH-R5 (4) [wherein R4 and R5 are independently Is a hydrogen atom or a fluorenyl group, p is an integer of 1 to 10] R6-CH=CH-0-(C2H40)q-CH=CH-R7 (5) wherein R6 and R7 are each independently a hydrogen atom or Methyl, q is an integer from i to 5]. An electrolyte protective film forming agent (F) according to any one of the items 1 to 3 of the invention. 5. The electrolyte of claim 4, further comprising a Lewis base (C). 6. The electrolyte according to claim 5, wherein the Lewis test (C) is an azacrown ether derivative (ci) and/or a triazole derivative (C2) 〇7. The electrolyte according to the item 6, wherein the azacrown derivative (C1) is a derivative in which one or more nitrogen atoms in the azacrown ether ring are bonded to a substituent having a polymerizable unsaturated double bond. 8. The electrolyte according to claim 7, wherein the substituent having a polymerizable unsaturated double bond is a substituent (b). 9. The electrolyte according to any one of claims 6 to 8, wherein the azacrown ether skeleton of the azacrown ether derivative (C1) is aza-12-crown-4- Ether, aza-14-crown-4-ether, aza-15-crown-5-ether or gas-hetero-18-crown-6-oxime. 10. The electrolyte according to claim 6, wherein the diterpenoid organism (C2) is 3-amino-1,2,4-tris-ol, 3,5-diamino-1,2 , 4_ triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-5-ethyl-1,2,4-tri-11, 3-amino-5 _propyl-1,2,4-tris- or 3-amino-5-butyl-1,2,4-tris. The electrolyte according to any one of claims 4 to 1, further comprising a 5-membered or 6-membered lactone compound as a solvent. The electrolyte according to any one of claims 4 to 7, which is for use in a lithium secondary battery or a lithium ion capacitor. A lithium secondary battery or a lithium ion capacitor comprising the electrolytic solution as described in claim 12 of the patent application. A lithium secondary battery or a lithium ion capacitor, which comprises a film (f) formed by reacting an electrode protective film forming agent (F) according to any one of claims 1 to 3 Overlying electrode active material. A lithium secondary battery or a lithium ion capacitor, which comprises the electrode protective film forming agent (F) according to any one of claims 1 to 3, in the positive electrode and/or the negative electrode. A method for forming an electrode protective film by forming a film on the surface of an electrode by charging an electrolytic solution containing the electrode protective film forming agent (F), wherein the electrode protective film forming agent (F) contains Select at least one compound (A) or compound (B) in the group consisting of the following (A1), (A2), (A3), (B1), and (B2): (A1): having the following An aliphatic hydrocarbon of the alkenyloxy group (a) represented by the formula (1); (A2): an ether of a polyhydric alcohol having a dilute oxy group (a); (A3): a polyoxyl extension having an alkenyloxy group (a) (B1): having a substituent represented by the following formula (2), a substituent represented by the following formula (3), a (fluorenyl) acryloxyalkyl group, and a polyol of at least one of the substituents (b) in the group consisting of methyl methacrylates; (B2): a polyoxyalkylene ether having a substituent; [Chemical 4] - 〇 - c = c—T3 II (1) T1 T2 [τ, T and τ3 are hydrogen atoms or a carbon number of 丨~3] [Chemical 5] 64 (2) (2) 201203678 A R2C=C —Q3 II Q1 Q2 [ Wherein R 2 is an alkylene group having 1 to 3 carbon atoms, Q1, Q2 and Q3 Each is independently a hydrogen atom, a halogen atom, a carbon number of 1 to 4, a calcined group having a carbon number of 1 f 2 , a strepto group, a cyano group, a carboxyl group, an alkoxy group having 1 to 3 carbon atoms or a carbon number of 1 ~4 alkoxycarbonyl] [Chemical 6]

[式中，R3為碳數1〜3的伸烷基，Q4為氫原子或鹵素原子，Q5、Q6及Q7分別獨立地為氫原子、齒素原子、碳，卜4的烷基、碳數i或2的氟烷基、苯基、氰基、羧基、奴數1〜3的烷氧基或碳數丨〜4的烷氧基羰基]。 65 201203678 (B2) is a polyoxyalkylene having a substituent (b). [1] 一 o—c=c—T3 II T1 T2 四、指定代表圖： (一）本案指定代表圖為：無。 (二）本代表圖之元件符號簡單說明：無。五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： T1 T2 3 201203678 爲第100109542號中文說明書無劃線修正本修正日期:1⑻年6月15日璧專利說明書順序’請勿任意更動，※記號部分請勿、填寫） ※工卩匚分類： (本說明書格式 ※申請案號： ※申請曰： <2006.01) {20(0 .01) 一、發明名稱：（中文/英文）電極保護膜形成劑以及電解液 ELECTRODE PROTECTIVE FILM-FORMING 〇 AGENT AND ELECTROLYTE 二、中文發明摘要·· 本發明提供一種高電壓、高容量，且充放電循環性能及高溫儲藏特性優異的鋰二次電池用電解液或鋰離子電容器用電解液。本發明是含有選自由下述（Ai)、（A2)、 (A3)、（B1)及（B2)所組成組群中的至少1種化合物 (A)或化合物（B)的電極保護膜形成劑（ρ)。 (A1):具有特定結構的烯氧基（a)的脂肪族烴； (A2):具有浠氧基（a)的多元醇的謎； (A3):具有烯氧基（a)的聚氧伸烷基醚； (B1):具有特定結構的取代基（b)的多元醇的醚； (B2):具有取代基（b)的聚氧伸烷基醚。三、英文發明摘要： Provided is an electrolyte used in a lithium ion secondary battery or a lithium ion capacitor with high valtage, 201203678 J / / /-rpiii 爲第100109542號中文說明書無劃修正日期:1〇〇年6月15日六、發明說明：【發明所屬之技術領域】本發明是有關於一種尤其對鋰二器有用的電極保護卿成劑以及電解液。S 電谷【先前技術】链二次電池等非水電解液二次電池由高能量密度之類的特徵，故而被廣泛用於可攜2電= 領域等，且其需要急速擴大，目前，作為以行動電話Ϊ 人電^為代表的行動資訊裝置用的標準電池的已確立。虽然、，隨者可攜式裝置等的高性能化及對作為其電_非水電駿二:欠電池亦財進―b = 量化及高能量密度化卜正在開發用^對該要未的各财法，例域由提高電極填充率的化、新顆高容量的活性物質等。而且雷二二次電池藉由該些方法而確實地高容量^實中非水電解液另外，為了實現非水電解液二次電池的進一步高容量而=正極活性物質的利用率的提高或高電壓：料的 :X ° 中’尤其受到關注岐由於充電電壓的上升而提尚正極活性物質的深度。例如，作為卫作電壓為42 ν 級的非水電解液二次電池的活性物質的姑複合氧化物 jLjCo〇2)若以目前的u基準充電至4 3 ν為止則充電容量約為155mAh/g，相對於此，若充電至45v，則約為刚mAh/g以上。如此，藉由充電電壓的提高正極活性物質的利用率變大。 201203678 修正日期:100年6月15曰胃H 100109542號中文說明書無劃線修正本但疋，隨著電池的高電壓化，電池的容量或能量密度方面’產生充放電循環特性的降低、或在高溫儲臧時的膨脹等問題。先别’已提出有解決電池的充放電循環的降低或電池脹㈣題的各種技術。例如於專利文獻丨及專利文獻 :提出有於電解液巾添加硫化合物作為添加劑。雖記〇〇化八^由雜硫化合物吸附於正極表面而抑制電解液的氧、^絲ί即便使用該些槪合物，紐1循環特性或高 /皿儲滅特性亦不充分。 [先前技術文獻] [專利文獻] [，文獻1]曰本專利特開平7_320779號公報【發^内容文】獻2]日本專利特開平10-_號公報性能及^溫於提供两電壓、高容量且充放電循環極保護膜、’優異的電極保護卿細，含有該電電電解液(尤其是鐘二次電池用或雜子容器1 4些電解液的鐘二次電池或鐘離子電成本ί:月二為而進行積極研究，結果完有選自由下述保護膜形成劑⑺，含成組群中的至少）(A3)、二)及⑽所組 (A1V目士物（）或化合物⑻。、下述通式⑴所表示的烯氧基（a)的 5 201203678 j / / /-τριιι 爲第100109542號中文說明書無劃線修正本修正日期:1〇〇年6月15日脂肪族烴； (A2):具有烯氧基（a)的多元醇的醚； (A3):具有烯氧基（a)的聚氧伸烷基醚 (polyoxyalkylene ether)； (Bl):具有選自由下述通式（2)所表示的取代基、下述通式（3)所表示的取代基、（曱基)丙烯醯氧基烷基、及（曱基）丙稀酿基烧基所組成組群中的至少1種取代基（b ) 的多元醇的鍵； (B2):具有取代基（b)的聚氧伸烷基醚； [化1] —〇 ....... —— Ο 一 1 =c —T3 I (1 ) T2 [T、T及T3為氫原子或碳數1 [化2] 〜3的烷基] —R2- —C = =C——Q3 ! Q1 I Q2 (2) [式中，R2為碳數1〜3的伸烷基，Qi、Q2及Q3分別獨立地為氫料、鹵素原子、碳數1〜4喊基、碳數1 201203678, 修正曰期:1⑻年6月15日爲第ώ〇109542號中文說明書無劃線修正本或2的氟烧基、苯基、氰基、缓基、碳數1〜3的燒氧基或碳數1〜4的烷氧基羰基] [化3] a Q4 Q5 Q 〇[wherein, R3 is an alkylene group having 1 to 3 carbon atoms, Q4 is a hydrogen atom or a halogen atom, and Q5, Q6 and Q7 are each independently a hydrogen atom, a dentate atom, carbon, an alkyl group of 4, and a carbon number. Ii or a fluoroalkyl group, a phenyl group, a cyano group, a carboxyl group, an alkoxy group having a number of 1 to 3 or an alkoxycarbonyl group having a carbon number of 丨4. 65 201203678 (B2) is a polyoxyalkylene having a substituent (b). [1] o o-c=c-T3 II T1 T2 IV. Designated representative figure: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: T1 T2 3 201203678 is the Chinese manual of No. 100109542. There is no slash correction. This revision date: 1 (8) June 15 璧 Patent specification order 'Do not arbitrarily Change, ※Please do not fill in the mark) ※Work classification: (This manual format ※Application number: ※Application曰: <2006.01) {20(0 .01) I. Invention name: (Chinese/English) Electrode protective film forming agent and electrolyte ELECTRODE PROTECTIVE FILM-FORMING 〇AGENT AND ELECTROLYTE 2. SUMMARY OF THE INVENTION The present invention provides a lithium secondary battery having high voltage, high capacity, excellent charge and discharge cycle performance and high temperature storage characteristics. Electrolyte or electrolyte for lithium ion capacitors. The present invention is formed by an electrode protective film containing at least one compound (A) or compound (B) selected from the group consisting of the following (Ai), (A2), (A3), (B1), and (B2). Agent (ρ). (A1): an aliphatic hydrocarbon having an alkenyloxy group (a) having a specific structure; (A2): an enigma of a polyhydric alcohol having a decyloxy group (a); (A3): a polyoxygen having an alkenyloxy group (a) An alkyl ether; (B1): an ether of a polyol having a substituent (b) having a specific structure; (B2): a polyoxyalkylene ether having a substituent (b). 3. English Abstract: Provided is an electrolyte used in a lithium ion secondary battery or a lithium ion capacitor with high valtage, 201203678 J / / /-rpiii No. 100109542 Chinese manual without revision date: 1 June 15th, VI. Description of the Invention: [Technical Field to Which the Invention Is Along] The present invention relates to an electrode protection agent and an electrolyte solution which are particularly useful for a lithium ion device. S Electric Valley [Prior Art] Non-aqueous electrolyte secondary batteries such as chain secondary batteries are characterized by high energy density, and are therefore widely used in portable 2 power = fields, etc., and they need to be rapidly expanded. A standard battery for mobile information devices represented by mobile phones and mobile phones has been established. In addition, the high performance of the portable devices and the like, as well as the electricity, the non-hydropower, the second, the battery, and the low-energy density, are being developed. The financial method, the case area is to increase the filling rate of the electrode, a new high-capacity active substance, and the like. Further, the second secondary battery of the second secondary battery has a high capacity and a non-aqueous electrolyte solution. In order to achieve a further high capacity of the nonaqueous electrolyte secondary battery, the utilization rate of the positive electrode active material is increased or increased. Voltage: Material: X ° Medium 'Special attention 岐 The depth of the positive active material is raised due to the rise of the charging voltage. For example, the charge compound capacity jLjCo〇2) which is an active material of a non-aqueous electrolyte secondary battery having a protection voltage of 42 ν is charged to a capacity of about 155 mAh/g when charged to 4 3 ν on the basis of the current u. On the other hand, when charging to 45v, it is about mAh/g or more. As a result, the utilization rate of the positive electrode active material is increased by the increase in the charging voltage. 201203678 Revision date: 100 years June 15 曰 stomach H 100109542 Chinese manual without scribe correction, but with the high voltage of the battery, the battery capacity or energy density 'generates the charge and discharge cycle characteristics, or Problems such as expansion during high temperature storage. First, various techniques have been proposed to solve the problem of lowering the charge and discharge cycle of the battery or the battery expansion (four). For example, in the patent documents and patent documents, it is proposed to add a sulfur compound as an additive to an electrolyte towel. Although it is adsorbed on the surface of the positive electrode by the heterosulfur compound, the oxygen of the electrolyte is suppressed, and even if these chelates are used, the cycle characteristics or the high/dish storage characteristics of the catalyst are insufficient. [Prior Art Document] [Patent Literature] [, Document 1] Japanese Patent Laid-Open No. Hei 7-320779 (issued in the contents of the text) 2] Japanese Patent Laid-Open No. 10-_ bulletin performance and temperature to provide two voltages, high Capacitor, charge and discharge cycle protective film, 'excellent electrode protection fine, containing the electric electrolyte (especially the clock secondary battery or the clock electrolyte or the hetero-ion container of the electrolyte) : On the second day of the active research, the results are selected from the following protective film forming agents (7), including at least (a), (b) and (10) of the group (A1V target () or compound (8) The olefinic group (a) represented by the following formula (1) is 5 201203678 j / / / - τριιι is the 100109542 Chinese manual without a slash correction. The date of revision: 1 June 15th, aliphatic hydrocarbons (A2): an ether of a polyhydric alcohol having an alkenyloxy group (a); (A3): a polyoxyalkylene ether having an alkenyloxy group (a); (Bl): having a selected from the group consisting of a substituent represented by the formula (2), a substituent represented by the following formula (3), or a (fluorenyl) propylene oxide a bond of a polyol of at least one substituent (b) in a group consisting of an alkyl group and a (fluorenyl) propylene group; (B2): a polyoxyalkylene group having a substituent (b) Ether; [1] - 〇....... —— Ο 1 = c - T3 I (1 ) T2 [T, T and T3 are hydrogen atoms or carbon number 1 [Chemical 2] ~ 3 alkane Base] —R2- —C ==C—Q3 ! Q1 I Q2 (2) [wherein R 2 is an alkylene group having a carbon number of 1 to 3, and Qi, Q 2 and Q 3 are independently hydrogen and halogen atoms, respectively. Carbon number 1~4 shouting base, carbon number 1 201203678, revised flood season: 1 (8) June 15th is No. 109542 Chinese manual without scribe line correction or 2 fluoroalkyl, phenyl, cyano, a suspending group, an alkoxy group having a carbon number of 1 to 3 or an alkoxycarbonyl group having a carbon number of 1 to 4] [Chemical 3] a Q4 Q5 Q 〇

7 (3) [式中，R3為碳數1〜3的伸烷基，Q4為氫原子或鹵素原子，Q5、Q6及Q7分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數1或2的氟烷基、苯基、氰基、竣基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基]。〇另外’本發明是含有該電極保護膜形成劑（F)的電解液、含有该電解液的經二次電池或經離子電容器、以及具有由該電極保護膜形成劑（F)所包覆的電極活性物質的鋰二次電池或鋰離子電容器。 [發明的效果] 本發明的電極保護膜形成劑（F)可抑制高電壓下的電極表面的電驗时解，提高充放電循環雖及高溫儲藏特性。藉由使用含有本發明的電極保護膜形成劑（F)的電解液尤其可獲彳電壓、局容量的鐘二:欠電池或链離子 201203678 ϊ^ώ〇109542號中文說明書無劃線修正本修正日期:1〇〇年6月i5日電容器，並且可提高該些鋰二次電池或鋰離子電容器的高電壓下的充放電循環性能及高溫儲藏特性。【實施方式】本發明的電極保護膜形成劑（F)是含有於電解液中而使用，此外亦可以混合於電極中、直接塗佈於電極表面等方法來使用。本發明的電極保護膜形成劑（F)含有選自由下述 (A1)、（A2)、（A3)、（B1)及（B2)所組成組群中的至少1種化合物（A)或化合物（b)。 (A1):具有通式⑴所表示的烯氧基（a)的脂肪族烴； (A2):具有烯氧基（a)的多元醇的醚； (A3):具有烯氧基⑷的聚氧伸燒基趟； (B1).具有選自由通式⑵所表示的取代基、通式 ϋ所表示的取代基、（曱基)丙烯酿氧基烧基、及(曱基) 2醯基隸所組絲群巾的至少丨餘代基⑻的醇的_ ; ^ .穴力π叭丞的聚氧伸烷基醚。人物„广)發揮作為正極保護膜形成劑的功能，化二（）發揮作為負極保護膜形成劑的功能。即，化合升H 化合物⑻在初次充電時，分別於正極及負極制溶劑分解的保護膜。該保護膜抑制高電壓下的電極表面的電解液的分解，提高充放電循環特性。電化口物（A)及化合物⑻中，較佳為化合物（八）。 201203678 -^/// -Tj^XX 1 爲第100109542號中文說明書無劃線修正本修正日期:1〇〇年6月15日作為化合物（A)的（A1)〜（A3)具有通式（1) 所表示的烯氧基（a)。通式（1)中，τ1、T2及T3為氫原子或碳數1〜3的烧基。具體而言’上述烯氧基（a)可列舉乙烯氧基 (vinyloxy )、1-丙稀氧基（1 _pr〇penyi〇Xy )、1_丁締氧基 (l_butenyloxy )及 1-甲基丙烯氧基（i_methyl pr〇penyi〇Xy ) 等。 0 該些烯氧基中，較佳為乙烯氧基及1-丙烯氧基。 [化4] 一〇 —C = C —τ3 丨丨⑴ Τ! 丁2 (Α1)中的脂肪族烴可列舉：碳數2〜2〇的直鏈或分支的烧烴（乙烷、丙烷、丁烷、戊烷、己烧、辛烷、癸烷、〇十二烷、十三烷、十四烷、十五烷、十八烷及二十烷等）以及碳數2〜20的直鏈或分支的烯烴（乙稀、丙烯、丁烯、戊稀、己稀、辛埽、癸稀、十一烯、十二烯、十三烯、十四烯、十五烯、十八烯及二十烯等）。 (Α1)可列舉自上述烧烴或者烯烴中1個以上的氫原子經烯氧基（a)[較佳為乙烯氧基及1-丙烯氧基]所取代的化合物。 (A2)中的多元醇可列舉2元〜6元的多元醇，具體而0 為.乙二醇（ethyleneglycol )、二乙二醇 9 201203678 J / / /-tpill 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15日 (diethyleneglycol )、三乙二醇（triethyleneglycol )、丙二醇（propyleneglycol)、二丙二醇（dipropyleneglycol)、三丙二醇（tripropyleneglycol)、1,3-丁二醇（1，3-butanediol)、 1，4-丁二醇（1,4-butanediol)、甘油（glycerin)、三經曱基乙烧（trimethylolethane )、三羥曱基丙燒 (trimethylolpropane )、2-曱基甘油（2-methylglycerin )、二甘油（diglycerin )、三甘油（triglycerin )、四甘油 (tetraglycerin)、季戊四醇（pentaerythritol)、二季戊四醇 (dipentaerythritol)及山梨糖醇（sorbitol)等。較佳為乙二醇、二乙二醇及三乙二醇。 (A2)可列舉由上述多元醇及具有烯氧基[較隹為乙稀氧基及1-丙烯氧基]的化合物所衍生的醚。 (A3)是由具有烯氧基（a)[較佳為乙烯氧基及丨兩烯氧基]的化合物所衍生的聚氧伸烷基醚。 (A3)是於具有烯氧基（a)的化合物上加成環氧燒 (alkyleneoxide，以下簡記為A0)而獲得。所加成的AO較佳為碳數為2〜4的AO，具體而言可列舉：環氧乙烷（ethylene oxide，以下簡記為E0)、環氧丙烷（propylene oxide，以下簡記為PO)、以—環氧丁烷 (U-butylene oxide)、2,3-環氧丁烷、1,3_ 環氧丁烷或者 ^ 氧異丁烷（isobutylene oxide)、四氫呋喃（tetrahydrofuran )、及該些AO的2種以上的併用。該些AO中，較佳為E0。A〇的加成莫耳數較佳為工莫耳〜10莫耳，尤佳為1莫耳〜5莫耳。 201203678 修正日期:1〇〇年6月15日爲第ώ〇109542號中文說明書無劃線修正本化合物（Α)中，就充放電循環特性的觀點而言，較佳為通式（4)所表示的化合物、通式（5)所表示的化合物及具有2個以上乙烯氧基或丨_丙烯氧基的環己烷衍生物。 (4) R4-CH=CH-0-(CH2)p-0-CH=CH-R5 Ο [式中，R4及R5分別獨立地為氫原子或曱基，p為j 10的整數。]7 (3) [wherein, R3 is an alkylene group having 1 to 3 carbon atoms, Q4 is a hydrogen atom or a halogen atom, and Q5, Q6 and Q7 are each independently a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms. A fluoroalkyl group having 1 or 2 carbon atoms, a phenyl group, a cyano group, a decyl group, an alkoxy group having 1 to 3 carbon atoms or an alkoxycarbonyl group having 1 to 4 carbon atoms. Further, the present invention relates to an electrolytic solution containing the electrode protective film forming agent (F), a secondary battery containing the electrolytic solution or an ion capacitor, and having the electrode protective film forming agent (F) coated thereon. A lithium secondary battery or a lithium ion capacitor of an electrode active material. [Effects of the Invention] The electrode protective film forming agent (F) of the present invention can suppress the on-time solution of the electrode surface at a high voltage, and improve the charge and discharge cycle and high-temperature storage characteristics. By using the electrolyte containing the electrode protective film forming agent (F) of the present invention, in particular, the voltage of the 、 voltage and the local capacity can be obtained: the battery or the chain ion 201203678 ϊ ώ〇 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 Date: The capacitor of the i5 day in June of the next year, and the charge and discharge cycle performance and high-temperature storage characteristics of the lithium secondary battery or the lithium ion capacitor at a high voltage can be improved. [Embodiment] The electrode protective film forming agent (F) of the present invention is used by being contained in an electrolytic solution, or may be used by being mixed in an electrode and directly applied to the surface of an electrode. The electrode protective film forming agent (F) of the present invention contains at least one compound (A) or compound selected from the group consisting of the following (A1), (A2), (A3), (B1) and (B2). (b). (A1): an aliphatic hydrocarbon having an alkenyloxy group (a) represented by the general formula (1); (A2): an ether of a polyhydric alcohol having an alkenyloxy group (a); (A3): a polycondensation having an alkenyloxy group (4) (B1). having a substituent represented by the formula (2), a substituent represented by the formula 、, a (fluorenyl) propylene oxyalkyl group, and a (fluorenyl) 2 fluorenyl group At least 丨代 ( ( ( ( ( ( ( 隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶隶The person „广” functions as a positive electrode protective film forming agent, and the second function acts as a negative electrode protective film forming agent. That is, the compound H8 (8) is protected against solvolysis of the positive electrode and the negative electrode at the time of initial charge. The protective film suppresses the decomposition of the electrolyte on the surface of the electrode at a high voltage, and improves the charge-discharge cycle characteristics. Among the electrochemical substances (A) and (8), the compound (VIII) is preferred. 201203678 -^/// - Tj^XX 1 is the Chinese manual of No. 100109542. There is no slash correction. The date of this revision is: (A1) to (A3) as the compound (A) on June 15, 1st, the olefin oxygen represented by the general formula (1) In the formula (1), τ1, T2 and T3 are a hydrogen atom or a carbon group having 1 to 3 carbon atoms. Specifically, the above-mentioned alkenyloxy group (a) may, for example, be a vinyloxy group. 1-propoxyl (1 _pr〇penyi〇Xy), 1-butenyloxy (l_butenyloxy), 1-methylpropenyloxy (i_methyl pr〇penyi〇Xy), etc. 0 of these alkenyloxy groups, Preferred is a vinyloxy group and a 1-propenyloxy group. [Chemical 4] 〇-C = C - τ3 丨丨 (1) Τ! Ding 2 (Α The aliphatic hydrocarbon in 1) may, for example, be a linear or branched hydrocarbon having 2 to 2 carbon atoms (ethane, propane, butane, pentane, hexane, octane, decane, decane, Tridecane, tetradecane, pentadecane, octadecane, eicosane, etc.) and linear or branched olefins having a carbon number of 2 to 20 (ethylene, propylene, butene, pentane, hexamelate, octyl埽, 癸, eleven, dodecene, tridecene, tetradecene, pentadecene, octadecene, eicosene, etc.) (Α1) may be exemplified by one or more of the above hydrocarbons or olefins a compound in which a hydrogen atom is substituted with an alkenyloxy group (a) [preferably a vinyloxy group and a 1-propenyloxy group]. The polyhydric alcohol in (A2) may be a polyhydric alcohol of 2 to 6 members, specifically 0. Ethylene glycol (ethyleneglycol), diethylene glycol 9 201203678 J / / /-tpill No. 100109542 Chinese specification without slash correction This revision date: June 15, 100 (diethyleneglycol), triethylene glycol ( Triethyleneglycol), propyleneglycol, dipropyleneglycol, tripropyleneglycol, 1,3-butanediol l), 1,4-butanediol, glycerin, trimethylolethane, trimethylolpropane, 2-mercaptoglycerol (2) -methylglycerin), diglycerin, triglycerin, tetraglycerin, pentaerythritol, dipentaerythritol, and sorbitol. Preferred are ethylene glycol, diethylene glycol and triethylene glycol. The (A2) may, for example, be an ether derived from the above polyol and a compound having an alkenyloxy group (compared to an ethyleneoxy group and a 1-propenyloxy group). (A3) is a polyoxyalkylene ether derived from a compound having an alkenyloxy group (a) [preferably a vinyloxy group and a fluorenyloxyalkylene group]. (A3) is obtained by adding an alkylene oxide (hereinafter abbreviated as A0) to a compound having an alkenyloxy group (a). The AO to be added is preferably AO having a carbon number of 2 to 4, and specific examples thereof include ethylene oxide (hereinafter abbreviated as E0) and propylene oxide (hereinafter abbreviated as PO). U-butylene oxide, 2,3-butylene oxide, 1,3_butylene oxide or isobutylene oxide, tetrahydrofuran, and AO Two or more types are used together. Among these AOs, E0 is preferred. The addition molar number of A 较佳 is preferably 0 to 10 moles, and more preferably 1 mole to 5 moles. 201203678 Revised date: June 15, 1999, No. 109542 Chinese manual No slash correction This compound (Α) is preferably a formula (4) from the viewpoint of charge and discharge cycle characteristics. The compound represented by the formula, the compound represented by the formula (5), and the cyclohexane derivative having two or more ethyleneoxy groups or hydrazine-propyleneoxy groups. (4) R4-CH=CH-0-(CH2)p-0-CH=CH-R5 Ο [wherein R4 and R5 are each independently a hydrogen atom or a fluorenyl group, and p is an integer of j10. ]

Nly R-CH=CH-0-(C2H40)q-CH=CH-R7 [式中，R6及R7分別獨立地為氫原子或甲基，q為i 〜5的整數。] 通式（4)所表示的化合物的具體例可列舉：ι，4·丁二醇二乙嫦謎（1,4-butanediol divinylether)、1,5-戊二醇二乙 Ο 稀趟（l，5-pentanediol divinylether)、1,6-己二醇二乙稀謎 (l，6-hexanediol divinylether )、1，7-庚二醇二乙稀趟 (l，7-heptanediol divinylether )、1,8-辛二醇二乙烯轉 (l，8-octanediol divinylether )、1，9-壬二醇二乙烯 _ (l，9-nonanediol divinylether )、1，10-癸二醇二乙烯謎 (l，10-decanedioldivinylether)、1,4-丁二醇(1-丙浠基）乙烯鱗（l，4-butanediol(l-propenyl)divinylether)、1,5-戊二醇（1-丙烯基）乙稀醚（l,5-pentanediol(l-propenyl)divinyletlier)、 11 201203678 爲第100109542號中文說明書無劃線修正本修正曰期:1〇〇年6月15日 1，6- 己二醇（1- 丙烯基）乙烯醚 (l，6-hexanediol(l-propenyl)divinylet:her)、1,7-庚二醇（1-丙烯基）乙稀醚（l，7-heptanediol(l-propenyl)divinylether)、 1,8- 辛二醇（1- 丙婦基）乙烯醚 (l，8-octanediol(l-propenyl)divinylether)、1，9-壬二醇（1-丙烯基）乙婦醚（l，9-nonanediol(l-propenyl)divinylether )、 1,10- 癸二醇（1- 丙烯基）乙烯醚 (1，10-decanediol( 1 -propenyl)divinylether )、1，4- 丁二醇二 (1-丙烯基)¾ (1,4-butanediol di(l-propenyl)ether)、1,5-戊二醇二（1-丙稀基）喊（l，5-pentanediol di(l-propenyl)ether )、1,6-己二醇二（1-丙烯基）醚 (l，6-hexanediol di(l-propenyl)ether)、1,7-庚二醇二（1-丙細基)謎（l，7-heptanediol di(l-propenyl)ether)、1,8-辛二醇一（I-丙稀基）驗（l，8-octanediol di(l-propenyl)ether)、1,9-壬一醇二（1-丙稀基)δ|( l，9-nonanediol di(l-propenyl)ether) 及 l，l〇-癸·一醇一（1-丙稀基）酸（l，l〇-decanediol di(l-propenyl)ether)。該些化合物可由市售品獲得。該些化合物中，就充放電循環特性的觀點而言，較佳為R4及R5分別為氫原子且p為6〜8的化合物。通式（5)所表示的化合物的具體例可列舉：乙二醇二乙烯醚、二乙二醇二乙烯醚、三乙二醇二乙烯醚、四乙二醇二乙烯醚、五乙二醇二乙烯醚、乙二醇（1_丙烯基）乙烯醚、二乙二醇(1-丙烯基）乙烯醚、三乙二醇丙烯基）乙烯醚、四乙二醇(1-丙烯基）乙烯醚、五乙二醇(丨_丙烯基）乙烯 12 201203678 d / / / 修正日期:100年6月15日爲第100109542號中文說明書無劃線修正本醚、乙二醇二(1-丙烯基)醚、二乙二醇二(1_丙烯基)醚、三乙二醇二(1-丙烯基)醚、四乙二醇二(1_丙烯基)醚及五乙二醇二(1-丙烯基)醚等。該些化合物可由市售品獲得。该些化合物中，就充放電循環特性的觀點而言，較佳為R及R為鼠原子且q為2或3的化合物。具有2個以上乙烯氧基或ι_丙烯氧基的環己烷衍生物的具體例可列舉.1,2-雙（1_丙烯氧基曱基）環己烷 0 ( i’LbisCl-propenoxymethyUcyclohexane)、1,3-雙（1-丙烯氧基曱基)環己烷、1,4-雙(1-丙烯氧基甲基)環己烷、135_ 二(卜丙烯氧基甲基)環己烧、1，2_雙（乙烯氧基甲基)環己烷、1，3-雙（乙烯氧基甲基)環己烷、14-雙（乙烯氧基甲基) 環己烷及1，3,5-三（乙烯氧基甲基)環己烷等。該些化合物可由市售品獲得。化合物（B)可列舉（B1)及（B2)。 (B1):具有選自由上述通式所表示的取代基、上述通式（3)所表示的取代基、（甲基)丙烯醯氧基烷基、 Ο 及（甲基)丙烯醯基烷基所組成組群中的至少2種取代基的多元醇的謎； (B2).具有取代基（b)的聚氧伸烧基縫。 (B1)及（B2)具有選自由通式（2)所表示的取代基、通式（3)所表示的取代基、（甲基)丙烯醯氧基烷基、及（甲基）丙烯醯基烷基所組成組群中的至少丨種取<武取代基（b)中，就負極保護膜的形成容易度的觀點而 13 201203678 Jill -TjJXJL A 修正曰期:1〇〇年6月15日通式（3)所表示爲第100109542號中文說明書無劃線修正# a ’較佳為通式（2)所表示的取代基的取代基及（曱基)丙烯醯氧基烷基。 [化5] r2——c C -—Q 3 Q1 Q 2 (2) 通式（2)中的R2為碳數丨〜3的伸烷基，、 Q分別獨立地為氫原子、鹵素原子、碳數卜4的燒義、石f數1〜2的氟絲、苯基、氰基、赫、碳數！〜3 ^燒乳基或碳數1〜4的烧氧基羰基。碳數1〜3的伸絲可列舉亞曱基、伸乙基、1，2_伸丙基及1，3_伸丙基。該些狀基巾，就充放電觀特點而言’較佳為亞甲基。娜碳數1〜4的烷基可列舉甲基、乙基、正丙基、異正丁基及第三丁基等。円丞 $素原子可列舉氟原子、氯原子、溴原子及碘原子。石厌數1〜2的氟烷基可列舉將曱基或乙基上的氫原子的1個〜5個取代為氟原子的烷基，例如可列舉氟 Γ氣甲基、二氟甲基、I乙基、二氟乙基、三氟乙基、四氟乙基及五氟乙基等。碳數1〜3的烷氧基例如可列舉曱氧基、乙氧基、氧基及異丙氧基。内 201203678 ^111 IJ^AX X 爲第100109542號中文說明書無劃線修正本修正日期:1〇〇年6月15曰碳數1〜4的烷氧基羰基例如可列舉甲氧基羰基、乙氧基羰基、正丙氧基羰基及異丙氧基羰基等。 R2、QKQ2及Q3的較佳組合可列舉以下的（1；)〜（6)。 (1) R —亞甲基，Q1=氫原子，Q2=氫原子，q3=苯基； (2) R亞甲基，（^1=氫原子，〇2=氫原子，q3=烧基羰基； (3) R2=亞甲基，Qi=苯基，q2=氫原子，q3=苯基； (4) R亞甲基，qi=苯基，〇2=氫原子，q3=燒氧基 ^ 羰基； (5 ) R亞曱基’ qi=烧氧基戴基，q2=氫原子苯基； (6) R2=亞甲基’ Q1=烧氧基羰基，Q2=氳原子，q3= 烷氧基羰基。該些組合中，尤佳為（2)的組合。 [化6]Nly R-CH=CH-0-(C2H40)q-CH=CH-R7 [wherein R6 and R7 are each independently a hydrogen atom or a methyl group, and q is an integer of i to 5. Specific examples of the compound represented by the formula (4) include: 1,4-butanediol divinylether, 1,5-pentanediol diacetone, and lanthanum (l) ,5-pentanediol divinylether), 1,6-hexanediol divinylether, 1,7-heptanediol divinylether, 1,8 -1,8-octanediol divinylether, 1,9-nonanediol divinylether, 1,10-decanediol divinyl mystery (l,10- Decanedioldivinylether), 1, 4-butanediol (l-propenyl) divinylether, 1,5-pentanediol (1-propenyl) ethylene ether ( l,5-pentanediol(l-propenyl)divinyletlier), 11 201203678 is the Chinese manual of No. 100109542. There is no slash correction. The revised period: June 6, 1 hexamethylene glycol (1-propenyl) ) 1,6-hexanediol (l-propenyl)divinylet:her), 1,7-heptanediol (l-propenyl)divinylether, 1 , 8-octanediol (1-propanyl) vinyl ether (l 8-octanediol (l-propenyl) divinylether), 1,9-nonanediol (l-propenyl) divinylether, 1,10-decanediol (1) - 1,10-decanediol (1 -propenyl)divinylether, 1,4-butanediol di(l-propenylether), 1,5-pentanediol di(1-propenyl)ether, 1,6-hexanediol di(1-propenyl)ether (1,6 -hexanediol di(l-propenyl)ether), 1,7-heptanediol di(l-propenyl)ether, 1,8-octanediol (I-propyl base) test (l,8-octanediol di(l-propenyl)ether), 1,9-nonanol di(1-propanyl)δ|(l,9-nonanediol di(l- Propenyl)ether) and l,l〇-decanediol di(l-propenyl)ether. These compounds are available from commercial products. Among these compounds, from the viewpoint of charge and discharge cycle characteristics, a compound in which R4 and R5 are each a hydrogen atom and p is 6 to 8 is preferable. Specific examples of the compound represented by the formula (5) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, and pentaethylene glycol. Divinyl ether, ethylene glycol (1-propenyl) vinyl ether, diethylene glycol (1-propenyl) vinyl ether, triethylene glycol propylene) vinyl ether, tetraethylene glycol (1-propenyl) ethylene Ether, pentaethylene glycol (丨_propylene) ethylene 12 201203678 d / / / Revision date: June 15, 100 is the 100109542 Chinese manual without a slash correction of the ether, ethylene glycol di(1-propenyl) Ether, diethylene glycol bis(1-propenyl)ether, triethylene glycol bis(1-propenyl)ether, tetraethylene glycol bis(1-propenyl)ether and pentaethylene glycol di(1-) Propylene) ether and the like. These compounds are available from commercial products. Among these compounds, from the viewpoint of charge and discharge cycle characteristics, a compound in which R and R are a mouse atom and q is 2 or 3 is preferable. Specific examples of the cyclohexane derivative having two or more ethyleneoxy groups or iota-propyleneoxy groups include 1,1,2-bis(1-propenyloxymethyl)cyclohexane (i'LbisCl-propenoxymethy Ucyclohexane). , 1,3-bis(1-propenyloxyindenyl)cyclohexane, 1,4-bis(1-propenyloxymethyl)cyclohexane, 135_bis(bu-propoxymethyl)cyclohexane 1,2_bis(vinyloxymethyl)cyclohexane, 1,3-bis(vinyloxymethyl)cyclohexane, 14-bis(vinyloxymethyl)cyclohexane and 1,3 , 5-tris(vinyloxymethyl)cyclohexane, and the like. These compounds are available from commercial products. Examples of the compound (B) include (B1) and (B2). (B1): having a substituent represented by the above formula, a substituent represented by the above formula (3), (meth)acryloxyalkyl, hydrazine, and (meth)acrylenylalkyl The mystery of the polyol of at least two substituents in the group; (B2). The polyoxyalkylene base slit having the substituent (b). (B1) and (B2) have a substituent represented by the formula (2), a substituent represented by the formula (3), a (meth) propylene decyloxyalkyl group, and a (meth) propylene oxime. At least the oxime species in the group consisting of the alkyl group is the same as the ease of formation of the negative electrode protective film in the group (b). 13 201203678 Jill -TjJXJL A Revision period: June of the next year The description of the Chinese Patent Specification (3) on the 15th is the no-line correction # a ' is preferably a substituent of the substituent represented by the formula (2) and a (fluorenyl) acryloxyalkyl group. r 2 - c C - - Q 3 Q1 Q 2 (2) R 2 in the formula (2) is an alkylene group having a carbon number of 丨〜 3, and Q is independently a hydrogen atom or a halogen atom, The number of carbon number b is 4, the fluorine number of the stone number 1 to 2, the phenyl group, the cyano group, the helium, the carbon number! ~3^ Burning the base or the alkoxycarbonyl group having a carbon number of 1 to 4. Examples of the wire having a carbon number of 1 to 3 include an anthracene group, an extended ethyl group, a 1,2-extended propyl group, and a 1,3 _ propyl group. The base sheets are preferably a methylene group in terms of charge and discharge characteristics. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an iso-butyl group, and a t-butyl group.円丞 The prime atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the fluoroalkyl group having 1 to 2 of the gas phase number include an alkyl group in which one to five hydrogen atoms of a mercapto group or an ethyl group are substituted with a fluorine atom, and examples thereof include a fluorine helium methyl group and a difluoromethyl group. Iethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl and pentafluoroethyl. Examples of the alkoxy group having 1 to 3 carbon atoms include a decyloxy group, an ethoxy group, an oxy group, and an isopropoxy group.内 201203678 ^111 IJ^AX X is the Chinese manual of No. 100109542. There is no slash correction. The date of this amendment: June 15 曰 15 曰 1 to 4 of the alkoxycarbonyl group, for example, methoxycarbonyl, ethoxy Alkylcarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and the like. Preferred combinations of R2, QKQ2 and Q3 include the following (1;) to (6). (1) R - methylene, Q1 = hydrogen atom, Q2 = hydrogen atom, q3 = phenyl; (2) R methylene, (^1 = hydrogen atom, 〇2 = hydrogen atom, q3 = alkylcarbonyl) (3) R2 = methylene, Qi = phenyl, q2 = hydrogen atom, q3 = phenyl; (4) R methylene, qi = phenyl, 〇 2 = hydrogen atom, q3 = alkoxy ^ Carbonyl; (5) R fluorenyl ' qi = alkoxy methoxy, q 2 = phenyl phenyl; (6) R 2 = methylene ' Q 1 = alkoxy carbonyl, Q 2 = fluorene atom, q 3 = alkoxy The carbonyl group. Among these combinations, a combination of (2) is particularly preferred.

通式（3)中的R3為碳數i〜3的伸烷基，Q4為氫原子或齒素原子’ Q5、q6及q7分別獨立地為氣原子、齒素原子、碳數1〜4的烷基、碳數丨或2的氟烷基、笨基、氰 15 201203678 修正曰期:1〇〇年6月15日 J / / / A 爲第100109542號中文說明書無劃線修正本基、羧基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基。通式（3)中的碳數1〜3的伸烷基、鹵素原子、碳數 1〜4的烷基、碳數1或2的氟烷基、碳數1〜3的烷氧基及碳數1〜4的烷氧基羰基的具體例可列舉與通式（2)中例示的例子相同的例子。就負極保護膜的形成容易度及通式（3 )所表示的取代基的穩定性的觀點而言’ Q4較佳為氫原子、氟原子及氯原子，尤佳為氫原子。 η 就負極保護膜的形成容易度的觀點而言，Q5較佳為氫原子、碳數1〜4的絲及鹵素原子，尤佳為氫原子及碳數 1〜4的烧基，特佳為氫原子。就負極保護膜的形成容易度的觀點而言及佳為氫原子、魏1〜4的絲及自及碳數1〜4的烷基，特佳尤仫為虱原千 R3、04、（Vί氧原子及甲基’最佳為氫原子。〜⑽。 Q 的較佳組合可列舉以下的⑴ 子基，料軒，料—氯原子子甲基f氯原…原子伽 Q、二R -亞甲基♦氫原子，Q5=氫原子，㈣基， 16 201203678, •Jill Ι^/ΛΧ 1 爲第100109542號中文說明書無劃線修正本修正曰期:100年6月15日 (5) R3=亞曱基’ Q4=氟原子，Q5=氫原子，q6=曱基， Q7=氫原子； (6) R3=亞曱基’ Q4=氯原子，（55=氫原子，Q6=曱基， Q7=氫原子； (7) R3=亞曱基，Q4=氫原子，q5=氫原子，q6=氫原子，Q7=曱基；R3 in the general formula (3) is an alkylene group having a carbon number of i to 3, and Q4 is a hydrogen atom or a dentate atom 'Q5, q6 and q7 are each independently a gas atom, a dentate atom, and a carbon number of 1 to 4. Alkyl group, carbon number 丨 or 2 fluoroalkyl group, stupid group, cyanide 15 201203678 Revision period: June 15th, 1st, J / / / A is No. 100109542 Chinese manual no underline correction base, carboxyl group An alkoxy group having 1 to 3 carbon atoms or an alkoxycarbonyl group having 1 to 4 carbon atoms. The alkylene group having 1 to 3 carbon atoms, the halogen atom, the alkyl group having 1 to 4 carbon atoms, the fluoroalkyl group having 1 or 2 carbon atoms, the alkoxy group having 1 to 3 carbon atoms, and carbon in the formula (3) Specific examples of the alkoxycarbonyl group having 1 to 4 may be the same as those exemplified in the formula (2). The Q4 is preferably a hydrogen atom, a fluorine atom or a chlorine atom from the viewpoint of easiness of formation of the negative electrode protective film and stability of the substituent represented by the formula (3), and particularly preferably a hydrogen atom. η In terms of easiness of formation of the negative electrode protective film, Q5 is preferably a hydrogen atom, a carbon number of 1 to 4, and a halogen atom, and more preferably a hydrogen atom and a carbon number of 1 to 4, particularly preferably A hydrogen atom. From the viewpoint of easiness of formation of the negative electrode protective film, and preferably a hydrogen atom, a filament of Wei 1 to 4, and an alkyl group having a carbon number of 1 to 4, Tejiayu is a R原千R3, 04, (V? The atom and the methyl group are preferably a hydrogen atom. ~(10). The preferred combination of Q can be exemplified by the following (1) subunits, materials, materials, chlorine atom, methyl group, methyl chloride, ... atomic gamma Q, two R - methylene Base ♦ hydrogen atom, Q5 = hydrogen atom, (d) base, 16 201203678, • Jill Ι^/ΛΧ 1 is the 100109109 Chinese manual without a slash correction. The revised period: June 15th, 100 (5) R3=Asia Sulfhydryl group Q4 = fluorine atom, Q5 = hydrogen atom, q6 = fluorenyl group, Q7 = hydrogen atom; (6) R3 = fluorenylene group Q4 = chlorine atom, (55 = hydrogen atom, Q6 = fluorenyl group, Q7 = a hydrogen atom; (7) R3 = a fluorenylene group, Q4 = a hydrogen atom, q5 = a hydrogen atom, q6 = a hydrogen atom, Q7 = a fluorenyl group;

(8) R3=亞甲基，Q4=氟原子，（^氫原子，q6=氳原子，Q7=甲基； (9) R3=亞曱基’ Q4=氣原子，（^5=氫原子，Q6=氳原子’ Q7=甲基； (10 ) R3=亞甲基，Q4=氫原子’ Q5=氫原子，q6=甲基， Q7=甲基； (11 ) R3=亞甲基’ Q4=氟原子，〇5=氫原子，q6=曱基， Q7=甲基； (12 ) R3=亞甲基，Q4=氣原子，(^5=氫原子，q6=甲基， Q7=甲基。該些組合中，尤佳為（1)的組合。 (甲基）丙烯醯氧基烷基較佳為丙烯醯氧基甲基、丙烯醯氧基乙基、甲基丙烯醯氧基曱基及甲基丙烯醯氧基乙基等烷基的碳數為i〜2的（甲基)丙烯醯氧基烷基。 (甲基）丙烯醯基烧基較佳為丙烯醯基甲基、丙稀醢基乙基、曱基丙歸醯基甲基及曱基丙烯醯基乙基等烷基的碳數為1〜2的（甲基)丙烯醯基烷基。 (Bl)中的多元醇可列舉與（A2)中例示的多元醇相 17 201203678 Ϊ第、00109542號中文說明書無劃線修正本修正日期:1〇〇年6月15日同的多元醇。較佳為乙二醇、二乙二醇及三乙二醇。 ⑻）是由多辑及具有上述取代所衍生的醚。口物較佳為通式（6)所表示的化合物。 X-(0-R1)r-〇-Y (6) 通式（6)中的X及γ分別獨立地為通式（2)所的取代基、通式（3)所表示的取代基、（曱基)丙烯醯氧基炫基或（甲基)丙烯醯基烷基。通式（6)申的R1為碳數i〜3的伸烧基，可列舉亞曱基、伸乙基、1，2-伸丙基及〗，3_伸丙基。該些伸烷基中就輸出特性的觀點而言，較佳為伸乙基。通式（6)中的Γ為1〜5的整數，就充放電循環特性的觀點而言’較佳為1〜4的整數，尤佳為2。 (B1)的具體例可列舉：乙二醇二(2_丁烯酸甲酯）醚 (ethyleneglycol di(2-butenoic acid methyl)ertier)、二乙二醇二(2-丁烯酸曱酯）醚、三乙二醇二(2_丁烯酸曱酯）醚、四乙二醇二(2-丁稀酸曱酯）趟、五乙二醇二(2_丁埽酸曱酯）喊、乙一醇一肉桂趟（ethyleneglycol dicinnamyl ether)、二乙二醇二肉桂鱗、三乙二醇二肉桂謎、四乙二醇二肉桂峻、五乙二醇二肉桂醚、乙二醇二（4-乙稀基苄基）¾ (ethyleneglycol di(4-vinylbenzyl)ether)、二乙二醇二(4-乙婦基卞基)鍵、二乙二醇二(4-乙稀基节基)驗、四乙二醇二 18 201203678, 爲第100109542號中文說明書無劃線修正本修正曰期:1〇〇年6月15日 (4-乙烯基苄基)驗、五乙二醇二(4-乙稀基苄基)趟、乙二醇二(1-丙烯醯氧基乙基)醚（ethyleneglycol di(l-acryloyloxy ethyl)ether)、二乙二醇二（1-丙稀醯氧基乙基)驗、三乙二醇 ·一(1-丙稀酿氧基乙基)鍵、四乙· —一(1-丙稀'酿氧基乙基) 醚、五乙二醇二(1-丙稀醯氧基乙基)鍵、二乙二醇(2_戊烯酸乙醋）醚（diethyleneglycol (2-pentenoic acid ethyl)ether)、三乙二醇(2-戊烯酸乙酯）醚等。 0 該些化合物可由市售品獲得，或者以公知的方法合成。 (B2)為具有取代基（b)的聚氧伸烷基醚，是於具有取代基（b)的化合物上加成環氧烧（以下簡記為A〇) 而獲得。所加成的AO可列舉與（A3 )中例示的A〇相同的 A0。較佳為EO。AO的加成莫耳數較佳為1莫耳〜1〇莫耳，尤佳為1莫耳〜5莫耳。、本發明的電極保護膜形成劑（F)含有選自由上述 (A1)、（A2)、（A3)、（B1)及（B2)所組成組群中的至〇少1種化合物（A)或化合物（B)。本發明的電解液含有電解質（G)、非水溶劑（H)及電極保護膜形成劑（F)作為必需成分。藉由使電極保護膜形成劑（F)含有於電極或電解液中’對電極施加f壓，而使電極倾卿成劑（F)於活性物質表面聚合形成被膜而成為保護膜。於使链二次電池或鐘離子電容器的電極或電解質中含有電極保護膜形成劑（F)的情況，於初次充電時形成上 19 201203678 J / / /-TJ^ill 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15曰述保護膜’但亦可使用另行於電極表面（活性物質表面）形成有電極保護膜形成劑（F)的聚合被膜的電極來作為链二次電池或链離子電容器的電極。電解質（G)可使用通常的電解液中使用的電解質，例如可列舉：LiPF6、LiBF4、LiSbF6、LiAsF6 及 LiC104 等無機酸的鋰鹽；LiN(CF3S02)2、LiN(C2F5S02)2、 LiC(〇F3S02)3等有機酸的鋰鹽。該些電解質中，就電池輸出及充放電循環特性的觀點而言，較佳為LiPF6。非水溶劑（H)可使用通常的電解液中使用的溶劑，例如可使用：内酯（lactone)化合物、環狀或鏈狀碳酸酯、鏈狀羧酸酯、環狀或鏈狀醚、磷酸酯、腈（nitrile)化合物、醯胺（amide)化合物、硪（sulfone)、環丁礙（sulfolane) 等以及該些化合物的混合物。内酉旨化合物可列舉5員環（γ_丁内醋（γ-butyrolactone) 及γ-戊内S旨（γ-valerolactone )等）及6員環的内S旨化合物 (δ-戊内酯等）等。環狀碳酸酯可列舉：碳酸丙二酯（propylene carbonate )、石炭酸乙二酯（ethylene carbonate )及碳酸丁二醋（butylene carbonate)等。鏈狀碳酸酯可列舉：碳酸二甲酯（dimethyl carbonate)、碳酸曱基乙酯（methyl ethyl carbonate )、碳酸二乙醋（diethyl carbonate )、碳酸甲基-正丙醋 (methyl-n-propyl carbonate )、碳酸乙基-正丙醋 (ethyl-n-propyl carbonate )及碳酸二-正丙酉旨（di-n-propyl 20 201203678 j / / /H-piii 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15曰 carbonate)等 ° 鏈狀缓酸酯可列舉：乙酸甲酯（methyl acetate)、乙酸乙 g旨（ethyl acetate )、乙酸丙醋（propyl acetate )及丙酸曱 Si ( methyl propionate )等。環狀醚可列舉：四氫呋喃、四氫吡喃 (tetrahydropyran)、1,3-二氧戊環（1,3-dioxolane)及 1，4-二0惡烧（l，4-dioxane)等。 ❹ 鏈狀鱗可列舉：二甲氧基曱烧（dimethoxy methane) 及 1，2-二甲氧基乙烧（l，2-dimethoxyethane)等。磷酸S旨可列舉：鱗酸三曱酯（trimethyl phosphate)、磷酸三乙酯、磷酸乙基二甲酯、磷酸二乙基甲酯、磷酸三丙酯、磷酸三丁酯、磷酸三（三氟曱基）酯 (tri(trifhioromertiyl)phosphate)、磷酸三(三氯曱基)酯、磷酸二(三氟乙基)醋、填酸三(三全氟乙基)醋、2-乙氧基_1，3,2_ 二氧磷雜環戊 -2- _ (2_ethoxy-l,3,2-dioxaphospholan-2-〇ne )、2-三氟乙氧基 €) -1，3,2-二氧磷雜環戊-2-酮、2-曱氧基乙氧基^心二氧磷雜環戊-2-酮等。腈化合物可列舉乙腈（acetonitrile)等。醯胺化合物可列舉二曱基甲醯胺（dimethylformamide)等。非水溶劑（H)可單獨使用，亦可併用2種以上。非水溶劑（H)中，就電池輸出及充放電循環特性的觀點而言，較佳為内酯化合物、鏈狀碳酸酯及磷酸酯，尤佳為内酯化合物及鏈狀碳酸酯，特佳為内酯化合物，最佳 21 201203678 •Jill T^fll. ± 爲第100109542號中文說明書無劃線修正本修正日期丨㈨年6月為5員環或6員環的内酯化合物，特佳為5員環的内酽化合物。内酯化合物由於與碳酸酯化合物相比電位窗狹窄，故而無法用作先剷鐘電池用途中的非水溶劑。然而，本發明的電解液由於存在由電極保護膜形成劑（F)形成的膜，故而内酯化合物亦可用作非水溶劑，與碳酸酯化合物相比較耐熱保存穩定性優異’因此可使高溫儲藏特性提°高。本發明的電解液較佳為更含有路易斯鹼（c)。上& 有歸氧基（a)的化合物（A)的反應性高，容易與例如^ 解液中微量混合存在的水分和LiPF0等電解質鹽反應產生的HF等酸性化合物進行反應。藉由在電解液中添^路易斯驗（C)，可增加化合物（A)於電解液中的穩定性。另外，於路易斯鹼（c)為後述的氮雜冠醚（azacr〇wnether) 衍生物（ci)的情況，由於氮雜冠醚衍生物（C1)形成負極保護膜’故而可使充放電循環特性進一步提高。路易斯鹼（c)可列舉氮雜冠醚衍生物（C1)及*** (triazole)衍生物（C2)等。該些化合物中，就循環特性的觀點而言，較佳為氮雜冠醚衍生物（ei)。氣雜冠峻衍生物（C1)具有包含1個〜4個氮原子的 9員環〜24員環的冠醚骨架，較佳為於該骨架的氮原子的 1個以上鍵結有具有聚合性不飽和雙鍵的取代基的化合物。具有1個〜4個H原子的9貢環〜24員環的冠驗骨架玎列舉：氮雜-9_冠-3-醚（4-氮雜_9-冠_3_醚及4,7_二氮雜_9_ 22 201203678^ 爲第-麵號中文說明書無劃線修正本修正曰期:1〇〇年6月15日冠-3-謎等）、氣雜二氮(4氮雜4冠销及邮醚及4,1〇_二氮雜ji、氛雜~14-冠_4-醚（4_氮雜-14-冠-4--i5-冠领、4 f 4，等）、氮雜_15_冠销（4-氮雜 Ο 及4，1〇，16-三氮雜:广冠·5_醚、4，14_二氮雜·15-冠·5 雜-18-冠·6,、4ι~〇冠:5-鍵等）、氮雜尊冠·6_鱗（4-氮唇冠-6·_ )、氮雜、18_冠_6·· 4，1G，16_三氮雜二氮雜=，(4·氮雜答冠冬醚、4，1〇_ 雜-24-冠|醚（4_氮雜^二亂雜_21_冠领等）以及氮醚及 4,1〇，16_: 4，10-二敗雜-24-冠各該些冠^骨4 較佳為氮雜必冠_4趟：^離子的配位力的觀點而言，醚及氮雜暴冠_6, U·14•冠_4务氮雜_15_冠-5- 氮雜-12-冠斗醚、4氣换f 4 4_氮雜_12_冠·4_醚、4，10_二醚。 ·氣雜_15·15·醚及4，10-二氮雜_15_冠_5 就對鐘離子的配% 氮原子數較佳為觀點而言，氮雜綱骨架中的鍵的物（C1)所具有的具有聚合性不飽和雙的取代基、(甲基)丙烯醯氧基烷基及(甲土）丙基絲等，較佳的取代基亦相同。氮雜冠崎生物（C1)的具體例可列舉：N_(2_丁烯酸甲醋 M-氮雜-12-冠-4-醚（N_(2_buten〇ic acid methyl)冰aza-12-crown-4-ether )、N，N-二-(2- 丁烯酸甲 23 201203678 ^/// Τ^/1Α Λ, 爲第100109542號中文說明書無劃線修正本修正日期:1〇〇年6月15日酉曰)-4,10-一乳雜-12-冠-4-謎、N-(2-丁烤酸曱g旨）_4_氣雜-15· 冠-5-醚、Ν,Ν-二-(2-丁烯酸曱酯)-4，1〇-二氮雜_15冠-5_醚、 Ν-(肉桂基)-4-氮雜-12-冠-4-醚、Ν,Ν-二-(肉桂基)_4,1〇_二氮雜-12-冠-4·_、Ν-(肉桂基)-4-氣雜-15-冠-5-醚、Ν，Ν-二-(肉桂基)-4，1〇-二氮雜_15_冠_5_醚、Ν·(4-乙烯基苄基)_4_氮雜 -12-冠-4-醚、Ν，Ν-二-(4-乙烯基节基)-4,10-二氮雜-12-冠_4-醚、N-(4-乙烯基节基)_4_氮雜-15-冠-5-醚、N，N-:-(4-乙烯基~基)-4，10-一鼠雜-15-冠-5-謎、Ν,Ν-二-(1·丙稀酿氧基乙基)-4，1〇-二氮雜_15_冠_5_醚、Ν_(1_丙烯醯氧基乙基)_4_氮雜 -14-冠-4-ϋ、Ν-(2·戊烯酸乙醋)-4-氮雜-18-冠-6-醚及Ν,Ν-•一_(2_戊婦酸曱醋)-4,14-二氣雜·18-冠-6-鍵等。本發明中的氮雜冠醚衍生物（C1)可以通常的方法製造。例如可列舉如下方法：於有機溶劑中，在無觸媒或者觸媒的存在下，使未經取代的氮雜冠醚與具有聚合性不飽和雙鍵的鹵化烷基進行反應。有機溶劑例如可列舉：腈系有機溶劑（乙腈、丙腈 (propionitrile)及笨甲腈（benzonitrile)等）、酮系有機溶劑（丙酮（acetone)及甲基乙基酮（methyl ethyl ketone) 等）、酿胺系有機溶劑（曱醯胺、乙醯胺、二甲基曱醯胺及二曱基乙醯胺等）、醚系有機溶劑（二甲醚、四氩呋喃及二 °惡院等）、酯系有機溶劑（乙酸乙酯及順丁烯二酸二乙酯等）、含硫有機溶劑（二曱基亞石風（dimethyl sulfoxide)及環丁颯等）、鹵化烴（氯仿及二氣甲烷等）、烴（己烷、庚炫*甲本及一甲苯等）以及該些溶劑的兩種以上的混合物。 24 201203678 J / / /^tpixi 爲第100109542號中文說明書無劃線修正本修正曰期:100年6月15日觸媒可列舉：驗金屬氩氧化物（例如氫氧化鐘、氣氧化納及氫氧化卸等）、驗金屬碳酸鹽（碳酸氳納、碳酸氫鉀、碳酸納及碳酸鉀等）及驗金屬氫化物（氫化鈉及氫化卸等）等。反應溫度通常為10°C〜150°C，反應時間通常為〇5 小時〜24小時。反應結束後’可視需要中和觸媒，以吸附劑進行處理而將觸媒去除，加以純化。具有聚合性不飽和雙鍵的齒化烧基例如可列舉：4_演 0 -2-丁烯酸曱酯（4-bromo-2-butenoic acid methyl ester)、4- ' 氯-2- 丁烯酸甲酯、1-溴-4-氰基_2_ 丁稀 (l-bromo-4-cyano-2-butene)、1-氣斗氱基_2_丁烯、丙烯酸氯曱酯（chloromethyl acrylate)、丙烯酸漠甲酯、丙烯酸 -2-氯乙酯、丙烯酸-2-溴乙酯、曱基丙烯酸氣甲酯、甲基丙烯酸>臭曱醋、甲基丙稀酸-2-氣乙酷、甲基丙烯酸_2_溴乙酯、肉桂基氯（cinnamylchloride)、肉桂基溴、心(氯甲基）苯乙烯（4-(chlorometliyl)styrene )及 4-(溴曱基)苯乙烯。三嗤衍生物（C2 )可列舉：ι，2,3Γ苯幷*** ◎ (l，2,3-benzotriazole)、5-曱基_1，2,3-苯幷三嗤、5,6_二甲基 _1，2,3-本幷二嗤、1，2,4-二唾、3-胺基-1，2,4-三11坐、3,5-二胺基-1，2,4-二嗤、3-胺基-5·甲基-1，2,4-三π坐、3_胺基_5_乙基 _1，2,4-***、3-胺基-5-丙基_l,2,4-三唾及3_脸美s 丁美衍生物中，就充放電循環特性的觀點而言，較佳為3_胺基 -1，2,4·三嗤。本發明的電騎可更含有彳t合物⑷聽合物⑻ 25 201203678 J / / /πριιι 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15日以外的負極保護膜形成劑（D)。藉由電解液含有負極膜形成劑⑼，負極保護膜的穩定性進一步提高使” 放電循環特性進一步提高。凡負極保護膜形成劑（D)可列舉：碳酸亞乙婦西旨 (vmyiene carbonate)、碳酸a乙二§旨、碳酸氣乙二醋硫酸乙二6旨（ethylene sulfite)、亞倾丙二缺㈣内醋等。該些化合物中’就循環特性的觀點而言碳酸亞乙烯酯。仪^马本發明的電解液中的電極保護膜形成劑⑺ 驗⑹、負極保護膜形成劑（D)、非水溶劑（h)及質（G)的各較佳含量或濃度為如下所述。就充放電循環特性、電池容量及高儲藏特性的觀吕’作為電極保賴形成劑（F)的化合物景於電解液的重量，較佳為〇.〇1重量百分比（wt= = Wt%，尤佳為 0.05 wt%〜1 wt%。 10 ▲=電池容#、電池輸出及纽電循轉二電形成劑(F)的化合物(B)的含量I 一就電池容量、電池㈣及統電循環特性言’路易嶋（C)的含量基於電解賴重量” ^10 wt〇/〇，〇.〇1 wt0/_ 10 wt〇/〇, 〇就電池容4、電池輸出及級電循環特性的觀點而 26 201203678 爲第ώο聰42號中文麵書無劃線修正本修正日期·年6月15日 S，負極保濩膜开>成劑（D)的含量基於電解液的重量，較佳為0 wt%〜5 wt%，更佳為〇〇1 wt%〜5 wt%，尤 0.01 wt%〜3 wt%。就電池輸出及充放電循環特性的觀點而言，非水溶劑 (H)的含直基於電解液的重量，較佳為wt%〜％奶％，尤佳為93 wt%〜99 wt%。就電池輸出及充放電循環特性的觀點而言，電解液中 0 的電解質（G)的濃度基於電解液的體積，較佳為0.01 m〇l/L 〜3 mol/L，尤佳為 0.05 m〇i/L〜1.5 mol/L。本發明的電解液可更含有過量充電防止劑、脫水劑及容量穩定劑等添加劑。過量充電防止劑可列舉：聯苯（biphenyl)、烷基聯苯 (alkyl biphenyl)、聯三苯、聯三苯的部分氫化物、環己基苯（cyclohexyl benzene)、第三丁基苯及第三戊基苯等芳香族化合物等。過量充電防止劑的使用量基於電解液的總重量，通常為〇 wt%〜5 wt%，較佳為〇 wt%〜〇 3 wt%。脫水劑可列舉沸石（zeolite)、矽膠（silica gel)及氧化鈣等。基於鋰二次電池用電解液的總重量，脫水劑的使用量通常為0 wt%〜5 wt%，較佳為0 wt%〜3 wt%。容量穩定劑可列舉：碳酸氟乙二酯、琥珀酸酐、1-曱基-2-n辰咬嗣（l-methyl-2-piperidone)、庚烧及氟苯等。基於電解液的總重量，容量穩定劑的使用量通常為〇wt%〜5 wt%，較佳為〇 wt%〜3 wt%。 27 201203678 修正日期:100年6月15日 Ϊ第1^109542號中文說明書無劃線修正本本發明的電解液尤其作為鐘二次電池用的電解液而有用。使用本發明的電解液的鐘二次電池是藉由在收納有正極、負極及分隔片的電池罐内注人本發明的電解液，將電池罐密封而獲得。鋰二次電池中的正極可使用以棒式塗佈機等塗佈裝置，將使正極活性物質、導電劑及黏合劑分散於溶劑中而漿料化者塗佈於正極用集電體上，加以乾燥而去除溶劑，視需要利用壓製機進行壓製而成的正極等。正極活性物質可列舉：鋰與過渡金屬的複合氧化物（例如 LiCo02、LiNi02、LiMn02 及 LiMn2〇4 等）、過渡金屬氧化物（例如Mn〇2及V2〇5等）、過渡金屬硫化物（例如m〇s2 及TiS2等）、以及導電性高分子（例如聚苯胺 (polyaniline)、聚偏二說乙烯（p〇iyvinyiidene fluoride)、聚口比嘻（polypyrrole)、聚噻吩（p〇lytliiophene)、聚乙炔 (polyacetylene )、聚對亞苯基（p〇iy_p_phenylene )及聚味 0坐（polycarbazole)等）等。導電劑可列舉：石墨（例如天然石墨及人工石墨等）、碳黑（carbon black)類（例如碳黑、乙炔黑（acetylene black )、柯琴黑（Ketjen black )、槽黑（channel black )、爐黑（furnace black)、燈黑（iamp black)及熱黑（thermal black) 等）、金屬粉末（例如鋁粉及鎳粉等）、導電性金屬氧化物 (例如氧化鋅及氧化鈦等）等。黏合劑例如可列舉：澱粉、聚偏二氟乙烯、聚乙烯醇 28 201203678 ^/// ~ryj*.x 1 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15日 (polyvinyl alcohol )、羧甲基纖維素（carboxymethyl cellulose)、聚乙稀基〇比哈咬_ (p0iyvinyl pyrrolidone)、四氟乙烯（tetrafluoroethylene)、聚乙烯及聚丙烯等高分子化合物。溶劑例如可列舉：1-甲基-2-吡咯啶酮、甲基乙基酮、二曱基曱醯胺、二甲基乙醯胺、N，N-二甲基胺基丙基胺及四氫咬喃等。(8) R3 = methylene, Q4 = fluorine atom, (^ hydrogen atom, q6 = deuterium atom, Q7 = methyl group; (9) R3 = anthracene group 'Q4 = gas atom, (^5 = hydrogen atom, Q6=氲 atom 'Q7=methyl; (10) R3=methylene, Q4=hydrogen atom 'Q5=hydrogen atom, q6=methyl, Q7=methyl; (11) R3=methylene' Q4= Fluorine atom, 〇5 = hydrogen atom, q6 = fluorenyl group, Q7 = methyl group; (12) R3 = methylene group, Q4 = gas atom, (^5 = hydrogen atom, q6 = methyl group, Q7 = methyl group). Among these combinations, a combination of (1) is particularly preferred. The (meth)acryloxyalkyl group is preferably an acryloxymethyl group, an acryloxyethyl group, a methacryloxy group and a (meth) propylene oxiranyl group having an alkyl group such as a methacryloxyethyl group having a carbon number of i to 2. The (meth) acrylonitrile group is preferably an acryloylmethyl group or a propylene group. a (meth) acrylonitrile alkyl group having 1 to 2 carbon atoms of an alkyl group such as mercaptoethyl, mercaptopropylmethylmethyl and mercaptopropenylethyl. The polyhydric alcohol in (Bl) may be used. Listed in the polyol phase exemplified in (A2) 17 201203678 Ϊ, 00109542 Chinese manual no slash correction this correction date : The same polyol as June 15 of the following year. Preferably, it is ethylene glycol, diethylene glycol and triethylene glycol. (8)) is an ether derived from a plurality of series and having the above substitution. A compound represented by the formula (6): X-(0-R1)r-〇-Y (6) X and γ in the formula (6) are each independently a substituent of the formula (2), a substituent represented by the formula (3), a (fluorenyl) propylene decyloxy group or a (meth) acrylonitrile group. The formula (6) wherein R1 is a carbon number i to 3 Examples thereof include an anthracene group, an ethylidene group, a 1,2-propyl group, and a 3-propyl group. Among these alkylene groups, from the viewpoint of output characteristics, an ethyl group is preferred. The enthalpy in (6) is an integer of 1 to 5, and is preferably an integer of 1 to 4, particularly preferably 2, from the viewpoint of charge and discharge cycle characteristics. Specific examples of (B1) include ethylene glycol II. (2-butenoic acid methyl) ertier, diethylene glycol bis(2-butenoic acid methyl ester) ether, triethylene glycol bis(2-butenoic acid) Ester ester) ether, tetraethylene glycol bis(2-butyl phthalate) oxime, pentaethylene glycol bis(2-butyric acid ruthenium) ) shout, ethyleneglycol dicinnamyl ether, diethylene glycol dicinctrine, triethylene glycol, two cinnamon mystery, tetraethylene glycol, two cinnamon, pentaethylene glycol dicinnamyl ether, ethylene glycol (4-ethylenebenzyl) 3⁄4 (ethyleneglycol di(4-vinylbenzyl)ether), diethylene glycol bis(4-ethylglycosyl) bond, diethylene glycol bis(4-ethylene benzyl) ), tetraethylene glycol II 18 201203678, No. 100109542 Chinese manual without a slash correction of this amendment period: June 15th (4-vinylbenzyl) test, pentaethylene glycol II ( 4-ethylene benzyl) oxime, ethyleneglycol di (l-acryloyloxy ethyl ether), diethylene glycol bis(1-propanyloxy) Ethyl), triethylene glycol, mono(1-propanyloxyethyl) linkage, tetraethyl-1-(1-propanyloxyethyl ether), pentaethylene glycol di(1) - acryloxyethyl) bond, diethyleneglycol (2-pentenoic acid ethyl ether), triethylene glycol (2-pentenoic acid ethyl ester) Ether, etc. 0 These compounds can be obtained from commercially available products or synthesized by a known method. (B2) is a polyoxyalkylene ether having a substituent (b) obtained by adding an epoxy burn (hereinafter abbreviated as A〇) to a compound having a substituent (b). The AO to be added may be the same as A0 exemplified in (A3). It is preferably EO. The addition molar amount of AO is preferably 1 mole to 1 mole, and particularly preferably 1 mole to 5 moles. The electrode protective film forming agent (F) of the present invention contains at least one compound (A) selected from the group consisting of the above (A1), (A2), (A3), (B1) and (B2). Or compound (B). The electrolytic solution of the present invention contains an electrolyte (G), a nonaqueous solvent (H), and an electrode protective film forming agent (F) as essential components. When the electrode protective film forming agent (F) is contained in the electrode or the electrolytic solution, f is applied to the electrode, and the electrode is poured onto the surface of the active material to form a film to form a protective film. In the case where the electrode protective film forming agent (F) is contained in the electrode or electrolyte of the chain secondary battery or the clock ion capacitor, it is formed on the first charge. 201203678 J / / /-TJ^ill is the Chinese manual No. 100109542 Correction date of the slash correction: The protective film of the electrode film of the electrode protective film forming agent (F) formed on the surface of the electrode (the surface of the active material) can be used as the chain secondary The electrode of a battery or chain ion capacitor. As the electrolyte (G), an electrolyte used in a usual electrolyte solution can be used, and examples thereof include lithium salts of inorganic acids such as LiPF6, LiBF4, LiSbF6, LiAsF6, and LiC104; LiN(CF3S02)2, LiN(C2F5S02)2, and LiC(〇) F3S02) 3 lithium salts of organic acids. Among these electrolytes, LiPF6 is preferred from the viewpoint of battery output and charge/discharge cycle characteristics. As the nonaqueous solvent (H), a solvent used in a usual electrolytic solution can be used, and for example, a lactone compound, a cyclic or chain carbonate, a chain carboxylate, a cyclic or chain ether, and a phosphoric acid can be used. An ester, a nitrile compound, an amide compound, a sulfone, a sulfolane, and the like, and a mixture of these compounds. Examples of the internal compound include a 5-membered ring (γ-butyrolactone, γ-valerolactone, etc.) and a 6-membered ring-based compound (δ-valerolactone, etc.) )Wait. Examples of the cyclic carbonate include propylene carbonate, ethylene carbonate, and butylene carbonate. Examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, and methyl-n-propyl carbonate. ), ethyl-n-propyl carbonate and di-n-propyl carbonate (di-n-propyl 20 201203678 j / / /H-piii is No. 100109542 Chinese manual without scribe correction This revision date: June 2015, 15 carbonate), etc. ° Chain-like buffer acid esters can be exemplified by methyl acetate, ethyl acetate, propyl acetate and cesium propionate. Si (methyl propionate) and the like. Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, and 1,4-dioxane. ❹ Chain-like scales include dimethoxy methane and 1,2-dimethoxyethane. Examples of the phosphoric acid S include: trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, and tris(trifluorophosphate). Tri(trifhioromertiyl)phosphate, tris(trichlorodecyl) phosphate, bis(trifluoroethyl) citrate, tris(tri-perfluoroethyl) vinegar, 2-ethoxy _ 1,3,2_ Dioxopenta-2-(2)-(2,ethoxy-l,3,2-dioxaphospholan-2-〇ne), 2-trifluoroethoxy-)-1,3,2-dioxo Phosphocyclopentan-2-one, 2-decyloxyethoxy, dioxopylan-2-one, and the like. Examples of the nitrile compound include acetonitrile and the like. The guanamine compound may, for example, be dimethylformamide or the like. The nonaqueous solvent (H) may be used singly or in combination of two or more. In the nonaqueous solvent (H), from the viewpoint of battery output and charge/discharge cycle characteristics, a lactone compound, a chain carbonate, and a phosphate ester are preferable, and a lactone compound and a chain carbonate are particularly preferable. For lactone compounds, the best 21 201203678 • Jill T^fll. ± No. 100109542 Chinese manual without slash correction This revision date 九 (Nine) is a 5-member ring or 6-membered ring lactone compound, especially good for A 5-membered ring of intrinsic compounds. Since the lactone compound has a narrow potential window as compared with the carbonate compound, it cannot be used as a nonaqueous solvent in the use of the first shovel battery. However, since the electrolyte solution of the present invention has a film formed of the electrode protective film forming agent (F), the lactone compound can also be used as a nonaqueous solvent, and is excellent in heat-resistant storage stability as compared with the carbonate compound. The storage characteristics are high. The electrolyte of the present invention preferably further contains a Lewis base (c). The compound (A) having an oxidized group (a) has high reactivity, and is easily reacted with an acidic compound such as HF which is produced by a reaction between a water which is mixed in a small amount in a solution and an electrolyte salt such as LiPF0. The stability of the compound (A) in the electrolyte can be increased by adding a Lewis test (C) to the electrolyte. Further, in the case where the Lewis base (c) is an azacr〇wnether derivative (ci) to be described later, the azacrown ether derivative (C1) forms a negative electrode protective film, so that charge and discharge cycle characteristics can be obtained. Further improve. The Lewis base (c) may, for example, be an azacrown ether derivative (C1) or a triazole derivative (C2). Among these compounds, an azacrown ether derivative (ei) is preferred from the viewpoint of cycle characteristics. The gas hybrid crown derivative (C1) has a crown ether skeleton of a 9-membered ring to a 24-membered ring containing 1 to 4 nitrogen atoms, preferably one or more bonds of nitrogen atoms of the skeleton are polymerizable. A compound of a substituent of an unsaturated double bond. Crown check skeleton with 9 to 4 H atoms with 1 to 4 H atoms. List: aza-9-crown-3-ether (4-aza-9-crown_3_ether and 4,7 _二氮杂_9_ 22 201203678^ For the first-face number Chinese manual, no slash correction, this revision period: 1 June, 15th, the crown -3- mystery, etc.), gas heteronitro nitrogen (4 aza 4 Crown pin and postal ether and 4,1 〇 _ diazepine ji, aroma ~ 14-crown _ 4-ether (4_aza-14-crown-4-i5-crown collar, 4 f 4, etc.) , aza _15_ crown pin (4-azaindole and 4,1 〇,16-triaza:guangguan·5_ether, 4,14-diaza·15-crown·5 hetero-18- Crown·6,4ι~〇冠:5-key, etc.), aza-qualified crown·6_scale (4-nitrogen lip--6·_), aza, 18_crown_6·· 4,1G, 16_triazadiazepine=, (4·aza-coronyl ether, 4,1〇_hetero-24-crown|ether (4_aza^2)#21_ crown collar, etc., and nitrogen Ether and 4,1〇,16_: 4,10-dioxa-24-crown each of these crowns ^bone 4 is preferably aza-capsid _4趟: ^ ion coordination point of view, ether And nitrogen violent crown _6, U·14• crown _4 nitrogen aza _15_ crown-5- aza-12-capsaid ether, 4 gas for f 4 4_aza _12_ crown·4_ Ether, 4,10-diether. _15·15·ether and 4,10-diaza _15_ crown _5 The ratio of the number of nitrogen atoms to the clock ion is preferably from the viewpoint that the bond (C1) in the aza skeleton is The substituent having a polymerizable unsaturated double, a (meth) propylene decyloxyalkyl group, and a (methane) propyl ray are preferable. The preferred substituents are also the same. Specific examples of the aza-Kanasaki organism (C1) may be used. List: N_(2_butenoic acid methyl acetonate M-aza-12-crown-4-ether (N_(2_buten〇ic acid methyl) ice aza-12-crown-4-ether), N,N-di- (2-butenoic acid A 23 201203678 ^/// Τ^/1Α Λ, for the Chinese manual No. 100109542, no slash correction. Amendment date: June 15th, 1st, 酉曰), 4,10-one乳杂-12-冠-4-谜, N-(2-丁烤酸曱g) _4_气杂-15· Crown-5-ether, hydrazine, Ν-bis-(2-butenoate) )-4,1〇-diaza-15 crown-5_ether, Ν-(cinnamyl)-4-aza-12-crown-4-ether, anthracene, fluorene-di-(cinnamyl)_4, 1〇_Diaza-12-crown-4·_, Ν-(cinnamyl)-4-aza-15-crown-5-ether, anthracene, fluorene-di-(cinnamyl)-4,1〇 -diazepine_15_crown_5_ether, Ν(4-vinylbenzyl)_4_aza-12-crown-4-ether, anthracene, fluorene-di-(4-ethylene Alkyl)-4,10-diaza-12-crown-4-ether, N-(4-vinylbenzyl)_4_aza-15-crown-5-ether, N,N-:-( 4-vinyl-yl)-4,10-one-rham-15-crown-5-mystery, anthraquinone, anthracene-di-(1·acryloyloxyethyl)-4,1〇-diaza _15_冠_5_ether, Ν_(1_propylene oxyethyl)_4_aza-14-crown-4-anthracene, Ν-(2. pentenoic acid ethyl acetate)-4-aza- 18-crown-6-ether and hydrazine, hydrazine-•one_(2_pentanoic acid vinegar)-4,14-dioxan, 18-crown-6-bond, and the like. The azacrown ether derivative (C1) in the present invention can be produced by a usual method. For example, a method of reacting an unsubstituted azacrown ether with a halogenated alkyl group having a polymerizable unsaturated double bond in the presence of a catalyst or a catalyst in an organic solvent may be mentioned. Examples of the organic solvent include nitrile-based organic solvents (such as acetonitrile, propionitrile, and benzonitrile) and ketone organic solvents (acetone, methyl ethyl ketone, etc.). , an amine-based organic solvent (amine, acetamide, dimethyl decylamine, dimethyl decylamine, etc.), an ether-based organic solvent (dimethyl ether, tetrahydrofuran, and bisphenol, etc.) , ester organic solvents (ethyl acetate and diethyl maleate, etc.), sulfur-containing organic solvents (dimethyl sulfoxide and cyclobutyl hydrazine, etc.), halogenated hydrocarbons (chloroform and two gases) Methane, etc.), hydrocarbons (hexane, heptane * methyl and mono-toluene, etc.) and mixtures of two or more of these solvents. 24 201203678 J / / /^tpixi For the Chinese manual No. 100109542, there is no slash correction. This revision period: June 15th, 100th, the catalyst can be enumerated: metal argon oxide (such as oxidized clock, gas oxidized sodium and hydrogen) Oxidation and unloading, etc., metal carbonates (sodium carbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, etc.) and metal hydrides (sodium hydride, hydrogenation, etc.). The reaction temperature is usually from 10 ° C to 150 ° C, and the reaction time is usually from 5 hours to 24 hours. After the completion of the reaction, the catalyst may be neutralized as needed, and treated with an adsorbent to remove the catalyst and purify it. Examples of the toothed alkyl group having a polymerizable unsaturated double bond include 4-bromo-2-butenoic acid methyl ester and 4- 'chloro-2-butene. Methyl ester, 1-bromo-4-cyano-2-butene, 1-piperidin-2-butene, chloromethyl acrylate , methyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, methyl methacrylate, methacrylic acid > skunk vinegar, methyl acrylate acid 2-Bromoethyl methacrylate, cinnamyl chloride, cinnamyl bromide, 4-(chlorometliyl)styrene, and 4-(bromoindolyl)styrene. The triterpene derivative (C2) may, for example, be ι, 2, 3 benzotriazole ◎ (l, 2, 3-benzotriazole), 5-mercapto-1, 2,3-benzoquinone, 5, 6_ Dimethyl_1,2,3-benzinium dioxime, 1,2,4-disaphthyl, 3-amino-1,2,4-tri-11, 3,5-diamino-1,2 , 4-diindole, 3-amino-5-methyl-1,2,4-tris-π, 3-amino-5-ethyl-1,2,4-triazole, 3-amino- In the viewpoint of charge-discharge cycle characteristics, 5-propyl-1, 2,4-tris- and 3-face s-butyl derivatives are preferably 3-amino-1, 2, 4·3. laugh. The electric rider of the present invention may further contain a ruthenium compound (4) a listener compound (8) 25 201203678 J / / / πριιι is the 100th 109542 Chinese manual without a slash correction. This correction date: the formation of a negative electrode protective film other than the June 15th, 100th. Agent (D). By the electrolyte solution containing the negative electrode film forming agent (9), the stability of the negative electrode protective film is further improved to further improve the discharge cycle characteristics. The negative electrode protective film forming agent (D) may, for example, be vmyiene carbonate. Ethylene carbonate, ethylene carbonate, ethylene sulfite, acetonitrile, etc. Among these compounds, vinylene carbonate is used in terms of cycle characteristics. The preferred content or concentration of the electrode protective film forming agent (7), the negative electrode protective film forming agent (D), the nonaqueous solvent (h) and the mass (G) in the electrolytic solution of the invention of the present invention is as follows. The weight of the electrolyte as the compound of the electrode retention agent (F) in terms of charge and discharge cycle characteristics, battery capacity, and high storage characteristics is preferably 〇.〇1 by weight (wt== Wt%, It is especially preferred to be 0.05 wt% to 1 wt%. 10 ▲=Battery capacity#, battery output and the content of the compound (B) of the second electric forming agent (F) I. The battery capacity, the battery (4) and the electricity The cycle characteristic says that the content of Louise (C) is based on electrolysis.重量 weight" ^10 wt〇 / 〇, 〇. 〇 1 wt0 / _ 10 wt 〇 / 〇, 〇 on the battery capacity 4, battery output and power cycle characteristics of the view 26 201203678 for the third 聪聪聪 42 Chinese noodles No correction of the correction date. On June 15th, S, the negative electrode film is opened, and the content of the agent (D) is preferably 0 wt% to 5 wt%, more preferably 〇, based on the weight of the electrolyte. 〇1 wt% 〜5 wt%, especially 0.01 wt% 〜3 wt%. From the viewpoint of battery output and charge and discharge cycle characteristics, the nonaqueous solvent (H) is directly based on the weight of the electrolyte, preferably wt. %〜%奶%, particularly preferably 93 wt% to 99 wt%. From the viewpoint of battery output and charge and discharge cycle characteristics, the concentration of the electrolyte (G) in the electrolyte is preferably based on the volume of the electrolyte. 0.01 m〇l/L 〜3 mol/L, particularly preferably 0.05 m〇i/L 〜1.5 mol/L. The electrolyte of the present invention may further contain an additive such as an excessive charge preventing agent, a dehydrating agent, and a capacity stabilizer. Examples of the charge preventing agent include biphenyl, alkyl biphenyl, terphenyl, a partial hydride of terphenyl, and cyclohexyl ben. Zene), an aromatic compound such as t-butylbenzene or tert-amylbenzene, etc. The amount of the overcharge preventing agent used is usually 〇wt% to 5 wt%, preferably 〇wt%, based on the total weight of the electrolyte. 〜3 wt% The dehydrating agent may, for example, be zeolite, silica gel or calcium oxide. The dehydrating agent is usually used in an amount of from 0 wt% to 5 wt%, preferably from 0 wt% to 3 wt%, based on the total mass of the electrolyte for lithium secondary batteries. Examples of the capacity stabilizer include fluoroethylene carbonate, succinic anhydride, 1-methyl-2-piperidone, heptane, and fluorobenzene. The capacity stabilizer is usually used in an amount of from 〇wt% to 5 wt%, preferably from 〇 wt% to 3 wt%, based on the total weight of the electrolyte. 27 201203678 Revision date: June 15, 100 Ϊ No. 1^109542 Chinese manual without scribe correction The electrolyte of the present invention is particularly useful as an electrolyte for a clock secondary battery. A clock secondary battery using the electrolytic solution of the present invention is obtained by injecting an electrolytic solution of the present invention into a battery can containing a positive electrode, a negative electrode, and a separator to seal the battery can. In the positive electrode of the lithium secondary battery, a positive electrode active material, a conductive agent, and a binder are dispersed in a solvent, and the slurry is applied to the positive electrode current collector by using a coating device such as a bar coater. The positive electrode obtained by drying and removing the solvent, if necessary, is pressed by a press. Examples of the positive electrode active material include composite oxides of lithium and transition metals (for example, LiCoO 2 , LiNi 2 , LiMn 2 , and LiMn 2 〇 4 ), transition metal oxides (for example, Mn 〇 2 and V 2 〇 5, etc.), and transition metal sulfides (for example). M〇s2 and TiS2, etc., and conductive polymers (for example, polyaniline, p〇iyvinyiidene fluoride, polypyrrole, polypyrrole, poly Polyacetylene, polyp-phenylene (p〇iy_p_phenylene), polycarbazole, etc. Examples of the conductive agent include graphite (for example, natural graphite and artificial graphite) and carbon black (for example, carbon black, acetylene black, Ketjen black, channel black, Furnace black, iamp black, thermal black, etc., metal powders (such as aluminum powder and nickel powder), conductive metal oxides (such as zinc oxide and titanium oxide), etc. . Examples of the binder include starch, polyvinylidene fluoride, and polyvinyl alcohol. 28 201203678 ^/// ~ryj*.x 1 is the 100th 109542 Chinese manual without a slash correction. Amendment date: June 15, 100 ( Polymeric compounds such as polyvinyl alcohol, carboxymethyl cellulose, polyethylene pyridine (p0iyvinyl pyrrolidone), tetrafluoroethylene, polyethylene and polypropylene. Examples of the solvent include 1-methyl-2-pyrrolidone, methyl ethyl ketone, dimethyl decylamine, dimethyl acetamide, N,N-dimethylaminopropylamine, and four. Hydrogen bites and so on.

正極用集電體可列舉：|呂、鈦、不鏽鋼、鎳、碳極（baked carbon)、導電性高分子及導電性玻璃等。鋰二次電池中，基於正極總重量的正極活性物質、導電劑及黏合劑的各較佳含量為如下所述。正極活性物質的含量較佳為7〇wt%〜98 wt%，尤佳為 90 wt%〜98 wt%。導電劑的含量較佳為丨wt%〜29 «，尤佳為1 wt%〜10 wt%。黏合劑的含量較佳為i wt%〜29 wt% ’ 尤佳為 1 wt%〜l〇wt%。、基於正極活性物質、導電劑及黏合劑的總重量，正極活f生物質、導電劑及黏合劑的漿料化時的溶劑使用量較佳為 20 wt%〜70 wt%，尤佳為 3〇 wt%〜6〇 wt%。鐘二次電池中的負極可使用以棒式塗佈機等塗佈裳 =，將使負極活性物質、導制及黏合劑分散於溶劑中而漿枓化者塗佈於貞细#電體上，加以乾燥而去除溶劑，視需要以壓製機進行壓製而成的負極等。 =活性物質可列舉：石墨、高分子化合物锻燒體（例如將_脂及料_旨#域碳細成的輯體）、焦炭類 29 201203678 J / / / -rpii a 爲第l〇_9542號中文說明書無劃線修正本修正日期:雨年6月15曰 (例如瀝青焦炭（pitch coke)、針狀焦炭（needlec〇ke)及石油焦炭等）、碳纖維、導電性高分子（例如聚乙炔及聚吡咯等）、金屬合金（例如鋰·鋁合金、鋰_鋁_錳合金等）等。導電劑、黏合劑及溶劑可使用與製造正極時所使用的材料相同的材料。負極用集電體可列舉：銅、不鐵鋼、錦、紹、鈦、碳極、導電性高分子、導電性玻璃及鋁_鎘合金等。鋰二次電池中，基於負極總重量的負極活性物質、導電劑及黏合劑的各較佳含量為如下所述。負極活性物質的含量較佳為7〇 wt%〜98 wt%，尤佳為 90 wt%〜98 Wt%。導電劑及黏合劑的含量與正極的情況相同。負極活性物質、導電劑及黏合劑的漿料化時的溶劑使用量與正極活性物質、導電劑及黏合綱漿料化時的使用量相同。鋰二次電池中的分隔片可列舉：聚乙烯、聚丙烯製膜的微多孔膜；纽性聚乙龍與聚_的多層膜；包含聚醋纖維、芳族雜胺纖維（araini(ifiber)、玻璃纖維等的不織布，以及於其等的表面附著有二氧化⑦、氧化銘匕鈦等陶究微粒子的分隔片。鋰一次電池中的電池罐可使用不鏽鋼丨as =吏【：二及錄的鋼等金屬材料，亦可根據電池用 Ϊ、= 任Γ罐可根據用途而形成圓筒 Φ ^乃孓其他任意的形狀。 30 201203678 t I · A X 修正日期:1〇〇年6月15日爲第100109542號中文說明書無劃線修正本有用本發明的電解液尤其作為姆子電容㈣的電解液亦使用本發明的電解液的鐘離子電容器是藉由在收納有正極、負極及分隔片的電容器罐内注入本發明的電解液，將電容器罐密封而獲得。鋰離子電容器中的正極可使用以棒式塗佈機等塗佈裝置，將使活性碳（正極活性物質）、導電劑及黏合劑分散於溶劑中而襞料化者塗佈於正極用集電體上，加以乾燥而去除溶劑，視需要利用壓製機進行壓製而成的正極等。導電劑、黏合劑、溶劑及正極用集電體可列舉與鐘二次電池的情況相同者。 ^ 鐘離子電谷器中，基於正極總重量的正極活性物質' ‘電劑及黏合劑的各較佳含量為如下所述。正極活性物質的含量較佳為70 wt%〜98 wt%，尤佳為 90wt%〜98wt%。導電劑的含量較佳為lwt%〜29wt%: 尤佳為1 wt%〜1〇 wt%。黏合劑的含量較佳為i加％〜29 O wt〇//° ’ 尤佳為 1 wt%〜1〇 wt〇/〇。基於正極活性物質、導電劑及黏合劑的總重量，正極活性物質、導電劑及黏合劑的漿料化時的溶劑使用量較佳為 20 wt%〜70 wt%，尤佳為 30 wt%〜60 Wt%。鋰離子電容器中的負極可使用以棒式塗佈機等塗佈裝置將使負極活性物質、導電劑及黏合劑分散於溶劑中而聚料化者塗佈於負極用集電體上，加以乾燥而去除溶劑，視需要利用壓製機進行壓製而成的負極等。 31 201203678 ^/// ΤρίΑ λ 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15曰負極活性物質可列舉：非晶碳（amorphous carbon)、石墨（graphite)、錫及其合金、矽及其合金等。導電劑、黏合劑及溶劑可使用與製造正極時所使用的材料相同的材料。負極用集電體可列舉：銅、不鏽鋼、鎳、鋁、鈦、碳極、導電性高分子、導電性玻璃及鋁_鎘合金等。鐘離子電容器中’基於負極總重量的負極活性物質、導電劑及黏合劑的各較佳含量為如下所述。負極活性物質的含量較佳為70 wt%〜98 wt%，尤佳為 90 Wt%〜98 wt%。導電劑及黏合劑的含量與正極的情況相同。負極活性物質、用量與正極活性物質使用量相同。導電劑及黏合劑的漿料化時的溶劑使、導電劑及黏合劑的漿料化時的溶劑鐘離子電容器中的分隔片可列舉：聚乙稀、聚丙稀 =微多孔膜；多孔性聚乙烯膜與聚丙烯的多層膜；包含聚S曰纖維、芳族聚酿胺纖維、玻璃纖維等的不織布；以及 ^其等的表面附著有二氧化妙、氧化紹、氧化鈦等陶竟微鋰離子電容器中的電池罐可使用不鏽鋼，鍍 J鎳=等金屬？料，亦可根據電池用途而使用塑膠木 ’、。另外，電池罐可根據用途而形成圓筒型、型、其他任意的形狀。更％型、2 本發明的電極保護膜形成劑CF)可添加、含有於鐘 32 201203678 -^/// 爲第⑽聰42號攸^ 修正曰期:1〇〇年6月15日二次子電容器的正極及/或負㈣添加於正極中的方法可列舉如性物質、導電劑及_合劑分散於溶劑中機進行壓製。餘而去除洛劑，視需要利用壓製 ο 性物Ϊ加= = = =，如下方法等：於使負極活等罨齊]及黏合劑分散於溶劑中負劑二：==:裝：機進行壓製。齊視需要利用壓製就充放電循環特性、電池容量為 0.5 wt%〜5 wt%。 /° 1〇 wt%，尤佳〇言藏特性的觀- 加量基於負梅的添為 0_5 wt%〜5 Wt%。 wt/i> ’ 尤佳 [實例] 以下，利用實例對本發明進一步進行並不限定於該些實例。以下，份表示重量^ 本發明 [路易斯驗（C)的合成] 习〈製造例1〉 33 201203678 J / / / 1 爲第100109542號中文說明書無劃線修正本修正曰期:1〇〇年6月15日 Ν,Ν-二-(2- 丁稀酸曱酯）_4，10_ 二氮雜-15-冠-5- _ (ΑΖ-1)的合成：於安裝有攪拌機、溫度計及冷卻管的燒瓶中，加入 4，10-二氮雜-15-冠-5-醚[東京化成工業（股）製造]〇61份 (2.8 mmol份）、4-溴-2-丁烯酸曱酯[東京化成工業（股）製造]1份（5.6 mmol份）及乙腈1〇份，一邊攪拌一邊使其均勻溶解，然後於攪拌下在室溫下反應24小時。於減塵 (10 mmHg)下去除乙腈後，利用以丙酮為溶劑的氧化鋁管柱[15〇 mesh，Brockman 1 ’ 標準級，Aldrich (股）製造] 將反應物純化，獲得N，N-二-(2-丁烯酸曱酯)_4，1〇_二氮雜 -15-冠-5-醚（AZ-1) 0.85 份（2.0 mmol 份）（產率 71%)。 (AZ-1)是通式（2)中，R2為亞甲基，Qi及q2為氫原子’ Q3為甲氧基羰基且具有聚合性不飽和雙鍵的取代基鍵結於氮原子上的二氮雜冠醚化合物。〈製造例2〉 Ν，Ν·二-(1-丙烯醯氧基乙基)_4，1〇_二氮雜·15_冠_5_醚 (ΑΖ-2)的合成：除了代替4-溴-2-丁烯酸甲酯1份而使用丙烯酸-2-氯乙酯[東京化成工業（股）製造]〇.76份（5 6 mm〇1份）以外，以與製造例1相同的方式獲得丙烯醯氧基乙基)_4，1〇-—氮雜-15,冠-5-醚（AZ-2) 0.60 份（1.9 mu10! 份）（產率68%)。此外，當將4-溴-2-丁烯酸曱酯丨份變更為丙烯酸-2-氣乙酯0.76份時，以反應成分的莫耳比及非反應成分（溶 34 201203678 爲第ώ〇109542號中文說明書無劃線修正本修正曰期:1〇〇年6月15曰劑等）的重量比成為與製造例1的情況同等的方式調整各原料的量而進行操作。對以下的製造例3亦同樣進行。 (AZ-2)是丙稀醯氧基乙基作為具有聚合性不飽和雙鍵的取代基而鍵結於氮原子上的二氮雜冠醚化合物。〈製造例3〉 N，N-二肉桂基-4，10_二氮雜-15•冠-5-醚（AZ-3 )的合成：除了代替4-溴-2-丁烯酸曱酯1份而使用肉桂基氯[東京化成工業（股）製造]0.85份（5.6 mmol份）以外，以與〇製造例1相同的方式獲得N，N-二肉桂基-4,10-二氮雜_15_ 冠-5-越（(：1-3)0.92份（2.〇111111〇1份）（產率73%)。（八7-3) 是通式（2)中，R2為亞曱基，Q1及Q2為氫原子，q3為苯基且具有聚合性不飽和雙鍵的取代基鍵結於氮原子上的二氮雜冠醚化合物。〈實例1〉二乙二醇二丁烯酸甲酯）醚（B-1)的合成：於安裝有攪拌機、溫度計及冷卻管的燒瓶中，加入二〇乙二醇[東京化成工業（股）製造]7.26份（68.4 mmol份）、 4-溴-2-丁烯酸甲酯[東京化成工業（股）製造]26·9份（150.3 mmol份）、氫氧化鈉6.00份（150 mmol份）及曱苯1〇〇份，一邊攪拌一邊使其均勻溶解後，於室溫下攪拌15分鐘，然後添加四丁基溪化錢1.32份（4.1 mmol份）。升溫至65°C後’攪拌4小時，進行_化反應。放置冷卻後，添加水200份，分離水層。進而將有機層以水2〇〇份加以清洗。藉由減壓〇0 mmHg)而去除甲苯後，利用以己烷為 35 2012036J8 爲第100109542號中文說明書無劃線修正本修正日期··丨〇〇年6月】$日溶劑的氧化鋁管柱[150 mesh，Brockman 1，標準級，Aldrich (股）製造]將反應物純化，獲得二乙二醇二(2-丁烯酸曱醋)醚（B-1) 15.5 份（51.3 mmol 份）（產率 75%)。〈實例2〉二乙二醇二(4-乙烯基苄基)醚（B_2)的合成：除了代替4-溴-2-丁烯酸曱酯26.9份（150.3 mmol份）而使用4-乙烯基苄基氣[東京化成工業（股）製造]22 9份 (150.3 mmol份）以外，以與實例1相同的方式獲得二乙二醇二(4-乙烯基苄基)_^_2)16.9份（49.91!1111〇1份）（產率 73%)。〈實例3〉 1，4-雙(1·丙烯氧基曱基)環己烷（a-ι)的合成：於安裝有攪拌機、溫度計及冷卻管的燒瓶中，加入1，4-環己燒二甲醇[東京化成工業（股）製造]9.86份（68 .4 mmol 份）、氯丙烯[東京化成工業（股）製造]11_51份（150.3 mmol 份）、氫氧化鈉6.00份（150 mmol份）及曱苯100份，一邊擾拌一邊使其均勻溶解後，於室溫下攪拌15分鐘，然後添加四丁基溴化錢1.32份（4.1 mmol份）。以2小時升溫至65°C ’進而攪拌4小時，進行醚化反應及重排反應。放置冷卻後’添加水200份，分離水層。進而將有機層以水 200份加以清洗。藉由減壓（10 mmHg)而去除曱苯後，利用以己燒為溶劑的氧化鋁管柱[150 mesh，Brockman 1，標準級’ Aldrich (股）製造]將反應物純化，獲得1,4-雙(1-丙烯氧基甲基)環己烷（A-1) 10.9份（48.6 mmol份）（產 36 201203678 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15曰率 71%)。此外，表1〜表3中記載的化合物（A)中的1,4-雙（乙烯氧基曱基)環己烷、1,4-丁二醇二乙烯醚及三乙二醇二乙浠醚是使用市售品[Nippon Carbide Industries (股）製造]。 [電解液的製備] 〈實例4〜實例35〉以表1〜表3所示的重量比例來調配化合物（A)、化 ^ 合物（B)、路易斯鹼（C)、負極保護膜形成劑（D)及非 Ο 水溶劑（H)，於其中以成為1 mol/L的濃度的方式溶解 LiPF6來調製實例4〜實例35的電解液。〈比較例1〉於碳酸乙二酯與碳酸二乙酯的混合溶劑（體積比率 3 : 7)中，使LiPF6以1 mol/L的比例溶解後，以2 wt%的比例混合碳酸亞乙烯酯，來調製比較例1的電解液。〈比較例2〉於碳酸乙二酯與碳酸二曱酯的混合溶劑（體積比率〇 1 : 2)中，使LiPF6以1 mol/L的比例溶解後，以成為0.1 mol/L的方式混合二曱基砜，來調製比較例2的電解液。〈比較例3〉於碳酸乙二酯與碳酸二曱酯的混合溶劑（體積比率 1 : 1 )中，使LiPF6以1 mol/L的比例溶解後，以5 wt%的比例混合1,3-丙烷磺内酯，來調製比較例3的電解液。 37 201203678 SSI 叨 9 肚 001:踩mHr 暴柃31揚11摧_郜舔扒*-黯356002^® li-aK£ 【14】實例13 S 〇 1 1 1 S c> 1 CS d 1 1 1 1 1 1 1 1 <N 1 1 實例12 S 〇 1 1 1 S 〇 1 CN d I 1 1 1 1 1 1 1 CN 1 實例11 1 1 1 S 〇 1 CN d 1 1 1 1 1 1 1 1 CN 1 實例10 S 〇 1 1 1 S 〇 1 fS o 1 1 1 1 1 1 i 1 (N 1 實例9 S 〇 1 1 1 S 〇 1 1 1 1 1 1 1 1 1 ΓΝΪ 1 實例8] 1 1 1 1 S 〇 1 (N d 1 1 1 1 1 1 1 1 (Ν 1 實例7! 1 1 1 S 〇 S 〇 1 CN o 1 1 1 t t 1 1 1 CN 1 實例6 1 1 S 〇 1 S 〇 I cs o 1 1 1 1 1 1 1 1 <Ν 1 實例5 1 S 〇 1 1 S 〇 1 CN o 1 1 1 1 1 1 1 1 cs 1 實例4 〇 1 1 1 S 〇 1 CN o 1 1 1 1 1 1 1 1 (Ν 1 化合物名 1，4-雙(1-丙烯氧基曱基)環己: 炫丨 1，4-雙(1-乙烯氧基曱基)環己！燒 1，4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)醚 (AZ-1) (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1,2,4-*** 1 1 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1，2,4-*** 1 3-胺基-5-丁基-1，2,4-*** 碳酸亞乙烯酯 γ-丁内酯 γ-戊内酯成分 1 化合物（A) (份） 1 ίί 路易斯鹼（c) (份）負極保護膜形成劑（D) (份）非水溶劑 (份） 201203678Examples of the current collector for the positive electrode include: Lu, titanium, stainless steel, nickel, baked carbon, conductive polymer, and conductive glass. In the lithium secondary battery, preferred contents of the positive electrode active material, the conductive agent and the binder based on the total weight of the positive electrode are as follows. The content of the positive electrode active material is preferably from 7 Å by weight to 98% by weight, particularly preferably from 90% by weight to 98% by weight. The content of the conductive agent is preferably 丨wt% to 29 «, and particularly preferably 1 wt% to 10 wt%. The content of the binder is preferably from i wt% to 29 wt% ', particularly preferably from 1 wt% to 1 wt%. The solvent used in the slurrying of the positive electrode active material, the conductive agent, and the binder is preferably 20 wt% to 70 wt%, and more preferably 3, based on the total weight of the positive electrode active material, the conductive agent, and the binder. 〇wt%~6〇wt%. The negative electrode in the secondary battery can be coated with a bar coater or the like, and the negative electrode active material, the conductive material and the binder are dispersed in a solvent, and the pulp is applied to the fine electrode. The anode is dried by drying to remove the solvent, and if necessary, pressed by a press. = active material: graphite, polymer compound calcined body (for example, a mixture of _ _ _ _ _ _ _ _ domain carbon fine), coke 29 201203678 J / / / - rpii a is the first 〇 _9542 No. Chinese manual, no correction of this revision date: June 15th of the rainy season (such as pitch coke, needlec〇ke and petroleum coke, etc.), carbon fiber, conductive polymer (such as polyacetylene) And polypyrrole, etc., metal alloys (for example, lithium aluminum alloy, lithium aluminum alloy, etc.). As the conductive agent, the binder, and the solvent, the same materials as those used in the production of the positive electrode can be used. Examples of the current collector for the negative electrode include copper, non-ferrous steel, brocade, titanium, carbon, conductive polymer, conductive glass, and aluminum-cadmium alloy. In the lithium secondary battery, preferred contents of the negative electrode active material, the conductive agent and the binder based on the total weight of the negative electrode are as follows. The content of the negative electrode active material is preferably from 7 〇 wt% to 98 wt%, particularly preferably from 90 wt% to 98 Wt%. The content of the conductive agent and the binder is the same as that of the positive electrode. The amount of the solvent used in the slurrying of the negative electrode active material, the conductive agent, and the binder is the same as that used when the positive electrode active material, the conductive agent, and the binder are slurried. The separator in the lithium secondary battery may, for example, be a microporous film made of a film made of polyethylene or polypropylene; a multilayer film of a neopolyethylene and a poly-poly film; and a polyester fiber and an aromatic amide fiber (araini (ifiber)). Non-woven fabrics such as glass fibers, and separators on the surface of the glass, such as titanium oxide and oxidized quartz, etc. The battery cans in lithium primary batteries can be used with stainless steel 丨 as = 吏 [: two and recorded Metal materials such as steel can also be used according to the battery. = Γ Γ can form a cylinder Φ ^ 孓孓 any other shape according to the application. 30 201203678 t I · AX Revision date: June 15th, 1st The Chinese version of the present invention is not slashed. The electrolytic solution of the present invention is particularly useful as an electrolyte for the ram capacitor (4). The cation capacitor of the electrolyte of the present invention is also used by accommodating the positive electrode, the negative electrode and the separator. The electrolytic solution of the present invention is injected into a capacitor can, and the capacitor can is sealed. The positive electrode in the lithium ion capacitor can be used as a coating device such as a bar coater to activate activated carbon (positive active material). The conductive agent and the binder are dispersed in a solvent, and the binder is applied to a current collector for a positive electrode, dried to remove a solvent, and a positive electrode obtained by pressing with a press as necessary. Conductive agent, adhesive The solvent and the current collector for the positive electrode are the same as those in the case of the clock secondary battery. ^ In the ion battery, the positive electrode active material based on the total weight of the positive electrode, 'the preferred content of the electric agent and the binder is as follows The content of the positive electrode active material is preferably from 70 wt% to 98 wt%, particularly preferably from 90 wt% to 98 wt%, and the content of the conductive agent is preferably from 1 wt% to 29 wt%: more preferably from 1 wt% to 1 wt. The content of the binder is preferably i plus % to 29 O wt 〇 / / ° ' is preferably 1 wt% ~ 1 〇 wt 〇 / 〇. Based on the total weight of the positive active material, the conductive agent and the binder, The solvent used in the slurrying of the positive electrode active material, the conductive agent and the binder is preferably from 20 wt% to 70 wt%, particularly preferably from 30 wt% to 60 wt%. The negative electrode in the lithium ion capacitor can be used as a rod. A coating device such as a coater disperses a negative electrode active material, a conductive agent, and a binder in a solvent. The polymerizer is applied to a current collector for a negative electrode, dried to remove a solvent, and a negative electrode obtained by pressing with a press as needed. 31 201203678 ^/// ΤρίΑ λ is No. 100109542 Amendment of this revision date: June 15th, 100 曰 negative active material can be listed as: amorphous carbon, graphite, tin and its alloys, niobium and its alloys, etc. Conductive agents, adhesives and solvents can be used The same material as used in the manufacture of the positive electrode. Examples of the current collector for the negative electrode include copper, stainless steel, nickel, aluminum, titanium, carbon, conductive polymer, conductive glass, and aluminum-cadmium alloy. In the bell ion capacitor, each of the preferred contents of the negative electrode active material, the conductive agent and the binder based on the total weight of the negative electrode is as follows. The content of the negative electrode active material is preferably from 70 wt% to 98 wt%, particularly preferably from 90 Wt% to 98 wt%. The content of the conductive agent and the binder is the same as that of the positive electrode. The amount of the negative electrode active material used is the same as that of the positive electrode active material. The solvent in the slurry of the conductive agent and the binder, and the separator in the solvent ionization capacitor when the conductive agent and the binder are slurried include polyethylene oxide, polypropylene = microporous membrane, and porous polycondensation. a multilayer film of a vinyl film and a polypropylene; a non-woven fabric comprising a poly-S-fiber, an aramid fiber, a glass fiber, or the like; and a surface of the surface of which is oxidized, oxidized, and titanium oxide The battery can in the ion capacitor can be made of stainless steel, plated with J nickel = metal? Plastic wood can also be used according to the purpose of the battery. Further, the battery can can be formed into a cylindrical shape, a shape, or any other shape depending on the application. More % type, 2 electrode protective film forming agent CF of the present invention can be added and contained in the clock 32 201203678 -^/// is the (10) Cong No. 42 攸 ^ Correction period: 2 years on June 15 The positive electrode and/or the negative (four) of the sub-capacitor may be added to the positive electrode by a method in which a substance, a conductive agent, and a mixture are dispersed in a solvent for pressing. After the removal of the agent, if necessary, use the suppression of the substance Ϊ add = = = =, the following methods, etc.: in order to make the negative electrode live and so on] and the adhesive dispersed in the solvent in the negative two: ==: loading: machine pressing. It is necessary to use the pressing to charge and discharge cycle characteristics, and the battery capacity is 0.5 wt% to 5 wt%. /° 1〇 wt%, especially good Opinions on the characteristics of rumors - the addition based on negative plum is 0_5 wt%~5 Wt%. Wt/i> ' Exceptional [Examples] Hereinafter, the present invention is further limited by the examples and is not limited to the examples. In the following, the weight is expressed by the present invention. [Synthesis of Luis Test (C)] [Manufacturing Example 1] 33 201203678 J / / / 1 For the Chinese manual No. 100109542, there is no slash correction. This revision period: 1 year 6 On the 15th of the month, the synthesis of Ν-bis-(2-butyl decanoate) _4,10_ diaza-15-crown-5- _ (ΑΖ-1): installed with a mixer, thermometer and cooling tube In the flask, 4,10-diaza-15-crown-5-ether [manufactured by Tokyo Chemical Industry Co., Ltd.] 〇61 parts (2.8 mmol parts), 4-bromo-2-butenoate (Tokyo) Chemical Industry Co., Ltd. Manufactured] 1 part (5.6 mmol part) and 1 part of acetonitrile were uniformly dissolved while stirring, and then reacted at room temperature for 24 hours with stirring. After removing acetonitrile under dust reduction (10 mmHg), the reaction was purified by using an alumina column (15 〇 mesh, Brockman 1 'standard grade, manufactured by Aldrich) using acetone as a solvent to obtain N, N-II. -(2-nonyl-2-butenoate)_4,1〇-diaza-15-crown-5-ether (AZ-1) 0.85 parts (2.0 mmol) (yield 71%). (AZ-1) is a compound of the formula (2), wherein R2 is a methylene group, and Qi and q2 are hydrogen atoms, and Q3 is a methoxycarbonyl group and a substituent having a polymerizable unsaturated double bond is bonded to a nitrogen atom. Diazacrown ether compound. <Production Example 2> Synthesis of ruthenium, Ν·di-(1-propenyloxyethyl)_4,1〇-diaza·15_crown-5-ether (ΑΖ-2): In addition to replacing 4-bromo 1 part of methyl 2-butenoate was used in the same manner as in Production Example 1 except that 2-chloroethyl acrylate [manufactured by Tokyo Chemical Industry Co., Ltd.] 76.76 parts (5 6 mm 〇 1 part) was used. There were obtained 0.60 parts (1.9 mu 10 parts) of propylene methoxyethyl)_4,1〇--aza-15, crown-5-ether (AZ-2) (yield 68%). Further, when the oxime portion of 4-bromo-2-butenoate was changed to 0.76 parts of 2-ethyl acrylate, the molar ratio of the reaction component and the non-reactive component (dissolved 34 201203678 was designated as 109542). In the Chinese manual, the weight ratio of the correction period is as follows: the amount of each raw material is adjusted in the same manner as in the case of Production Example 1 and the operation is performed. The same applies to the following Production Example 3. (AZ-2) is a diazacrown ether compound in which acryloxyethyl group is bonded to a nitrogen atom as a substituent having a polymerizable unsaturated double bond. <Production Example 3> Synthesis of N,N-dicinnamoyl-4,10-diaza-15-crown-5-ether (AZ-3): In addition to replacing 4-bromo-2-butenoate 1 N,N-dicinnamyl-4,10-diaza _ was obtained in the same manner as in Production Example 1, except that 0.85 parts (5.6 mmol parts) of cinnamyl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] was used. 15_ Crown-5-over ((:1-3) 0.92 parts (2.〇111111〇1 parts) (yield 73%). (8-7-3) is in the formula (2), R2 is an anthracene group a diazepane ether compound in which Q1 and Q2 are a hydrogen atom, q3 is a phenyl group and a substituent having a polymerizable unsaturated double bond is bonded to a nitrogen atom. <Example 1> Diethylene glycol dibutenoic acid Synthesis of Ester) Ether (B-1): In a flask equipped with a stirrer, a thermometer and a cooling tube, dithiethylene glycol [manufactured by Tokyo Chemical Industry Co., Ltd.] 7.26 parts (68.4 mmol), 4-bromo Methyl 2-butenoate [manufactured by Tokyo Chemical Industry Co., Ltd.] 26·9 parts (150.3 mmol parts), 6.00 parts of sodium hydroxide (150 mmol parts) and 1 part of toluene, and stirred while stirring After homogeneous dissolution, stir at room temperature for 15 minutes, then add 1.32 parts of tetrabutyl citrate (4.1 mmol). After raising the temperature to 65 ° C, the mixture was stirred for 4 hours to carry out a crystallization reaction. After standing to cool, 200 parts of water was added and the aqueous layer was separated. Further, the organic layer was washed with 2 parts of water. After the toluene was removed by decompression 〇 0 mmHg), the alumina column of the solvent was corrected by using the hexane as 35 2012036J8 as the 100109109 Chinese manual without a slash correction date. [150 mesh, Brockman 1, standard grade, manufactured by Aldrich Co., Ltd.] The reaction was purified to obtain 15.5 parts (51.3 mmol) of diethylene glycol bis(2-butenoate) (B-1) ( Yield 75%). <Example 2> Synthesis of diethylene glycol bis(4-vinylbenzyl)ether (B_2): 4-vinyl was used instead of 26.9 parts (150.3 mmol) of 4-bromo-2-butenoic acid ester. In the same manner as in Example 1, except that benzyl gas [manufactured by Tokyo Chemical Industry Co., Ltd.] 22 parts (150.3 mmol parts), 16.9 parts of diethylene glycol bis(4-vinylbenzyl)_^_2) was obtained ( 49.91!1111〇1 serving) (yield 73%). <Example 3> Synthesis of 1,4-bis(1·acryloxyfluorenyl)cyclohexane (a-ι): In a flask equipped with a stirrer, a thermometer, and a cooling tube, 1,4-cyclohexane was added. Dimethanol [manufactured by Tokyo Chemical Industry Co., Ltd.] 9.86 parts (66.4 mmol), chloropropene [manufactured by Tokyo Chemical Industry Co., Ltd.] 11_51 parts (150.3 mmol parts), sodium hydroxide 6.00 parts (150 mmol parts) After 100 parts of toluene was uniformly dissolved by stirring, the mixture was stirred at room temperature for 15 minutes, and then 1.32 parts (4.1 mmol) of tetrabutyl bromide was added. The mixture was heated to 65 ° C for 2 hours and further stirred for 4 hours to carry out an etherification reaction and a rearrangement reaction. After cooling, 200 parts of water was added, and the aqueous layer was separated. Further, the organic layer was washed with 200 parts of water. After the benzene was removed by decompression (10 mmHg), the reaction was purified using an alumina column (150 mesh, Brockman 1, standard grade 'Aldrich (manufactured)). -Bis(1-propenyloxymethyl)cyclohexane (A-1) 10.9 parts (48.6 mmol parts) (Production 36 201203678 is No. 100109542 Chinese manual without scribe correction This revision date: 100 years June 15曰The rate is 71%). Further, in the compound (A) shown in Tables 1 to 3, 1,4-bis(ethyleneoxymercapto)cyclohexane, 1,4-butanediol divinyl ether and triethylene glycol diethylamine The ether is a commercially available product [manufactured by Nippon Carbide Industries Co., Ltd.]. [Preparation of Electrolyte Solution] <Example 4 to Example 35> The compound (A), the compound (B), the Lewis base (C), and the negative electrode protective film forming agent were blended in the weight ratios shown in Tables 1 to 3. (D) and a non-aqueous solvent (H), in which LiPF6 was dissolved at a concentration of 1 mol/L to prepare an electrolytic solution of Examples 4 to 35. <Comparative Example 1> In a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 3: 7), LiPF6 was dissolved at a ratio of 1 mol/L, and then vinylene carbonate was mixed at a ratio of 2 wt%. The electrolytic solution of Comparative Example 1 was prepared. <Comparative Example 2> In a mixed solvent of ethylene carbonate and dinonyl carbonate (volume ratio 〇1:2), LiPF6 was dissolved at a ratio of 1 mol/L, and then mixed in a manner of 0.1 mol/L. The electrolyte of Comparative Example 2 was prepared by mercaptosulfone. <Comparative Example 3> In a mixed solvent of ethylene carbonate and dinonyl carbonate (volume ratio: 1:1), LiPF6 was dissolved at a ratio of 1 mol/L, and then mixed at a ratio of 5 wt%. Propane sultone was used to prepare the electrolytic solution of Comparative Example 3. 37 201203678 SSI 叨9 Belly 001: Stepping on mHr Storm 31 Yang 11 Destruction _郜舔扒*-黯356002^® li-aK£ [14] Example 13 S 〇1 1 1 S c> 1 CS d 1 1 1 1 1 1 1 1 <N 1 1 Example 12 S 〇1 1 1 S 〇1 CN d I 1 1 1 1 1 1 1 CN 1 Example 11 1 1 1 S 〇1 CN d 1 1 1 1 1 1 1 1 CN 1 Example 10 S 〇1 1 1 S 〇1 fS o 1 1 1 1 1 1 i 1 (N 1 Example 9 S 〇1 1 1 S 〇1 1 1 1 1 1 1 1 1 ΓΝΪ 1 Example 8] 1 1 1 1 S 〇1 (N d 1 1 1 1 1 1 1 1 (Ν 1 Example 7! 1 1 1 S 〇S 〇1 CN o 1 1 1 tt 1 1 1 CN 1 Example 6 1 1 S 〇1 S 〇I Cs o 1 1 1 1 1 1 1 1 <Ν 1 Example 5 1 S 〇1 1 S 〇1 CN o 1 1 1 1 1 1 1 1 cs 1 Example 4 〇1 1 1 S 〇1 CN o 1 1 1 1 1 1 1 1 (Ν 1 compound name 1,4-bis(1-propenyloxyfluorenyl)cyclohexyl: fluorene 1,4-bis(1-vinyloxyfluorenyl)cyclohexane! - Butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol bis(2-methylbutenoate) ether diethylene glycol bis(4-vinylbenzyl) ether (AZ-1) (AZ -2) (AZ-3) 3-Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-methyl-1,2 , 4- Triazole 1 1 3-amino-5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 1 3-amino-5-butyl -1,2,4-triazole vinylene carbonate γ-butyrolactone γ-valerolactone component 1 Compound (A) (part) 1 ίί Lewis base (c) (part) Negative electrode protective film forming agent (D) (part) Non-aqueous solvent (parts) 201203678

m J —oso- 00J Uu17a 卜 ε 1 47.73 Τ-Η 1 1 47.73 1 46.78 1 47.75 1 47.93 1 47.78 1 47.73 1 47.73 1 47.73 1 47.73 δ-戊内酯碳酸乙二酯碳酸二乙酯碳酸二曱酯碳酸乙基甲酯 LiPF6 電解質（mol/L) 201203678 S slnc9壯001:踩ΠΙΗΙ· 特31擊擊1*壊||1睜館^旮繫〔芝601001濉載UUKA 卜ε t(N<】 S 〇 1 1 S d cs 〇 I 1 1 1 i-H 1 1 1 CN S d S 〇 CN 〇 1 1 1 i 1 1 S 〇 S 〇〇 1 r*H 1 1 1 1 1 CN 實例！ 21 S d S d 1 1 1 d 1 1 1 1 fN η ^ s ο s ο 1 1 ΐ—( 1 1 1 1 1 實例i 19 S ο s ο 1 (S 〇 1 1 1 1 1 1 ίΝ 實例 18 S d s d CN d 1 i 1 1 1 1 1 CN r S o s o fS d 1 1 1 1 1 1 1 CS 實例 16 s d s o d I 1 1 1 1 1 1 實例 15 S o s d ίΝ Ο 1 1 1 1 1 1 1 <N 駟2 s o s o ίΝ d 1 1 1 1 1 1 1 CN 化合物名 1，4-雙(1-丙烯氧基甲基)環己烷 1，4-雙(1-乙烯氧基甲基)環1 己烧 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯）醚二乙二醇二(4-乙烯基苄基）醚 (ΑΖ-1) (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1,2,4-*** 3-胺基-5-乙基-1，2,4-*** 3-胺基-5-丙基-1，2,4-*** 3-胺基-5-丁基-1，2,4-*** 碳酸亞乙烯酯 % L |ί 化合物（B) (份）路易斯鹼（c) (份）負極保護膜形成劑 (D) (份） 201203678 ο mslnl:9 壯〇〇1:踩031_ q uu寸卜αε 1 1 47,63 1 1 47.63 1 1 »—Η 47,63 1 1 47.83 1 1 i—Η 47.83 1 1 47.73 1 1 97.73 1 1 1 97.73 1 1 » * 〇 1 1 69.73 〇 1 67.73 1 〇 67.73 » 1 r-H γ-丁内酯 γ-戊内酯 δ-戊内S旨碳酸乙二酯碳酸二乙酯碳酸二甲酯碳酸乙基甲酯 LiPF6 m 電解質（mol/L) 201203678 m ^ ^ oo^..sm§ §11—^^ loso- iu-aHae 【ε<〕 S 〇 1 1 1 1 S d CN ο 1 1 1 1 军〇〇 1 1 1 S 〇 1 (Ν ο 1 1 1 S 〇 1 1 1 CS 〇 1 CN Ο 1 1 CS 军 S d 1 1 1 1 1 ίΝ Ο 1 1 CN 军 d._. »-h ^ m s ο 1 1 1 1 g o <Ν Ο I 1 cs ο 1 1 1 S 〇 ^Η I 1 cs s d 1 1 1 S 〇 1 I 1 CN 军 s d 1 1 1 S 〇 1 S ο I 1 CN 军 s o 1 1 1 S 〇 1 CN Ο I 1 (N s o 1 1 1 S 〇 1 CN Ο I 1 1 ίΝ W ViQ s o 1 1 1 S 〇 1 CN Ο I 1 r-H 1 I (Ν 化合物名 1 1，4-雙(1-丙烯氧基甲基)環己烷 M-雙(1-乙烯氧基甲基)環己烷 1,4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯）醚二乙二醇二(4-乙烯基苄基）醚 (ΑΖ-1) (ΑΖ-2) (ΑΖ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1，2,4-*** 3-胺基-5-乙基-1，2,4-二°坐 3-胺基-5-丙基-1，2,4-*** 3-胺基-5-丁基-1,2,4-*** 碳酸亞乙烯酯成分 | 化合物（A) (份） iDS 路易斯鹼（C) (份）宏裔a 郷ί梁一 201203678 冚51叨9 壯 00I:^m3Es u-as 卜 ε 1 1 49.73 1 1 1 1 49.73 1 1 1 47.55 1 1 1 47.75 1 ^Η 1 1 47.73 幽 ^Η 1 1 46.93 1 1 1 47.83 1 1 1 47.88 1 1 1 47.63 1 Τ·Η 1 1 47.63 1 »-Η 1 1 47.63 1 »-Η γ·丁内酯 γ-戍内酯 δ-戊内醋碳酸乙二酯碳酸二乙酯碳酸二甲酯碳酸乙基甲酯 1 LiPF6 蘅 J1L \^/ την 電解質 (mol/L ) ε寸 201203678 〇 / / /^tpm 修正日期:100年6月15日爲第100109542號中文說明書無劃線修正本 [鋰離子電池用正極的製作] 基於表4〜表7所不的配方，利用以下方法製成添加有電極保護膜形成劑（F)的正極。將LiCo〇2粉末90.0份、柯琴黑[Aldrich公司製造]5 伤、聚偏二氟乙烯[Aldrich公司製造]5份、及表4〜表7 所示重量的電極保護膜形成劑（F)於研绰中充分混合後，添加1_甲基-2·姆咬酮[東京化成工業（股）製造]7〇〇份，進而於研料充分混合轉得漿料。將所得的漿料於大氣中使用線棒來塗佈於厚度20μιη的紹電解紅的單面，於 1〇〇'下乾燥15分鐘後，進而於減壓下（1()麵取）在航下乾燥5分鐘，衝壓為15.95麵9，製作實例％〜實例Q 的鋰離子電池用正極。 ' [鐘離子電池用負極的製作] 基於表4〜表7所示的配方，利用以有電極保護卿成冑lUF)的貞極。域添加將平均粒徑約8 u 二氟乙稀7.5份、心2:二的石墨粉末92·5份、聚偏製造]細份及表4〜表^東京化成工業（股）於研蛛中充分混合而電f保護膜形成劑（F) 發後，衝壓為i6.15二H乾無15分鐘而使溶劑蒸製作實例36〜實例壓製機形成厚度30帅，貝67的鋰離子電池用負極。陶子電容器用正極的製作] 基於表7所不的配方，利用以下方法製成添加有電極 44 201203678 */ / / /-rpiil 修正日期:100年6月15日爲第100109542號中文說明書無劃線修正本保遵膜形成劑（F )的正極。m J —oso- 00J Uu17a 卜 ε 1 47.73 Τ-Η 1 1 47.73 1 46.78 1 47.75 1 47.93 1 47.78 1 47.73 1 47.73 1 47.73 1 47.73 δ-valerolactone ethylene carbonate diethyl carbonate dinonyl carbonate Ethyl Carbonate LiPF6 Electrolyte (mol/L) 201203678 S slnc9 Zhuang 001: Hi-Hat · Special 31 Strike 1*壊||1睁馆^旮系[芝 601001濉 UUKA 卜ε t(N<] S 〇1 1 S d cs 〇I 1 1 1 iH 1 1 1 CN S d S 〇CN 〇1 1 1 i 1 1 S 〇S 〇〇1 r*H 1 1 1 1 1 CN Example! 21 S d S d 1 1 1 d 1 1 1 1 fN η ^ s ο s ο 1 1 ΐ—( 1 1 1 1 1 Example i 19 S ο s ο 1 (S 〇1 1 1 1 1 1 ίΝ Example 18 S dsd CN d 1 i 1 1 1 1 1 CN r S oso fS d 1 1 1 1 1 1 1 CS Example 16 sdsod I 1 1 1 1 1 1 Example 15 S osd ίΝ Ο 1 1 1 1 1 1 1 <N 驷2 soso ίΝ d 1 1 1 1 1 1 1 CN Compound name 1,4-bis(1-propenyloxymethyl)cyclohexane 1,4-bis(1-vinyloxymethyl)cyclo 1 hexane 1,4- Butanediol divinyl ether Ethylene glycol divinyl ether diethylene glycol bis(methyl 2-butenoate) ether diethylene glycol bis(4-vinylbenzyl) ether (ΑΖ-1) (AZ-2) (AZ-3) 3-Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-methyl-1,2,4-triazole 3-amine 5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 3-amino-5-butyl-1,2,4-tri Pyrazole vinylene carbonate% L | ί Compound (B) (part) Lewis base (c) (part) Negative electrode protective film forming agent (D) (part) 201203678 ο mslnl: 9 Strong 〇〇 1: Step 031_ q uu inch卜αε 1 1 47,63 1 1 47.63 1 1 »—Η 47,63 1 1 47.83 1 1 i—Η 47.83 1 1 47.73 1 1 97.73 1 1 1 97.73 1 1 » * 〇1 1 69.73 〇1 67.73 1 〇 67.73 » 1 rH γ-butyrolactone γ-valerolactone δ-pentane S-ethylene carbonate diethyl ester diethyl carbonate dimethyl carbonate ethyl methyl carbonate LiPF6 m electrolyte (mol/L) 201203678 m ^ ^ oo ^..sm§ §11—^^ loso- iu-aHae [ε<] S 〇1 1 1 1 S d CN ο 1 1 1 1 Army 1 1 1 S 〇1 (Ν ο 1 1 1 S 〇 1 1 1 CS 1 CN Ο 1 1 CS Army S d 1 1 1 1 1 ίΝ Ο 1 1 CN 军d._. »-h ^ ms ο 1 1 1 1 go <Ν Ο I 1 cs ο 1 1 1 S 〇^Η I 1 cs sd 1 1 1 S 〇1 I 1 CN sd 1 1 1 S 〇1 S ο I 1 CN 军so 1 1 1 S 〇1 CN Ο I 1 (N so 1 1 1 S 〇1 CN Ο I 1 1 ίΝ W ViQ so 1 1 1 S 〇1 CN Ο I 1 rH 1 I (Ν Compound name 1 1,4-bis(1-propenyloxymethyl)cyclohexane M-bis(1-vinyloxy) Methyl)cyclohexane 1,4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol bis(methyl 2-butenoate) ether diethylene glycol bis(4-vinylbenzyl Ether (ΑΖ-1) (ΑΖ-2) (ΑΖ-3) 3-amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino 5-5-methyl-1,2,4-triazole 3-amino-5-ethyl-1,2,4-dipyran-3-amino-5-propyl-1,2,4-tri Oxazol 3-Amino-5-butyl-1,2,4-triazole vinylene carbonate component | Compound (A) (part) iDS Lewis base (C) (part) Hongyi a 郷ί梁一201203678 冚51叨9 Zhuang 00I:^m3Es u-as Bu ε 1 1 49.73 1 1 1 1 49.73 1 1 1 47.55 1 1 1 47.75 1 ^Η 1 1 47.73 幽^Η 1 1 46.93 1 1 1 47.83 1 1 1 47.88 1 1 1 47.63 1 Τ·Η 1 1 47.63 1 »-Η 1 1 47.63 1 »-Η γ·丁Lactone γ-decalactone δ-pentane vinegar ethylene carbonate diethyl carbonate diethyl carbonate dimethyl carbonate ethyl methyl carbonate 1 LiPF6 蘅 J1L \^/ την electrolyte (mol / L) ε inch 201203678 〇 / / / ^tpm Correction date: June 15, 100, No. 100109542 Chinese manual No scribe correction [Production of positive electrode for lithium ion battery] Based on the formulation of Table 4 to Table 7, the following method was used to make the electrode The positive electrode of the protective film forming agent (F). 90.0 parts of LiCo〇2 powder, Ketchen Black [manufactured by Aldrich] 5, polyvinylidene fluoride [manufactured by Aldrich] 5 parts, and electrode protective film forming agent (F) shown in Tables 4 to 7 After thoroughly mixing in a mortar, 7 parts of 1-methyl-2·miketone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and the slurry was thoroughly mixed and transferred to a slurry. The obtained slurry was applied to a single surface of a 20 μm thick Sodium Electrolytic Red in the air using a wire bar, dried at 1 〇〇 ' for 15 minutes, and further dried under reduced pressure (1 () surface). The film was dried for 5 minutes, punched to 15.95 face 9, and the positive electrode for the lithium ion battery of Example % to Example Q was produced. [Preparation of Negative Electrode for Clock Ion Battery] Based on the formulation shown in Tables 4 to 7, the electrode with the electrode protection 胄1UF) was used. The domain is added with an average particle size of about 8 u 1.25 parts of difluoroethylene, 92:5 parts of the core 2:2, and a mixture of the fine parts and the table 4~Table ^Tokyo Chemical Industry Co., Ltd. After fully mixing and electric f protective film forming agent (F), after punching into i6.15 two H dry for 15 minutes and solvent evaporation to make example 36~ example press to form a thickness of 30 handsome, Bay 67 lithium ion battery negative electrode . [Preparation of positive electrode for ceramic capacitor] Based on the formulation of Table 7, the following method was used to add electrode 44 201203678 */ / / /-rpiil Revision date: June 15, 100 is the 100109542 Chinese manual without line Correct the positive electrode of this film-forming agent (F).

〇將活性碳粉末90.0份、柯琴黑[Aldrich公司製造]5 〇伤:聚偏二氟乙烯[Aldrich公司製造]5 〇份及表4〜表7 所不重1的電極保護膜形成劑（1?)於研缽中充分混合後，添加1-曱基-2“比較酮[東京化成工業（股）製造]7〇〇份，進而於研缽中充分混合而獲得漿料。將所得的漿料於大氣中使用線棒來塗佈於厚度2()μιη_電解壯的單面，於 100C下乾燥15分鐘後，進而減壓下（1〇mmHg)在下乾燥5分鐘，衝壓為15 95 mm(p，製作實例砧〜實例η 的兹離子電容器用正極。 [鋰離子電容器用負極的製作] 基於表7㈣的配方，利用以下方法製成添加保護膜形成劑（F)的負極。 ^ 一將平均粒徑約8 μιη〜12 μηι的石墨粉末92 5份、 ^氟乙稀7.5份、I甲基〜比咯侧[東京化成工股 ^造]200份及表4〜表7所示重量的電極保護膜形成劑 ^研銶巾充分齡而獲得。㈣得的祕的銅箱的單面，於峨下乾燥15分鐘而使溶= 二後二衝壓為16.15 mm(p，利用壓製機形成厚度^了 =斤得的電極、及鐘金屬箱以分隔片（聚丙稀製不 =持而設置於·單元，使負極理論容量的約75%的& 以約10小時吸藏於負極中，製作實例68〜離子電容器用負極。貝列71的鋰〈比較例4〉 45 201203678 ο / / /Ηρηι —1_95：_書無劃線修正本修正日期:100年6月15曰除了代替電極保護膜形成劑（F)而添加甲基砜1.5份以外’以與實例36〜實例67相同的方法製成比較例4的鋰離子電池用正極。除了不添加電極保護膜形成劑（F)以外，以與實例 36〜實例67相同的方法製成比較例4的鋰離子電池用負極。〈比較例5 > 除了代替電極保護膜形成劑（F)而添加ι，3-丙烷磺内酯I.5份以外，以與實例36〜實例67相同的方法製成比較例5的鋰離子電池用正極。除了不添加電極保護膜形成劑（F)以外，以與實例 36〜實例67相同的方法製成比較例5的鐘離子電池用負極。〈比較例6〉除了代替電極保護膜形成劑（F)而添加二甲基砜15 份以外’以與實例68〜實例71洲的方法製成比較例6 的鋰離子電容器用正極。除了不添加電極保護膜形成劑（F)以外’以與實例 68〜實例71相同的方法製成比較例6的鐘離子電容器用負〈比較例7〉除了代替電極保護膜形成劑（F)而添加1,3-丙烷磺内醋I.5份以外’以與實例砧〜實例Ή相同的方法製' 較例7的鋰離子電容器用正極。 46 201203678 爲第ΐί〇109542號中文說明書無劃線修正本修正曰期:100年ό月15日除了不添加電極保護膜形成劑（F)以外，以與實例 6 8〜實例71相同的方法製成比較例7的鋰離子電容器用負極090.0 parts of activated carbon powder, Keqin black [manufactured by Aldrich] 5 〇 injury: polyvinylidene fluoride [made by Aldrich] 5 parts and Table 4 to Table 7 are not heavy 1 electrode protective film forming agent (1?) After thoroughly mixing in a mortar, 7 parts of 1-mercapto-2 "Comparative ketone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further mixed in a mortar to obtain a slurry. The slurry was applied to a single surface of a thickness of 2 (1 μm) by electrolysis in a bar, dried at 100 C for 15 minutes, and then dried under reduced pressure (1 〇 mmHg) for 5 minutes, and punched into 15 pieces. 95 mm (p, the positive electrode for the ion capacitor of the example anvil to the example η. [Production of the negative electrode for lithium ion capacitors] Based on the formulation of Table 7 (d), the negative electrode to which the protective film forming agent (F) was added was produced by the following method. A total of 92 parts of graphite powder having an average particle diameter of about 8 μm to 12 μηι, 7.5 parts of fluoroethylene, 1.7 parts of I methyl to pycnole, and 200 parts of Tokyo Chemical Industry Co., Ltd. and Table 4 to Table 7 The weight of the electrode protective film forming agent is obtained at a sufficient age. (4) The single side of the secret copper box is dried under the armpit. After 15 minutes, the solution was dissolved and the second and second stampings were 16.15 mm (p, the thickness of the press was used to form the electrode, and the bell metal box was used to separate the sheets (the polypropylene was not placed in the unit). About 75% of the theoretical capacity of the negative electrode & was absorbed in the negative electrode for about 10 hours to prepare Example 68 to the negative electrode for ion capacitors. Lithium of Behr 71 (Comparative Example 4) 45 201203678 ο / / /Ηρηι —1_95:_ The book has no scribing correction. The date of this correction is: in addition to the addition of 1.5 parts of methyl sulfone instead of the electrode protective film forming agent (F), in the same manner as in Example 36 to Example 67, the preparation of Comparative Example 4 was carried out. A positive electrode for a lithium ion battery of Comparative Example 4 was produced in the same manner as in Example 36 to Example 67 except that the electrode protective film forming agent (F) was not added. <Comparative Example 5 > A positive electrode for a lithium ion battery of Comparative Example 5 was prepared in the same manner as in Example 36 to Example 67 except that the protective film forming agent (F) was added with i.sub.3,3-propane sultone (1.5 parts). Other than film forming agent (F), with examples In the same manner as in Example 67, the negative electrode for a clock ion battery of Comparative Example 5 was produced. <Comparative Example 6> In addition to the addition of dimethyl sulfone 15 parts instead of the electrode protective film forming agent (F), The cathode of the lithium ion capacitor of Comparative Example 6 was prepared by the method of the method of the method of 71. The negative electrode of the comparative example 6 was produced in the same manner as in Example 68 to Example 71 except that the electrode protective film forming agent (F) was not added. <Comparative Example 7> A lithium ion capacitor of Comparative Example 7 was prepared except that 1,3-propane sulphuric acid vinegar was added in place of the electrode protective film forming agent (F), in the same manner as in the example anvil to the example Ή. Use the positive electrode. 46 201203678 For the Chinese manual of ΐί〇109542, there is no slash correction. The revision period: 100 years, 15th of the month, except for the absence of the electrode protective film forming agent (F), the same method as in the case of Example 68 to Example 71 The negative electrode for the lithium ion capacitor of Comparative Example 7

47 201203678 ΕΠςΙΠΙ:9 扯 001:踩mHI犧1} 挎Hr·}繼福.郜盔払旮黯is寸S60I00I搬載呈寸卜卜卜ε 【寸<】實例44 1 1 1 1 1 1 1 1 iri 1 i 1 1 t 實例43 棚C邀 1 1 1 1 1 1 1 f 1 1 I 實例42 郷C邀 1 1 1 1 1 1 1 1 in 1 1 1 實例41 «邀 1 1 1 1 1 1 Η4 « 1 ^Ti 1 1 1 t 實例40 恤C邀 1 ^Ti 1 1 1 1 1 1 1 1 1 1 1 實例39 1 to 1 1 1 1 1 1 *ri 1—^ 1 1 1 1 1 1 實例38 1 1 1 1 1 1 1 in 1 1 1 1 1 1 實例37 « ^ 1 1 1 1 1 1 1 1 1 1 1 1 1 實例36 «邀 1 1 1 1 1 1 1 1 1 1 1 1 化合物名邀 ιί»Β<ΐ fpBT 1，4-雙(1-丙烯氧基甲基）環己烷 Μ-雙(1-乙烯氧基曱基）環己烷 1,4-丁二醇二乙烯醚三乙二醇二乙稀醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)醚 (ΑΖ-1) (AZ-2) 1 (AZ-3) 3-胺基-1,2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1，2,4-*** 'Ί ri n3 ιΛ 绪 rn 3-胺基-5-丙基-1，2,4-*** 3-胺基-5-丁基-1,2,4-*** 成分化合物（A) (份） 1 |5 路易斯鹼 (C) (份） 201203678 〇 ΙΉςΙΠΙ:9 壯 001:踩mHTs 恃 ««黯tN寸 S60I00I 城脈 0¾寸 Εε I實例53 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 實例52 權（璁 1 1 1 1 1 1 唄埤 »Τ) 1 1 1 1 1 1 實例51 1 in r-H 1 1 1 1 1 1 1 1 1 1 1 1 實例50 1 in ί-Η 1 1 1 1 1 1 Θ璁 in 1 1 1 1 1 1 實例49 權c邀 1 in 1 1 1 1 1 Θ坶 1 1 1 1 1 實例48 邀 1 in 1 1 1 1 1 唄埤 in· 1 d 1 i 1 1 實例47 1 1 1 1 1 1 V"i 1 1 1 1 1 實例46 «璁 1 1 1 1 1 1 -— 1 1 1 1 1 實例45 «邀 1 in 1 1 1 1 1 Η4璁 1 1 1 1 1 1 iTi 化合物名缉㈣ 1，4-雙(1-丙烯氧基甲基）環己烷 1，4-雙(1-乙烯氧基甲基）環己烷 1，4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)醚 (AZ-1) (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1,2,4-*** 3-胺基-5-甲基-1,2,4-*** 3-胺基-5-乙基-1，2,4-*** 3-胺基-5-丙基-1，2,4-*** 3-胺基-5-丁基-1，2,4-*** 成分化合物（A) (份） _1 客广N $ W 路易斯鹼 (C) (份） 6寸 201203678 mslm:9 壯 001:踩ΕΠ3Γ. 讲 Hrflla裝.器縮扒仵黯<N寸 5601001 塒_ CU寸卜ae 【9<】實例62 1 I d 1 1 1 1 1 1 1 1 1 1 1 1 1 1 實例61 1 1 1 1 1 1 啕埤 i〇 1 1 1 1 1 實例60 總 1 1 1 1 1 Η埤 1 1 ( 1 畜實例59 棚（邀 t 1 1 1 iTi 1 i〇 1 1 1 1 1 實例58 郷C邀 1 1 1 1 1 ιτΐ 1 1 1 1 1 實例57 棚（邀 1 咖 IT) 1 1 1 哞想 1 1 1 1 1 實例56 郷ζ邀 1 1 1 1 1 1 1 1 1 1 實例55 柳C逍 1 vn 1 1 1 1 1 1 1 1 1 1 實例54 (奥 1 in 1 1 1 1 < >M邀 ^T) 1 • 1 1 1 1 化合物名 1,4-雙(1-丙烯氧基甲基）環己烷 1,4-雙(1-乙烯氧基甲基）環己烷 1,4-丁二醇二乙烯醚三乙二醇二己烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)鍵 (AZ-1) 1 (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-甲基-1,2,4-*** 3-胺基-5-乙基-1，2,4-*** 3-胺基-5-丙基-1，2,4-*** 3-胺基-5-丁基-1,2,4-*** 成分 |ί 化合物（B) (份）路易斯鹼 (C) (份） 201203678 q uu寸 Εε raloI 叹 9壯00I:sSHr_ 1實例71 1 郷（想 1 1 1 1 1 1 1 1 1 Η4想 in 1 1 1 1 1 1 1 1 實例70 C邀 1 1 1 1 1 1 1 1 1 1 'T) 1 1 1 1 1 實例69 1 1 1 1 1 i 1 1 Θ邀 V) 1 1 in 1 1 1 1 1 實例68 C邀 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 實例67 ζ邀 1 1 1 V) 1 1 1 1 1 Θ埤 1 1 1 1 1 1 1 1 實例66 «坶 1 1 1 1 1 1 1 1 V) 1 1 1 I I 1 1 1 實例65 C邀 1 1 Vi 1 1 1 1 1 1 l〇 1 1 1 1 1 1 1 1 |實例64 c璁 1 1 1 1 唯 1 1 1 Θ想 Ό 1 1 1 1 1 1 1 1 實例63 權（邀 1 1 in 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 化合物名 1，4-雙(1·丙烯氧基曱基）環己烧 1,4-雙(1-乙烯氧基甲基）環己烷 1，4-丁二醇二乙烯醚三乙二醇二乙烯醚二乙二醇二(2-丁烯酸甲酯)醚二乙二醇二(4-乙烯基苄基)鍵 ! (AZ-1) (AZ-2) (AZ-3) 3-胺基-1，2,4-*** 3,5-二胺基-1，2,4-*** 3-胺基-5-曱基-1,2,4-*** 3-胺基-5-乙基-1,2,4-*** 3-胺基-5-丙基-1,2,4-*** 3·胺基_5_ 丁基-1，2,4-三°坐成分 |ί « |5 路易斯驗 (C) (份） 201203678 J / / i ^tpiA 1 修正日期:100年6月15日爲第100109542號中文說明書無劃線修正本 [鐘離子電池、鐘離子電容器的製作] (1) 鋰離子電池的製作 (1-1)正極的製作、=LlCo〇2粉末9.0份、柯琴黑[Aldrich公司製造]〇 5 =及聚偏二氟乙烯[Aldrich公司製造]〇 5份於研缽中充分 ΐ合後’\添加1_甲基_2‘吡咯啶酮[東京化成工業（股）製造]7.0份^進而於研缽中充分混合而獲得漿料。將所得的水料於大氧中使用線棒來塗佈於厚度的銘電解箔上〇的單面，於UKTC下乾燥15分鐘後，進而於減壓下（1〇 mmHg)在80°c下乾燥5分鐘，衝壓為15.95 mmcp，製作膜厚30 μπι的鋰離子電池用的正極。 (1-2)負極的製作 -惫3:=徑約8帅〜12 μΠ1的石碰末92·5份、聚偏涂搞於厘Λ 充獲传漿料。將所得的漿料塗佈於厚度20 μ„ι軸㈣單面，於而使溶劑蒗發德，输蔽* 1/c , L卜乾踩15刀鐘 έ: η 声30um制从衝壓為.l5mmtP，利用壓製機形成厚度μΐη，製作鋰離子電池用的負極。 (1-3)二次電池用單元的製作自： (2) 鋰離子電容器的製作 (2-1)正極的製作使用利用驗活化法而獲得的比表面積約為謂m2/g 52 201203678 ^ , f « ^ Λ.Λ. 爲第100109542號中文說明書無_0]£;$：修正日期:100年6月15日的活性碳作為正極活性物質。將活性碳粉末、乙块里聚偏二氟乙烯分別以重量比成為8〇: 1〇: 例的、混合，將紐合麵純料賴的 2^式猜混合而獲得裝料。將該聚料以到刀法塗佈^中〇 μιη的紹箱上，暫時乾燥後，子，的方式切取。電極的厚度約為50 Ο =空中以12叱乾燥心、時，製成_二: (2-2)負極的製作將平均粒徑約8师〜12师的黑10份、及聚偏二氟乙嫌1(W八、曰人刀末80伤、乙块作為溶劑㈣Λ t 合’將該混合物添加於槳二T，合’獲得漿料。將該以雷二:f? μιη的銅箱上，暫時乾燥後， =尺寸成為2。mmx3() mm的方式切取 ^ 約為50卿。於單元的組裝前 =厚度 G 小時，製成鐘離子電容器用的負極。中以12〇C乾燥5 (2_3)於負極令的鐘的換雜於以上述方式獲得的負極中，以下述方彳娘μ 負極與鐘金屬落以分隔片达方式摻雜鐘。將於燒杯稀製不織布）夾持而設置 :燒，’將預定量的鋰離子以約1〇小中鐘的摻雜量為負極理論容量的約75〇/〇。 ' (2-4)電容器單元的組裝丙婦式獲得的正極與負極之間***分隔片（聚不織布），使其中含浸電解液，放人包含層壓膜的收 53 201203678 «； / / / Λ 爲第100109542號中文說明書無劃線修正本修正日期:100年6月15曰納箱中並密封，製成鋰離子電容器。 [評價] 電解液的評價將實例4〜實例35以及比較例1〜比較例3中調製的電解液分別注入上述二次電池用單元中後密封，以下述方法來評價高電壓充放電循環特性及高溫保存特性，並且注入電容器單元中後密封，以下述方法來評價高電壓充放電循環特性及高溫保存特性，將上述兩種評價結果示於表8 中。 54 201203678 »/ / / / I 1. 修正日期:1〇〇年6月15曰爲第100109542號中文說明書無劃線修正本 [表8] 鋰離子電池鋰離子電容器項目高電壓循環特性（％) 高溫保存特性 (%) 高電壓循環特性 (%) 高溫保存特性 (%) 實例4 92.0 96.7 88.5 94.2 實例5 89.3 94.9 86.6 93.0 實例6 89.0 94.7 88.2 90.3 實例7 89.6 94.3 86.1 92.0 實例8 87.1 93.6 86.1 90.9 實例9 91.5 94.6 89.0 89.6 實例10 87.9 92.6 83.7 87.7 實例11 90.5 95.6 86.3 90.6 實例12 87.8 92.5 83.2 88.0 實例13 86.9 91.1 85.4 91.0 實例14 90.6 85.4 86.2 83.8 實例15 89.7 84.2 85.1 83.7 實例16 89.4 84.4 87.3 80.0 實例17 88.8 93.6 83.9 89.0 實例18 87.8 92.2 85.5 88.0 實例19 87.7 92.5 83.1 91.8 實例20 86.8 91.2 83.0 89.8 實例21 86.9 91.7 83.1 90.6 實例22 90.8 96.2 90.3 95.4 實例23 90.1 96.5 85.9 91.9 實例24 90.2 96.2 89.9 93.4 實例25 90.1 96.3 85.6 95.3 實例26 90.3 96.1 88.3 93.0 實例27 90.2 96.4 87.2 94.3 實例28 86.9 86.5 83.2 85.8 實例29 86.9 91.8 84.9 88.9 實例30 86.9 91.1 84.2 90.3 實例31 89.4 94.2 85_7 90.9 實例32 89.7 94.7 85.5 93.2 實例33 90.1 95.4 88.9 93.6 實例34 89.5 93.2 88.2 89.1 實例35 88.9 91.9 84.4 89.8 比較例1 50.2 55.9 46.2 53.6 比較例2 71.3 76.7 67.8 75.6 比較例3 76.3 81.6 72.1 78.947 201203678 ΕΠςΙΠΙ:9 001001: Step on mHI sacrifice 1} 挎Hr·}Following. 郜払旮黯払旮黯寸寸 S S60I00I moving in 寸卜 ε ε [inch <] Example 44 1 1 1 1 1 1 1 1 iri 1 i 1 1 t Example 43 Shed C invite 1 1 1 1 1 1 1 f 1 1 I Example 42 郷C invite 1 1 1 1 1 1 1 1 in 1 1 1 Example 41 «Invite 1 1 1 1 1 1 Η4 « 1 ^Ti 1 1 1 t Example 40 shirt C invite 1 ^Ti 1 1 1 1 1 1 1 1 1 1 1 Example 39 1 to 1 1 1 1 1 1 *ri 1—^ 1 1 1 1 1 1 Example 38 1 1 1 1 1 1 1 in 1 1 1 1 1 1 Example 37 « ^ 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 36 «Invite 1 1 1 1 1 1 1 1 1 1 1 1 Compound name Invited to ιί»Β<ΐ fpBT 1,4-bis(1-propenyloxymethyl)cyclohexaneΜ-bis(1-vinyloxyindenyl)cyclohexane 1,4-butanediol divinyl ether Ethylene glycol diethyl ether diethylene glycol bis(2-methylbutanoate) ether diethylene glycol bis(4-vinylbenzyl) ether (ΑΖ-1) (AZ-2) 1 (AZ- 3) 3-Amino-1,2,4-triazole 3,5-di Amino-1,2,4-triazole 3-amino-5-methyl-1,2,4-triazole 'Ί ri n3 ιΛ rnrn 3-amino-5-propyl-1,2, 4-triazole 3-amino-5-butyl-1,2,4-triazole component compound (A) (part) 1 |5 Lewis base (C) (part) 201203678 〇ΙΉςΙΠΙ:9 Zhuang 001: step on mHTs 恃««黯tN inch S60I00I city pulse 03⁄4 inch Εε I example 53 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 52 weight (璁1 1 1 1 1 1 呗埤»Τ) 1 1 1 1 1 1 Example 51 1 in rH 1 1 1 1 1 1 1 1 1 1 1 1 Example 50 1 in ί-Η 1 1 1 1 1 1 Θ璁in 1 1 1 1 1 1 Example 49 1 in 1 1 1 1 1 Θ坶1 1 1 1 1 Example 48 Invite 1 in 1 1 1 1 1 呗埤in· 1 d 1 i 1 1 Example 47 1 1 1 1 1 1 V"i 1 1 1 1 1 Example 46 «璁1 1 1 1 1 1 -1 1 1 1 1 Example 45 «Invitation 1 in 1 1 1 1 1 Η4璁1 1 1 1 1 1 iTi Compound name 四 (4) 1,4-bis(1-propene Oxymethyl) cyclohexane 1,4-bis(1-vinyloxymethyl) Cyclohexane 1,4-butanediol divinyl ether triethylene glycol divinyl ether diethylene glycol bis(2-butenoate) ether diethylene glycol bis(4-vinylbenzyl) ether ( AZ-1) (AZ-2) (AZ-3) 3-Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5- Methyl-1,2,4-triazole 3-amino-5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 3-amine Base-5-butyl-1,2,4-triazole component compound (A) (part) _1 Keguang N $ W Lewis base (C) (part) 6 inch 201203678 mslm:9 Zhuang 001: hi-hat 3ΕΠ. Hrflla device shrinkage <N inch 5601001 埘 _ CU inch ae [9<] Example 62 1 I d 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 61 1 1 1 1 1 1啕埤i〇1 1 1 1 1 Example 60 Total 1 1 1 1 1 Η埤1 1 ( 1 animal example 59 shed (inviting t 1 1 1 iTi 1 i〇1 1 1 1 1 instance 58 郷C invitation 1 1 1 1 1 ιτΐ 1 1 1 1 1 Example 57 Shed (Inviting 1 Coffee IT) 1 1 1 Imagine 1 1 1 1 1 Example 56 郷ζ 1 1 1 1 1 1 1 1 1 1 Example 5 5 柳C逍1 vn 1 1 1 1 1 1 1 1 1 1 Example 54 (Olympic 1 in 1 1 1 1 <> M invited ^T) 1 • 1 1 1 1 Compound name 1,4-double (1 -propenyloxymethyl)cyclohexane 1,4-bis(1-vinyloxymethyl)cyclohexane 1,4-butanediol divinyl ether triethylene glycol dihexene ether diethylene glycol (2-methylbutenoate) ether diethylene glycol bis(4-vinylbenzyl) bond (AZ-1) 1 (AZ-2) (AZ-3) 3-amino-1,2,4 -Triazole 3,5-diamino-1,2,4-triazole 3-amino-5-methyl-1,2,4-triazole 3-amino-5-ethyl-1,2 , 4-triazole 3-amino-5-propyl-1,2,4-triazole 3-amino-5-butyl-1,2,4-triazole component | ί Compound (B) (parts Lewis base (C) (part) 201203678 q uu inch Εε raloI sigh 9 00 00: sSHr_ 1 instance 71 1 郷 (Think 1 1 1 1 1 1 1 1 1 Η 4 want in 1 1 1 1 1 1 1 1 Instance 70 C invite 1 1 1 1 1 1 1 1 1 1 'T) 1 1 1 1 1 Example 69 1 1 1 1 1 i 1 1 ΘV) 1 1 in 1 1 1 1 1 Example 68 C invite 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Example 67 ζ Invitation 1 1 1 V) 1 1 1 1 1 Θ埤1 1 1 1 1 1 1 1 Example 66 «坶1 1 1 1 1 1 1 1 V) 1 1 1 II 1 1 1 Example 65 C Invitation 1 1 Vi 1 1 1 1 1 1 l〇1 1 1 1 1 1 1 1 |Example 64 c璁1 1 1 1 Only 1 1 1 Θ想Ό 1 1 1 1 1 1 1 1 Example 63 Right (Inviting 1 1 in 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Compound name 1,4-bis(1.propenyloxyindenyl) cyclohexene 1,4-bis(1-vinyloxymethyl)cyclohexane 1,4-butanediol divinyl ether triethylene glycol Divinyl ether diethylene glycol di(2-butenoate) ether diethylene glycol bis(4-vinylbenzyl) bond! (AZ-1) (AZ-2) (AZ-3) 3- Amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole 3-amino-5-mercapto-1,2,4-triazole 3-amino group- 5-ethyl-1,2,4-triazole 3-amino-5-propyl-1,2,4-triazole 3·amino _5_ butyl-1,2,4-trisole | ί « |5 Louis test (C) (part) 201203678 J / / i ^tpiA 1 Revision date: June 15, 100 is the 100109542 Chinese manual without scribe correction [clock ion battery, clock ion capacitor Production] (1) Production of lithium ion battery (1-1) Production of positive electrode, = 9.0 parts of LlCo〇2 powder, Keqin black [manufactured by Aldrich] 〇5 = and polyvinylidene fluoride [manufactured by Aldrich] 〇 5 parts fully blended in the mortar '\Add 1_methyl_2 'Pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] 7.0 parts and further thoroughly mixed in a mortar to obtain a slurry. The obtained water was applied to a single side of the enamel on the thickness of the electrolytic foil by using a wire rod in a large oxygen, dried under UKTC for 15 minutes, and further under reduced pressure (1 〇 mmHg) at 80 ° C. After drying for 5 minutes, the film was punched to 15.95 mmcp to prepare a positive electrode for a lithium ion battery having a film thickness of 30 μm. (1-2) Preparation of the negative electrode - 惫3: = diameter of about 8 handsome ~ 12 μΠ1 of stone rubbing 92. 5 parts, poly-biasing applied to centistokes to obtain the slurry. The obtained slurry is applied to a thickness of 20 μ „axis (four) on one side, so that the solvent is 蒗德德, the concealing is *1/c, and the L 卜 is stepped on 15 knives: η 声 30 um from the stamping. l5mmtP, a thickness of μΐη is formed by a press machine to produce a negative electrode for a lithium ion battery. (1-3) Production of a secondary battery unit from: (2) Production of a lithium ion capacitor (2-1) Preparation and use of a positive electrode The specific surface area obtained by the activation method is about m2/g 52 201203678 ^ , f « ^ Λ.Λ. is the Chinese manual No. 100109542 No _0] £;$: Revision date: Activated carbon on June 15, 100 As the positive electrode active material, the activated carbon powder and the polyvinylidene fluoride in the block are respectively made into a weight ratio of 8 〇: 1 〇: for example, mixed, and the mixture of the pure surface of the bonded surface is obtained by guessing and mixing. The material is applied to the processing box of the 〇μιη by the knife method, and temporarily dried, and then cut out. The thickness of the electrode is about 50 Ο = 12 叱 dry heart, time, system Cheng _ 2: (2-2) The production of the negative electrode will have an average particle size of about 8 divisions to 12 divisions of black 10, and polyvinylidene fluoride II 1 (W eight, 曰人刀80 wounds, B block as a solvent (4) Λ t Combine 'Add this mixture to the paddle two T, and 'to obtain the slurry. After the copper box of the thunder: f? μιη, temporarily dry, = size becomes 2. mmx3 () mm way to cut ^ about 50 qing. Before the assembly of the unit = thickness G hour, make the negative electrode for the clock ion capacitor. In the middle of the 12 〇 C dry 5 (2_3) in the negative ring of the clock In the negative electrode obtained in the above manner, the bell is doped in the form of a separator by the following method: the negative electrode of the beaker and the metal of the bell are placed in a separator. The burnt is set to burn: 'The predetermined amount of lithium ions is about 1 The doping amount of the small Zhongzhong is about 75 〇/〇 of the theoretical capacity of the negative electrode. ' (2-4) The assembly of the capacitor unit is inserted into the separator between the positive electrode and the negative electrode (poly non-woven fabric) to make it impregnated. Electrolyte, put people in the laminate film containing 53 201203678 «; / / / Λ For the 100109542 Chinese manual no scribe correction This correction date: 100 years June 15 can be sealed in the box, made lithium ion capacitor [Evaluation] Evaluation of electrolyte will be Example 4~ 35 and the electrolytic solutions prepared in Comparative Example 1 to Comparative Example 3 were respectively injected into the secondary battery cells, and then sealed, and the high voltage charge and discharge cycle characteristics and high temperature storage characteristics were evaluated by the following methods, and injected into the capacitor unit to be sealed. The high voltage charge and discharge cycle characteristics and high temperature storage characteristics were evaluated by the following methods, and the results of the above two evaluations are shown in Table 8. 54 201203678 »/ / / / I 1. Date of revision: June 15th, 1st year No. 100109542 Chinese manual without scribe correction [Table 8] Lithium-ion battery lithium ion capacitor project high voltage cycle characteristics (%) High temperature storage characteristics (%) High voltage cycle characteristics (%) High temperature storage characteristics (%) Example 4 92.0 96.7 88.5 94.2 Example 5 89.3 94.9 86.6 93.0 Example 6 89.0 94.7 88.2 90.3 Example 7 89.6 94.3 86.1 92.0 Example 8 87.1 93.6 86.1 90.9 Example 9 91.5 94.6 89.0 89.6 Example 10 87.9 92.6 83.7 87.7 Example 11 90.5 95.6 86.3 90.6 Example 12 87.8 92.5 83.2 88.0 Example 13 86.9 91.1 85.4 91.0 Example 14 90.6 85.4 86.2 83.8 Example 15 89.7 84.2 85.1 83.7 Example 16 89.4 84.4 87.3 80.0 Example 17 88.8 93.6 83.9 89.0 Example 18 87.8 92.2 85.5 88.0 Example 19 87.7 92.5 83.1 91.8 Example 20 86.8 91.2 83.0 89.8 Example 21 86.9 91.7 83.1 90.6 Example 22 90.8 96.2 90.3 95.4 Example 23 90.1 96.5 85.9 91.9 Example 24 90.2 96.2 89.9 93.4 Example 25 90.1 96.3 85.6 95.3 Example 26 90.3 96.1 88.3 93.0 Example 27 90.2 96.4 87.2 94.3 Example 28 86.9 86.5 83.2 85.8 Example 29 86.9 91.8 84.9 88.9 Example 30 86.9 91.1 84.2 90.3 Example 31 89.4 94.2 85_7 90.9 Example 32 89.7 94.7 85.5 93.2 Example 33 90.1 95.4 88.9 93.6 Example 34 89.5 93.2 88.2 89.1 Example 35 88.9 91.9 84.4 89.8 Comparative Example 1 50.2 55.9 46.2 53.6 Comparative Example 2 71.3 76.7 67.8 75.6 Comparative Example 3 76.3 81.6 72.1 78.9

電極的評價 55 201203678 爲第麵觀2號中文說明書無劃線修正本修正日期·年6月15日 (1) 鐘二次電池的製作於2032型硬幣單元内的兩端，將實例36〜實例67以及比較例4、比較例5的正極及負極以各自的塗佈面相對的方式配置而製作二次電池用單元。將於碳酸乙二醋與妒酸二甲醋的混合溶劑（體積比率i: i )中使LipF6以1 的比例溶解而成的電解液注入至所製成的單元中並密封，將利用以下方法評價高電壓充放電#環特性及高溫保存性的結果示於表9中。 ' (2) 鋰離子電容器的製作於包含層壓膜的收納箱中，將實例68〜實例71以及比較例6、比較例7的正極及負極以各自的塗佈面相方式配置而製作電容器用單元。將於碳酸乙二酯與碳酸二甲酉旨的混合溶劑（體積比率i :丨）中使LiPF6a 1 的比例溶解而成的電解液注入至所製成的單元中並密封，將利用以下方法評價高電壓充放電㈣特性及高溫性的結果示於表9中。 W 56 201203678 爲第100109542號中文說明書無劃線修正本修正曰期:1〇〇年6月15日 [表9]Electrode evaluation 55 201203678 For the first view No. 2 Chinese manual without sizing correction this correction date · June 15 (1) The secondary battery is fabricated at both ends of the 2032 type coin unit, and the example 36~ example 67. The positive electrode and the negative electrode of Comparative Example 4 and Comparative Example 5 were disposed so that the respective coated surfaces thereof faced each other to produce a secondary battery unit. An electrolyte obtained by dissolving LipF6 in a ratio of 1 in a mixed solvent of ethylene carbonate and dimethyl vinegar (volume ratio i: i ) is injected into the produced unit and sealed, and the following method is used. The results of evaluating the high voltage charge and discharge #ring characteristics and high temperature preservability are shown in Table 9. (2) Preparation of a lithium ion capacitor In a storage box including a laminate film, the positive electrode and the negative electrode of Examples 68 to 71 and Comparative Example 6 and Comparative Example 7 were placed in a coating surface phase to form a capacitor unit. . An electrolyte obtained by dissolving a ratio of LiPF6a 1 in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio i: 丨) is injected into the produced unit and sealed, and evaluated by the following method. The results of high voltage charge and discharge (IV) characteristics and high temperature properties are shown in Table 9. W 56 201203678 For the Chinese manual No. 100109542, there is no slash correction. The revised period: June 15th, 1st year [Table 9]

正極單元的種類※ 高電壓循環特性（％) 高溫保存特性（％) 實例36 LIB 88.9 91.5 實例37 LIB 88.2 91.1 實例38 LIB 89.6 92.9 實例39 LIB 89.2 91.5 實例40 LIB 88.4 92.2 實例41 LIB 88.6 91.5 實例42 LIB 89.5 91.5 實例43 LIB 89.3 91.4 實例44 LIB 89.3 91.6 實例45 LIB 88.9 91.2 實例46 LIB 83.3 89.7 實例47 LIB 84.7 88.8 實例48 LIB 84.1 90.0 實例49 LIB 84.7 88.9 實例50 LIB 89.0 92.0 實例51 LIB 88.7 92.9 實例52 LIB 89.3 91.5 實例53 LIB 88.1 91.6 實例54 LIB 88.0 92.8 實例55 LIB 89.4 91,4 實例56 LIB 88.5 91.3 實例57 LIB 88.1 91.8 實例58 LIB 89.2 91.6 實例59 LIB 88.9 91.1 實例60 LIB 89.0 92.9 實例61 LIB 91.1 93.2 實例62 LIB 84.1 89.2 實例63 LIB 83.4 88.4 實例64 LIB 84.5 89.8 實例65 LIB 83.3 88.8 實例66 LIB 84.9 89.7 實例67 LIB 83.9 89.0 實例68 LIC 88.8 91.4 實例69 LIC 87.2 90.0 實例70 LIC 83.2 89.5 實例71 LIC 83.8 89.9 比較例4 LIB 49.3 55.1 比較例5 LIB 70.9 76.0 比較例6 LIC 45.4 53.1 比較例7 LIC 46.0 53.2 ※：LIB (鋰離子電池），LIC (鋰離子電容器） 57 201203678 jiii -tyit x 爲第画魏號Φ文麵書__正本修正日期_心月15日〈高電壓充放電循環特性的評價〉使用充放電測定裝置「電池分析儀147〇型」 T^chmca (股）製造]，以〇 ic的電流充電至電壓4 5/ 停頓10分鐘後，以0.1 C的電流將電池電壓放電至3 s v，反覆進行該充放電。測定此時的初次充電時的電池第50循％充電時的電池容量，由下述式算出充放電循環性。數值越大，表示充放電循環特性越良好。高電壓充放電循環特性（％)==(第50循環充電時的電池谷1/初次充電時的電池容量）xl〇〇〈而溫保存特性的評價〉使用充放電測定裝置「電池分析儀147〇型」[T0y〇 Techmca (股）製造]，以〇丨c的電流充電至電壓4.5 V，停頓10分鐘後’以〇.丨C的電流放電至電壓3.5 V，測定容量（初次電池容量）。進而以0.1 C的電流充電至電壓4.5 V ’於85°C下保存7日後，以〇.1 C的電流進行放電至3.5 V ’測定電池容量（高溫保存後電池容量）。由下述式算出高溫保存特性。數值越大，表示高溫保存特性越良好。高溫保存特性（％)=(高溫保存後電池容量/初次電池容量）X 1〇〇 [產業上之可利用性] 58 201203678 I I t 太丄 1 爲第100109542號中文說明書無劃線修正本修正曰期:100年ό月15日使用本發明的電極保護膜形成劑（F)的電解液由於高電壓下的循環特性及高溫儲藏穩定性優異，故而尤其作為鋰二次電池用電解液或鋰離子電容器用電解液而有用，適合用於電動汽車。【圖式簡單說明】無。【主要元件符號說明】Type of positive electrode unit ※ High voltage cycle characteristics (%) High temperature storage characteristics (%) Example 36 LIB 88.9 91.5 Example 37 LIB 88.2 91.1 Example 38 LIB 89.6 92.9 Example 39 LIB 89.2 91.5 Example 40 LIB 88.4 92.2 Example 41 LIB 88.6 91.5 Example 42 LIB 89.5 91.5 Example 43 LIB 89.3 91.4 Example 44 LIB 89.3 91.6 Example 45 LIB 88.9 91.2 Example 46 LIB 83.3 89.7 Example 47 LIB 84.7 88.8 Example 48 LIB 84.1 90.0 Example 49 LIB 84.7 88.9 Example 50 LIB 89.0 92.0 Example 51 LIB 88.7 92.9 Example 52 LIB 89.3 91.5 Example 53 LIB 88.1 91.6 Example 54 LIB 88.0 92.8 Example 55 LIB 89.4 91,4 Example 56 LIB 88.5 91.3 Example 57 LIB 88.1 91.8 Example 58 LIB 89.2 91.6 Example 59 LIB 88.9 91.1 Example 60 LIB 89.0 92.9 Example 61 LIB 91.1 93.2 Example 62 LIB 84.1 89.2 Example 63 LIB 83.4 88.4 Example 64 LIB 84.5 89.8 Example 65 LIB 83.3 88.8 Example 66 LIB 84.9 89.7 Example 67 LIB 83.9 89.0 Example 68 LIC 88.8 91.4 Example 69 LIC 87.2 90.0 Example 70 LIC 83.2 89.5 Example 71 LIC 83.8 89.9 Comparative Example 4 LIB 49.3 55.1 Comparative Example 5 LIB 70.9 76.0 Comparative Example 6 LIC 45.4 53.1 Comparative Example 7 LIC 46.0 53.2 ※: LIB (Lithium Ion Battery), LIC (Lithium Ion Capacitor) 57 201203678 jiii -tyit x is the first drawing Wei Φ fascia __ original revision date _ heart month 15th <Evaluation of high-voltage charge-discharge cycle characteristics> Using a charge-discharge measuring device "battery analyzer 147〇" T^chmca (manufactured by T2), the current is charged to a voltage of 4 5 / pause for 10 minutes. The battery voltage was discharged to 3 sv at a current of 0.1 C, and the charge and discharge were repeated. The battery capacity at the time of initial charging at this time was measured. The battery capacity at the 50th%% charge was calculated from the following equation. The larger the value, the better the charge-discharge cycle characteristics. High-voltage charge and discharge cycle characteristic (%) == (battery in the 50th cycle charge 1 / battery capacity at the time of initial charge) xl 〇〇 <Evaluation of temperature storage characteristics> The charge and discharge measurement device "Battery analyzer 147" was used. 〇"[T0y〇Techmca (manufacturing)], charged with a current of 〇丨c to a voltage of 4.5 V, after a pause of 10 minutes, 'discharges with a current of 〇.丨C to a voltage of 3.5 V, and measures the capacity (primary battery capacity) . Further, the battery was charged at a voltage of 0.1 C until a voltage of 4.5 V was stored at 85 ° C for 7 days, and then discharged at a current of 0.1 C to 3.5 V ′ to measure the battery capacity (battery capacity after high-temperature storage). The high temperature storage characteristics were calculated by the following formula. The larger the value, the better the high temperature storage characteristics. High-temperature storage characteristics (%) = (battery capacity after high-temperature storage / primary battery capacity) X 1〇〇 [industrial availability] 58 201203678 II t Too 1 is the 100109542 Chinese manual without a slash correction. The electrolyte solution using the electrode protective film forming agent (F) of the present invention is excellent in cycle characteristics at high voltage and high-temperature storage stability, and is particularly useful as an electrolyte or lithium ion for a lithium secondary battery. Capacitors are useful for electrolytes and are suitable for use in electric vehicles. [Simple description of the diagram] None. [Main component symbol description]

59 201203678 爲第100109542號中文說明書無劃線修正本修正日期:1⑻年6月15日璧專利說明書順序’請勿任意更動，※記號部分請勿、填寫） ※工卩匚分類： (本說明書格式 ※申請案號： ※申請曰： <2006.01) {20(0 .01) 一、發明名稱：（中文/英文）電極保護膜形成劑以及電解液 ELECTRODE PROTECTIVE FILM-FORMING 〇 AGENT AND ELECTROLYTE 二、中文發明摘要·· 本發明提供一種高電壓、高容量，且充放電循環性能及高溫儲藏特性優異的鋰二次電池用電解液或鋰離子電容器用電解液。本發明是含有選自由下述（Ai)、（A2)、 (A3)、（B1)及（B2)所組成組群中的至少1種化合物 (A)或化合物（B)的電極保護膜形成劑（ρ)。 (A1):具有特定結構的烯氧基（a)的脂肪族烴； (A2):具有浠氧基（a)的多元醇的謎； (A3):具有烯氧基（a)的聚氧伸烷基醚； (B1):具有特定結構的取代基（b)的多元醇的醚； (B2):具有取代基（b)的聚氧伸烷基醚。三、英文發明摘要： Provided is an electrolyte used in a lithium ion secondary battery or a lithium ion capacitor with high valtage, 201203678 爲第1^0109542號中文說明書無劃線修正本修正日期:1〇〇年ό月15日 high capacity, excellent charge-discharge cycle performance and high-temperature storage characteristics. The invention provides an electrode protective film-forming agent (F) comprising at least one compound (A) or compound (B), which is selected from a group consisting of the following (Al), (A2), (A3), (Bl), and (B2). (Al) is an aliphatic hydrocarbon having alkenyloxy (a) of specific structure; (A2) is a polyhydric alcohol ether having alkenyloxy (a); (A3) is a polyoxyalkylene ether having alkenyloxy (a ); (Bl) is a polyhydric alcohol ether having at least one substituent (b) selected from the group consisting of a substituent represented by general formula (2), a substituent represented by general formula (3), (meth)acryloyloxyalkyl and (meth)acryloylalkyl; (B2) is a polyoxyalkylene having a substituent (b) of specific structure. 四、指定代表圖： (一）本案指定代表圖為：無。 (二）本代表圖之元件符號簡單說明：無。五、本案若有化學式時’請揭示最能顯示發明特徽的化學式： 201203678 修正臼期:1〇〇年6月15日爲第100109542號中文說明書無劃線修正本七、申請專利範圍： 1· 一種電極保護膜形成劑（F)，含有選自由下述 (A1)、（A2)、（A3)、（B1)及（B2)所組成組群中的至少1種化合物（A)或化合物（B): (A1):具有下述通式（1)所表示的烯氧基（a)的脂肪族烴； (A2):具有烯氧基（a)的多元醇的醚； (A3) ·具有烯氧基（a)的聚氧伸烧基驗； (B1):具有選自由下述通式（2)所表示的取代基、下述通式（3)所表示的取代基、（甲基)丙烯醯氧基烷基、及（甲基)丙烯酿基燒基所組成組群中的至少丨種取代基（b) 的多元醇的趟； (B2):具有取代基（b)的聚氧伸烷基醚； [化1] —〇-〇 =0 -ΊΓ3 I I (1) [Τ1、T2及τ3為氫原子或碳數1〜3的烷基] [化2] 60 20120367 玉爲第100109542號中文說明書無劃線修正本修正日期:1〇〇年6月Μ曰 —R2—C = C —Q3 I I (2) Q1 Q2 [式中’ R2為碳數1〜3的伸烧基，Q1、q2及q3分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數j 或2的氟烷基、苯基、氰基、羧基、碳數〖〜3的烷氧基或碳數1〜4的烷氧基羰基] 〇 [化 3] Q4 Q5 Q659 201203678 For the Chinese manual No. 100109542, there is no slash correction. The date of this revision: 1 (8) June 15th 璧 Patent specification order 'Do not change any more, ※ Do not fill in the mark part. ※ ※Work classification: (This manual format ※Application number: ※Application曰: <2006.01) {20(0 .01) I. Name of the invention: (Chinese/English) Electrode protective film forming agent and electrolyte ELECTRODE PROTECTIVE FILM-FORMING 〇AGENT AND ELECTROLYTE II. SUMMARY OF THE INVENTION The present invention provides an electrolyte solution for a lithium secondary battery or an electrolyte solution for a lithium ion capacitor which is high in voltage and high in capacity and excellent in charge/discharge cycle performance and high-temperature storage characteristics. The present invention is formed by an electrode protective film containing at least one compound (A) or compound (B) selected from the group consisting of the following (Ai), (A2), (A3), (B1), and (B2). Agent (ρ). (A1): an aliphatic hydrocarbon having an alkenyloxy group (a) having a specific structure; (A2): an enigma of a polyhydric alcohol having a decyloxy group (a); (A3): a polyoxygen having an alkenyloxy group (a) An alkyl ether; (B1): an ether of a polyol having a substituent (b) having a specific structure; (B2): a polyoxyalkylene ether having a substituent (b). III. English Abstract: Provided is an electrolyte used in a lithium ion secondary battery or a lithium ion capacitor with high valtage, 201203678 No. 1 0 019 954 Chinese manual without a slash correction. Amendment date: 1 ό ό 15 High capacity, excellent charge-discharge cycle performance and high-temperature storage characteristics. The invention provides an electrode protective film-forming agent (F) comprising at least one compound (A) or compound (B), which is selected from a group Consisting of the following (Al), (A2), (A3), (Bl), and (B2). (Al) is an aliphatic hydrocarbon having alkenyloxy (a) of specific structure; (A2) is a polyhydric alcohol ether having Alkenyloxy (a); (A3) is a polyoxyalkylene ether having alkenyloxy (a ); (Bl) is a polyhydric alcohol ether having at least one substituent (b) selected from the group consisting of a partial represented by general formula (2), a substituent represented by general formula (3), (meth)acryloyloxyalkyl and (meth (b) is a polyoxyalkylene having a substituent (b) of specific structure. IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best displays the invention emblem: 201203678 Revision period: June 15, 2015 is the 100109542 Chinese manual without a slash correction. 7. Patent application scope: 1 An electrode protective film forming agent (F) containing at least one compound (A) or compound selected from the group consisting of the following (A1), (A2), (A3), (B1), and (B2) (B): (A1): an aliphatic hydrocarbon having an alkenyloxy group (a) represented by the following formula (1); (A2): an ether of a polyhydric alcohol having an alkenyloxy group (a); (A3) - a polyoxyalkylene extension test having an alkenyloxy group (a); (B1): having a substituent represented by the following formula (2), a substituent represented by the following formula (3), a hydrazine of a polyol of at least a hydrazine substituent (b) in a group consisting of a methyl propylene oxyalkyl group and a (meth) propylene group; (B2): having a substituent (b) Polyoxyalkylene ether; [Chemical 1] —〇-〇=0 -ΊΓ3 II (1) [Τ1, T2 and τ3 are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms] [Chemical 2] 60 20120367 Jade Description for Chinese No. 100109542 No slash correction This correction date: 1〇〇June Μ曰—R2—C = C —Q3 II (2) Q1 Q2 [In the formula, R2 is the carbon number 1~3 extension base, Q1, q2 and Each of q3 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having a carbon number of j or 2, a phenyl group, a cyano group, a carboxyl group, an alkoxy group having a carbon number of 〜3 or a carbon number. 1 to 4 alkoxycarbonyl] 〇 [3] Q4 Q5 Q6

〇 [式中，r3為碳數1〜3的伸烷基，Q4為氫原子或鹵素原子，Q5、Q6及Q7分別獨立地為氫原子、鹵素原子、碳數1〜4的烷基、碳數丨或2的氟烷基、苯基、氰基、羧基、奴數1〜3的烧氧基或碳數ι〜4的烧氧基羰基]。 2.如申料利範圍第丨項所狀電極㈣膜形成劑 ⑺’其巾上述烯氧基（a)為乙烯氧基或〗丙婦氧基。請ί利範圍第1項或第2項所述之電極保護膜形成劑⑺，其中上述電極賴卿成劑（f)是含有選 61 201203678 t i I Λ. 修正日期:100年6月15日爲第100109542號中文說明書無劃線修正本自由（Al )、（ A2 )及（A3 )所組成組群中的至少1種化合物（A)而成，上述化合物（A)為通式（4)所表示的化合物、通式（5)所表示的化合物或者具有2個以上乙烯氧基或1_丙烯氧基的環己烷衍生物： R4-CH=CH-0-(CH2)p-0-CH=CH-R5 (4) [式中，R4及R5分別獨立地為氫原子或曱基，卩為i 〜10的整數] R6-CH=CH-0-(C2H40)q-CH=CH-R7 ⑴ [式中，R6及R7分別獨立地為氫原子或甲基，q為i 5的整數]。 4. ‘種電解液’含有如申請專利範圍第1項至第3項中任一項所述之電極保護膜形成劑（F)。 5. 如中請專利範圍第4項所述之電解液，其路易斯鹼（C)。 6. 如中請專利範圍第5項所述之電解液，其中上述路 (C2^ (C)為氮雜冠崎生物（C1)及/或三°坐衍生物 Ή睛專利範圍第6項所述之電解液，其中上述氣 ^喊何生物（Cl)是在氮雜冠_環中的氮原子的1個以釔具有聚合性不飽和雙鍵的取代基而成的衍生物。 62 20120367^ 修正曰期:100年6月15日爲第ΐίο 109542號中文說明書無劃線修正本 8. 如申請專利範圍第7項所述之電解液，其中上述具有聚合性不飽和雙鍵的取代基為取代基（b)。、 9. 如申请專利範圍第6項所述之電解液，其中上 f冠醚衍生物（C1)的氮雜冠醚骨架為氮雜‘冠斗醚虱雜14冠-4-_、氮雜_15•冠_5_崎或者氮雜魯冠峻。一 10.如申明專利範圍第6項所述之電解液，其中 =衍生物（C2)為3•胺基_1>2,4•三唾、3 5m j 唑胺基-5-丙基-U，4-***或者3-胺基_5_丁基十认三電解H申Λ專包7圍。第Λ項Λ第10項中任一項所述之劑。〃匕35貝環或6員環的内醋化合物作為溶電解L2.=請專利範圍第4項至第10項中任一項所述之解液，其用於鋰二次電池或鋰離子電容器。 ◎述之電池’包含如申_範圍第12項所至第1^一由種鐘二次電池’具有由如申請專利範圍第1項形成的膜⑴壬2=3極保護卿成劑（F)反應而凡π膜u)所包覆的電極活性物質。 I5. —種鋰二次電池，其於正極專利範圍第！項至第3項中任及有如申請劑（P)。 M斤述之電極保護膜形成 16· 一種電極保護膜形成方法，其藉由對含有電極保 63 201203678 J / / / T|^1X X 修正日期:100年6月15日爲第100109542號中文說明書無劃線修正本護膜形成劑⑺的f解液進行充電而於電極表面形成膜，上述電極保濩膜形成劑（F)含有選自由下述（a1)、（A2)、 (A3)、（B1)及（B2)所組成組群中的至少1種化合物 (A)或化合物（B): (A1):具有下述通式（丨）所表示的烯氧基（a)的脂肪族烴； (A2).具有烯氧基（a)的多元醇的醚； (A3 ).具有烯氧基（a)的聚氧伸烧基驗； (B1):具有選自由下述通式（2)所表示的取代基、下述通式（3)所表示的取代基、（曱基)丙烯醯氧基烷基、及（曱基）丙稀醯基烧基所組成組群中的至少1種取代基（b) 的多元醇的_ ; (B2)：具有取代基（b)的聚氧伸烧基醚； [化4] —o - —C — =〇~τ3 1 | ⑴ 丁 1 γ2 [T、T及T為氫原子或碳數1〜3的烷基] [化5] —R2—C^=c—Q3 ln I Q1 ¥ 64 (2) 201203678 I t I (J^/χ A 1. 修正日期⑽年6月15日爲第100109542號中文說明書無劃線修正本 [式中，R2為碳數1〜3的伸烷基，qi、q2及獨立地為氫原子、i素原子、魏卜4的烧基、碳^ 或2的氟烧基、苯基、氰基、羧基、碳數丨〜3的碳數1〜4的烷氧基羰基] 土 3 [化6] 〇 Q4 Q5 Q6〇 [wherein, r3 is an alkylene group having 1 to 3 carbon atoms, Q4 is a hydrogen atom or a halogen atom, and Q5, Q6 and Q7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and carbon. A number of fluorenyl groups of 2 or 2, a phenyl group, a cyano group, a carboxyl group, an alkoxy group having a number of 1 to 3, or an alkoxycarbonyl group having a carbon number of 1-4. 2. The electrode (4) film forming agent (7)' of the above-mentioned item of the invention is in the form of a vinyloxy group or a propylene group. The electrode protective film forming agent (7) according to item 1 or item 2, wherein the electrode Laiqing agent (f) is included in the selection 61 201203678 ti I Λ. Amendment date: June 15, 100 The Chinese manual No. 100109542 is obtained by modifying at least one compound (A) in the group consisting of the free (Al), (A2) and (A3), and the above compound (A) is a compound of the formula (4) a compound represented by the formula, a compound represented by the formula (5) or a cyclohexane derivative having two or more ethyleneoxy groups or 1-propyleneoxy groups: R4-CH=CH-0-(CH2)p-0-CH =CH-R5 (4) [wherein, R4 and R5 are each independently a hydrogen atom or a fluorenyl group, and 卩 is an integer of i to 10] R6-CH=CH-0-(C2H40)q-CH=CH-R7 (1) wherein R6 and R7 are each independently a hydrogen atom or a methyl group, and q is an integer of i5. The 'electrolyte electrolyte' contains the electrode protective film forming agent (F) according to any one of the above claims. 5. The electrolyte of the fourth aspect of the patent, the Lewis base (C). 6. The electrolyte according to item 5 of the patent application, wherein the above-mentioned road (C2^(C) is a nitrogen azuki creature (C1) and/or a three-dimensional derivative derivative The electrolyte, wherein the above-mentioned gas (Cl) is a derivative of a nitrogen atom in the aza-ring-ring, which is a substituent having a polymerizable unsaturated double bond. 62 20120367^曰 : : 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 542 109 109 109 109 109 109 109 109 109 109 109 109 109 109 109 109 109 109 109 109 (b). 9. The electrolyte according to claim 6, wherein the azacrown ether skeleton of the upper f crown ether derivative (C1) is aza 'gypsum ether noisy 14 crown-4 - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ; 2, 4 • three saliva, 3 5m j oxazolyl-5-propyl-U,4-triazole or 3-amino _5-butyl ten recognized three electrolysis H Shen Λ special package 7 circumference. Item (10) The solution of the internal vinegar compound of the 贝35-shell or the 6-membered ring is used as the solution for the dissolution of the liquid. The solution of any one of the above-mentioned items of item 4 to 10 is used for a lithium secondary battery or lithium. The ion capacitor ◎ the battery described above includes the second battery of the clock from the 12th to the 1st, and has a film formed by the first item of the patent application (1) 壬 2 = 3 pole protection. The electrode active material coated with the agent (F) and coated with the π film u). I5. A kind of lithium secondary battery, which is in the scope of the positive electrode patent! From item to item 3, and as application (P). M electrode description of the electrode protective film formation 16 · A method for forming an electrode protective film, which is provided by the electrode holder 63 201203678 J / / / T|^1X X Revision date: June 15, 100 is the Chinese manual No. 100109542 The solution of the protective film forming agent (7) is charged to form a film on the surface of the electrode, and the electrode film forming agent (F) is selected from the following (a1), (A2), (A3), At least one compound (A) or compound (B) in the group consisting of (B1) and (B2): (A1): an aliphatic group having an alkenyloxy group (a) represented by the following formula (丨) (A2). an ether of a polyol having an alkenyloxy group (a); (A3). a polyoxyalkylene extension test having an alkenyloxy group (a); (B1): having a formula selected from the group consisting of 2) at least a substituent group, a substituent represented by the following formula (3), a (fluorenyl) acryloxyalkyl group, and a (fluorenyl) acrylonitrile group a polyol of one substituent (b); (B2): a polyoxyalkylene ether having a substituent (b); [Chemical 4] —o — —C — =〇~τ3 1 | (1) Γ2 [T, T and T are hydrogenogens Subunit or alkyl group having a carbon number of 1 to 3] [Chemical 5] —R 2 —C^=c—Q3 ln I Q1 ¥ 64 (2) 201203678 I t I (J^/χ A 1. Amendment date (10) June On the 15th, the Chinese manual No. 100109542 has no underline correction. [In the formula, R2 is an alkylene group having a carbon number of 1 to 3, qi, q2, and independently a hydrogen atom, an i atom, and a Weibu 4 group. a fluoroalkyl group of carbon^ or 2, a phenyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group having a carbon number of 33 and a carbon number of 1 to 4] soil 3 [Chemical 6] 〇Q4 Q5 Q6

(3) 〇 e nt 6 f1〜3的伸烧基，Q4為氯原子或鹵素 ^子’ Q、Q6及Q7分別獨立地為氫原子、齒素原子破數i〜4的燒基、碳數i或2的氣燒基、苯基、氛基、碳數1〜3的烷氧基或碳數1〜4的烷氧基羰基]。土 Π· —種鋰離子電容器，包含如申請專利範圍所述之電解液。項 18.-種雜子電容器’具有由如巾請專利範圍第！ 3項中任—項所述之電極保護膜形成劑而形成的膜⑺所包覆的電極活性物質。汉愿咬19· 一種鋰離子電容器，其於正極及/或負極含有如申响專利範圍第1項至第3項中任—項所述之電極保護膜二 65 201203678 ^"S)V〇9542號中文說明書無劃線修正本修正日期:100年6月15日成劑（F ) ° 66 201203678 爲第1^0109542號中文說明書無劃線修正本修正日期:1〇〇年ό月15日 high capacity, excellent charge-discharge cycle performance and high-temperature storage characteristics. The invention provides an electrode protective film-forming agent (F) comprising at least one compound (A) or compound (B), which is selected from a group consisting of the following (Al), (A2), (A3), (Bl), and (B2). (Al) is an aliphatic hydrocarbon having alkenyloxy (a) of specific structure; (A2) is a polyhydric alcohol ether having alkenyloxy (a); (A3) is a polyoxyalkylene ether having alkenyloxy (a ); (Bl) is a polyhydric alcohol ether having at least one substituent (b) selected from the group consisting of a substituent represented by general formula (2), a substituent represented by general formula (3), (meth)acryloyloxyalkyl and (meth)acryloylalkyl; (B2) is a polyoxyalkylene having a substituent (b) of specific structure. 四、指定代表圖： (一）本案指定代表圖為：無。 (二）本代表圖之元件符號簡單說明：無。五、本案若有化學式時’請揭示最能顯示發明特徽的化學式： 201203678 修正日期:1〇〇年6月15日爲第1^)109542號中文說明書無劃線修正本 Ο—c C .3 (1 ) .2(3) 伸e nt 6 f1~3 stretching base, Q4 is a chlorine atom or a halogen ^' Q, Q6 and Q7 are each independently a hydrogen atom, a dentine atom breaking number i~4, a carbon number, a carbon number The gas-burning group of i or 2, a phenyl group, an aryl group, an alkoxy group having 1 to 3 carbon atoms or an alkoxycarbonyl group having 1 to 4 carbon atoms]. A lithium ion capacitor comprising an electrolyte as described in the patent application. Item 18.---------- An electrode active material coated with a film (7) formed by the electrode protective film forming agent according to any one of the three items. Han will bite 19· A lithium-ion capacitor containing the electrode protective film as described in Item 1 to Item 3 of the patent scope of the patent and the negative electrode 65 201203678 ^"S)V〇 No. 9542 Chinese manual without slash correction This revision date: June 15th, 100th agent (F) ° 66 201203678 For the Chinese manual No. 1 0 019954, no slash correction. Amendment date: 1 ό ό 15 High capacity, excellent charge-discharge cycle performance and high-temperature storage characteristics. The invention provides an electrode protective film-forming agent (F) comprising at least one compound (A) or compound (B), which is selected from a group consisting Of the following (Al), (A2), (A3), (Bl), and (B2). (Al) is an aliphatic hydrocarbon having alkenyloxy (a) of specific structure; (A2) is a polyhydric alcohol ether having alkenyloxy (a); (A3) is a polyoxyalkylene ether having alkenyloxy (a ); (Bl) is a polyhydric alcohol ether having at least one substituent (b) selected from the group consisting of as Ubstituent represented by general formula (2), a substituent represented by general formula (3), (meth)acryloyloxyalkyl and (meth)acryloylalkyl; (B2) is a polyoxyalkylene having a substituent (b) of specific structure. : (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best displays the invention emblem: 201203678 Revision date: June 15th, 1st, 1st, 1st, 109,542 Chinese manual, no slash correction, Ο-c C. 3 (1 ) .2

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