JP2017188640A - Electrolyte solution, power storage device arranged by use thereof, and electric field capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an electrolyte solution which enables the stable operation of a capacitor even under a high-temperature condition when used in the capacitor; a power storage device arranged by use of the electrolyte solution; and an electric field capacitor.SOLUTION: An electrolyte solution comprises, as a solvent component, a compound A having a repeating structure expressed by the formula (1) below, and a terminal structure composed of hydrogen, a hydroxyl group or an alkoxy group, and/or a compound B having a repeating structure expressed by the formula (2) below, and a terminal structure composed of hydrogen, a hydroxyl group or an alkoxy group.SELECTED DRAWING: None

Description

  The present invention relates to an electrolytic solution, an electric storage device using the electrolytic solution, and an electric field capacitor.

  An electrolytic capacitor is generally manufactured by the following method. First, high-purity aluminum formed in a strip shape is chemically or electrochemically etched to expand the surface, and then subjected to a chemical conversion treatment in a chemical conversion solution such as an aqueous ammonium borate solution, so that the surface of the aluminum is formed. An oxide film layer is formed. While this is used as an anode foil, a high-purity aluminum is similarly subjected to a surface expansion treatment to form a cathode foil, and the anode foil and the cathode foil are wound through a separator to form a capacitor element. Next, the capacitor element is impregnated with a driving electrolyte solution and stored in a metal bottomed cylindrical outer case. Further, a sealing body (sealing rubber) made of elastic rubber is accommodated in the opening end portion of the outer case, and the opening end portion of the outer case is sealed by drawing to form an electrolytic capacitor.

However, the electrolytic capacitor as described above has a problem that when used at a high temperature, for example, 120 ° C. or more, the electrolytic solution is decomposed or volatilized, the capacitor function is lowered, and the life is shortened.
In an aluminum electrolytic capacitor, γ-butyrolactone and sulfolane are generally used as a solvent for the electrolytic solution. The use limit temperature is around 120 ° C. Aluminum electrolytic capacitors that will be used in automotive applications in the future will be provided with a cooling mechanism when installed in the engine room or in the vicinity of power devices that generate heat. In some cases, heat resistance of 150 ° C. or higher is required.

  In addition, when an aluminum electrolytic capacitor is used for in-vehicle use, it may be used even at a low temperature of −50 ° C. in winter in a cold region. Conventionally, it was not possible to operate stably at such a low temperature.

  Patent Document 1 describes an α, α′-substituted dibasic acid into which a dioxa skeleton structure is introduced as an electrolyte contained in an electrolytic solution for an aluminum electrolytic capacitor having both withstand voltage performance and heat resistance.

Japanese Patent Laying-Open No. 2015-032726

  An object of the present invention is to provide an electrolytic solution in which a capacitor operates stably at a high temperature when used in a capacitor, and an electric storage device and an electric field capacitor using the electrolytic solution.

（式（１）中、Ｒ^１は、水素；炭素数１〜２０の直鎖状炭化水素基；炭素数３〜２０の分岐状炭化水素基；炭素数３〜２０の環状炭化水素基；炭素数１〜２０のアルコキシル基；又は炭素数１〜２０の直鎖状炭化水素基、炭素数３〜２０の分岐状炭化水素基、炭素数３〜２０の環状炭化水素基、及び炭素数１〜２０のアルコキシル基から選択される２以上の置換基が組み合わさってなる基である。複数存在するＲ^１は互いに同じでも異なってもよい。
ｎは、平均繰返し数であり、５〜１０００の数である。）
（式（２）中、Ｒ^２は、炭素数１〜２０の直鎖状炭化水素基；炭素数３〜２０の分岐状炭化水素基；炭素数３〜２０の環状炭化水素基；炭素数１〜２０の直鎖状炭化水素基、炭素数３〜２０の分岐状炭化水素基、及び炭素数３〜２０の環状炭化水素基から選択される２以上の置換基が組み合わさってなる基；又は炭素数１〜２０の直鎖状炭化水素基、炭素数３〜２０の分岐状炭化水素基、及び炭素数３〜２０の環状炭化水素基から選択される２以上の置換基が組み合わさってなる基と、炭素数１〜２０のアルコキシル基が結合した基である。複数存在するＲ^２は互いに同じでも異なってもよい。
ｍは、平均繰返し数であり、５〜１０００の数である。）
２．前記化合物Ａが、下記式（１ａ）で表される繰返し構造と、下記式（１ｂ）で表される繰返し構造を有し、
前記式（１ａ）で表される繰返し構造と、前記式（１ｂ）で表される繰返し構造のモル比は、９９：１〜１：９９であり、
末端構造は水素、水酸基又はアルコキシ基である共重合体である１に記載の電解液。

（式（１ａ）及び式（１ｂ）中、Ｒ^１１及びＲ^１２は、式（１）のＲ^１と同じであるが、Ｒ^１１とＲ^１２は互いに異なる。Ｒ^１１が複数のときＲ^１１は互いに同じでも異なってもよい。Ｒ^１２が複数のときＲ^１２は互いに同じでも異なってもよい。）
３．前記化合物Ｂを含む１又は２に記載の電解液。
４．前記溶媒成分に含まれるＡｇ、Ａｌ、Ｂａ、Ｃａ、Ｃｄ、Ｃｏ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎａ、Ｎｉ、Ｐｂ、Ｓｎ、Ｖ及びＺｎの含有量が、それぞれ１ｐｐｍ以下である１〜３のいずれかに記載の電解液。
５．前記溶媒成分に含まれるフッ素、塩素、臭素及びヨウ素の含有量が、それぞれ２ｐｐｍ以下である１〜４のいずれかに記載の電解液。
６．１〜５のいずれかに記載の電解液を含む蓄電デバイス。
７．１〜５のいずれかに記載の電解液を含むアルミ電解コンデンサ。
８．１〜５のいずれかに記載の電解液を含む、液系アルミ電解コンデンサ又はハイブリッド型アルミ電解コンデンサ。
９．１〜５のいずれかに記載の電解液を含むキャパシタ。
１０．１〜５のいずれかに記載の電解液を含むリチウムイオン電池。 According to the present invention, the following electrolytic solution and the like can be provided.
1. The compound has a repeating structure represented by the following formula (1), the terminal structure is a compound A which is hydrogen, a hydroxyl group or an alkoxy group, and / or has a repeating structure represented by the following formula (2), and the terminal structure is Compound B which is hydrogen, hydroxyl group or alkoxy group
Electrolyte solution containing as a solvent component.

(In Formula (1), R ¹ is hydrogen; a linear hydrocarbon group having 1 to 20 carbon atoms; a branched hydrocarbon group having 3 to 20 carbon atoms; a cyclic hydrocarbon group having 3 to 20 carbon atoms; carbon A C1-C20 linear hydrocarbon group, a C3-C20 branched hydrocarbon group, a C3-C20 cyclic hydrocarbon group, and a C1-C20 alkoxyl group; It is a group formed by combining two or more substituents selected from 20 alkoxyl groups, and a plurality of R ¹ may be the same or different.
n is an average number of repetitions, and is a number of 5 to 1000. )
(In the formula (2), R ² represents a linear hydrocarbon group having 1 to 20 carbon atoms; a branched hydrocarbon group having 3 to 20 carbon atoms; a cyclic hydrocarbon group having 3 to 20 carbon atoms; A group formed by combining two or more substituents selected from a linear hydrocarbon group of -20, a branched hydrocarbon group of 3 to 20 carbon atoms, and a cyclic hydrocarbon group of 3 to 20 carbon atoms; or Two or more substituents selected from a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon group having 3 to 20 carbon atoms are combined. A group bonded to an alkoxyl group having 1 to 20 carbon atoms, and a plurality of R ² may be the same or different from each other.
m is an average number of repetitions, and is a number of 5 to 1000. )
2. Compound A has a repeating structure represented by the following formula (1a) and a repeating structure represented by the following formula (1b),
The molar ratio of the repeating structure represented by the formula (1a) and the repeating structure represented by the formula (1b) is 99: 1 to 1:99,
2. The electrolytic solution according to 1, wherein the terminal structure is a copolymer having hydrogen, a hydroxyl group, or an alkoxy group.

(In the formula (1a) and the formula ^{(1b), R 11} and ^{R 12} are the same as ^{R 1} of formula ^(1), when different ^{.R 11 R 11} and ^{R 12} are each of a plurality ^{R 11} is together when good .R ¹² be the same or different is a multiple R ¹² may be the same or different.)
3. The electrolyte solution according to 1 or 2 containing the compound B.
4). The contents of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sn, V, and Zn contained in the solvent component are each 1 ppm. The electrolyte solution in any one of 1-3 which is the following.
5. Electrolyte solution in any one of 1-4 whose content of the fluorine, chlorine, bromine, and iodine contained in the said solvent component is 2 ppm or less, respectively.
The electrical storage device containing the electrolyte solution in any one of 6.1-5.
An aluminum electrolytic capacitor containing the electrolytic solution according to any one of 7.1 to 5.
A liquid type aluminum electrolytic capacitor or a hybrid type aluminum electrolytic capacitor containing the electrolytic solution according to any one of 8.1 to 5.
The capacitor containing the electrolyte solution in any one of 9.1-5.
The lithium ion battery containing the electrolyte solution in any one of 10.1-5.

  ADVANTAGE OF THE INVENTION According to this invention, when used for a capacitor | condenser, the electrolyte solution which a capacitor | condenser operate | moves stably at high temperature, an electrical storage device using the same, and an electric field capacitor can be provided.

式（１）中、Ｒ^１は、水素；炭素数１〜２０の直鎖状炭化水素基；炭素数３〜２０の分岐状炭化水素基；炭素数３〜２０の環状炭化水素基；炭素数１〜２０のアルコキシル基；又は炭素数１〜２０の直鎖状炭化水素基、炭素数３〜２０の分岐状炭化水素基、炭素数３〜２０の環状炭化水素基、及び炭素数１〜２０のアルコキシル基から選択される２以上の置換基が組み合わさってなる基である。複数存在するＲ^１は互いに同じでも異なってもよい。
ｎは、平均繰返し数であり、５〜１０００の数である。
式（２）中、Ｒ^２は、炭素数１〜２０の直鎖状炭化水素基；炭素数３〜２０の分岐状炭化水素基；炭素数３〜２０の環状炭化水素基；炭素数１〜２０の直鎖状炭化水素基、炭素数３〜２０の分岐状炭化水素基、及び炭素数３〜２０の環状炭化水素基から選択される２以上の置換基が組み合わさってなる基；又は炭素数１〜２０の直鎖状炭化水素基、炭素数３〜２０の分岐状炭化水素基、及び炭素数３〜２０の環状炭化水素基から選択される２以上の置換基が組み合わさってなる基と、炭素数１〜２０のアルコキシル基が結合した基である。複数存在するＲ^２は互いに同じでも異なってもよい。
ｍは、平均繰返し数であり、５〜１０００の数である。
化合物Ａ，Ｂの重量平均分子量は、好ましくは２００〜２００００、より好ましくは２００〜１００００である。
重量平均分子量並びに平均繰返し数ｎ及びｍはＧＰＣ測定により算出できる。 Hereinafter, the electrolytic solution of the present invention will be described.
<Solvent>
The electrolytic solution of the present invention has a repeating structure represented by the following formula (1), and the terminal structure is hydrogen, a hydroxyl group or an alkoxy group, compound A (polyalkylene glycol (PAG) derivative), and / or Compound B (polyvinyl ether (PVE) derivative) having a repeating structure represented by formula (2) and having a terminal structure of hydrogen, a hydroxyl group or an alkoxy group is included as a solvent component.

In the formula (1), R ¹ is hydrogen; a linear hydrocarbon group having 1 to 20 carbon atoms; a branched hydrocarbon group having 3 to 20 carbon atoms; a cyclic hydrocarbon group having 3 to 20 carbon atoms; An alkoxyl group having 1 to 20 carbon atoms; or a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, a cyclic hydrocarbon group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms. These are groups formed by combining two or more substituents selected from the alkoxyl groups. A plurality of R ¹ may be the same as or different from each other.
n is an average number of repetitions, and is a number of 5 to 1000.
In the formula (2), R ² represents a linear hydrocarbon group having 1 to 20 carbon atoms; a branched hydrocarbon group having 3 to 20 carbon atoms; a cyclic hydrocarbon group having 3 to 20 carbon atoms; A group formed by combining two or more substituents selected from 20 linear hydrocarbon groups, branched hydrocarbon groups having 3 to 20 carbon atoms, and cyclic hydrocarbon groups having 3 to 20 carbon atoms; or carbon A group formed by combining two or more substituents selected from a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon group having 3 to 20 carbon atoms And a group to which an alkoxyl group having 1 to 20 carbon atoms is bonded. A plurality of R ² may be the same or different.
m is an average number of repetitions, and is a number of 5 to 1000.
The weight average molecular weight of the compounds A and B is preferably 200 to 20000, more preferably 200 to 10,000.
The weight average molecular weight and the average repeating numbers n and m can be calculated by GPC measurement.

Each of the compounds A and B may be a homopolymer or a copolymer, and the copolymer may be an alternating copolymer, a random copolymer, a graft copolymer, or a block copolymer. For example, in the compound A, a homopolymer can be formed when n pieces of R ¹ are the same, and a copolymer can be formed when n pieces of R ¹ are different. The melting point (freezing point) can be lowered by using a copolymer. As a result, it is possible to maintain a liquid state without condensing and solidifying even at a low temperature of −40 ° C. or lower. For example, when used for a capacitor, the capacitor can be stably operated.

式（１ａ）及び式（１ｂ）中、Ｒ^１１及びＲ^１２は、式（１）のＲ^１と同じであるが、Ｒ^１１とＲ^１２は互いに異なる。Ｒ^１１が複数のときＲ^１１は互いに同じでも異なってもよい。Ｒ^１２が複数のときＲ^１２は互いに同じでも異なってもよい。
式（１ａ）で表される繰返し構造と、式（１ｂ）で表される繰返し構造のモル比は、繰返し構造（１ａ）：繰返し構造（１ｂ）＝９９：１〜１：９９である。
構造及び組成は、^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲにより分析できる。 For example, Compound A is a copolymer having a repeating structure represented by the following formula (1a) and a repeating structure represented by the following formula (1b), and the terminal structure is hydrogen, a hydroxyl group or an alkoxy group. .

In formula (1a) and formula (1b), R ¹¹ and R ¹² are the same as R ^{1 in} formula (1), but R ¹¹ and R ¹² are different from each other. When R ¹¹ is plural, R ¹¹ may be the same as or different from each other. When R ¹² is plural, R ¹² may be the same as or different from each other.
The molar ratio of the repeating structure represented by the formula (1a) and the repeating structure represented by the formula (1b) is the repeating structure (1a): the repeating structure (1b) = 99: 1 to 1:99.
The structure and composition can be analyzed by ¹ H-NMR and ¹³ C-NMR.

  The electrolytic solution of the present invention contains compound A and / or compound B, so that it does not disappear even at high temperatures. For example, when used in a capacitor, the capacitor operates stably.

In the above formulas (1) and (2), the linear hydrocarbon group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. It is a linear alkyl group, More preferably, it is a C1-C6 linear alkyl group. Specific examples include a methyl group and an ethyl group.
The branched hydrocarbon group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and further preferably 3 carbon atoms. -6 branched alkyl groups. Specific examples include isopropyl group and isobutyl group.
The cyclic hydrocarbon group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 20 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxyl group having 1 to 10 carbon atoms, and more preferably an alkoxyl group having 1 to 6 carbon atoms. Specific examples include methoxy group, ethoxy group, isopropyloxy group and the like.
2 selected from a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, a cyclic hydrocarbon group having 3 to 20 carbon atoms, and an alkoxyl group having 1 to 20 carbon atoms. Preferable examples and specific examples of the groups constituting the group formed by combining the above substituents are the same as described above. Specific examples of the combined group include 2-methoxyethyl group, 2-ethoxyethyl and the like.
Two or more substituents selected from a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon group having 3 to 20 carbon atoms are combined. The suitable example and specific example of each group which comprise the group which group and the C1-C20 alkoxyl group couple | bonded are the same as the above. Specific examples of the bonded group include 2- (cyclohexylmethoxy) ethyl and the like.

n is preferably 5 to 500, more preferably 5 to 200.
m is preferably 5 to 400, and more preferably 5 to 150.

  Among the compounds A, the compound having a hydroxyl group at the terminal (polyalkylene glycol derivative) preferably has a hydroxyl group content of 50 mol% or less based on the total terminal groups. When the hydroxyl group content exceeds 50 mol%, the hygroscopicity increases and the viscosity index may be lowered.

  As such a polyalkylene glycol derivative, for example, polypropylene glycol dimethyl ether, polyoxyethylene, polypropylene glycol dimethyl ether, polypropylene glycol monobutyl ether, polypropylene glycol diacetate and the like are preferable in terms of economy and effect. In the case of a copolymer comprising polyoxypropylene (PO) units and polyoxyethylene (EO) units such as polyoxypropylene polyoxyethylene copolymer dimethyl ether, the molar ratio of PO / EO is 99: 1 to 1. : 99, and either a random polymer or a block polymer may be used.

  Furthermore, any of the polyalkylene glycol derivatives described in detail in JP-A-2-305893 can be used.

  Examples of compound B are those obtained by polymerizing vinyl ether monomers (hereinafter referred to as polyvinyl ether I), and those obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having olefinic double bonds. (Hereinafter referred to as polyvinyl ether copolymer II) and a copolymer of polyvinyl ether and alkylene glycol or polyalkylene glycol, or a monoether thereof (hereinafter referred to as polyvinyl ether copolymer III). .

  Examples of the vinyl ether monomer used as a raw material for the polyvinyl ether I include vinyl methyl ether; vinyl ethyl ether; vinyl-n-propyl ether; vinyl-isopropyl ether; vinyl-n-butyl ether; vinyl-isobutyl ether; Vinyl-tert-butyl ether; vinyl-n-pentyl ether; vinyl-n-hexyl ether; vinyl-2-methoxyethyl ether; vinyl-2-ethoxyethyl ether; vinyl-2-methoxy-1-methylethyl ether; 2-methoxy-propyl ether; vinyl-3,6-dioxaheptyl ether; vinyl-3,6,9-trioxadecyl ether; vinyl-1,4-dimethyl-3,6-dioxaheptyl ether Ter; vinyl-1,4,7-trimethyl-3,6,9-trioxadecyl ether; vinyl-2,6-dioxa-4-heptyl ether; vinyl-2,6,9-trioxa-4-decyl ether 1-methoxypropene; 1-ethoxypropene; 1-n-propoxypropene; 1-isopropoxypropene; 1-n-butoxypropene; 1-isobutoxypropene; 1-sec-butoxypropene; 1-tert-butoxypropene; 2-methoxypropene; 2-ethoxypropene; 2-n-propoxypropene; 2-isopropoxypropene; 2-n-butoxypropene; 2-isobutoxypropene; 2-sec-butoxypropene; 2-tert-butoxypropene 1-methoxy-1-butene; 1-ethoxy-1-butene; 1-n- 1-isopropoxy-1-butene; 1-n-butoxy-1-butene; 1-isobutoxy-1-butene; 1-sec-butoxy-1-butene; 1-tert-butoxy-1 2-butene; 2-methoxy-1-butene; 2-ethoxy-1-butene; 2-n-propoxy-1-butene; 2-isopropoxy-1-butene; 2-n-butoxy-1-butene; Isobutoxy-1-butene; 2-sec-butoxy-1-butene; 2-tert-butoxy-1-butene; 2-methoxy-2-butene; 2-ethoxy-2-butene; 2-n-propoxy-2- 2-isopropoxy-2-butene; 2-n-butoxy-2-butene; 2-isobutoxy-2-butene; 2-sec-butoxy-2-butene; 2-tert-butoxy-2 -Butene etc. are mentioned. These vinyl ether monomers can be produced by known methods.

  These vinyl ether monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the vinyl ether monomer used as a raw material for the polyvinyl ether copolymer II include the same vinyl ether monomers as those exemplified above, and these may be used alone or in combination of two or more. May be.

  Further, as another raw material hydrocarbon monomer having an olefinic double bond, for example, ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, α -Methyl styrene, various alkyl substituted styrenes, etc. can be mentioned.

  These hydrocarbon monomers having an olefinic double bond may be used alone or in combination of two or more. Moreover, this polyvinyl ether copolymer II may be either a block or a random copolymer.

  The polyvinyl ether I and the polyvinyl ether copolymer II can be produced, for example, by the following method.

  For the initiation of the polymerization, a combination of an adduct of water, alcohols, phenols, acetals or vinyl ethers with a carboxylic acid may be used for Bronsted acids, Lewis acids or organometallic compounds. it can. Examples of Bronsted acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid and the like. Examples of Lewis acids include boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, and ferric chloride. Among these Lewis acids, boron trifluoride is particularly preferred. Is preferred. Examples of the organometallic compound include diethyl aluminum chloride, ethyl aluminum chloride, diethyl zinc and the like.

  The polymerization initiation terminal of the polymer is such that when water, alcohols or phenols are used, hydrogen is bonded, and when acetals are used, one alkoxy group is eliminated from hydrogen or the used acetals. When an adduct of vinyl ethers and carboxylic acid is used, the alkylcarbonyloxy group derived from the carboxylic acid moiety is eliminated from the adduct of vinyl ethers and carboxylic acid.

  On the other hand, when water, alcohols, phenols, or acetals are used, the terminal ends are acetals, olefins, or aldehydes. In the case of an adduct of vinyl ethers and carboxylic acid, it becomes a carboxylic acid ester of hemiacetal. The terminal of the polymer thus obtained can be converted into a predetermined group by a known method.

  Although this polymerization reaction depends on the type of raw material and initiator, it can be initiated between -80 and 150 ° C, and can usually be carried out at a temperature in the range of -80 to 50 ° C. The polymerization reaction is completed in about 10 seconds to 10 hours from the start of the reaction. The polymerization reaction is usually performed in the presence of a solvent. The solvent is not particularly limited as long as it dissolves a necessary amount of the reaction raw material and is inert to the reaction. For example, hydrocarbons such as hexane, benzene, and toluene, and ethyl ether, 1,2- Ether solvents such as dimethoxyethane and tetrahydrofuran can be preferably used.

  On the other hand, the polyvinyl ether copolymer III can be produced by polymerizing a vinyl ether monomer according to the polymerization method using an alkylene glycol or polyalkylene glycol, or a monoether thereof as an initiator.

  Examples of the alkylene glycol or polyalkylene glycol, or monoethers thereof include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol, and polyalkylene glycols. ; Mentioning alkylene glycol monoethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and polyalkylene glycol monoethers; It can be.

  Moreover, as a vinyl ether monomer used as a raw material, the same thing as what was illustrated as a vinyl ether monomer in description of the said polyvinyl ether I can be mentioned. This vinyl ether monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The electrolytic solution of the present invention preferably contains at least Compound B. For example, only compound B may be included, or both compounds A and B may be included. Further, the compound A may include a plurality of different compounds A, and the compound B may include a plurality of different compounds B.

The swelling of the sealing rubber can be arbitrarily controlled by selecting a rubber material according to the SP value of the solvent to be used (selecting a rubber and a solvent having a large ΔSP value), but Compound A and Compound B are polymers and have a molecular weight distribution. For this reason, the swelling due to the high molecular weight material having a particularly small SP value becomes dominant.
From the viewpoint of the SP value, Compound B is less sensitive to the SP value due to the difference in molecular weight, and even when the molecular weight of Compound B changes, the swelling property of the sealing rubber does not change stably. In Compound A, when there is a difference in molecular weight, the influence on the swelling property of the sealing rubber is greatly changed. Therefore, as a result, the swelling property of the sealing rubber is larger in the compound A due to the influence of the high molecular weight component, and the swelling by the high molecular weight material is relatively less in the compound B. Therefore, the durability of the aluminum electrolytic capacitor is higher when the compound B is used.

The solvent of the electrolytic solution is preferably low in the content of metal ions and halogen ions.
For example, in a liquid electrolytic capacitor, if the electrolytic solution contains metal ions and / or halogen ions, corrosion of the anode foil, the cathode foil, the separator, the sealing body, and the outer case may be accelerated. Also, during the operation of the electrolytic capacitor, the electrolytic solution is decomposed by an electrochemical reaction, the positive foil, the negative foil and the outer case are corroded, the separator is deteriorated and short-circuited, the sealing body is deteriorated and the electrolytic solution is leaked, Events such as deposition of metal components derived from metal ions contained on the cathode foil may occur, resulting in a decrease in durability and life. Furthermore, these problems are exacerbated as the electrolytic capacitors are placed at higher temperatures.

The contents of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sn, V, and Zn contained in the solvent component of the electrolyte are: Each is preferably 1 ppm or less.
The content of fluorine, chlorine, bromine and iodine contained in the solvent component of the electrolytic solution is preferably as small as possible, specifically 2 ppm or less, more preferably 1 ppm or less.
The content of the metal element and the halogen element is a weight fraction in the solvent component and can be confirmed by the method described in the examples.

  The allowable content of metal ions and halogen ions in the solvent of the electrolytic solution cannot be generally defined by the type of storage device using the electrolytic solution, the structure, the type of member used, or the conditions of use. In the case of a type electrolytic capacitor, the above range is preferable.

The solvent can contain other solvent components in addition to the above-mentioned compounds A and B.
Other solvent components include, for example, water, protic polar solvents, aprotic solvents, and mixtures thereof. Specifically, as the protic polar solvent, monohydric alcohol (methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, cyclopentanol, benzyl alcohol, etc.), polyhydric alcohol and oxyalcohol compounds (ethylene glycol, propylene) Glycol, glycerin, methyl cellosolve, ethyl cellosolve, 1,3-butanediol, methoxypropylene glycol, etc.). As aprotic solvents, amides (N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, hexamethylphosphoric amide, etc.), cyclic amides (N-methyl-2-pyrrolidone, etc.), lactones (γ-butyrolactone, δ-valerolactone, γ-valerolactone, etc.), sulfolanes (sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, etc.), carbonate (Ethylene carbonate, propylene carbonate, etc.), nitriles (acetonitrile), sulfoxides (dimethyl sulfoxide, etc.) and the like. Preferred are γ-butyrolactone, sulfolane and the like.

  The solvent of the electrolytic solution preferably contains Compound A and / or B in an amount of 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more. The compounds A and B may be contained by 100% by weight.

<Solute>
As the solute of the electrolytic solution, amine salts or ammonium salts of carboxylic acids such as adipic acid, formic acid, benzoic acid and the like can be used. As amines constituting the amine salt, primary amines (methylamine, ethylamine, propylamine, butylamine, ethylenediamine, monoethanolamine, etc.), secondary amines (dimethylamine, diethylamine, dipropylamine, ethylmethylamine, diphenylamine, diethanolamine) Etc.), tertiary amines (trimethylamine, triethylamine, ethyldimethylamine, tributylamine, 1,8-diazabicyclo (5,4,0) -undecene-7, triethanolamine, etc.).

  Furthermore, the following acids can also be used as the carboxylic acid. Formic acid, glutaric acid, adipic acid, succinic acid, isophthalic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, toluic acid, enanthic acid, malonic acid, 1,6-decanedicarboxylic acid and 5,6-decanedicarboxylic acid Decanedicarboxylic acid such as 1,7-octanedicarboxylic acid, and carboxylic acid such as azelaic acid and sebacic acid. In addition, boric acid, a polyhydric alcohol complex compound of boric acid obtained from boric acid and a polyhydric alcohol, and inorganic acids such as phosphoric acid, carbonic acid, and silicic acid can also be used. Among these, decanedicarboxylic acid, octanedicarboxylic acid, azelaic acid, sebacic acid, adipic acid, glutaric acid, succinic acid, benzoic acid, isophthalic acid, formic acid and other organic carboxylic acids, or boric acid and boric acid are preferred. It is a polyhydric alcohol complex compound.

As the solute, an N-acylglutamic acid compound represented by the following formula can be used. This compound is N-acylglutamic acid having 17 to 36 carbon atoms and / or an ammonium salt thereof and an organic ammonium salt. Note that the dotted bond in the formula represents an ionic bond.

In the formula, R ¹ and R ² represent a hydrogen ion, an ammonium ion, or an organic ammonium ion, and R ¹ and R ² may be the same or different from each other. R ³ represents an alkyl group having 11 or 12 carbon atoms, a benzyl group or a naphthyl group, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a benzyl group. The alkyl group represents a linear, branched, cyclic, or a combination thereof. Here, R ³ is preferably an alkyl group having 11 or 12 carbon atoms, and R ⁴ is preferably a hydrogen atom.

Specific examples of R ¹ and R ^{2 in} the above formula include hydrogen ions (H ⁺ ), ammonium ions (NH ₄ ⁺ ); quaternary ammonium ions of primary amines such as methylamine, ethylamine, and t-butylamine (of primary amines). Proton adduct); quaternary ammonium ions of secondary amines such as dimethylamine, ethylmethylamine, and diethylamine (proton adducts of secondary amine); tertiary amines such as trimethylamine, diethylmethylamine, ethyldimethylamine, and triethylamine Quaternary ammonium ion (proton adduct of tertiary amine); quaternary ammonium ion such as tetramethylammonium ion, triethylmethylammonium ion, tetraethylammonium ion; 1,2,3,4-tetramethylimidazolinium ion, 1,3,4 -Trimethyl-2-ethylimidazolinium ion, 1,3-dimethyl-2,4-diethylimidazolinium ion, 1,2-dimethyl-3,4-diethylimidazolinium ion, 1-methyl-2,3 , 4-triethylimidazolinium ion, 1,2,3,4-tetraethylimidazolinium ion, 1,2,3-trimethylimidazolinium ion, 1,3-dimethyl-2-ethylimidazolinium ion, 1 -Ethyl-2,3-dimethylimidazolinium ion, 1,2,3-triethylimidazolinium ion, 4-cyano-1,2,3-trimethylimidazolinium ion, 3-cyanomethyl-1,2-dimethyl Imidazolinium ion, 2-cyanomethyl-1,3-dimethylimidazolinium ion, 4-acetyl-1,2, -Trimethylimidazolinium ion, 3-acetylmethyl-1,2-dimethylimidazolinium ion, 4-methylcarbooxymethyl-1,2,3-trimethylimidazolinium ion, 3-methylcarbooxymethyl-1, 2-dimethylimidazolinium ion, 4-methoxy-1,2,3-trimethylimidazolinium ion, 3-methoxymethyl-1,2-dimethylimidazolinium ion, 4-formyl-1,2,3-trimethyl Imidazolinium ion, 3-formylmethyl-1,2-dimethylimidazolinium ion, 3-hydroxyethyl-1,2-dimethylimidazolinium ion, 4-hydroxymethyl-1,2,3-trimethylimidazolinium Ion, 2-hydroxyethyl-1,3-dimethylimidazolinium Imidazolinium ions (cations having an imidazole ring), etc. etc., but is preferably an ammonium ion.

式中、Ｒ_１，Ｒ_２，Ｒ_３及びＲ_４は、それぞれ水素又は炭素数１〜６のアルキル基を示す。ただし、Ｒ_１，Ｒ_２，Ｒ_３，及びＲ_４のうち少なくとも１つはアルキル基を示す。 As the solute, a compound represented by the following formula (α, α′-substituted dibasic acid) or a salt of the compound can be used.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent hydrogen or an alkyl group having 1 to 6 carbon atoms. However, at least one of R ₁ , R ₂ , R ₃ , and R ₄ represents an alkyl group.

R ₀ is a branched alkyl group having 4 to 16 carbon atoms, a group having an aliphatic ring represented by any of the following formulas,

からなる群より選ばれたものである。 And a group having an aromatic ring represented by any of the following formulae:

Is selected from the group consisting of

Examples of the branched alkyl group having 4 to 16 carbon atoms of R ₀ include a branched alkyl group represented by the following formula.

R ₀ is a branched alkyl group having 4 to 16 carbon atoms, but has a group having an aliphatic ring represented by the above formula (a group having a cyclohexanedimethanol skeleton, a group having a hydrogenated bisphenol A skeleton, a tricyclo group). A group having a decanedimethanol skeleton) having an aromatic ring represented by the above formula (a group in which a certain number of alkylene oxide units are bonded to the OH groups at both ends of bisphenol A), Also good. When R ₀ is a group having an aliphatic ring, a part of these aliphatic rings may be substituted, and when R ₀ is a group having an aromatic ring, Some may be substituted.
In the case where R ₀ is a branched alkyl group, the effect of improving the withstand voltage is lowered when the number of carbons in the group is 3 or less, and the solubility is lowered when the number of carbons exceeds 16. The number is 4-16 or more preferably 4-12.

R ₁ , R ₂ , R ₃ , and R ₄ in the above formula are hydrogen, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc., and may include one or more of them. , R ₁ , R ₂ , R ₃ , R ₄ are more preferably an alkyl group, and at least one of R ₁ and R ₂ and at least one of R ₃ and R ₄ are an alkyl group Is particularly preferred. When there is an alkyl group at the α-position of the carboxyl group, steric hindrance occurs due to the bulkiness of the alkyl group, and due to the adjacent electron-donating group, the esterification reaction with the OH group of ethylene glycol, which is the solvent, occurs There is merit to be suppressed.

  Preferred salts of the above α, α′-substituted dibasic acids include diammonium salts, primary amine salts such as methylamine, ethylamine and t-butylamine, and secondary amines such as dimethylamine, ethylmethylamine and diethylamine. Salts, tertiary amine salts such as trimethylamine, diethylmethylamine, ethyldimethylamine, and triethylamine, quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium, and tetraethylammonium, molten salts such as imidazolinium salts and imidazolium salts Particularly preferred are the diammonium salts.

The solute may contain only one type of the above electrolyte or two or more types.
In the electrolytic solution, the amount of solvent and the dissolved mass differ depending on the use of the electrolytic solution and the operating voltage, and are not particularly limited. However, the amount of solvent is 50.0 to 99.5% by mass, and the dissolved mass is 0.5 to 50. 0% by mass is preferred.

<Additives>
When the electrolytic solution is used in an electrolytic capacitor, nitrophenol, nitrobenzoic acid, nitroacetophenone, nitrobenzyl alcohol, 2- (nitrophenoxy) ethanol, nitroanisole, nitrophenetole, Aromatic nitro compounds such as nitrotoluene and dinitrobenzene can be added.

  In addition, for the purpose of improving the safety of electrolytic capacitors, nonionic surfactants that can improve the withstand voltage of electrolytic solutions, polyoxygens obtained by addition polymerization of polyhydric alcohols and ethylene oxide and / or propylene oxide An alkylene polyhydric alcohol ether compound and polyvinyl alcohol can also be added.

  Furthermore, as additives, orthophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, methyl phosphate, ethyl phosphate, butyl phosphate, isopropyl phosphate, dibutyl phosphate, dioctyl phosphate, etc. Boric acid compounds such as phosphoric acid compounds, boric acid and complex compounds thereof, polyhydric alcohols such as mannitol, sorbitol, xylitol, pentaerythritol, polyvinyl alcohol, nitro compounds such as p-nitrobenzoic acid, m-nitroacetophenone, Colloidal silica, aluminosilicate and silicone compounds (for example, reactive-modified hydroxy-modified silicone, amino-modified silicone, carboxyl-modified silicone, alcohol-modified silicone, epoxy-modified silicone, etc.) and silane coupling agents (for example, 3-glycidoxy Trimethoxysilane, vinyl trimethoxysilane, ethyl triethoxysilane, etc.) silicon compounds such as and the like.

  Adipic acid, azelaic acid, sebacic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid, etc., which are higher dibasic acids as required in the electrolyte An aromatic carboxylic acid such as an aliphatic carboxylic acid or benzoic acid, or a salt thereof can also be contained.

  When the electrolytic solution of the present invention is used in an electrolytic capacitor, various additives can be added for the purpose of reducing leakage current, improving withstand voltage, and gas absorbents. Examples of these additives include phosphoric acid compounds and boric acid compounds. , Polyhydric alcohols, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyoxyethylene, polymer compounds represented by random copolymers and block copolymers of polyoxypropylene glycol, nitro compounds, and the like.

<Electrode foil>
It does not specifically limit as electrode foil used for an electrolytic capacitor, For example, aluminum, titanium, niobium, a tantalum etc. are mentioned.

  The electrolytic solution of the present invention can be used for power storage devices such as capacitors (for example, liquid electrolytic capacitors, hybrid aluminum electrolytic capacitors), capacitors, lithium ion batteries and the like. In particular, the present invention is useful for liquid capacitors that require durability at high temperatures. For example, it can be used for a liquid type aluminum electrolytic capacitor.

  A liquid type aluminum electrolytic capacitor is generally an aluminum anode foil having an oxide film layer formed on the surface thereof and an aluminum cathode foil wound through a separator to form a capacitor element, which is impregnated with an electrolytic solution. It is.

Such a capacitor can be manufactured by the following method.
First, an anode lead and a cathode lead were respectively joined to an anode foil and an aluminum cathode foil having a dielectric oxide film formed on the surface of the aluminum foil, and then the foil was wound through a separator, A capacitor element is obtained by impregnating the electrolytic solution of the invention.

  Next, the element is placed in a metal cylindrical container, the positive electrode lead is passed through the sealing rubber, the opening is sealed, and the aluminum electrolytic capacitor is completed.

  The liquid electrolytic capacitor of the present invention has an advantage of higher electrostatic capacity than solid aluminum electrolytic capacitors and hybrid aluminum electrolytic capacitors.

  The hybrid aluminum electrolytic capacitor of the present invention has the advantages that the ESR (equivalent series resistance) is low and the ripple current is high at the same level as the conductive polymer capacitor, compared to the liquid electrolytic capacitor.

  The capacitor of the present invention is inferior in terms of output density as compared with the capacitor, but has an advantage of high energy density.

  The lithium ion battery of the present invention has an advantage that the energy density is extremely high as compared with a capacitor and a capacitor.

  Hereinafter, the present invention will be described using examples and comparative examples. However, the present invention is not limited to these examples.

Examples 1 to 3, Comparative Examples 1 and 2
Using 0.5 g of tetraethylammonium phthalate as a solute, 0.01 g of diphosphorus pentoxide as an additive, and 10 ml of a solvent component shown in Table 1 as a solvent, these were mixed to prepare an electrolytic solution.
The weight average molecular weight, structure and composition of the solvent components shown in Table 1 were analyzed by GPC (polystyrene conversion), ¹ H-NMR and ¹³ C-NMR.

Evaluation Example 1 (Evaluation of heat resistance)
The boiling points of the solvent components described in Table 1 were measured using an automatic distillation tester ADU 5 (manufactured by Anton Paar). The results are listed in Table 1. From the results of Table 2, assuming that an aluminum electrolytic capacitor containing an electrolytic solution using each solvent component is operated at 150 ° C., the internal pressure of the capacitor is increased in the GBL of Comparative Example 1 and the SF of Comparative Example 2 due to the sealing. The solvent component evaporates from the butyl rubber to reduce the amount of the capacitor electrolyte, and the electrolyte concentration increases. However, the PPG / PEG of Example 1 and the PVE of Example 2 do not flow out to the outside, and the amount of electrolyte decreases. It can be seen that no increase in concentration occurs.

Evaluation Example 2 (Evaluation of swelling)
Among the solvent components used in Evaluation Example 1, 5 g of PPG / PEG (Example 1) and PVE (Example 2) were put in a screw tube bottle with a capacity of 20 cc, and a butyl rubber piece (3 mm thickness × 10 mm) therein. X 10 mm, manufactured by Yawata Screw) was immersed for 7 days, and the change in weight was measured from the weight before immersion of the butyl rubber piece and the weight after immersion. The results are listed in Table 3. From Table 3, it can be seen that PVE has less elution of additives such as plasticizers from the sealed butyl rubber, and less alteration and deterioration than PPG / PVE. Therefore, when these solvent components are in direct contact with the sealing rubber, PVE has a smaller effect of promoting deterioration on the sealing rubber, and as a result, the life and durability of the aluminum electrolytic capacitor are increased.

Evaluation Example 3 (Evaluation of low temperature resistance)
The low temperature resistance of polyalkylene glycol homopolymer and copolymer was compared.
The state of PPG / PEG (Example 2) and PEG (Example 3) at low temperatures was visually observed. Comparing the two solvent components, PPG / PEG is liquid at −50 ° C., but PEG is solid because its freezing point is 38 to 41 ° C. From these low temperature conditions, PEG does not function as a solvent component of the electrolytic solution of the aluminum electrolytic capacitor at temperatures below the freezing point, but PPG / PEG functions even at -50 ° C.

Evaluation Example 4 (Halogen Analysis)
Of the solvent components used in Evaluation Example 1, 50 mg each of PPG / PEG (Example 1) and PVE (Example 2) is pretreated with a combustion apparatus (product name “AQF-100” manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The aqueous solution in which the combustion gas was burned and absorbed was measured by ion chromatography (manufactured by Thermo Fisher Scientific, product name “DX-120”), and the halogen content in the solvent component was measured. The lower limit of determination of this measurement condition is 2 ppm for F and Cl, and 1 ppm for Br and I.
The results obtained are shown in Table 5.

Evaluation Example 5 (metal analysis)
Of the solvent components used in Evaluation Example 1, 2.5 g of concentrated sulfuric acid was added to 2.5 g of each of PPG / PEG (Example 1) and PVE (Example 2), heated to dryness on a hot plate, and then an electric furnace At 550 ° C. for 12 hours. After allowing to cool, 0.1 g of a mixture of lithium tetraborate and lithium fluoride as an alkali flux was added and melted in an electric furnace, and then 15 mL of a tartaric acid / nitric acid mixed solution was added and stirred with heating to dissolve the sample. . The solution was made up to 25 mL and used as an aqueous solution sample for measurement. Measurement was performed with an ICP-OES apparatus (manufactured by Agilent Technologies, product name “5100 ICP-OES”) using the measurement aqueous solution, and the metal content contained in the solvent component was calculated.
The obtained results are shown in Table 6-1, Table 6-2, Table 6-3, and Table 6-4.

  The electrolytic solution of the present invention can be used for various power storage devices. The electrolytic capacitor of the present invention can be used as a circuit element mounted on an electric / electronic circuit board, particularly as a circuit element mounted on an automobile or the like.

Claims (10)

The compound has a repeating structure represented by the following formula (1), the terminal structure is a compound A which is hydrogen, a hydroxyl group or an alkoxy group, and / or has a repeating structure represented by the following formula (2), and the terminal structure is Compound B which is hydrogen, hydroxyl group or alkoxy group
Electrolyte solution containing as a solvent component.

(In Formula (1), R ¹ is hydrogen; a linear hydrocarbon group having 1 to 20 carbon atoms; a branched hydrocarbon group having 3 to 20 carbon atoms; a cyclic hydrocarbon group having 3 to 20 carbon atoms; carbon A C1-C20 linear hydrocarbon group, a C3-C20 branched hydrocarbon group, a C3-C20 cyclic hydrocarbon group, and a C1-C20 alkoxyl group; It is a group formed by combining two or more substituents selected from 20 alkoxyl groups, and a plurality of R ¹ may be the same or different.
n is an average number of repetitions, and is a number of 5 to 1000. )
(In the formula (2), R ² represents a linear hydrocarbon group having 1 to 20 carbon atoms; a branched hydrocarbon group having 3 to 20 carbon atoms; a cyclic hydrocarbon group having 3 to 20 carbon atoms; A group formed by combining two or more substituents selected from a linear hydrocarbon group of -20, a branched hydrocarbon group of 3 to 20 carbon atoms, and a cyclic hydrocarbon group of 3 to 20 carbon atoms; or Two or more substituents selected from a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon group having 3 to 20 carbon atoms are combined. A group bonded to an alkoxyl group having 1 to 20 carbon atoms, and a plurality of R ² may be the same or different from each other.
m is an average number of repetitions, and is a number of 5 to 1000. ) Compound A has a repeating structure represented by the following formula (1a) and a repeating structure represented by the following formula (1b),
The molar ratio of the repeating structure represented by the formula (1a) and the repeating structure represented by the formula (1b) is 99: 1 to 1:99,
The electrolytic solution according to claim 1, wherein the terminal structure is a copolymer having hydrogen, a hydroxyl group, or an alkoxy group.

(In the formula (1a) and the formula ^{(1b), R 11} and ^{R 12} are the same as ^{R 1} of formula ^(1), when different ^{.R 11 R 11} and ^{R 12} are each of a plurality ^{R 11} is together when good .R ¹² be the same or different is a multiple R ¹² may be the same or different.)   The electrolytic solution according to claim 1 or 2, comprising the compound B.   The contents of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sn, V, and Zn contained in the solvent component are each 1 ppm. The electrolytic solution according to claim 1, which is:   5. The electrolytic solution according to claim 1, wherein the content of fluorine, chlorine, bromine and iodine contained in the solvent component is 2 ppm or less.   The electrical storage device containing the electrolyte solution in any one of Claims 1-5.   The aluminum electrolytic capacitor containing the electrolyte solution in any one of Claims 1-5.   A liquid aluminum electrolytic capacitor or a hybrid aluminum electrolytic capacitor comprising the electrolytic solution according to claim 1.   The capacitor containing the electrolyte solution in any one of Claims 1-5.   The lithium ion battery containing the electrolyte solution in any one of Claims 1-5.