JPH10265674A - Polymer compound composite material and its production - Google Patents
Polymer compound composite material and its productionInfo
- Publication number
- JPH10265674A JPH10265674A JP9071211A JP7121197A JPH10265674A JP H10265674 A JPH10265674 A JP H10265674A JP 9071211 A JP9071211 A JP 9071211A JP 7121197 A JP7121197 A JP 7121197A JP H10265674 A JPH10265674 A JP H10265674A
- Authority
- JP
- Japan
- Prior art keywords
- polymer compound
- polymer
- ionic liquid
- acid
- pyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- Y02E60/122—
Landscapes
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高分子化合物複合
体およびその製造方法に関するものである。詳しくは、
電気化学的デバイスの固体電解質および電子機器の帯電
防止材や静電気シールド材として利用可能な高分子化合
物複合体に関するものである。TECHNICAL FIELD The present invention relates to a polymer compound complex and a method for producing the same. For more information,
The present invention relates to a polymer compound composite that can be used as a solid electrolyte for an electrochemical device and an antistatic material and an electrostatic shielding material for electronic devices.
【０００２】[0002]
【従来の技術】従来より、リチウム一次電池、リチウム
二次電池、電解コンデンサー、電気二重層コンデンサ
ー、エレクトロクロミック表示素子などの電気化学的デ
バイスの電解質としては、例えば、ガンマーブチロラク
トン、Ｎ，Ｎ−ジメチルホルムアミド、プロピレンカー
ボネート、テトラヒドロフラン等の液体溶媒に、例え
ば、過塩素酸リチウム、ホウフッ化テトラエチルアンモ
ニウム、フタル酸テトラメチルアンモニウム等のイオノ
ーゲンとしてのイオン性化合物を溶解した電解液が使用
されている。2. Description of the Related Art Conventionally, as an electrolyte of an electrochemical device such as a lithium primary battery, a lithium secondary battery, an electrolytic capacitor, an electric double layer capacitor, and an electrochromic display element, for example, gamma-butyrolactone, N, N-dimethyl For example, an electrolytic solution in which an ionic compound as an ionogen such as lithium perchlorate, tetraethylammonium borofluoride, or tetramethylammonium phthalate is dissolved in a liquid solvent such as formamide, propylene carbonate, or tetrahydrofuran is used.
【０００３】しかしながら、電解液は、漏液が発生し易
く、また、揮発し易く、長期間の信頼性に欠けるという
欠点を有している。一方、固体電解質は、この様な欠点
がなく、上記の電気化学的デバイスに使用すると、製造
工程の簡略化を図れると共に、デバイス自身の軽薄短小
化を図ることができる。特に、高分子固体電解質は、柔
軟性、軽量性、弾性、薄膜成形性、加工性、透明性など
に優れており、電気自動車用高エネルギー電池やＩＣカ
ード等の薄型製品の内蔵電池などに応用が考えられてい
る（渡辺、電気化学、６２巻、３０４頁、１９９４
年）。[0003] However, the electrolytic solution has a drawback that it easily leaks, is easily volatilized, and lacks long-term reliability. On the other hand, the solid electrolyte does not have such a drawback, and when used in the above-mentioned electrochemical device, the manufacturing process can be simplified, and the device itself can be reduced in size and weight. In particular, polymer solid electrolytes are excellent in flexibility, light weight, elasticity, thin film formability, processability, transparency, etc., and are applied to high-energy batteries for electric vehicles and built-in batteries in thin products such as IC cards. (Watanabe, Electrochemistry, 62, 304, 1994)
Year).
【０００４】上記の高分子固体電解質としては、ポリエ
チレンオキサイド、ポリプロピレンオキサイド等のポリ
アルキレンエーテル系高分子化合物に、リチウムスルホ
ンイミド、ＬｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 等のアルカ
リ金属塩を複合させた固体電解質（Ｓａｌｔ−ｉｎ−Ｐ
ｏｌｙｍｅｒ型）が研究されてきたが、イオン伝導性
は、高分子鎖の熱運動に起因することが明らかになり、
アモルファス化など種々の試みがなされてきたものの、
イオン伝導性と形状安定性の面から技術的な限界に至っ
ている。The above-mentioned solid polymer electrolyte is a solid electrolyte obtained by compounding a polyalkylene ether polymer compound such as polyethylene oxide or polypropylene oxide with an alkali metal salt such as lithium sulfonimide, LiClO 4 or LiCF 3 SO 3. (Salt-in-P
polymer type) has been studied, but it has been revealed that ionic conductivity is caused by thermal motion of polymer chains,
Although various attempts such as amorphization have been made,
Technical limits have been reached in terms of ion conductivity and shape stability.
【０００５】そこで、イオン伝導性はイオン性液体が担
い、力学的特性は高分子化合物が担うという機能分離型
の高分子固体電解質（Ｐｏｌｙｍｅｒ−ｉｎ−Ｓａｌｔ
型）の概念が二つの研究グループより独立に提案され
た。その一つは、イオン性液体として知られているＮ−
ブチルピリジニウムハロゲン化物とハロゲン化アルミニ
ウムとの錯体を高分子化合物で固定化したものである
（渡辺ら、Ｊ．Ｃ．Ｓ．Ｃｈｅｍ．Ｃｏｍｍｕｎ．，９
２９頁、１９９３年）。そして、他の一つは、２種以上
のリチウム塩を混合した過冷却液体を高分子化合物で固
定化したものである（Ｃ．Ａ．Ａｎｇｅｌｌら、Ｎａｔ
ｕｒｅ、３６２巻、１３７頁、１９９３年）。しかしな
がら、前者の複合体は、ハロゲン化物イオンによる腐食
性に問題があり、後者の複合体は、熱力学的に不安定な
過冷却液体を固定化したものであるから、経時的に結晶
化するという問題点がある。[0005] Therefore, a ionic liquid is responsible for ionic conductivity and a polymer compound is responsible for mechanical properties. A polymer solid electrolyte of a function separation type (Polymer-in-Salt).
The concept of type was proposed independently by two research groups. One is N-, which is known as an ionic liquid.
A complex of butylpyridinium halide and aluminum halide immobilized with a polymer compound (Watanabe et al., JCS Chem. Commun., 9
29, 1993). Another is a supercooled liquid in which two or more lithium salts are mixed and immobilized with a polymer compound (CA Angell et al., Nat.
ure, 362, 137, 1993). However, the former complex has a problem in corrosiveness due to halide ions, and the latter complex crystallizes with time because a thermodynamically unstable supercooled liquid is immobilized. There is a problem.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、腐食性がな
く、経時的に安定で、且つ高いイオン導電性を有する固
体電解質としての高分子化合物複合体の提供を目的とす
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer compound composite as a solid electrolyte which is non-corrosive, stable over time, and has high ionic conductivity.
【０００７】[0007]
【課題を解決するための手段】本発明は、高分子化合物
（Ａ）でイオン性液体（Ｂ）を固体化させた高分子化合
物複合体であって、イオン性液体（Ｂ）がリチウム塩
（ｂ１）及び環状アミジン又はピリジンのオニウム塩
（ｂ２）との混合物から成ることを特徴とする高分子化
合物複合体を提供するものである。The present invention relates to a polymer compound composite obtained by solidifying an ionic liquid (B) with a polymer compound (A), wherein the ionic liquid (B) is a lithium salt ( a polymer compound complex comprising a mixture of b1) and an onium salt of a cyclic amidine or pyridine (b2).
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。 高分子化合物（Ａ）：本発明で使用される高分子化合物
としては、イオン性液体をフィルム又は注型品状に固体
化し得るもので合成高分子化合物が好ましい。具体的に
は、ポリ塩化ビニル、ポリアクリロニトリル、ポリメタ
クリル酸メチル、ポリフッ化ビニリデン等のポリビニル
系高分子化合物、ポリオキシメチレン、ポリエチレンオ
キシド、ポリプロピレンオキシド等のポリエーテル系高
分子化合物、ナイロン６、ナイロン６６等のポリアミド
系高分子化合物、ポリエチレンテレフタレート等のポリ
エステル系高分子化合物、ポリカーボネート系高分子化
合物またはアイオネン系高分子化合物などが挙げられる
が、ポリメチルメタクリレート系高分子、ポリアクリロ
ニトリル、ポリエチレンオキシド及びアイオネン系高分
子化合物が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Polymer compound (A): The polymer compound used in the present invention is a compound which can solidify an ionic liquid into a film or a cast product, and is preferably a synthetic polymer compound. Specifically, polyvinyl polymer compounds such as polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene fluoride; polyether polymer compounds such as polyoxymethylene, polyethylene oxide, and polypropylene oxide; nylon 6, nylon 66, a polyester-based polymer compound such as polyethylene terephthalate, a polycarbonate-based polymer compound, an ionene-based polymer compound, and the like. Polymethylmethacrylate-based polymers, polyacrylonitrile, polyethylene oxide, and ionene Preferred are high molecular compounds.
【０００９】イオン性液体（Ｂ）：本発明において、イ
オン性液体（Ｂ）はリチウム塩（ｂ１）及び環状アミジ
ン又はピリジンのオニウム塩（ｂ２）との混合物を使用
する。リチウム塩としては、有機酸のリチウム塩または
無機酸のリチウム塩が挙げられる。有機酸のリチウム塩
としては、例えば、酢酸リチウム、トリフルオロ酢酸リ
チウム、安息香酸リチウム、トリフルオロメタンスルホ
ン酸リチウム、ｐ−トルエンスルホン酸リチウム、ビス
（トリフルオロメチルスルホニル）イミド酸リチウム、
トリス（トリフルオロメチルスルホニル）炭素酸リチウ
ム等が挙げられ、無機酸のリチウム塩としては、例え
ば、ＬｉＮＯ3 、ＬｉＳＣＮ、ＬｉＣｌＯ 3 、ＬｉＣｌ
Ｏ4 、ＬｉＢＦ4 、ＬｉＰＦ6 、ＬｉＡｓＦ6 、ＬｉＳ
ｂＦ6 等が挙げられる。これらの中で好ましいリチウム
塩は、ビス（トリフルオロメチルスルホニル）イミド酸
リチウム、トリス（トリフルオロメチルスルホニル）炭
素酸リチウム、ＬｉＢＦ4 、ＬｉＰＦ4 等のリチウム塩
である。他方のイオン性液体（Ｂ）の成分は、式（Ｉ）
で示される環状アミジンの陽イオンIonic liquid (B): In the present invention,
The ionic liquid (B) comprises a lithium salt (b1) and a cyclic amidi.
Or a mixture with pyridine or onium salt of pyridine (b2)
I do. As the lithium salt, a lithium salt of an organic acid or
And lithium salts of inorganic acids. Lithium salt of organic acid
Examples include, for example, lithium acetate, trifluoroacetic acid
Titanium, lithium benzoate, trifluoromethanesulfo
Lithium phosphate, lithium p-toluenesulfonate, bis
Lithium (trifluoromethylsulfonyl) imidate,
Lithium tris (trifluoromethylsulfonyl) carboxylate
And lithium salts of inorganic acids, for example,
If LiNOThree, LiSCN, LiClO Three, LiCl
OFour, LiBFFour, LiPF6, LiAsF6, LiS
bF6And the like. Preferred lithium among these
The salt is bis (trifluoromethylsulfonyl) imidic acid
Lithium, tris (trifluoromethylsulfonyl) charcoal
Lithium oxide, LiBFFour, LiPFFourEtc. lithium salt
It is. The component of the other ionic liquid (B) has the formula (I)
Cation of cyclic amidine represented by
【００１０】[0010]
【化３】 Embedded image
【００１１】〔式中、Ｒ1 とＲ3 は各々、独立して炭素
数１〜５のアルキル基を、Ｒ2 は水素又は炭素数１〜５
のアルキル基を表し、Ｑは炭素数２〜５のアルキレン、
アリーレン又はアルケニレンを表す。〕又は式（II）で
示されるピリジンの陽イオン[Wherein R 1 and R 3 each independently represent an alkyl group having 1 to 5 carbon atoms, and R 2 represents hydrogen or 1 to 5 carbon atoms.
Q is an alkylene having 2 to 5 carbon atoms,
Represents arylene or alkenylene. Or a cation of pyridine represented by the formula (II)
【００１２】[0012]
【化４】 Embedded image
【００１３】〔式中、Ｒ4 は炭素数１〜６のアルキル基
を、Ｒ5 はメチル又はエチル基を表す。〕と陰イオンと
からなる。陰イオンとしては、ビス（トリフロロメチル
スルホニル）イミド酸、過塩素酸、テトラフルオロホウ
酸、ヘキサフルオロリン酸、トリス（トリフロロメチル
スルホニル）炭素酸、トリフロロメタンスルホン酸、ト
リフロロ酢酸、プロピオン酸、酪酸、イソ酪酸、マレイ
ン酸、フタル酸、安息香酸、サリチル酸、コハク酸、ア
シピン酸等の有機カルボン酸が挙げられる。[Wherein R 4 represents an alkyl group having 1 to 6 carbon atoms, and R 5 represents a methyl or ethyl group. ] And an anion. Examples of anions include bis (trifluoromethylsulfonyl) imidic acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, tris (trifluoromethylsulfonyl) carbonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and propionic acid And organic carboxylic acids such as butyric acid, isobutyric acid, maleic acid, phthalic acid, benzoic acid, salicylic acid, succinic acid, and apicin acid.
【００１４】環状アミジン又はピリジンのオニウム陽イ
オンとしては、１，３−ジアルキルイミダゾリウム、
１，２，３−トリアルキルイミダゾリウム等のイミダゾ
ール環を有するもの、１，３−ジアルキル−イミダゾリ
ニウム等のイミダゾリン環を有するもの、１，３−ジア
ルキルテトラヒドロピリミジニウム等のピリミジン環を
有するもの、１，５−ジアザビシクロ［４．３．０］ノ
ネン−５等のジアザビシクロ環を有するもの、１−アル
キルピリジニウム等のピリジン環を有するもの等の環状
イミン化合物を例示することができる。As the onium cation of cyclic amidine or pyridine, 1,3-dialkylimidazolium,
Those having an imidazole ring such as 1,2,3-trialkylimidazolium, those having an imidazoline ring such as 1,3-dialkyl-imidazolinium, and those having a pyrimidine ring such as 1,3-dialkyltetrahydropyrimidinium And cyclic imine compounds such as those having a diazabicyclo ring such as 1,5-diazabicyclo [4.3.0] nonene-5 and those having a pyridine ring such as 1-alkylpyridinium.
【００１５】環状アミジン又はピリジンのオニウム塩の
具体的例としては、１−エチル−３−メチルイミダゾリ
ウムテトラフルオロボレート、１，２−ジメチル−３−
エチルイミダゾリウムテトラフルオロボレート、１，３
−ジメチル−イミダゾリニウムテトラフルオロボレー
ト、１−エチルピリジニウムテトラフルオロボレート、
１，５−ジアザビシクロ［４．３．０］ノネン−５−メ
チルテトラフルオロボレート、１−エチル−３−メチル
イミダゾリウムビス（トリフロロメチルスルホニル）イ
ミド、１−ブチルピリジニウムビス（トリフロロメチル
スルホニル）イミド、１−エチル−３−メチルイミダゾ
リウムトリフロロメタンスルホネート、１−エチル−３
−メチルイミダゾリウムトリフロロアセテートなどが挙
げられる。Specific examples of the onium salt of cyclic amidine or pyridine include 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-
Ethyl imidazolium tetrafluoroborate, 1,3
-Dimethyl-imidazolinium tetrafluoroborate, 1-ethylpyridinium tetrafluoroborate,
1,5-diazabicyclo [4.3.0] nonene-5-methyltetrafluoroborate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butylpyridinium bis (trifluoromethylsulfonyl) Imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3
-Methylimidazolium trifluoroacetate.
【００１６】イオン性液状の構成成分であるリチウム塩
（ｂ１）と環状アミジン又はピリジンのオニウム塩（ｂ
２）との配合比は、互いに相溶する範囲内であって、一
般的には、リチウム塩（ｂ１）は、オニウム塩１００重
量部に対し、０．１〜９９重量部、好ましくは１〜３０
重量部の割合で使用される。The ionic liquid component lithium salt (b1) and a cyclic amidine or pyridine onium salt (b
The compounding ratio with 2) is within a range compatible with each other, and generally, the lithium salt (b1) is used in an amount of 0.1 to 99 parts by weight, preferably 1 to 99 parts by weight, based on 100 parts by weight of the onium salt. 30
Used in parts by weight.
【００１７】高分子化合物複合体：高分子化合物複合体
は、上記イオン性液体（Ｂ）中に高分子化合物（Ａ）を
直接加え加熱溶解し、冷却して成形するか、または、適
当な有機溶媒中で両者を混合し成形した後、減圧乾燥な
どの方法で溶媒を留去して得られる。また、上記イオン
性液体中で、高分子化合物の原料モノマーを混合し、重
合開始剤を加え、原料を加熱重合または縮合反応させて
高分子化合物複合体を得る。Polymer compound composite: The polymer compound composite is prepared by directly adding the polymer compound (A) to the above ionic liquid (B), heating and dissolving the mixture, cooling it, or forming it by an appropriate organic compound. It is obtained by mixing and molding both in a solvent, and then distilling off the solvent by a method such as drying under reduced pressure. Further, in the ionic liquid, a raw material monomer of the polymer compound is mixed, a polymerization initiator is added, and the raw material is subjected to heat polymerization or condensation reaction to obtain a polymer compound complex.
【００１８】加熱温度は、室温から１５０℃迄の温度が
好ましい。また、前記重合開始剤としては、過酸化ベン
ゾイル等の過酸化ジアシル、クメンヒドロペルオキシ
ド、過酸化水素等のペルオキシド類、２，２−アゾビス
イソブチロニトリル等のアゾ化合物、ジベンゾイルジス
ルフィド等のジスルフィド類、ｐ−トルエンスルフィン
酸等のスルフィン酸類を例示することができる。The heating temperature is preferably from room temperature to 150 ° C. Examples of the polymerization initiator include diacyl peroxides such as benzoyl peroxide, peroxides such as cumene hydroperoxide and hydrogen peroxide, azo compounds such as 2,2-azobisisobutyronitrile, and dibenzoyl disulfides. Examples thereof include disulfides and sulfinic acids such as p-toluenesulfinic acid.
【００１９】イオン性液体（Ｂ）と高分子化合物（Ａ）
との配合比は、互いに相溶する範囲内であれば何れの混
合比であってもよいが、一般的には、高分子化合物
（Ａ）の使用量は、イオン性液体（Ｂ）１００重量部に
対し、１〜９９重量部、好ましくは５〜６０重量部であ
る。高分子化合物複合体は、漏液の問題がなく、腐食性
もなく、安定なので、長期間の信頼性に耐える電気化学
的デバイス用の固体電解質となる。また、そのイオン伝
導性を利用して電子機器の帯電防止材や静電気シールド
材として利用することができる。Ionic liquid (B) and polymer compound (A)
May be any mixing ratio as long as they are compatible with each other, but generally, the amount of the polymer compound (A) used is 100 parts by weight of the ionic liquid (B). 1 to 99 parts by weight, preferably 5 to 60 parts by weight based on parts. The polymer compound composite has no problem of liquid leakage, is not corrosive, and is stable, and thus is a solid electrolyte for an electrochemical device that can withstand long-term reliability. Further, it can be used as an antistatic material or an electrostatic shielding material for electronic devices by utilizing its ionic conductivity.
【００２０】[0020]
【実施例】以下、本発明を実施例により更に詳細に説明
する。 実施例１ アルゴン雰囲気下のグローブボックス中で、ポリアクリ
ロニトリル（ＰＡＮ：平均分子量８６，０００）１００
ｍｇ、１−エチル−３−メチルイミダゾリウムテトラフ
ルオロボレート３８４ｍｇ、リチウムテトラフルオロボ
レート１６ｍｇ及びＮ，Ｎ−ジメチルホルムアミド（Ｄ
ＭＦ）５．５ｇを加え、９５℃で３０分加熱撹拌して透
明な溶液を得た。The present invention will be described in more detail with reference to the following examples. Example 1 In a glove box under an argon atmosphere, polyacrylonitrile (PAN: average molecular weight 86,000) 100
mg, 1-ethyl-3-methylimidazolium tetrafluoroborate 384 mg, lithium tetrafluoroborate 16 mg and N, N-dimethylformamide (D
MF) was added, and the mixture was heated and stirred at 95 ° C. for 30 minutes to obtain a clear solution.
【００２１】この溶液を放冷後、加熱減圧下（７０℃、
１ｍｍＨｇ）で溶媒のＤＭＦを留去し、厚さ６０μｍの
高分子複合体の薄膜を得た。この高分子化合物複合体を
よく研磨したステンレス電極間に直径１ｃｍ、厚さ１ｍ
ｍのテフロン性スペーサーを介して挟み、密閉型導電率
測定用セル、インピーダンスアナライザー及び恒温槽を
使用して、周波数範囲５〜１３ＭＨｚ、温度範囲１００
〜０℃でセルのインピーダンスを発振レベル５００ｍＶ
にしてイオン導電率を測定した。After allowing this solution to cool, it is heated under reduced pressure (70 ° C.,
The solvent DMF was distilled off at 1 mmHg) to obtain a polymer composite thin film having a thickness of 60 μm. 1 cm in diameter and 1 m in thickness between stainless steel electrodes which have been polished with this polymer compound composite.
m, using a sealed conductivity measuring cell, an impedance analyzer and a thermostat, with a frequency range of 5 to 13 MHz and a temperature range of 100.
Oscillation level 500mV at ~ 0 ° C
And the ionic conductivity was measured.
【００２２】３０℃に於けるイオン導電率は、１．６×
１０-3Ｓ／ｃｍであった。また、引張り強度を測定した
ところ、７０ｋｇ／ｃｍ2 であった。６ケ月保存しても
ステンレスの腐食は認められなかった。なお、実施例１
で得られた高分子化合物複合体薄膜について、異なる温
度に於けるイオン導電率を測定し、高分子化合物複合体
の温度−イオン伝導率の相関図として図１に示した。The ionic conductivity at 30 ° C. is 1.6 ×
It was 10 -3 S / cm. Further, the tensile strength was measured and found to be 70 kg / cm 2 . No corrosion of stainless steel was observed after storage for 6 months. Example 1
The ionic conductivity of the polymer compound composite thin film obtained at the above was measured at different temperatures and shown in FIG. 1 as a temperature-ion conductivity correlation diagram of the polymer compound composite.
【００２３】実施例２ アルゴン雰囲気下のグローブボックス中で、ポリエチレ
ンオキサイド（ＰＥＯ：平均分子量６００，０００）８
４ｍｇ、１−エチル−３−メチルイミダゾリウムテトラ
フルオロボレート２５８ｍｇ、リチウムテトラフルオロ
ボレート１０．８ｍｇ及びＮ，Ｎ−ジメチルホルムアミ
ド（ＤＭＦ）５．５ｇを加え、９５℃で３０分加熱撹拌
して透明な溶液を得た。Example 2 In a glove box under an argon atmosphere, polyethylene oxide (PEO: average molecular weight 600,000) 8
4 mg, 1-ethyl-3-methylimidazolium tetrafluoroborate (258 mg), lithium tetrafluoroborate (10.8 mg) and N, N-dimethylformamide (DMF) (5.5 g) were added, and the mixture was heated and stirred at 95 ° C. for 30 minutes to give a transparent solution. A solution was obtained.
【００２４】この溶液を放冷後、加熱減圧下で溶媒のＤ
ＭＦを留去し厚さ１００μｍの高分子複合体の薄膜を得
た。この高分子化合物複合体の薄膜の３０℃に於けるイ
オン導電率は、１．１×１０-3Ｓ／ｃｍであった。ま
た、引張強度は６０ｋｇ／ｃｍ 2 であった。６カ月保存
後のステンレスの腐食も認められなかった。なお、実施
例２で得られた高分子化合物複合体薄膜について、異な
る温度に於けるイオン導電率を測定し、高分子化合物複
合体の温度−イオン導電率の相関図として図１に示し
た。After allowing the solution to cool, the solvent D
The MF was distilled off to obtain a polymer composite thin film having a thickness of 100 μm.
Was. The thin film of this polymer compound composite at 30 ° C.
The on-conductivity is 1.1 × 10-3S / cm. Ma
The tensile strength is 60 kg / cm TwoMet. 6 months storage
No subsequent corrosion of stainless steel was observed. The implementation
With respect to the polymer compound composite thin film obtained in Example 2,
The ionic conductivity at different temperatures was measured and
FIG. 1 shows a correlation diagram between the temperature of the coalescence and the ionic conductivity.
Was.
【００２５】比較例１ アルゴン雰囲気下のグローブボックス中で、ＰＡＮ２０
０ｍｇ、安息香酸トリエチルメチルアンモニウム３３２
ｍｇ、酢酸リチウム２６．４ｍｇ、ＬｉＴＦＳＩ５７．
４ｍｇ及びＤＭＦ５．５ｇを加え、９５℃で３０分加熱
撹拌して透明な溶液を得た。この溶液を放冷後、加熱減
圧下（７０℃、１ｍｍＨｇ）で溶媒のＤＭＦを留去し高
分子複合体の薄膜を得た。この高分子化合物複合体の薄
膜の３０℃に於けるイオン導電率は３．２×１０-6Ｓ／
ｃｍであった。Comparative Example 1 In a glove box under an argon atmosphere, PAN20 was
0 mg, triethylmethylammonium benzoate 332
mg, lithium acetate 26.4 mg, LiTFSI
4 mg and 5.5 g of DMF were added, and the mixture was heated and stirred at 95 ° C. for 30 minutes to obtain a clear solution. After allowing this solution to cool, DMF as a solvent was distilled off under reduced pressure while heating (70 ° C., 1 mmHg) to obtain a thin film of a polymer composite. The ionic conductivity of this thin film of the polymer compound composite at 30 ° C. was 3.2 × 10 −6 S /
cm.
【００２６】[0026]
【発明の効果】本発明の高分子化合物複合体は、漏液の
問題がなく、腐食性もなく、安定なので、長期間の信頼
性に耐えることができ、リチウム一次電池、リチウム二
次電池、電解コンデンサー、電気二重層コンデンサー、
エレクトロクロミック表示素子などの電気化学的デバイ
ス用の固体電解質として好適である。また、そのイオン
伝導性を利用して、電子機器の帯電防止材や静電気シー
ルド材として利用することもできる。The polymer compound complex of the present invention has no problem of liquid leakage, is not corrosive, and is stable, so it can withstand long-term reliability, and can be used for lithium primary batteries, lithium secondary batteries, Electrolytic capacitors, electric double layer capacitors,
It is suitable as a solid electrolyte for an electrochemical device such as an electrochromic display element. Further, by utilizing the ionic conductivity, it can be used as an antistatic material or an electrostatic shielding material for electronic devices.
【図１】高分子化合物複合体の温度−イオン導電率の相
関図である。FIG. 1 is a correlation diagram of temperature-ionic conductivity of a polymer compound composite.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 69/00 Ｃ０８Ｌ 69/00 71/00 71/00 77/00 77/00 Ｈ０１Ｂ 1/12 Ｈ０１Ｂ 1/12 Ｚ // Ｈ０１Ｍ 6/18 Ｈ０１Ｍ 6/18 Ｅ 10/40 10/40 Ｂ (72)発明者 米井 綾子 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 69/00 C08L 69/00 71/00 71/00 77/00 77/00 H01B 1/12 H01B 1/12 Z // H01M 6/18 H01M 6/18 E 10/40 10/40 B (72) Inventor Ayako Yonei 3-1-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref.
Claims (9)
（Ｂ）を固体化させた高分子化合物複合体であって、イ
オン性液体（Ｂ）がリチウム塩（ｂ１）及び環状アミジ
ン又はピリジンのオニウム塩（ｂ２）との混合物から成
ることを特徴とする高分子化合物複合体。1. A polymer compound complex obtained by solidifying an ionic liquid (B) with a polymer compound (A), wherein the ionic liquid (B) is composed of a lithium salt (b1) and a cyclic amidine or pyridine. A polymer compound complex comprising a mixture with an onium salt (b2).
２）が、式（Ｉ） 【化１】 〔式中、Ｒ1 とＲ3 は各々、独立して炭素数１〜５のア
ルキル基を、Ｒ2 は水素又は炭素数１〜５のアルキル基
を表し、Ｑは炭素数２〜５のアルキレン、アリーレン又
はアルケニレンを表す。〕で示される環状アミジン又は
式（II） 【化２】 〔式中、Ｒ4 は炭素数１〜６のアルキル基を、Ｒ5 はメ
チル又はエチル基を表す。〕で示されるピリジンのオニ
ウム塩である請求項１記載の高分子化合物複合体。2. An onium salt (b) of an ionic liquid (B)
2) has the formula (I) [Wherein, R 1 and R 3 each independently represent an alkyl group having 1 to 5 carbon atoms, R 2 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and Q represents an alkylene having 2 to 5 carbon atoms. , Arylene or alkenylene. Or a cyclic amidine represented by the formula (II): [In the formula, R 4 represents an alkyl group having 1 to 6 carbon atoms, and R 5 represents a methyl or ethyl group. The polymer compound complex according to claim 1, which is an onium salt of pyridine represented by the formula:
イミダゾリン環、テトラヒドロピリミジン環、ジアザビ
シクロ環もしくはピリジン環より選ばれた環を有する化
合物である請求項２記載の高分子化合物複合体。3. The cyclic amidine has an imidazole ring, 2-
The polymer compound complex according to claim 2, which is a compound having a ring selected from an imidazoline ring, a tetrahydropyrimidine ring, a diazabicyclo ring, and a pyridine ring.
する陰イオンが、ビス（トリフロロメチルスルホニル）
イミド酸、過塩素酸、テトラフルオロホウ酸、ヘキサフ
ルオロリン酸、トリス（トリフロロメチルスルホニル）
炭素酸、トリフロロメタンスルホン酸、トリフロロ酢酸
又は有機カルボン酸より選ばれた少なくとも１種であ
る、請求項１記載の高分子化合物複合体。4. An anion constituting an onium salt of the ionic liquid (B) is bis (trifluoromethylsulfonyl)
Imidic acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, tris (trifluoromethylsulfonyl)
The polymer compound complex according to claim 1, wherein the complex is at least one selected from carbon acids, trifluoromethanesulfonic acid, trifluoroacetic acid, and organic carboxylic acids.
分子、ポリエーテル系高分子、ポリアミド系高分子、ポ
リエステル系高分子、ポリカーボネート系高分子および
イオネン系高分子より選ばれた少くとも１種以上のも
の、である請求項１記載の高分子化合物複合体。5. The polymer compound (A) is at least one selected from the group consisting of a polyvillyl polymer, a polyether polymer, a polyamide polymer, a polyester polymer, a polycarbonate polymer and an ionene polymer. The polymer compound complex according to claim 1, which is at least one kind.
し、高分子化合物（Ａ）は１〜９９重量部用いられるこ
とを特徴とする、請求項１記載の高分子化合物複合体。6. The polymer compound composite according to claim 1, wherein the polymer compound (A) is used in an amount of 1 to 99 parts by weight based on 100 parts by weight of the ionic liquid (B).
２）１００重量部に対し、０．１〜９９重量部の割合で
用いられる、請求項１記載の高分子化合物複合体。7. The lithium salt (b1) is an onium salt (b
2) The polymer compound composite according to claim 1, which is used in a ratio of 0.1 to 99 parts by weight based on 100 parts by weight.
媒に溶解した後、溶媒を除去することにより請求項１に
記載の高分子化合物複合体を製造する方法。8. The method for producing a polymer compound complex according to claim 1, wherein the polymer (A) and the ionic liquid (B) are dissolved in a solvent, and then the solvent is removed.
オン性液体（Ｂ）及び重合開始剤を添加し、これを重合
することを特徴とする、請求項１記載の高分子化合物複
合体を製造する方法。9. The polymer compound composite according to claim 1, wherein an ionic liquid (B) and a polymerization initiator are added to the raw material monomer of the polymer compound (A), and the polymerization is carried out. How to make.
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|---|---|---|---|
| JP9071211A JPH10265674A (en) | 1997-03-25 | 1997-03-25 | Polymer compound composite material and its production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9071211A JPH10265674A (en) | 1997-03-25 | 1997-03-25 | Polymer compound composite material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10265674A true JPH10265674A (en) | 1998-10-06 |
Family
ID=13454131
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9071211A Pending JPH10265674A (en) | 1997-03-25 | 1997-03-25 | Polymer compound composite material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10265674A (en) |
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