JP2001015166A - Ion conductive element and lithium ion secondary battery using the same - Google Patents

Ion conductive element and lithium ion secondary battery using the same

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Publication number
JP2001015166A
JP2001015166A JP11187276A JP18727699A JP2001015166A JP 2001015166 A JP2001015166 A JP 2001015166A JP 11187276 A JP11187276 A JP 11187276A JP 18727699 A JP18727699 A JP 18727699A JP 2001015166 A JP2001015166 A JP 2001015166A
Authority
JP
Japan
Prior art keywords
ion
group
derivative
copolymer
ionic conductor
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
Application number
JP11187276A
Other languages
Japanese (ja)
Inventor
Soji Tsuchiya
宗次 土屋
Satoshige Nanai
識成 七井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP11187276A priority Critical patent/JP2001015166A/en
Publication of JP2001015166A publication Critical patent/JP2001015166A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

PROBLEM TO BE SOLVED: To prevent leakage of liquid, to improve the shape such as a thin type, and to provide an electrolyte material with superior ion conductivity and contact with electrodes by using non-ionic polymer or ionic polymer, ion including a specific structure and its derivative, gel or solid ion conductive element including cation different from the ion or its derivative as coexisting ion. SOLUTION: This secondary battery uses ions including a structure expressed by formula I (R1 and R2 are each an aliphatic group and their carbon atoms are directly connected to nitrogen atoms) and its derivative. Preferably, it uses non-ionic polymer or ionic polymer, ion including a structure expressed by formula II (R3 is an aromatic group and R4, R5, and R6 are groups with aliphatic carbon directly connected to nitrogen atoms) and its derivative, gel or solid ionic conductive element, at least, including cation different from the ion and its derivative as coexisting ion, and the cation includes, at least, metallic ion selected from alkali metal ions, silver ion, etc.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、電気化学素子に用
いられるイオン伝導体に関するもので、特にリチウムイ
オン２次電池に利用可能なイオン伝導体に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion conductor used for an electrochemical device, and more particularly to an ion conductor which can be used for a lithium ion secondary battery.

【０００２】[0002]

【従来の技術】近年、充放電が可能ないわゆる２次電池
の用途はますます広がり、それに伴って高容量化に対す
る要求が高まっている。リチウムイオン２次電池はエネ
ルギー密度が優れているということで、携帯用情報機器
等の電源としてこのような要求に対して用いられてい
る。現在、さらなる高容量化、高安定化をめざした研究
開発が精力的になされている。2. Description of the Related Art In recent years, the use of chargeable / dischargeable secondary batteries has been increasingly widespread, and accordingly, demands for higher capacity have been increasing. Lithium ion secondary batteries are used for such demands as power sources for portable information devices and the like because of their excellent energy density. At present, research and development for higher capacity and higher stability are being vigorously made.

【０００３】実用化されているリチウムイオン２次電池
の多くは負極として炭素材料が用いられ、電解質として
は液体のものが用いられていて、長期使用中の漏液や分
解などの劣化による電池特性の劣化現象がある。また、
最近、薄型や高分子型の２次電池でゲル状の高分子電解
質が一部実用化されているが、イオン伝導性の低下によ
る低下や長期信頼性にまだ課題を残している。将来的に
有望とされている負極としてリチウム金属を用いたリチ
ウム２次電池にしても、現状の液状の電解質を用いた場
合は、負極上に金属がデンドライト状に析出したりし
て、電池特性の劣化、安全性の課題を同様に有してい
る。金属リチウムが負極として利用可能になれば、酸化
還元反応を行うリチウムをそのまま電極として利用可能
になり、炭素を用いる時に課題となる容量上限も大きく
なり高容量化が可能となる。また、従来の電池では電解
液の漏液を防ぐために丈夫な容器とシール構造が用いら
れており、これによって重量や厚さを小さくできないと
いう課題もあった。[0003] Many of the lithium ion secondary batteries that are put into practical use use a carbon material as a negative electrode and a liquid electrolyte as an electrolyte, and battery characteristics due to deterioration such as leakage or decomposition during long-term use. Degradation phenomenon. Also,
In recent years, gel polymer electrolytes have been partially put to practical use in thin or polymer type secondary batteries, but there are still problems in deterioration due to reduction in ionic conductivity and long-term reliability. Even if a lithium secondary battery using lithium metal is used as a negative electrode, which is promising in the future, if the current liquid electrolyte is used, the metal will precipitate in a dendrite shape on the negative electrode, and the battery characteristics will deteriorate. Has the same problems of deterioration and safety. If metal lithium can be used as a negative electrode, lithium that undergoes an oxidation-reduction reaction can be used as an electrode as it is, and the upper limit of capacity, which is a problem when carbon is used, is increased, so that high capacity can be achieved. Further, in a conventional battery, a durable container and a sealing structure are used in order to prevent leakage of the electrolyte, and thus there is a problem that the weight and thickness cannot be reduced.

【０００４】以上の課題を解決するために、固体状ある
いはゲル状の電解質が研究開発されている。理想的には
漏液の現象がなく、高イオン伝導性の固体電解質が望ま
れている。しかし、現実は流動性がなくなることで、電
極との接触やイオン伝導性の低下などに問題がある。そ
のため、溶媒を若干含んだようなゲル状の電解質が多く
検討されている。材料としては、高分子、電解質、溶媒
が混合された系が一般的である。また、電解液を固体状
あるいはゲル状によって、液体使用時よりも簡易な容器
やシール構造が利用可能となり、電池を薄型化したり自
由な形状とするのも可能となる。さらには、発火点など
の耐熱安定性も液体に比べて高くなる傾向にあり、電池
製造プロセス工程においても有利になると期待される。
また、電解質は電池ばかりでなくコンデンサ、エレクト
ロクロミック表示素子などのデバイスにも利用される。In order to solve the above problems, a solid or gel electrolyte has been researched and developed. Ideally, a solid electrolyte having no phenomena of liquid leakage and high ionic conductivity is desired. However, in reality, there is a problem in that the fluidity is lost and the contact with the electrode and the decrease in ionic conductivity are caused. For this reason, many gel electrolytes containing a small amount of solvent have been studied. As a material, a system in which a polymer, an electrolyte, and a solvent are mixed is generally used. In addition, when the electrolyte is in a solid or gel state, a simpler container or seal structure can be used than in the case of using a liquid, and the battery can be made thinner and can have a free shape. Furthermore, the heat resistance such as the ignition point tends to be higher than that of the liquid, which is expected to be advantageous in the battery manufacturing process.
The electrolyte is used not only for batteries but also for devices such as capacitors and electrochromic display elements.

【０００５】[0005]

【発明が解決しようとする課題】本発明は液状の電解質
で課題となる液の漏出、薄型などの形状の容易さの改善
を図るばかりでなくイオン伝導性が良好で、電極との接
触も良好にとれる電解質材料を提供する。DISCLOSURE OF THE INVENTION The present invention not only aims to improve the shape of a liquid electrolyte, which is a problem with a liquid electrolyte, such as leakage and thinness, but also has good ion conductivity and good contact with electrodes. The present invention provides an electrolyte material which can be used.

【０００６】[0006]

【課題を解決するための手段】上記課題を解決するため
に、本発明のイオン伝導体は、高分子に請求項にあげた
ようなある特徴を有する構造をもつイオンあるいは誘導
体の混合物からなることを特徴としたものである。According to the present invention, there is provided an ion conductor comprising a mixture of a polymer and an ion or derivative having a structure having certain characteristics as described in the claims. It is characterized by.

【０００７】本発明により、炭素材料のリチウムイオン
吸蔵率に対する電位変動が小さくて容量の大きな電池電
極およびこの電極を用いた電池を得ることができる。According to the present invention, it is possible to obtain a battery electrode having a small capacity and a large capacity with respect to the lithium ion occlusion rate of the carbon material, and a battery using this electrode.

【０００８】[0008]

【発明の実施の形態】本発明の請求項1に記載の発明
は、非イオン性高分子またはイオン性高分子と、（化
１）に示す構造を含むイオンまたはその誘導体と、前記
イオンまたはその誘導体と異なる陽イオンを共存イオン
として少なくとも含むゲルまたは固体のイオン伝導体で
ある。但し（化１）において、Ｒ１とＲ２は脂肪族性基
であり、その炭素原子が窒素原子に直接結合するもので
ある。本発明により、固体状あるいはゲル状で良好なイ
オン伝導性な電解質が得られる。BEST MODE FOR CARRYING OUT THE INVENTION The invention described in claim 1 of the present invention provides a nonionic polymer or an ionic polymer, an ion having a structure represented by the following formula (1), a derivative thereof, It is a gel or solid ionic conductor containing at least a cation different from the derivative as a coexisting ion. However, in (Chemical Formula 1), R1 and R2 are aliphatic groups, and the carbon atoms thereof are directly bonded to the nitrogen atom. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【０００９】本発明の請求項２に記載の発明は、非イオ
ン性高分子またはイオン性高分子と、（化２）に示す構
造を含むイオンまたはその誘導体と、前記イオンまたは
その誘導体と異なる陽イオンを共存イオンとして少なく
とも含むゲルまたは固体をイオン伝導体である。但し
（化２）において、Ｒ３は芳香族基であり、Ｒ４、Ｒ５
又はＲ６は窒素原子に脂肪族性炭素が直接結合する基で
ある。本発明により、固体状あるいはゲル状で良好なイ
オン伝導性な電解質が得られる。According to a second aspect of the present invention, there is provided a nonionic polymer or an ionic polymer, an ion having the structure shown in Chemical formula (2) or a derivative thereof, and a positive electrode different from the ion or the derivative thereof. The ion conductor is a gel or a solid containing at least ions as coexisting ions. However, in (Chemical formula 2), R3 is an aromatic group, and R4, R5
Alternatively, R6 is a group in which aliphatic carbon is directly bonded to a nitrogen atom. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１０】本発明の請求項３に記載の発明は、非イオ
ン性高分子またはイオン性高分子と、（化３）に示す構
造を含むイオンまたはその誘導体と、前記イオンまたは
その誘導体と異なる陽イオンを共存イオンとして少なく
とも含むゲルまたは固体のイオン伝導体である。但し
（化３）において、Ｒ７とＲ８は窒素原子に脂肪族性炭
素が直接結合する基であり、Ｒ９は炭素数が１以上１６
以下であり、アルキル基、芳香族基、エーテル結合を含
む基、カルボニル基を含む基、ニトリル性シアノ基又は
アルコール性水酸基のうちの少なくともひとつを含んで
いる。本発明により、固体状あるいはゲル状で良好なイ
オン伝導性な電解質が得られる。According to a third aspect of the present invention, there is provided a nonionic polymer or an ionic polymer, an ion or a derivative thereof having the structure shown in Chemical Formula 3, and a positive electrode different from the ion or the derivative thereof. It is a gel or solid ionic conductor containing at least ions as coexisting ions. However, in the chemical formula 3, R7 and R8 are groups in which an aliphatic carbon is directly bonded to a nitrogen atom, and R9 has 1 to 16 carbon atoms.
The following includes at least one of an alkyl group, an aromatic group, a group containing an ether bond, a group containing a carbonyl group, a nitrile cyano group and an alcoholic hydroxyl group. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１１】本発明の請求項４に記載の発明は、非イオ
ン性高分子またはイオン性高分子と、（化４）に示す構
造を含むイオンまたはその誘導体と、前記イオンまたは
その誘導体と異なる陽イオンを共存イオンとして少なく
とも含むゲルまたは固体のイオン伝導体である。但し
（化４）において、Ｒ１３、Ｒ１４、Ｒ１５及びＲ１６
は窒素原子に脂肪族性炭素が直接結合する基である。ま
た、Ｒ１０、Ｒ１１又はＲ１２のうち少なくともひとつ
は芳香族基であり、芳香族でない基は炭素を含む基であ
る。Ｒ１２は炭素数が１以上１６以下であり、アルキル
基、芳香族基、エーテル結合を含む基、カルボニル基を
含む基、ニトリル性シアノ基又はアルコール性水酸基の
うちの少なくともひとつを含んでいる。本発明により、
固体状あるいはゲル状で良好なイオン伝導性な電解質が
得られる。According to a fourth aspect of the present invention, there is provided a nonionic polymer or an ionic polymer, an ion having the structure shown in Chemical formula 4, or a derivative thereof, and a positive ion different from the ion or the derivative thereof. It is a gel or solid ionic conductor containing at least ions as coexisting ions. However, in (Chem. 4), R13, R14, R15 and R16
Is a group in which aliphatic carbon is directly bonded to a nitrogen atom. Further, at least one of R10, R11 and R12 is an aromatic group, and the non-aromatic group is a group containing carbon. R12 has 1 to 16 carbon atoms and includes at least one of an alkyl group, an aromatic group, a group containing an ether bond, a group containing a carbonyl group, a nitrile cyano group, and an alcoholic hydroxyl group. According to the present invention,
A solid or gel electrolyte having good ion conductivity can be obtained.

【００１２】本発明の請求項５に記載の発明は、（化
１）ないし（化４）のいずれかより選ばれる二つ以上の
構造またはそれらから誘導される構造を同一イオン内に
持つイオンと、前記イオンと異なる陽イオンを共存イオ
ンとして少なくとも含むゲルまたは固体のイオン伝導体
である。本発明により、固体状あるいはゲル状で良好な
イオン伝導性な電解質が得られる。According to a fifth aspect of the present invention, there is provided an ion having two or more structures selected from any of the following (Chemical Formula 1) to (Chemical Formula 4) or a structure derived therefrom in the same ion. And a gel or solid ionic conductor containing at least a cation different from the above ion as a coexisting ion. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１３】本発明の請求項６に記載の発明は、室温で
液体の非イオン性有機溶媒を含んだゲルであることを特
徴とする請求項１ないし５のいずれか記載のイオン伝導
体である。本発明により、固体状あるいはゲル状で良好
なイオン伝導性な電解質が得られる。The invention according to claim 6 of the present invention is the ionic conductor according to any one of claims 1 to 5, characterized in that the gel is a gel containing a nonionic organic solvent which is liquid at room temperature. . According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１４】本発明の請求項７に記載の発明は、陽イオ
ンが少なくともアルカリ金属、アルカリ土類金属、銀イ
オン、銅イオン又は亜鉛イオンより選ばれる金属イオン
含んでいることを特徴とする請求項１ないし５のいずれ
か記載のイオン伝導体である。本発明により、固体状あ
るいはゲル状で良好なイオン伝導性な電解質が得られ
る。[0014] The invention according to claim 7 of the present invention is characterized in that the cation contains at least a metal ion selected from alkali metals, alkaline earth metals, silver ions, copper ions and zinc ions. 6. The ionic conductor according to any one of 1 to 5. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１５】本発明の請求項８に記載の発明は、陽イオ
ンが少なくとも直鎖アルキル４級アンモニウムイオンを
含んでいることを特徴とする請求項１ないし５のいずれ
か記載のイオン伝導体である。但し、前記直鎖アルキル
４級アンモニウムイオンアルキル基の炭素数は１ないし
６のいずれかである。本発明により、固体状あるいはゲ
ル状で良好なイオン伝導性な電解質が得られる。The invention according to claim 8 of the present invention is the ionic conductor according to any one of claims 1 to 5, wherein the cation contains at least a straight-chain alkyl quaternary ammonium ion. . However, the straight-chain alkyl quaternary ammonium ion alkyl group has 1 to 6 carbon atoms. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１６】本発明の請求項９に記載の発明は、非イオ
ン性高分子が、フッ化ビニリデンと六フッ化プロピレン
の共重合体、ポリ（２−ヒドロキシエチルメタクリレー
ト）またはその共重合体、ポリアクリロニトリルまたは
その共重合体、ポリメタクリレートまたはその共重合
体、ポリアクリレートまたはその共重合体もしくはポリ
エチレンオキサイドまたはその共重合体より選ばれるも
のを少なくとも含んでいることを特徴とする請求項１な
いし５のいずれか記載のイオン伝導体である。本発明に
より、固体状あるいはゲル状で良好なイオン伝導性な電
解質が得られる。According to a ninth aspect of the present invention, the nonionic polymer is a copolymer of vinylidene fluoride and propylene hexafluoride, poly (2-hydroxyethyl methacrylate) or a copolymer thereof, The acrylonitrile or its copolymer, polymethacrylate or its copolymer, polyacrylate or its copolymer or polyethylene oxide or its copolymer selected from the group consisting of at least one selected from the group consisting of: An ionic conductor according to any of the above. According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１７】本発明の請求項１０に記載の発明は、イオ
ン性高分子としてポリメタクリル酸またはその共重合
体、ポリアクリル酸またはその共重合体、ポリフェノー
ルまたはその共重合体、ポリエチレンオキサイドの共重
合体もしくはポアクリロニトリルの共重合体より選ばれ
るもを少なくても含んでいることを特徴とする請求項１
ないし５のいずれか記載のイオン伝導体である。本発明
により、固体状あるいはゲル状で良好なイオン伝導性な
電解質が得られる。According to a tenth aspect of the present invention, there is provided an ionic polymer comprising polymethacrylic acid or a copolymer thereof, polyacrylic acid or a copolymer thereof, polyphenol or a copolymer thereof, and a copolymer of polyethylene oxide. 2. The composition according to claim 1, wherein at least one selected from the group consisting of coalesced or polyacrylonitrile copolymers is contained.
6. The ionic conductor according to any one of 5. to 5., According to the present invention, a solid or gel electrolyte having good ion conductivity can be obtained.

【００１８】本発明の請求項１１に記載の発明は、請求
項１ないし１０のいずれか記載のイオン伝導体を用いる
ことを特徴とするリチウムイオン２次電池である。本発
明により、信頼性が高く、薄型で高容量の２次電池の作
製に有用となる。An eleventh aspect of the present invention is a lithium ion secondary battery using the ionic conductor according to any one of the first to tenth aspects. The present invention is useful for manufacturing a highly reliable, thin, and high-capacity secondary battery.

【００１９】[0019]

【実施例】次に、本発明の具体例を説明する。Next, specific examples of the present invention will be described.

【００２０】なお、以下の説明では、本発明を実験結果
に基づいて説明するが、本発明は下記実施例により限定
されるものではなく、主旨を変更しない範囲で適宜変更
して実施できるものである。In the following description, the present invention will be described on the basis of experimental results. However, the present invention is not limited to the following examples, but can be carried out by appropriately changing the scope without changing the gist. is there.

【００２１】（実施例１）本実施例は（化３）に示す構
造を含むイオンまたはその誘導体と、これと異なる陽イ
オンを共存イオンとして少なくとも含むゲルまたは固体
のイオン伝導体に関するものである。Example 1 This example relates to a gel or solid ionic conductor containing at least an ion having the structure shown in Chemical formula 3 or a derivative thereof and a different cation as coexisting ions.

【００２２】１−メチルイミダゾール０．２ｍｏｌと
１，２−ジブロモエタン０．０８ｍｏｌとをアセトニト
リル５０ｍｌに溶解し、この溶液を入れた容器に冷却器
を取り付け蒸発成分が回収できるようにし、水浴に入れ
８０℃で４時間加熱反応させた。得られた反応液をロー
タリーエバポレータで減圧加熱し溶媒を除去した。0.2 mol of 1-methylimidazole and 0.08 mol of 1,2-dibromoethane are dissolved in 50 ml of acetonitrile. The mixture was heated and reacted at 80 ° C. for 4 hours. The obtained reaction solution was heated under reduced pressure by a rotary evaporator to remove the solvent.

【００２３】得られた物質を水１５０ｍｌに溶解し、こ
の溶液を攪拌しつつ水１５０ｍｌにＮＨ4ＰＦ6を０．２
５ｍｏｌ溶解した水溶液を注ぎ粗沈殿を得た。The obtained substance was dissolved in 150 ml of water, and this solution was stirred while adding 0.2 mL of NH 4 PF 6 to 150 ml of water.
An aqueous solution in which 5 mol was dissolved was poured to obtain a crude precipitate.

【００２４】得られた粗沈殿を温メタノール中に溶解
し、冷却して再結晶させろ過後乾燥し精製物を得た。The obtained crude precipitate was dissolved in warm methanol, cooled, recrystallized, filtered and dried to obtain a purified product.

【００２５】ＬｉＰＦ6と精製物とをＬｉ原子数とイミ
ダゾール環（Ｉｍと略す）の数の比がＬｉ／Ｉｍ＝０．
７となるように混合し、加熱して溶融混合して冷却固化
して固形のものを得た。これをさらにメタクリル酸とメ
タクリルアミドとの共重合体とを１：４の割合で溶液混
合し、その後溶媒の除去を行って、高分子の固体状のイ
オン伝導体を得た。For LiPF 6 and the purified product, the ratio of the number of Li atoms to the number of imidazole rings (Im) is Li / Im = 0.
The mixture was heated, melt-mixed, cooled and solidified to obtain a solid. This was further mixed with a solution of methacrylic acid and a copolymer of methacrylamide at a ratio of 1: 4, and then the solvent was removed to obtain a polymer solid ion conductor.

【００２６】得られた固体イオン伝導体を２枚のＰｔ金
属電極間にはさみ、一旦加熱後放置冷却して電気伝導率
測定用素子とした。この素子のＰｔ電極に１２０Ｈｚの
交流をかけ固体イオン伝導体の電気伝導率を測定したと
ころ、３×１０-3Ｓ／ｃｍであった。また、直流をかけ
たところ測定限界（１０-8Ｓ／ｃｍ）以下の電気伝導率
であった。The obtained solid ionic conductor was sandwiched between two Pt metal electrodes, heated once, left to cool, and used as an electric conductivity measuring element. The electric conductivity of the solid ionic conductor was measured by applying an alternating current of 120 Hz to the Pt electrode of this device, and it was 3 × 10 −3 S / cm. When a direct current was applied, the electric conductivity was lower than the measurement limit (10 −8 S / cm).

【００２７】さらに、上記電気伝導率測定用素子の２枚
のＰｔ金属電極を２枚のＬｉ金属電極に変更して、直流
で固体イオン伝導体の電気伝導率を測定したところ６×
１０ -4Ｓ／ｃｍであった。Further, two sheets of the above-mentioned electric conductivity measuring element
Was changed to two Li metal electrodes,
When the electric conductivity of the solid ionic conductor was measured by 6 ×
10 -FourS / cm.

【００２８】１，２―ジブロモエタンに換えて１，６−
ジブロモヘキサンを用いた以外は前期と同様にして固体
イオン伝導体を得た。Instead of 1,2-dibromoethane, 1,6-
A solid ion conductor was obtained in the same manner as in the previous period except that dibromohexane was used.

【００２９】得られた固体イオン伝導体を２枚のＰｔ金
属電極間にはさみ、一旦加熱後放置冷却して電気伝導率
測定用素子とした。この素子のＰｔ電極に１２０Ｈｚの
交流をかけ固体イオン伝導体の電気伝導率を測定したと
ころ、８×１０-4Ｓ／ｃｍであった。また、直流をかけ
たところ測定限界（１０-8Ｓ／ｃｍ）以下の電気伝導率
であった。The obtained solid ionic conductor was sandwiched between two Pt metal electrodes, heated once and left to cool to obtain an electric conductivity measuring element. An electric current of 120 Hz was applied to the Pt electrode of this device, and the electric conductivity of the solid ionic conductor was measured. As a result, it was 8 × 10 −4 S / cm. When a direct current was applied, the electric conductivity was lower than the measurement limit (10 −8 S / cm).

【００３０】さらに、上記電気伝導率測定用素子の２枚
のＰｔ金属電極を２枚のＬｉ金属電極に変更して、直流
で固体イオン伝導体の電気伝導率を測定したところ２×
１０ -4Ｓ／ｃｍであった。Further, two sheets of the above-mentioned electric conductivity measuring element
Was changed to two Li metal electrodes,
The electric conductivity of the solid ionic conductor was measured at 2 ×
10 -FourS / cm.

【００３１】（実施例２）本実施例は（化１）に示す構
造を含むイオンまたはその誘導体と、これと異なる陽イ
オンを共存イオンとして少なくとも含むゲルまたは固体
をイオン伝導体に関するものである。Example 2 This example relates to an ion conductor containing a gel or a solid containing at least an ion having the structure shown in Chemical formula 1 or a derivative thereof and a different cation as a coexisting ion.

【００３２】１−メチルイミダゾール０．１ｍｏｌと臭
化エチル０．１３ｍｏｌとをアセトニトリル５０ｍｌに
溶解し、この溶液を入れた容器に冷却器を取り付け蒸発
成分が回収できるようにし、水浴に入れ８０℃で４時間
加熱反応させた。得られた反応液をロータリーエバポレ
ータで減圧加熱し溶媒を除去した。得られた物質を水２
００ｍｌに溶解し、この溶液を攪拌しつつ水１００ｍｌ
にＮＨ4ＰＦ6を０．１２ｍｏｌ溶解した水溶液を注ぎ、
六弗化りん酸１−エチル−３−メチルイミダゾリウム
（Ｅｔ−Ｉｍ−Ｍｅ・ＰＦ6と略す）の粗沈殿を得た。
得られた粗沈殿を温メタノール中に溶解し、冷却して再
結晶させろ過後乾燥し精製Ｅｔ−Ｉｍ−Ｍｅ・ＰＦ6を
得た。0.1 mol of 1-methylimidazole and 0.13 mol of ethyl bromide are dissolved in 50 ml of acetonitrile. The reaction was carried out by heating for 4 hours. The obtained reaction solution was heated under reduced pressure by a rotary evaporator to remove the solvent. The obtained substance is
100 ml of water while stirring the solution.
An aqueous solution in which 0.12 mol of NH 4 PF 6 is dissolved is poured into
A crude precipitate of 1-ethyl-3-methylimidazolium hexafluorophosphate (abbreviated as Et-Im-Me.PF 6 ) was obtained.
Obtained was dissolved crude precipitate in hot methanol and cooled recrystallized and dried after filtration to give the purified Et-Im-Me · PF 6 .

【００３３】ＬｉＰＦ6と精製Ｅｔ−Ｉｍ−Ｍｅ・ＰＦ6
とをＬｉ原子数とイミダゾール環（Ｉｍと略す）の数の
比がＬｉ／Ｉｍ＝０．７となるように混合し、さらにこ
のイオン伝導体に対して、３倍の重量比のポリブチルメ
タクリレートとをプロピレンカーボネート溶媒を用いて
混合後、溶媒を除去することにより、固体イオン伝導体
を得た。LiPF 6 and purified Et-Im-Me.PF 6
Are mixed so that the ratio of the number of Li atoms to the number of imidazole rings (abbreviated as Im) becomes Li / Im = 0.7, and further, the weight ratio of polybutyl methacrylate to the ionic conductor is tripled. Was mixed using a propylene carbonate solvent, and then the solvent was removed to obtain a solid ion conductor.

【００３４】このようにして得た固体イオン伝導体につ
いて、実施例１と同様の方法で電気伝導率を測定したと
ころ、良好な結果が得られた。The solid ionic conductor thus obtained was measured for electric conductivity in the same manner as in Example 1. As a result, good results were obtained.

【００３５】（実施例３）本実施例は（化２）に示す構
造を含むイオンまたはその誘導体と、これと異なる陽イ
オンを共存イオンとして少なくとも含むゲルまたは固体
をイオン伝導体に関するものである。Example 3 This example relates to an ion conductor having an ion or a derivative thereof having the structure shown in (Chemical Formula 2) and a gel or a solid containing at least a different cation as a coexisting ion.

【００３６】トリエチルフェニルアンモニウムブロマイ
ド０．１ｍｏｌを水２００ｍｌに溶解し、この溶液を攪
拌しつつ水１００ｍｌにＮＨ4ＰＦ6を０．１２ｍｏｌ溶
解した水溶液を注ぎ、六弗化りん酸トリエチルフェニル
アンモニウムの粗沈殿を得た。得られた粗沈殿を温メタ
ノール中に溶解し、冷却して再結晶させろ過後乾燥し精
製六弗化りん酸トリエチルフェニルアンモニウムを得
た。[0036] The triethyl phenyl ammonium bromide 0.1mol was dissolved in water 200 ml, crude solution of NH 4 PF 6 in water 100ml with stirring poured an aqueous solution prepared by dissolving 0.12 mol, hexafluoride phosphate triethylphenyl ammonium A precipitate was obtained. The obtained crude precipitate was dissolved in warm methanol, cooled, recrystallized, filtered and dried to obtain purified triethylphenylammonium hexafluorophosphate.

【００３７】ＬｉＰＦ6と精製六弗化りん酸トリエチル
フェニルアンモニウムとをＬｉ原子数と４級アンモニウ
ム窒素（Ｎ＋と略す）の数の比がＬｉ／Ｎ＋＝０．７と
なるように混合し、高分子であるＡＢＳ樹脂とを溶媒メ
チルイソブチルケトンいい混合して冷却固化後、固体イ
オン伝導体を得た。LiPF 6 and purified triethylphenylammonium hexafluorophosphate are mixed so that the ratio of the number of Li atoms to the number of quaternary ammonium nitrogen (abbreviated as N +) becomes Li / N + = 0.7, and An ABS resin as a molecule was mixed with a solvent, methyl isobutyl ketone, and cooled and solidified to obtain a solid ion conductor.

【００３８】このようにして得た固体イオン伝導体につ
いて、実施例１と同様の方法で電気伝導率を測定したと
ころ、良好な結果が得られた。The solid ionic conductor thus obtained was measured for electric conductivity in the same manner as in Example 1, and good results were obtained.

【００３９】（実施例４）本実施例は（化４）に示す構
造を含むイオンまたはその誘導体と、これと異なる陽イ
オンを共存イオンとして少なくとも含むゲルまたは固体
のイオン伝導体に関するものである。Example 4 This example relates to a gel or solid ion conductor containing at least an ion having the structure shown in Chemical formula 4 or a derivative thereof and a different cation as coexisting ions.

【００４０】実施例１の１−メチルイミダゾールに換え
てトリエチルアミンを、１，２−ジブロモエタンに換え
て１，２−ジヨードエタンを用いた以外は実施例１と同
様にしてまず低分子の固体イオン伝導体を得た。これと
ウレタンとエチレングリコールからなる重合体と１：
２．５の割合で溶液中で混合し、その後溶媒の除去を行
った。First, low-molecular solid ionic conductivity was obtained in the same manner as in Example 1 except that triethylamine was used instead of 1-methylimidazole and 1,2-diiodoethane was used instead of 1,2-dibromoethane. I got a body. This and a polymer consisting of urethane and ethylene glycol and 1:
Mixing in the solution at a ratio of 2.5 was followed by removal of the solvent.

【００４１】得られた固体イオン伝導体を２枚のＰｔ金
属電極間にはさんで、電気伝導率の測定を行った。この
素子のＰｔ電極に１２０Ｈｚの交流をかけ固体イオン伝
導体の電気伝導率を測定したところ、３×１０-4Ｓ／ｃ
ｍであった。また、直流をかけたところ測定限界（１０
-8Ｓ／ｃｍ）以下の電気伝導率であった。The obtained solid ionic conductor was sandwiched between two Pt metal electrodes, and the electric conductivity was measured. When an electric current of 120 Hz was applied to the Pt electrode of this element to measure the electric conductivity of the solid ionic conductor, it was 3 × 10 -4 S / c.
m. When a direct current was applied, the measurement limit (10
-8 S / cm) or less.

【００４２】さらに、上記電気伝導率測定用素子の２枚
のＰｔ金属電極を２枚のＬｉ金属電極に変更して、直流
で固体イオン伝導体の電気伝導率を測定したところ１×
１０ -4Ｓ／ｃｍであった。Further, two sheets of the above-mentioned electric conductivity measuring element
Was changed to two Li metal electrodes,
The electric conductivity of the solid ionic conductor was measured at 1 ×
10 -FourS / cm.

【００４３】（実施例５）実施例１のＬｉＰＦ6に変更
して、六弗化りん酸テトラエチルアンモニウムを用いた
以外は実施例１と同様にして高分子の固体イオン伝導体
を得た。Example 5 A polymer solid ionic conductor was obtained in the same manner as in Example 1 except that LiPF 6 of Example 1 was replaced with tetraethylammonium hexafluorophosphate.

【００４４】なお、本実施例は、実施例１のＬｉをテト
ラエチルアンモニウムに置き換えたものと同等である。This embodiment is the same as Embodiment 1 except that Li is replaced by tetraethylammonium.

【００４５】得られた固体イオン伝導体を２枚のＰｔ金
属電極間にはさみ、電気伝導率の測定を行った。この素
子のＰｔ電極に１２０Ｈｚの交流をかけ固体イオン伝導
体の電気伝導率を測定したところ、８×１０-4Ｓ／ｃｍ
であった。また、直流をかけたところ測定限界（１０-8
Ｓ／ｃｍ）以下の電気伝導率であった。The obtained solid ion conductor was sandwiched between two Pt metal electrodes, and the electric conductivity was measured. When an electric current of 120 Hz was applied to the Pt electrode of this element and the electric conductivity of the solid ionic conductor was measured, it was 8 × 10 −4 S / cm.
Met. When a direct current was applied, the measurement limit (10 -8
S / cm) or less.

【００４６】（実施例６）実施例１のＬｉＰＦ6に換え
て、ＡｇＰＦ6を用いて高分子の固体イオン伝導体を得
た。得られた固体イオン伝導体の電気伝導率を実施例５
と同様に測定したところ、Ｐｔ電極を用いた交流法では
７×１０-4Ｓ／ｃｍ、直流法では測定限界値以下であっ
た。ＰｔをＡｇ金属に換えて直流で測定したところ、電
気伝導率は９×１０-5Ｓ／ｃｍであった。Example 6 A polymer solid ion conductor was obtained by using AgPF 6 instead of LiPF 6 of Example 1. The electric conductivity of the obtained solid ionic conductor was measured in Example 5.
As a result, it was 7 × 10 −4 S / cm by the AC method using a Pt electrode, and was below the measurement limit value by the DC method. When Pt was changed to Ag metal and measured by direct current, the electrical conductivity was 9 × 10 −5 S / cm.

【００４７】（実施例７）実施例１のＬｉＰＦ6に換え
て、Ｚｎ（ＢＦ4）2を用いて高分子固体イオン伝導体を
得た。得られた固体イオン伝導体の電気伝導率を実施例
５と同様に測定したところ、Ｐｔ電極を用いた交流法で
は２×１０-4Ｓ／ｃｍ、直流法では測定限界値以下であ
った。Example 7 A solid polymer ion conductor was obtained using Zn (BF 4 ) 2 instead of LiPF 6 of Example 1. When the electric conductivity of the obtained solid ionic conductor was measured in the same manner as in Example 5, it was 2 × 10 −4 S / cm by the AC method using a Pt electrode, and was below the measurement limit value by the DC method.

【００４８】（実施例８）実施例１のＬｉＰＦ6に換え
て、Ｃａ（ＢＦ4）2を用いて高分子の固体イオン伝導体
を得た。得られた固体イオン伝導体の電気伝導率を実施
例５と同様に測定したところ、Ｐｔ電極を用いた交流法
では３×１０-4Ｓ／ｃｍ、直流法では測定限界値以下で
あった。Example 8 A polymer solid ionic conductor was obtained using Ca (BF 4 ) 2 instead of LiPF 6 of Example 1. When the electric conductivity of the obtained solid ionic conductor was measured in the same manner as in Example 5, it was 3 × 10 −4 S / cm by the AC method using a Pt electrode, and was below the measurement limit value by the DC method.

【００４９】（実施例９）実施例２のＬｉＰＦ6に換え
て、ＡｇＰＦ6を用いて実施例２と同様に高分子固体イ
オン伝導体を得た。得られた固体イオン伝導体の電気伝
導率を実施例６と同様に測定したところ、Ｐｔ電極を用
いた交流法では８×１０-4Ｓ／ｃｍ、直流法では測定限
界値以下であった。ＰｔをＡｇ金属に換えて直流で測定
したところ、電気伝導率は４×１０-5Ｓ／ｃｍであっ
た。Example 9 A polymer solid ionic conductor was obtained in the same manner as in Example 2 except that AgPF 6 was used instead of LiPF 6 of Example 2. The electric conductivity of the obtained solid ionic conductor was measured in the same manner as in Example 6. As a result, the electric conductivity was 8 × 10 −4 S / cm by the AC method using a Pt electrode, and was below the measurement limit value by the DC method. When Pt was changed to Ag metal and measured by direct current, the electric conductivity was 4 × 10 −5 S / cm.

【００５０】（実施例１０）実施例２のＬｉＰＦ6に換
えて、Ｚｎ（ＢＦ4）2を用いて実施例２と同様に高分子
固体イオン伝導体を得た。得られた固体イオン伝導体の
電気伝導率を実施例２と同様に測定したところ、Ｐｔ電
極を用いた交流法では１×１０-5Ｓ／ｃｍ、直流法では
測定限界値以下であった。Example 10 A solid polymer ion conductor was obtained in the same manner as in Example 2 except that Zn (BF 4 ) 2 was used instead of LiPF 6 of Example 2. When the electric conductivity of the obtained solid ionic conductor was measured in the same manner as in Example 2, it was 1 × 10 −5 S / cm by the AC method using a Pt electrode, and was below the measurement limit value by the DC method.

【００５１】（実施例１１）実施例２のＬｉＰＦ6に換
えて、Ｃａ（ＢＦ4）2を用いて実施例２と同様に固体イ
オン伝導体を得た。得られた固体イオン伝導体の電気伝
導率を実施例２と同様に測定したところ、Ｐｔ電極を用
いた交流法では６×１０-5Ｓ／ｃｍ、直流法では測定限
界値以下であった。Example 11 A solid ionic conductor was obtained in the same manner as in Example 2 except that Ca (BF 4 ) 2 was used instead of LiPF 6 of Example 2. When the electric conductivity of the obtained solid ionic conductor was measured in the same manner as in Example 2, it was 6 × 10 −5 S / cm by the AC method using a Pt electrode, and was below the measurement limit by the DC method.

【００５２】（実施例１２）次に、Ｌｉイオン２次電池
としての電解質としての特性評価を行った。黒鉛粉末材
料に、結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）
を１０重量％混合し、厚さ２０μｍの銅箔上に塗布して
電極を作製した。Example 12 Next, the characteristics of an electrolyte as a Li-ion secondary battery were evaluated. Graphite powder material, polyvinylidene fluoride (PVDF) as binder
Was mixed at 10% by weight and applied on a copper foil having a thickness of 20 μm to prepare an electrode.

【００５３】また、炭酸エチレンと炭酸ジエチルを１：
１の比で混合した有機溶媒にＬｉＰＦ6を１ｍｏｌ／ｌ
溶解して電解液を作製した。Further, ethylene carbonate and diethyl carbonate were mixed at a ratio of 1:
1 mol / l of LiPF 6 in an organic solvent mixed at a ratio of 1
It melt | dissolved and the electrolyte solution was produced.

【００５４】対極としてＬｉ箔を用いて、前記の電極の
間に、電解液を多孔質ポリプロピレンに含侵させたもの
を狭持してコイン電池を作製した。Using a Li foil as a counter electrode, a coin battery was produced by sandwiching a porous polypropylene impregnated with an electrolytic solution between the above-mentioned electrodes.

【００５５】このようにしてつくられた電池の炭素の容
量特性を測定することにより、電解質の評価を行った。
前記実施例１、２、３、４に示した高分子の固体状イオ
ン伝導体を、電解液のかわりに、電解質として用いて同
様に容量特性の評価を行った。The electrolyte was evaluated by measuring the carbon capacity characteristics of the battery thus produced.
The polymer solid ionic conductor shown in Examples 1, 2, 3, and 4 was used as an electrolyte instead of the electrolytic solution, and the capacity characteristics were similarly evaluated.

【００５６】炭素の容量として電解液のみでの場合は３
３０ｍＡｈ／ｇが得られる。高分子状固体イオン伝導体
の電解質を用いると２５０から３００ｍＡｈ／ｇであっ
た。この固体状の電解質に溶媒を含ませてゲル状にする
と容量は３００から３３０ｍＡｈ／ｇが得られた。In the case of using only the electrolytic solution, the capacity of carbon is 3
30 mAh / g is obtained. The value was 250 to 300 mAh / g when the polymer solid electrolyte was used as the electrolyte. When a gel was formed by adding a solvent to the solid electrolyte, a capacity of 300 to 330 mAh / g was obtained.

【００５７】[0057]

【発明の効果】以上の説明から明らかなように、本発明
によりイオン伝導性に優れた高分子固体状のものが得ら
れる。また、Ｌｉイオン２次電池の電解質としても固体
状、ゲル状でも良好な特性を有し、良好な電池特性を提
供できる。As is apparent from the above description, a solid polymer having excellent ionic conductivity can be obtained according to the present invention. In addition, the electrolyte of the Li-ion secondary battery has good characteristics whether it is solid or gel, and can provide good battery characteristics.

Claims (11)

【特許請求の範囲】[Claims] 【請求項１】 非イオン性高分子またはイオン性高分子
と、（化１）に示す構造を含むイオンまたはその誘導体
と、前記イオンまたはその誘導体と異なる陽イオンを共
存イオンとして少なくとも含むゲルまたは固体のイオン
伝導体。但し（化１）において、Ｒ１とＲ２は脂肪族性
基であり、その炭素原子が窒素原子に直接結合するもの
である。 【化１】 1. A gel or a solid containing at least a nonionic polymer or an ionic polymer, an ion or a derivative thereof having the structure shown in Chemical formula 1, and a cation different from the ion or the derivative as a coexisting ion. Ionic conductor. However, in (Chemical Formula 1), R1 and R2 are aliphatic groups, and the carbon atoms thereof are directly bonded to the nitrogen atom. Embedded image 【請求項２】 非イオン性高分子またはイオン性高分子
と、（化２）に示す構造を含むイオンまたはその誘導体
と、前記イオンまたはその誘導体と異なる陽イオンを共
存イオンとして少なくとも含むゲルまたは固体をイオン
伝導体。但し（化２）において、Ｒ３は芳香族基であ
り、Ｒ４、Ｒ５又はＲ６は窒素原子に脂肪族性炭素が直
接結合する基である。 【化２】 2. A gel or solid containing at least a nonionic polymer or an ionic polymer, an ion having the structure shown in Chemical formula 2, or a derivative thereof, and a cation different from the ion or the derivative thereof as a coexisting ion. The ionic conductor. However, in (Formula 2), R3 is an aromatic group, and R4, R5 or R6 is a group in which aliphatic carbon is directly bonded to a nitrogen atom. Embedded image 【請求項３】 非イオン性高分子またはイオン性高分子
と、（化３）に示す構造を含むイオンまたはその誘導体
と、前記イオンまたはその誘導体と異なる陽イオンを共
存イオンとして少なくとも含むゲルまたは固体のイオン
伝導体。但し（化３）において、Ｒ７とＲ８は窒素原子
に脂肪族性炭素が直接結合する基であり、Ｒ９は炭素数
が１以上１６以下であり、アルキル基、芳香族基、エー
テル結合を含む基、カルボニル基を含む基、ニトリル性
シアノ基又はアルコール性水酸基のうちの少なくともひ
とつを含んでいる。 【化３】 3. A gel or solid containing at least a nonionic polymer or an ionic polymer, an ion having the structure shown in Chemical formula 3, or a derivative thereof, and a cation different from the ion or the derivative thereof as a coexisting ion. Ionic conductor. In formula (3), R7 and R8 are groups in which aliphatic carbon is directly bonded to a nitrogen atom, and R9 is a group having 1 to 16 carbon atoms and containing an alkyl group, an aromatic group, or an ether bond. , A group containing a carbonyl group, a nitrile cyano group or an alcoholic hydroxyl group. Embedded image 【請求項４】 非イオン性高分子またはイオン性高分子
と、（化４）に示す構造を含むイオンまたはその誘導体
と、前記イオンまたはその誘導体と異なる陽イオンを共
存イオンとして少なくとも含むゲルまたは固体のイオン
伝導体。但し（化４）において、Ｒ１３、Ｒ１４、Ｒ１
５及びＲ１６は窒素原子に脂肪族性炭素が直接結合する
基である。また、Ｒ１０、Ｒ１１又はＲ１２のうち少な
くともひとつは芳香族基であり、芳香族でない基は炭素
を含む基である。Ｒ１２は炭素数が１以上１６以下であ
り、アルキル基、芳香族基、エーテル結合を含む基、カ
ルボニル基を含む基、ニトリル性シアノ基又はアルコー
ル性水酸基のうちの少なくともひとつを含んでいる。 【化４】 4. A gel or solid containing at least a nonionic polymer or an ionic polymer, an ion having the structure shown in Chemical Formula 4, or a derivative thereof, and a cation different from the ion or the derivative thereof as a coexisting ion. Ionic conductor. However, in (Chem. 4), R13, R14, R1
5 and R16 are groups in which aliphatic carbon is directly bonded to a nitrogen atom. Further, at least one of R10, R11 and R12 is an aromatic group, and the non-aromatic group is a group containing carbon. R12 has 1 to 16 carbon atoms and contains at least one of an alkyl group, an aromatic group, a group containing an ether bond, a group containing a carbonyl group, a nitrile cyano group and an alcoholic hydroxyl group. Embedded image 【請求項５】 （化１）ないし（化４）のいずれかより
選ばれる二つ以上の構造またはそれらから誘導される構
造を同一イオン内に持つイオンと、前記イオンと異なる
陽イオンを共存イオンとして少なくとも含むゲルまたは
固体のイオン伝導体。5. An ion having two or more structures selected from any of (1) to (4) or a structure derived from them in the same ion, and a cation different from said ion. A gel or solid ionic conductor containing at least as a. 【請求項６】 室温で液体の非イオン性有機溶媒を含ん
だゲルであることを特徴とする請求項１ないし５のいず
れか記載のイオン伝導体。6. The ionic conductor according to claim 1, which is a gel containing a nonionic organic solvent which is liquid at room temperature. 【請求項７】 陽イオンが少なくともアルカリ金属、ア
ルカリ土類金属、銀イオン、銅イオン又は亜鉛イオンよ
り選ばれる金属イオン含んでいることを特徴とする請求
項１ないし５のいずれか記載のイオン伝導体。7. The ionic conduction according to claim 1, wherein the cation contains at least a metal ion selected from an alkali metal, an alkaline earth metal, a silver ion, a copper ion and a zinc ion. body. 【請求項８】 陽イオンが少なくとも直鎖アルキル４級
アンモニウムイオンを含んでいることを特徴とする請求
項１ないし５のいずれか記載のイオン伝導体。但し、前
記直鎖アルキル４級アンモニウムイオンアルキル基の炭
素数は１ないし６のいずれかである。8. The ionic conductor according to claim 1, wherein the cation contains at least a straight-chain alkyl quaternary ammonium ion. However, the straight-chain alkyl quaternary ammonium ion alkyl group has 1 to 6 carbon atoms. 【請求項９】 非イオン性高分子が、フッ化ビニリデン
と六フッ化プロピレンの共重合体、ポリ（２−ヒドロキ
シエチルメタクリレート）またはその共重合体、ポリア
クリロニトリルまたはその共重合体、ポリメタクリレー
トまたはその共重合体、ポリアクリレートまたはその共
重合体もしくはポリエチレンオキサイドまたはその共重
合体より選ばれるものを少なくとも含んでいることを特
徴とする請求項１ないし５のいずれか記載のイオン伝導
体。9. The nonionic polymer is a copolymer of vinylidene fluoride and propylene hexafluoride, poly (2-hydroxyethyl methacrylate) or a copolymer thereof, polyacrylonitrile or a copolymer thereof, polymethacrylate or The ionic conductor according to any one of claims 1 to 5, wherein the ionic conductor contains at least one selected from the group consisting of a copolymer, a polyacrylate, a copolymer thereof, and a polyethylene oxide or a copolymer thereof. 【請求項１０】 イオン性高分子としてポリメタクリル
酸またはその共重合体、ポリアクリル酸またはその共重
合体、ポリフェノールまたはその共重合体、ポリエチレ
ンオキサイドの共重合体もしくはポアクリロニトリルの
共重合体より選ばれるもを少なくても含んでいることを
特徴とする請求項１ないし５のいずれか記載のイオン伝
導体。10. The ionic polymer is selected from polymethacrylic acid or a copolymer thereof, polyacrylic acid or a copolymer thereof, polyphenol or a copolymer thereof, a copolymer of polyethylene oxide or a copolymer of polyacrylonitrile. The ionic conductor according to any one of claims 1 to 5, wherein the ionic conductor includes at least one of the following. 【請求項１１】 請求項１ないし１０のいずれか記載の
イオン伝導体を用いることを特徴とするリチウムイオン
２次電池。11. A lithium ion secondary battery using the ionic conductor according to claim 1. Description:
JP11187276A 1999-07-01 1999-07-01 Ion conductive element and lithium ion secondary battery using the same Pending JP2001015166A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007134282A (en) * 2005-11-14 2007-05-31 Gs Yuasa Corporation:Kk Non-aqueous electrolyte battery
US7452635B2 (en) 2001-12-03 2008-11-18 Samsung Sdi Co., Ltd. Rechargeable lithium battery and method of fabricating same
US20100275979A1 (en) * 2006-08-14 2010-11-04 The Yokohama Rubber Co., Ltd. Clay modified electrolyte for a dye-sensitized solar cell
JP2016533400A (en) * 2013-09-26 2016-10-27 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ Lithium ion conducting polymer composition for lithium electrochemical generators
US9780348B2 (en) 2013-12-19 2017-10-03 Sony Corporation Electrode, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7452635B2 (en) 2001-12-03 2008-11-18 Samsung Sdi Co., Ltd. Rechargeable lithium battery and method of fabricating same
US8541128B2 (en) 2001-12-03 2013-09-24 Samsung Sdi Co., Ltd. Rechargeable lithium battery and method of fabricating same
JP2007134282A (en) * 2005-11-14 2007-05-31 Gs Yuasa Corporation:Kk Non-aqueous electrolyte battery
US20100275979A1 (en) * 2006-08-14 2010-11-04 The Yokohama Rubber Co., Ltd. Clay modified electrolyte for a dye-sensitized solar cell
US8299270B2 (en) * 2006-08-14 2012-10-30 The Yokohama Rubber Co., Ltd. Clay modified electrolyte for a dye-sensitized solar cell
JP2016533400A (en) * 2013-09-26 2016-10-27 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ Lithium ion conducting polymer composition for lithium electrochemical generators
US9780348B2 (en) 2013-12-19 2017-10-03 Sony Corporation Electrode, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus
US10559800B2 (en) 2013-12-19 2020-02-11 Murata Manufacturing Co., Ltd. Electrode, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus

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