JP2000048639A - Composite structure gel electrolyte sheet laminated body - Google Patents
Composite structure gel electrolyte sheet laminated bodyInfo
- Publication number
- JP2000048639A JP2000048639A JP10214275A JP21427598A JP2000048639A JP 2000048639 A JP2000048639 A JP 2000048639A JP 10214275 A JP10214275 A JP 10214275A JP 21427598 A JP21427598 A JP 21427598A JP 2000048639 A JP2000048639 A JP 2000048639A
- Authority
- JP
- Japan
- Prior art keywords
- sea
- electrolyte
- island
- gel electrolyte
- polymer
- 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.)
- Withdrawn
Links
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イオン伝導性高分
子材料およびこれをイオン移動媒体として用いた電池に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion conductive polymer material and a battery using the same as an ion transfer medium.
【０００２】[0002]
【従来の技術】固体電解質をイオン移動媒体として構成
した固体電池は、従来の電解液をイオン移動媒体とした
電池に比べ、液漏れがないため電池の信頼性、安全性が
向上するとともに、薄膜化や積層体形成の容易さ、電池
形態の自由度が高いこと、パッケージの簡略化、軽量化
が期待されている。この固体電解質材料として、イオン
伝導性のセラミック材料またはポリマー材料が提案され
ている。このうち前者のセラミック系材料はもろい性質
を有し、加工性に乏しく電極との積層体形成が難しい。
一方イオン伝導性ポリマー材料は加工性、柔軟性に優れ
るため固体電解質材料として電極との接合体形成、電極
のイオン授受に伴う電極体積変化に追随した界面保持が
できるなど好ましい。2. Description of the Related Art A solid battery comprising a solid electrolyte as an ion transfer medium has less liquid leakage than a conventional battery using an electrolyte as an ion transfer medium, so that the reliability and safety of the battery are improved and a thin film is formed. It is expected that simplicity and ease of formation of a laminate, high degree of freedom in battery form, simplification of the package, and weight reduction are expected. As this solid electrolyte material, an ion conductive ceramic material or a polymer material has been proposed. Among them, the former ceramic material has fragile properties, poor workability, and makes it difficult to form a laminate with an electrode.
On the other hand, an ion conductive polymer material is preferable because it is excellent in processability and flexibility because it can be used as a solid electrolyte material because it can form a bonded body with an electrode and maintain an interface that follows a change in electrode volume due to ion transfer of the electrode.
【０００３】この固体電解質として、Ｗｒｉｇｈｔによ
りポリエチレンオキシドのアルカリ金属塩複合体の報告
（Ｂｒｉｔｉｓｈ Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ、
７巻、３１９ページ（１９７５年）以来、ポリエチレン
オキシド、ポリプロピレンオキシドなどのポリアルキレ
ンエーテル系材料を中心とする材料、ポリアクリロニト
リル、ポリフォスファゼン、ポリシロキサンなどの材料
を骨格としたポリマー固体電解質材料が活発に研究され
ている。As a solid electrolyte, Wright reported an alkali metal salt complex of polyethylene oxide (British Polymer Journal,
Since Volume 7, p. 319 (1975), materials based on polyalkylene ether materials such as polyethylene oxide and polypropylene oxide, and polymer solid electrolyte materials based on materials such as polyacrylonitrile, polyphosphazene and polysiloxane have been developed. Actively researched.
【０００４】これらのポリマー固体電解質は通常はポリ
マー中に電解質が固溶した形態をとり、ドライ系ポリマ
ー固体電解質として知られている。また、電解質解離度
を増大させたり、ポリマーの分子運動を促進してイオン
伝導度を向上させるために、電解質溶媒を添加し、ポリ
マー中に電解質および電解質溶媒を含有させたゲル電解
質が知られている（例えば、特許公開昭５６−１４３３
５６号）。この電解質溶媒に電解質を溶解させたもの
（以下、電解液と称する）をポリマーに導入する方法と
して、ポリマーと可塑剤を混合して均一溶液とした後固
化成形、可塑剤を一旦抽出してから、電解液を含浸する
か、もしくは該可塑剤を電解液で置換する方法が知られ
ている。また、ポリマーと電解液の均一溶液をキャスト
する方法（例えば、米国特許公報５２９６３１８号）も
知られており、ポリマーには電解液に用いられる電解質
溶媒と加温時に均一溶液を形成しやすいポリマーが用い
られ、例えばエチレンカーボネート、プロピレンカーボ
ネート等を電解質溶媒に用いたポリフッ化ビニリデン系
ポリマーが一般的である。しかしながら、従来のゲル電
解質は８５℃〜１１０℃の温度で融解し流動性を示すた
め、電池として短絡を起こす危険があり安全性が問題で
あった。そこで、ポリマー、可塑剤とともに重合性のビ
ニルモノマーを共存させ、この重合性モノマーを架橋さ
せて、可塑剤抽出後電解液を含浸させたゲル電解質も提
案されている（米国特許５４２９８９１号）が、この方
法は重合性ビニルモノマーが電気化学的に不安定である
ことおよび架橋時に可塑剤、重合性ビニルモノマーが副
反応を起こしやすいことから電池用材料として問題があ
った。[0004] These polymer solid electrolytes usually take the form of a solid solution of the electrolyte in a polymer, and are known as dry polymer solid electrolytes. In addition, in order to increase the degree of dissociation of the electrolyte or to promote the molecular motion of the polymer to improve the ionic conductivity, an electrolyte solvent is added, and an electrolyte and a gel electrolyte in which the electrolyte solvent is contained in the polymer are known. (For example, Japanese Patent Publication No. 56-1433)
No. 56). As a method of introducing a solution in which an electrolyte is dissolved in this electrolyte solvent (hereinafter referred to as an electrolyte solution) into a polymer, a polymer and a plasticizer are mixed to form a uniform solution, and then solidification molding, and once the plasticizer is extracted, A method of impregnating with an electrolytic solution or replacing the plasticizer with an electrolytic solution is known. A method of casting a homogeneous solution of a polymer and an electrolyte is also known (for example, US Pat. No. 5,296,318). The polymer includes an electrolyte solvent used for the electrolyte and a polymer which easily forms a uniform solution when heated. For example, polyvinylidene fluoride polymers using ethylene carbonate, propylene carbonate or the like as an electrolyte solvent are generally used. However, since the conventional gel electrolyte melts at a temperature of 85 ° C. to 110 ° C. and exhibits fluidity, there is a danger of causing a short circuit as a battery, and safety is a problem. Therefore, a gel electrolyte in which a polymerizable vinyl monomer coexists with a polymer and a plasticizer, the polymerizable monomer is cross-linked, and a plasticizer is extracted and impregnated with an electrolyte solution has been proposed (US Pat. No. 5,429,891). This method has a problem as a battery material because the polymerizable vinyl monomer is electrochemically unstable and the plasticizer and the polymerizable vinyl monomer easily cause side reactions during crosslinking.
【０００５】また、ゲル電解質シートの機械的強度向上
のため、貫通孔をもつポリオレフィン系ポリマー多孔質
媒体中にポリエチレンオキシドなどのイオン伝導性高分
子を導入したポリマー固体電解質（特許公開昭６３−１
０２１０４号）や、イオン伝導性高分子ラテックスとイ
オン非伝導性ラテックスの混合体を塗布成形したポリマ
ー固体電解質（特許公開平４−３２５９９０号）が提案
されている。ところが、これらの材料はイオン非伝導性
マトリックスを持つためイオン伝導度が低くなり問題で
あった。Further, in order to improve the mechanical strength of the gel electrolyte sheet, a polymer solid electrolyte in which an ion-conductive polymer such as polyethylene oxide is introduced into a polyolefin polymer porous medium having through holes (Japanese Patent Publication No. 63-1)
No. 02104) and a polymer solid electrolyte obtained by coating and forming a mixture of an ion-conductive polymer latex and an ion-non-conductive latex (Japanese Patent Application Laid-Open No. 4-325990). However, these materials have a problem in that they have an ionic non-conductive matrix and thus have low ionic conductivity.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、高いイオン
伝導度を有するゲル電解質シートであり、かつ室温およ
び加熱加工時の機械的強度を兼ね備えたゲル電解質シー
トの提供を目的とし、さらにこの材料を用いた、高速充
放電性、繰り返し充放電性や安全性に優れた電池やキャ
パシターなどの電気化学素子を提供することを目的とす
るSUMMARY OF THE INVENTION An object of the present invention is to provide a gel electrolyte sheet having high ionic conductivity and having both room temperature and mechanical strength at the time of heat processing. An object of the present invention is to provide an electrochemical element such as a battery and a capacitor which is excellent in high-speed charge / discharge property, repetitive charge / discharge property and safety using the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前記課題を
解決するために、ゲル電解質シートの研究を進めた結
果、高いイオン伝導度を有し、高温構造安定性に優れた
複合構造ゲル電解質シートを見出し、さらにそれを用い
て高速充放電性、繰り返し充放電性や安全性に優れた電
池やキャパシターなどの電気化学素子を見出し、本発明
をなすに至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied a gel electrolyte sheet, and as a result, have found that a composite gel having high ionic conductivity and excellent high-temperature structural stability has been obtained. The present inventors have found an electrolyte sheet, and have further found an electrochemical element such as a battery or a capacitor which is excellent in high-speed charge / discharge property, repetitive charge / discharge property and safety by using the electrolyte sheet, and has accomplished the present invention.
【０００８】即ち、本発明は １， 液体窒素による凍結状態で下記（Ｉ）および（Ｉ
Ｉ）の海島構造を有するゲル電解質シートが積層されて
いることを特徴とする複合構造ゲル電解質シート積層
体。 （Ｉ） 海が電解質を溶解した電解質溶媒からなる電解
液を含浸したポリマー相、および島が該電解液からなる
海島構造。 （ＩＩ）島が電解質を溶解した電解質溶媒からなる電解
液を含浸したポリマー相、および海が該電解液からなる
海島構造。 ２、 少なくとも一方の面が（ＩＩ）の構造であること
を特徴とする１記載の複合構造ゲル電解質シート積層
体。 ３、 ポリマーがポリフッ化ビニリデン系ポリマーであ
ることを特徴とする１または２の複合構造ゲル電解質シ
ート積層体。 ４， １〜３いずれかの複合構造ゲル電解質シート積層
体が電極に接合した電気化学素子に関する。That is, the present invention relates to the following (I) and (I) when frozen in liquid nitrogen.
A composite gel electrolyte sheet laminate, wherein the gel electrolyte sheet having the sea-island structure of I) is laminated. (I) A polymer phase in which the sea is impregnated with an electrolytic solution composed of an electrolyte solvent in which an electrolyte is dissolved, and a sea-island structure in which islands are composed of the electrolytic solution. (II) A polymer phase in which an island is impregnated with an electrolytic solution comprising an electrolyte solvent in which an electrolyte is dissolved, and a sea-island structure in which the sea is composed of the electrolytic solution. 2. The composite gel electrolyte sheet laminate according to 1, wherein at least one surface has the structure of (II). 3. The composite electrolyte gel electrolyte sheet according to 1 or 2, wherein the polymer is a polyvinylidene fluoride-based polymer. The present invention relates to an electrochemical device in which any one of the composite structure gel electrolyte sheet laminates 4 and 1 to 3 is bonded to an electrode.
【０００９】以下に、本発明の構成要件について説明す
る。本発明におけるゲル電解質シートの海島構造とは、
電解液を含浸したポリマーからなる相（以下、イオン伝
導性ポリマー相と称する）と、該電解液が相分離した状
態の構造をしており、−３０℃〜−１０℃でその断面を
観察したときにイオン伝導性ポリマー相と電解液の一方
の相が他方の相の中に孤立した粒子状に分散した状態が
あたかも海島状に見えることから海島構造と言う。Hereinafter, the constituent requirements of the present invention will be described. The sea-island structure of the gel electrolyte sheet in the present invention,
A phase composed of a polymer impregnated with an electrolytic solution (hereinafter referred to as an ion-conductive polymer phase) and a structure in which the electrolytic solution is phase-separated, and its cross section was observed at −30 ° C. to −10 ° C. Sometimes the state in which one phase of the ion-conductive polymer phase and the electrolyte is dispersed in the other phase in the form of isolated particles looks like a sea-island structure.
【００１０】これらの海島構造の観察は、試料を液体窒
素で凍結後凍結割断などによって断面を作製し、この断
面を電子顕微鏡の試料ステージを前記温度に保持しなが
ら試料観察する方法で行うことができる。例えば、ポリ
フッ化ビニリデン系ポリマーとエチレンカーボネート系
電解液を用いた場合の第一の海島構造では、ポリマーが
ポリマーマトリックスとして断面がフラットな形状の海
構造となり、電解液が島構造と判別できる。断面構造に
おける島部の平均粒径は長径と短径の平均径を単純積算
平均として表す。Observation of these sea-island structures can be performed by freezing a sample in liquid nitrogen, forming a cross section by freezing cleavage, and observing the cross section while holding the sample stage of the electron microscope at the above temperature. it can. For example, in the first sea-island structure in which a polyvinylidene fluoride-based polymer and an ethylene carbonate-based electrolyte are used, the polymer has a polymer matrix to form a sea structure having a flat cross section, and the electrolyte can be discriminated as an island structure. The average particle diameter of the island portion in the cross-sectional structure is represented by a simple integrated average of the average diameter of the major axis and the minor axis.
【００１１】本発明は、以下に示す第一、第二の２種類
の海島構造を含むことを特徴とする複合構造のゲル電解
質シートに関するものである。本発明の複合構造を形成
する第一の海島構造は、海島構造の海の部分にイオン伝
導性ポリマー相が分布し、島の部分に電解液が分布する
構造である。また、第二の海島構造は、海島構造の島の
部分にイオン伝導性ポリマー相が分布し、海の部分に電
解液が分布する構造である。The present invention relates to a gel electrolyte sheet having a composite structure characterized by including the following first and second types of sea-island structures. The first sea-island structure forming the composite structure of the present invention is a structure in which the ion-conductive polymer phase is distributed in the sea portion of the sea-island structure and the electrolyte is distributed in the island portion. Further, the second sea-island structure is a structure in which the ion-conductive polymer phase is distributed in the island portion of the sea-island structure and the electrolyte is distributed in the sea portion.
【００１２】これらの構造はそれぞれの効果として、第
一の海島構造は海部を形成するイオン伝導性ポリマー相
が機械的強度を強める効果を有すると考えられる。その
ためには、イオン伝導性ポリマー相の面積が断面積全体
に占める面積の割合が５０％以上、好ましくは６０％以
上、さらに好ましくは７０％以上である。この海部分の
占有面積が全面積に対して５０％未満では液相の部分が
大きくなりすぎ、ゲル電解質シートの機械的強度が低下
する。また、加工時にポリマー相が偏析した場合は強度
および性能低下を伴う。逆に面積占有率の上限は１００
％でも機械的強度の面からは問題はないが、ポリマーに
含浸する電解液だけではイオン伝導性が不十分となる。
従って、第一の海島構造の島部を形成する電解液はイオ
ン伝導に重要な役割を果たしていると言える。さらに、
この第一の海島構造はゲル電解質シートを電池に応用し
た場合、海部の果たす機械強度が、加工工程上や電池と
して使う際の電極間の短絡を防止に大きな効果を果た
す。島部の平均粒径の上限はゲル電解質シートの厚み未
満であり、好ましくは３０μｍ以下、さらに好ましくは
２０μｍ以下である。そして、平均粒径の下限は、本発
明においては０．０１μｍ以上である。一方、第二の海
島構造は海部を形成する電解液の存在で第一の海島構造
以上にイオン伝導度を高めることができる。この構造の
場合は島部であるイオン伝導性ポリマー相がこの電解液
を保持する構造を形成している。そのため、島部の面積
は断面全体の面積に対して２０％以上８０％以下が好ま
しい。さらに電池として電極に接合する場合には、電極
表面の形状に追随した変形が可能なため界面接合しやす
く、単なる積層体と異なり、ずれによる短絡が防止で
き、イオン伝導性も良好となり高い電池性能を示す。第
二の海島構造において島部の平均粒径は微細であるほど
イオン伝導性が良好となる。この範囲は好ましくは２０
μｍ以下、さらに好ましくは１０μｍ以下である。ま
た、ポリマー粒子径の下限は本発明においては０．０１
μｍ以上である。このように第一の海島構造はイオン伝
導度を保持しつつ高い機械強度を持ち、第二の海島構造
は高いイオン伝導度を保持しつつ機械強度を持ち、さら
に界面接合性も良好な性質を持つ。As these structures have respective effects, it is considered that the first sea-island structure has an effect of enhancing the mechanical strength of the ion-conductive polymer phase forming the sea part. For this purpose, the area ratio of the area of the ion-conductive polymer phase to the entire cross-sectional area is 50% or more, preferably 60% or more, and more preferably 70% or more. If the area occupied by the sea portion is less than 50% of the total area, the liquid phase portion becomes too large, and the mechanical strength of the gel electrolyte sheet decreases. Further, when the polymer phase segregates during processing, the strength and performance are reduced. Conversely, the upper limit of the area occupancy is 100
%, There is no problem in terms of mechanical strength, but the ionic conductivity of the electrolyte impregnating the polymer alone is insufficient.
Therefore, it can be said that the electrolytic solution forming the island portion of the first sea-island structure plays an important role in ion conduction. further,
In the first sea-island structure, when the gel electrolyte sheet is applied to a battery, the mechanical strength provided by the sea portion has a great effect in preventing a short circuit between electrodes in a processing step or when used as a battery. The upper limit of the average particle size of the island portion is less than the thickness of the gel electrolyte sheet, preferably 30 μm or less, more preferably 20 μm or less. The lower limit of the average particle size is 0.01 μm or more in the present invention. On the other hand, the second sea-island structure can enhance the ionic conductivity more than the first sea-island structure due to the presence of the electrolyte forming the sea part. In the case of this structure, the ion-conductive polymer phase, which is an island portion, forms a structure that holds the electrolytic solution. Therefore, the area of the island is preferably 20% or more and 80% or less with respect to the area of the entire cross section. Furthermore, when joining to an electrode as a battery, it is possible to deform according to the shape of the electrode surface, so it is easy to join at the interface. Is shown. In the second sea-island structure, the smaller the average particle size of the island portion, the better the ion conductivity. This range is preferably 20
μm or less, more preferably 10 μm or less. The lower limit of the polymer particle diameter is 0.01 in the present invention.
μm or more. Thus, the first sea-island structure has high mechanical strength while maintaining ionic conductivity, and the second sea-island structure has high mechanical strength while maintaining high ionic conductivity, and also has good interfacial bonding properties. Have.
【００１３】本発明は、第一、第二の海島構造を持つゲ
ル電解質シートを有する複合体とすることで、高機械強
度、高イオン伝導度を達成し、電極と複合構造ゲル電解
質シート積層体を積層一体化した電池に用いた場合には
電極間の短絡を防止し、高いイオン伝導度を達成するこ
とが可能となった。電池において好ましくは、電極界面
付近にイオン伝導度の高い第二の海島構造が分布し、複
合構造ゲル電解質シート積層体の内部側には第一の海島
構造が分布したものである。この構造は、イオン伝導度
の高い第二の海島構造を電極界面に配置することで電極
界面付近のイオン伝導に関与できる電極面積を最大限に
活用することができ、電極界面のインピーダンス低減、
イオン分極の抑制も図ることがでる。そして機械強度を
兼ね備えた第一の海島構造を電解質の内部に配置するこ
とで構造の安定性が達成できる。The present invention provides a composite having a gel electrolyte sheet having first and second sea-island structures to achieve high mechanical strength and high ionic conductivity, and to provide an electrode and a composite gel electrolyte sheet laminate. When used in a battery integrated with a laminate, a short circuit between the electrodes was prevented, and high ionic conductivity could be achieved. Preferably, in the battery, the second sea-island structure having high ionic conductivity is distributed near the electrode interface, and the first sea-island structure is distributed inside the composite structure gel electrolyte sheet laminate. By arranging the second sea-island structure with high ionic conductivity at the electrode interface, this structure can maximize the electrode area that can participate in ionic conduction near the electrode interface, reduce the impedance at the electrode interface,
It is also possible to suppress ionic polarization. By arranging the first sea-island structure having mechanical strength inside the electrolyte, the stability of the structure can be achieved.
【００１４】次に本発明のゲル電解質シートを構成する
ポリマーについて説明する。このポリマーの例として、
ポリエチレンオキシド、ポリプロピレンオキシド、ポリ
テトラメチレングリコールなどの脂肪族ポリエーテル化
合物およびポリエチレンオキシドが分岐したポリフォス
ファゼン、シロキサン系ポリマーなどのポリエーテルを
分子鎖中に含むポリマー、ポリメチルメタクリレート、
ポリメチルアクリレートなどのエステル基を含有するポ
リマー、ポリアクリロニトリル、スチレン−アクリロニ
トリル共重合体などニトリル基を含有するポリマー、ポ
リフッ化ビニリデン系ポリマーを挙げることができる。Next, the polymer constituting the gel electrolyte sheet of the present invention will be described. As an example of this polymer,
Polyethylene oxide, polypropylene oxide, aliphatic polyether compounds such as polytetramethylene glycol and polyethylene oxide-branched polyphosphazene, a polymer containing a polyether such as a siloxane-based polymer in the molecular chain, polymethyl methacrylate,
Examples thereof include polymers containing ester groups such as polymethyl acrylate, polymers containing nitrile groups such as polyacrylonitrile and styrene-acrylonitrile copolymer, and polyvinylidene fluoride-based polymers.
【００１５】このうちポリフッ化ビニリデン系ポリマー
を用いて作製したゲルは高強度、高イオン伝導度を持つ
ため、より好ましい。この例として、ポリ（ビニリデン
フロライド）、ポリ（ヘキサフルオロプロピレン−ビニ
リデンフロライド）共重合体、ポリ（パーフルオロビニ
ルエーテル−ビニリデンフロライド）共重合体、ポリ
（テトラフルオロエチレン−ビニリデンフロライド）共
重合体、ポリ（ヘキサフルオロプロピレンオキシド−ビ
ニリデンフロライド）共重合体、ポリ（ヘキサフルオロ
プロピレンオキシド−テトラフルオロエチレン−ビニリ
デンフロライド）共重合体、ポリ（ヘキサフルオロプロ
ピレン−テトラフルオロエチレン−ビニリデンフロライ
ド）共重合体、ポリ（フルオロエチレン−ビニリデンフ
ロライド）共重合体などの単独体、またはこれらの成分
の混合体を挙げることができるがこれらに限定されるも
のでない。Among them, a gel prepared using a polyvinylidene fluoride-based polymer is more preferable because it has high strength and high ionic conductivity. Examples of this include poly (vinylidene fluoride), poly (hexafluoropropylene-vinylidene fluoride) copolymer, poly (perfluorovinyl ether-vinylidene fluoride) copolymer, and poly (tetrafluoroethylene-vinylidene fluoride) copolymer. Polymer, poly (hexafluoropropylene oxide-vinylidene fluoride) copolymer, poly (hexafluoropropylene oxide-tetrafluoroethylene-vinylidene fluoride) copolymer, poly (hexafluoropropylene-tetrafluoroethylene-vinylidene fluoride) ) Copolymers, homopolymers such as poly (fluoroethylene-vinylidene fluoride) copolymer, and mixtures of these components, but are not limited thereto.
【００１６】また、ポリマーが架橋構造を有することが
強度、耐熱性、電気化学素子性能の点でさらに好まし
い。例えば、ポリフッ化ビニリデン系ポリマーを架橋す
る方法として、電子線、ガンマ線、Ｘ線、紫外線、赤外
線などの輻射エネルギー照射、ラジカル開始剤を含有さ
せて反応架橋させる方法、アルカリ処理（脱ＨＦ）処理
後反応性基を反応架橋させる方法、などを用いることが
できる。例えば電子線照射を用いる場合の架橋条件とし
て、この照射量が充分でない場合架橋効果が充分でな
く、照射量が多すぎる場合ポリマー構造が崩壊するため
好ましくない。この照射量は５Ｍｒａｄ以上１００Ｍｒ
ａｄ以下であることが好ましい。このようなポリマーの
架橋によって複合構造のゲル電解質膜が高強度となり加
工性に好ましい性質を付与できる。また、これを用いた
電気化学素子においても電極間の短絡を抑制することが
でき素子の安全性が高められ好ましい。Further, it is more preferable that the polymer has a crosslinked structure in view of strength, heat resistance, and performance of an electrochemical device. For example, as a method of cross-linking a polyvinylidene fluoride-based polymer, irradiation of radiation energy such as electron beam, gamma ray, X-ray, ultraviolet ray, or infrared ray, a method of containing and reacting a radical initiator to cross-link, and after alkali treatment (de-HF treatment) A method in which a reactive group is reactively crosslinked can be used. For example, as the cross-linking conditions when using electron beam irradiation, if the irradiation amount is not sufficient, the cross-linking effect is not sufficient, and if the irradiation amount is too large, the polymer structure is undesirably collapsed. This irradiation amount is 5Mrad or more and 100Mr.
It is preferably equal to or less than ad. The cross-linking of such a polymer makes the gel electrolyte membrane having a composite structure high in strength, and can impart favorable properties to workability. Further, in an electrochemical device using the same, a short circuit between the electrodes can be suppressed, and the safety of the device is improved, which is preferable.
【００１７】次に、本発明の複合構造ゲル電解質シート
積層体に含有される電解液について説明する。本発明の
複合構造ゲル電解質シート積層体に含有される電解液は
電解質溶媒と電解質からなる。この電解質溶媒として、
エチレンカーボネート、プロピレンカーボネート、ビチ
レンカーボネートなどの環状カーボネート、ジメチルカ
ーボネート、メチルエチルカーボネートなどの鎖状カー
ボネート、テトラヒドロフラン、メチルテトラヒドロフ
ランなどのエーテル、γ−ブチルラクトン、プロピオラ
クトン、酢酸メチルなどのエステル、アセトニトリル、
プロピオニトリルなどのニトリル化合物、炭化水素など
の有機低分子化合物、シリコンオイル、オリゴエチレン
グリコール、ポリエチレンオキシド、ポリプロピレンオ
キシドなどの脂肪族エーテル化合物、ポリアクリロニト
リル、脂肪族ポリエステル、脂肪族ポリカーボネートな
どの極性基含有高分子有機化合物を挙げることができ
る。Next, the electrolytic solution contained in the composite gel electrolyte sheet laminate of the present invention will be described. The electrolytic solution contained in the composite structure gel electrolyte sheet laminate of the present invention comprises an electrolyte solvent and an electrolyte. As this electrolyte solvent,
Cyclic carbonates such as ethylene carbonate, propylene carbonate and bitylene carbonate, chain carbonates such as dimethyl carbonate and methyl ethyl carbonate, ethers such as tetrahydrofuran and methyl tetrahydrofuran, esters such as γ-butyl lactone, propiolactone and methyl acetate, and acetonitrile ,
Nitrile compounds such as propionitrile, organic low-molecular compounds such as hydrocarbons, polar groups such as silicone oil, aliphatic ether compounds such as oligoethylene glycol, polyethylene oxide and polypropylene oxide, polyacrylonitrile, aliphatic polyester and aliphatic polycarbonate Containing high molecular organic compounds.
【００１８】一方、電解質としては有機酸、有機塩、無
機酸、無機塩のいずれも使用可能である。この例として
テトラフルオロホウ酸、過塩素酸、硫酸、リン酸、フッ
化水素酸、塩酸などの無機酸、トリフルオロメタンスル
ホン酸、トリフルオロプロピルスルホン酸、ビス（トリ
フルオロメタンスルホニル）イミド酸、酢酸、チルフル
オロ酢酸、プロピオン酸などの有機酸、およびこれら有
機酸、無機酸の金属塩が挙げられる。これらは単独で用
いることもできるし、複数の電解質を混合して用いるこ
ともできる。さらにパーフルオロスルホン酸系ポリマー
やパーフルオロカルボン酸系ポリマー、あるいはこれら
の金属塩も本発明の電解質として使用できる。これら電
解質のカチオンとしてプロトン、アルカリ金属カチオ
ン、アルカリ土類金属カチオン、遷移金属カチオン、希
土類金属カチオンなどから選ばれるカチオンを一種類
で、また複数混合して使用することができる。このカチ
オン種は使用する用途によって異なるため限定されな
い。例えば、本発明の複合構造ゲル電解質シート積層体
をリチウムイオン二次電池に使用する場合は、添加する
電解質としてリチウム塩を使用することが好ましい。特
にリチウムイオン二次電池に利用する場合、充放電を繰
り返し行う必要から、電解質に電気化学的安定性に富む
リチウム塩を選ぶことが好ましく、この例として、ＣＦ
3ＳＯ3Ｌｉ、Ｃ4Ｆ9ＳＯ3Ｌｉ、（ＣＦ3ＳＯ2）2ＮＬ
ｉ、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＡｓＦ6
等を挙げることができる。本発明の複合構造ゲル電解質
シート積層体における電解液含量は全体重量に対して３
０重量％以上、９８重量％以下である。より好ましくは
４０重量％以上９７重量％以下であり、さらに好ましく
は５０重量％以上９５重量％以下の範囲である。電解液
含量が３０％未満ではイオン伝導度が低く、９８％を越
える場合は機械強度低下を引き起こす。その内、第一の
海島構造の電解液含量は３０％以上９０％以下であり、
好ましくは４０％以上８５％以下である。また第二の海
島構造の電解液含量は、４０％以上９８％以下であり、
好ましくは５０％以上９７％以下である。また、複合構
造ゲル電解質シート積層体の厚みは特に制限はないが一
般的には１０μｍ以上５００μｍ以下が好ましい。On the other hand, any of organic acids, organic salts, inorganic acids, and inorganic salts can be used as the electrolyte. Examples thereof include inorganic acids such as tetrafluoroboric acid, perchloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and hydrochloric acid, trifluoromethanesulfonic acid, trifluoropropylsulfonic acid, bis (trifluoromethanesulfonyl) imidic acid, acetic acid, Examples include organic acids such as tylfluoroacetic acid and propionic acid, and metal salts of these organic acids and inorganic acids. These can be used alone, or a plurality of electrolytes can be mixed and used. Further, a perfluorosulfonic acid-based polymer or perfluorocarboxylic acid-based polymer, or a metal salt thereof can also be used as the electrolyte of the present invention. As the cation of these electrolytes, one kind of cation selected from protons, alkali metal cations, alkaline earth metal cations, transition metal cations, rare earth metal cations and the like can be used alone, or a mixture of a plurality of them can be used. The cationic species is not limited because it varies depending on the use. For example, when the composite gel electrolyte sheet laminate of the present invention is used for a lithium ion secondary battery, it is preferable to use a lithium salt as an electrolyte to be added. In particular, when used for a lithium ion secondary battery, it is preferable to select a lithium salt having high electrochemical stability for the electrolyte since charge and discharge must be repeatedly performed.
3 SO 3 Li, C 4 F 9 SO 3 Li, (CF 3 SO 2 ) 2 NL
i, LiBF 4 , LiPF 6 , LiClO 4 , LiAsF 6
And the like. The electrolyte content of the composite structure gel electrolyte sheet laminate of the present invention is 3 to the total weight.
0 wt% or more and 98 wt% or less. The content is more preferably from 40% by weight to 97% by weight, and further preferably from 50% by weight to 95% by weight. If the electrolyte content is less than 30%, the ionic conductivity is low, and if it exceeds 98%, the mechanical strength is reduced. Among them, the electrolyte content of the first sea-island structure is 30% or more and 90% or less,
Preferably it is 40% or more and 85% or less. The electrolyte content of the second sea-island structure is 40% or more and 98% or less,
Preferably it is 50% or more and 97% or less. The thickness of the composite gel electrolyte sheet laminate is not particularly limited, but is generally preferably 10 μm or more and 500 μm or less.
【００１９】次に本発明の複合構造ゲル電解質シート積
層体の作製方法を説明する。まず第一の海島構造、第二
の海島構造のゲル電解質シートそれぞれの作製方法につ
いて説明し、その次に複合シートの作製方法について説
明する。第一の海島構造を持つゲル電解質シートは、た
とえば市販のポリフッ化ビニリデンシートに電子線照射
して三次元化を行いフロンを含浸して発泡体とした後、
加熱延伸して得た発泡体シートに電解液を含浸させるこ
とで得ることができる。Next, a method for producing the composite structure gel electrolyte sheet laminate of the present invention will be described. First, a method for producing each of the gel electrolyte sheets having the first sea-island structure and the second sea-island structure will be described, and then a method for preparing a composite sheet will be described. The gel electrolyte sheet having the first sea-island structure is, for example, a commercially available polyvinylidene fluoride sheet, which is irradiated with an electron beam to form a three-dimensional foam and impregnated with chlorofluorocarbon to form a foam.
It can be obtained by impregnating an electrolytic solution into a foam sheet obtained by heating and stretching.
【００２０】一方、第二の海島構造を持つゲル電解質シ
ートは、ポリフッ化ビニリデンを電解液に加温下溶解し
た液をガラス板上にキャストして得ることができる。そ
して、このようにして作製した第一、第二の海島構造を
持つゲル電解質シートを複数枚重ねることで複合体とす
ることができる。ゲル電解質シート間の接触を高めるた
めに、重ねたものを加熱プレスすることも可能である。
また、第一の海島構造を持つゲル電解質シートを加熱プ
レスし、加熱温度と加熱時間を制御することでシート内
に温度勾配を持たせ、部分的に第一の海島構造を第二の
海島構造に変化させ本発明の複合構造ゲル電解質シート
積層体を製造することもできる。例えば、第一の海島構
造を電極で挟みこみ、用いるポリマーの融点以上で加熱
ロールプレスを行えば、第一の海島構造の電極に面した
側が第二の海島構造に構造変化をおこし、電極との接着
強度があがると共に、電極面側に配置された第二の海島
構造によりイオン伝導度も向上する効果がある。この場
合の構造変化を起こさせるための条件は、具体的には用
いるポリマーが電解液を含んだ状態の融点以上であるこ
とが好ましく、より好ましくは融点以上、融点＋３０℃
以下の温度域である。また加温する時間は処理法によっ
て異なるので限定されないが、例えば加圧ロールプレス
あるいは加圧プレスを行う場合は０．１秒以上１０分以
下の間が好ましく、加熱時間を制御することでゲル電解
質シート内に温度勾配を持たせることが可能となり構造
変化の領域を自由に制御することができる。その他にも
第一の海島構造のゲル電解質シート表面に加温下ポリマ
ーを電解液に溶解した液を塗布して後、室温固化するこ
とにより第二の海島構造を配置する複合構造ゲル電解質
シート積層体を形成することも可能である。On the other hand, the gel electrolyte sheet having the second sea-island structure can be obtained by casting a solution obtained by dissolving polyvinylidene fluoride in an electrolytic solution while heating it on a glass plate. Then, a composite can be obtained by laminating a plurality of gel electrolyte sheets having the first and second sea-island structures thus produced. It is also possible to heat press the stacks to increase the contact between the gel electrolyte sheets.
Also, the gel electrolyte sheet having the first sea-island structure is heated and pressed, and the heating temperature and the heating time are controlled to give a temperature gradient within the sheet, and the first sea-island structure is partially changed to the second sea-island structure. To produce the composite structure gel electrolyte sheet laminate of the present invention. For example, if the first sea-island structure is sandwiched between electrodes and a heating roll press is performed at a temperature equal to or higher than the melting point of the polymer to be used, the side of the first sea-island structure facing the electrode undergoes a structural change to the second sea-island structure, and And the second sea-island structure disposed on the electrode surface side has an effect of improving ionic conductivity. In this case, the condition for causing the structural change is, specifically, the polymer used is preferably at least the melting point of the state including the electrolyte, more preferably the melting point or more, and the melting point + 30 ° C.
The temperature range is as follows. The heating time is not limited because it varies depending on the treatment method. For example, in the case of performing a pressure roll press or a pressure press, the time is preferably 0.1 second or more and 10 minutes or less. A temperature gradient can be provided in the sheet, and the region of the structural change can be freely controlled. In addition, a composite gel electrolyte sheet laminate in which the second sea-island structure is arranged by applying a solution prepared by dissolving a polymer in an electrolytic solution under heating on the surface of a gel electrolyte sheet having the first sea-island structure and then solidifying it at room temperature It is also possible to form a body.
【００２１】また、ゲル電解質の寸法安定化、強度向上
などの目的でポリマーに無機フィラーを含有させること
もできる。この例として、アルミナ、シリカ、ムライ
ト、マイカ、マグネシア、フッ化カルシウム、フッ化マ
グネシウム、窒化ケイ素、酸化セリウム、酸化鉄、酸化
チタン、アルカリ金属やアルカリ土類金属チタン酸複合
酸化物、ダイアモンドなどが挙げられる。フィラ−とし
て電子伝導性でない材料が好ましく、イオン伝導性を有
するフィラ−の場合は電解質膜としてイオンの透過性が
高められるので好ましいものとなる。このフィラ−の形
状として、球状、角状、針状、板状などが挙げられる。Further, the polymer may contain an inorganic filler for the purpose of stabilizing the size of the gel electrolyte and improving the strength. Examples of this include alumina, silica, mullite, mica, magnesia, calcium fluoride, magnesium fluoride, silicon nitride, cerium oxide, iron oxide, titanium oxide, alkali metal and alkaline earth metal titanate composite oxides, diamond and the like. No. As the filler, a material that is not electronically conductive is preferable. In the case of a filler having ion conductivity, it is preferable because the permeability of ions is increased as an electrolyte membrane. Examples of the shape of the filler include a sphere, a square, a needle, and a plate.
【００２２】また、本発明の複合構造ゲル電解質シート
積層体のイオン伝導度は１０-6Ｓ／ｃｍ以上であること
が好ましく、さらに好ましくは１０-5Ｓ／ｃｍ以上、最
も好ましくは１０-3Ｓ／ｃｍ以上である。次に本発明の
複合構造ゲル電解質シート積層体を用いた、電気化学素
子について説明する。The ionic conductivity of the composite gel electrolyte sheet laminate of the present invention is preferably 10 -6 S / cm or more, more preferably 10 -5 S / cm or more, and most preferably 10 -3 S / cm or more. S / cm or more. Next, an electrochemical device using the composite structure gel electrolyte sheet laminate of the present invention will be described.
【００２３】電気化学素子がリチウムイオン二次電池の
場合、電極の正極および負極にリチウムイオン吸蔵放出
可能な物質を用いる。この正極物質として、負極に対し
て高い電位を有する材料、この例としては、コバルト酸
リチウム、ニッケル酸リチウム、マンガン酸リチウム、
Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅの複合リチウム酸化物、結晶性
リチウムバナジウム複合酸化物、アモルファス状リチウ
ムバナジウム複合酸化物、リチウムニオブ複合酸化物な
どの酸化物、リチウムチタン複合硫化物、リチウムモリ
ブデン複合硫化物、リチウムニオブ複合セレン化物など
の金属カルコゲナイド、ポリピロール、ポリチオフェ
ン、ポリアニリン、ポリアセン誘導体、ポリアセチレ
ン、ポリチエニレンビニレン、ポリアリレンビニレン、
ジチオール誘導体、ジスルフィド誘導体などの有機化合
物を挙げることができる。When the electrochemical element is a lithium ion secondary battery, a material capable of inserting and extracting lithium ions is used for the positive electrode and the negative electrode of the electrode. As the positive electrode material, a material having a higher potential than the negative electrode, such as lithium cobaltate, lithium nickelate, lithium manganate,
Co, Ni, Mn, Fe complex lithium oxide, crystalline lithium vanadium complex oxide, amorphous lithium vanadium complex oxide, oxide such as lithium niobium complex oxide, lithium titanium complex sulfide, lithium molybdenum complex sulfide Metal chalcogenides such as lithium niobium composite selenide, polypyrrole, polythiophene, polyaniline, polyacene derivatives, polyacetylene, polythienylenevinylene, polyarylenevinylene,
Organic compounds such as dithiol derivatives and disulfide derivatives can be mentioned.
【００２４】また負極として、上記正極に対して低い電
位を有する材料を用いる。この例として、金属リチウ
ム、アルミ・リチウム合金、マグネシウム・アルミ・リ
チウム合金などの金属リチウム、ＡｌＳｂ、Ｍｇ2 Ｇ
ｅ、ＮｉＳｉ2 などの金属間化合物、グラファイト、コ
ークス、低温焼成高分子などの炭素系材料、ＳｎＭ系酸
化物（ＭはＳｉ，Ｇｅ，Ｐｂを表す。）、Ｓｉ1−ｙ
Ｍ′ｙＯｚ（Ｍ′はＷ，Ｓｎ，Ｐｂ，Ｂなどを表す。０
＜ｙ＜１、０＜ｚ＜３）の複合酸化物、酸化チタン、酸
化鉄などの金属酸化物のリチウム固溶体、リチウムマン
ガン窒化物、リチウム鉄窒化物、リチウムコバルト窒化
物、リチウムニッケル窒化物、リチウム銅窒化物、リチ
ウムボロンナイトライド、リチウムアルミナイトライ
ド、リチウムシリコンナイトライド等の窒化物などのセ
ラミックス等が挙げられる。ただし、リチウムイオンを
負極で還元して金属リチウムとして利用する場合は、導
電性を有する材料であればよいので、上記に限定されな
い。As the negative electrode, a material having a lower potential than the above positive electrode is used. Examples of this include metallic lithium such as metallic lithium, aluminum / lithium alloy, magnesium / aluminum / lithium alloy, AlSb, Mg 2 G
e, intermetallic compounds such as NiSi 2, graphite, coke, carbon-based materials such as low-temperature sintered polymer, SNM based oxide (representing M is Si, Ge, and Pb.), Si 1 -y
M'yOz (M 'represents W, Sn, Pb, B, etc. 0
A composite oxide of <y <1, 0 <z <3), a lithium solid solution of a metal oxide such as titanium oxide or iron oxide, lithium manganese nitride, lithium iron nitride, lithium cobalt nitride, lithium nickel nitride, Ceramics such as nitrides such as lithium copper nitride, lithium boron nitride, lithium aluminum nitride, and lithium silicon nitride are exemplified. However, when lithium ions are reduced at the negative electrode and used as metallic lithium, the material is not limited to the above, as long as the material has conductivity.
【００２５】電池に用いる正極電極および負極電極は、
上記の材料を所定の形状に成型加工して用いられる。例
えば、基盤上に電解析出、蒸着、スパッタリング、ＣＶ
Ｄによって電極を作製した後成型加工したもの、焼結体
から成型加工したもの、溶融加工したもの、微粉を圧縮
して加工したもの、微粉状の電極材料をバインダーの溶
解した溶剤に分散させ、その分散体をシート状の担持体
上に塗工後乾燥させて得られたものを成型加工するもの
などが用いられる。このバインダー材料としては、ポリ
ビニリデンフロライド、ポリ（ヘキサフルオロプロピレ
ン−ビニリデンフロライド）共重合体などポリフッ化ビ
ニリデン系樹脂、ポリテトラフルオロエチレンなどのフ
ッ素系ポリマー、スチレン−ブタジエン共重合体、スチ
レン−アクリロニトリル共重合体、スチレン−アクリロ
ニトリル−ブタジエン共重合体などの炭化水素系ポリマ
ー、ポリマー前駆体、金属などが用いられ、本発明の架
橋構造を有するポリフッ化ビニリデン系樹脂をバインダ
ーに用いることもできる。The positive electrode and the negative electrode used for the battery are:
The above-mentioned material is used after being formed into a predetermined shape. For example, electrolytic deposition, deposition, sputtering, CV on a substrate
D after forming the electrode by D, molded, sintered from the sintered body, melt processed, compressed and processed fine powder, fine powder electrode material is dispersed in a solvent in which the binder is dissolved, A dispersion obtained by coating the dispersion on a sheet-like support and then drying the resulting dispersion is used. Examples of the binder material include polyvinylidene fluoride, polyvinylidene fluoride resin such as poly (hexafluoropropylene-vinylidene fluoride) copolymer, fluorine polymer such as polytetrafluoroethylene, styrene-butadiene copolymer, styrene- A hydrocarbon-based polymer such as an acrylonitrile copolymer, a styrene-acrylonitrile-butadiene copolymer, a polymer precursor, a metal, or the like is used, and the polyvinylidene fluoride resin having a crosslinked structure of the present invention can be used as a binder.
【００２６】電池の形態は、正極と負極が複合構造ゲル
電解質シート積層体を介して接合した電池要素およびそ
の集合体（以下、電池要素集合体と称する）を有する。
その際、電池要素集合体を有する電池は使用目的により
電池要素を並列または／および直列に接続することも可
能である。また、電池要素をロール状、折り畳み状にし
た構造とすることもできる。また、必要があれば電極に
電流取り出し、注入のための外部端子接続部分、電流電
圧制御素子、発熱時に電極接続を阻止する機能素子を設
けることができる。また、電池に防湿防止、構造保護な
どの保護層を設けたりパッケージ化することもできる。The battery has a battery element in which a positive electrode and a negative electrode are joined via a composite gel electrolyte sheet laminate, and an assembly thereof (hereinafter, referred to as a battery element assembly).
At this time, the battery having the battery element assembly may have the battery elements connected in parallel or / and in series depending on the purpose of use. In addition, a structure in which the battery element is rolled or folded may be used. If necessary, an electrode can be provided with an external terminal connection portion for taking out and injecting current, a current-voltage control element, and a functional element for preventing electrode connection when heat is generated. Further, the battery may be provided with a protective layer such as moisture proof prevention and structural protection, or may be packaged.
【００２７】本発明の複合構造ゲル電解質シート積層体
は、リチウムイオン二次電池に限らずアルカリ電池、鉛
電池、ニッケル水素電池、燃料電池などの各種電池、キ
ャパシター、電気化学センサー、エレクトロクロミック
デイスプレー素子などのイオン移動媒体として応用する
ことも可能であり、工業的価値が高い製品を提供できる
ため好ましいものとなる。The composite-structured gel electrolyte sheet laminate of the present invention is not limited to lithium ion secondary batteries, but includes various batteries such as alkaline batteries, lead batteries, nickel-metal hydride batteries, and fuel cells, capacitors, electrochemical sensors, and electrochromic displays. It is also possible to apply it as an ion transfer medium such as an element, and it is preferable because a product having high industrial value can be provided.
【００２８】[0028]
【発明の実施の形態】以下実施例によって本発明をさら
に詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples.
【００２９】[0029]
【実施例１】ポリ（フッ化ビニリデン−ヘキサフルオロ
プロピレン）共重合体（ヘキサフルオロプロピレン含量
３重量％、エルフアトケム社製カイナ−ル２８５０）の
長尺シ−ト（厚み８０μｍ、幅５００ｍｍ）に電子線照
射（照射量１０Ｍｒａｄ）を行い架橋処理した後、フロ
ン（ＨＦＣ−１３４ａ）を７重量部含浸、加熱延伸処理
して得られた発泡体シート（発泡倍率４倍、厚み８０μ
ｍ）を幅１００ｍｍに切断する。続いて、電解液として
エチレンカ−ボネ−ト、γ−ブチルラクトンを体積比
１：１で混合したＬｉＢＦ4 の１．５モル／リットル溶
液を６０℃の温度で加熱含浸させて第一の海島構造のゲ
ル電解質シート（電解液含量７５重量％、平均厚み６５
μｍ）を作製した。Example 1 A long sheet (thickness: 80 μm, width: 500 mm) of a poly (vinylidene fluoride-hexafluoropropylene) copolymer (hexafluoropropylene content: 3% by weight, Kynal 2850 manufactured by Elphatochem Co., Ltd.) After irradiation with X-rays (irradiation amount: 10 Mrad) and crosslinking treatment, a foam sheet (foaming ratio: 4 times, thickness: 80 μm) obtained by impregnating with 7 parts by weight of CFC (HFC-134a) and heating and stretching.
m) is cut to a width of 100 mm. Subsequently, Echirenka as an electrolytic solution - Bonnet - DOO, .gamma.-butyrolactone volume ratio of 1: 1 1.5 mol / l solution of LiBF 4 were mixed in a heated impregnated at a temperature of 60 ° C. The by first sea- Gel electrolyte sheet (electrolyte content 75% by weight, average thickness 65
μm).
【００３０】前記のポリ（フッ化ビニリデン−ヘキサフ
ルオロプロピレン）共重合体ペレットに前記組成の電解
液を加え（ポリマー２０重量％、電解液８０重量％）、
１００℃に加熱して均一溶液に調製した後、ガラス板上
にキャストし、冷却して厚み２４μｍの第二の海島構造
のゲル電解質シートを作製した。この第一の海島構造の
ゲル電解質シートと第二の海島構造のゲル電解質シート
を１枚ずつ計２枚を重ね合わせ８０℃の温度で１分間加
熱プレスして積層体を作製した。該積層体の両面をステ
ンレスシート（厚さ１０μｍ、１ｃｍ×１０ｃｍ短冊）
で挟み込んで交流インピーダンス法によりイオン伝導度
を測定した結果、３．２×１０-3Ｓ／ｃｍであった。An electrolyte of the above composition was added to the poly (vinylidene fluoride-hexafluoropropylene) copolymer pellets (polymer 20% by weight, electrolyte 80% by weight),
After heating to 100 ° C. to prepare a uniform solution, the solution was cast on a glass plate and cooled to produce a 24 μm-thick gel electrolyte sheet having a second sea-island structure. The gel electrolyte sheet having the first sea-island structure and the gel electrolyte sheet having the second sea-island structure were laminated one by one, and were heated and pressed at a temperature of 80 ° C. for 1 minute to produce a laminate. Stainless steel sheets (10 μm thick, 1 cm × 10 cm strip) on both sides of the laminate
As a result of measuring the ionic conductivity by the alternating current impedance method, the value was 3.2 × 10 −3 S / cm.
【００３１】該積層体を液体窒素で冷却した後凍結割断
して断面を形成し、電子顕微鏡（日立製作所製、ＳＥＭ
Ｓ５７０型）を用い観察ステージ冷却状態で観察して断
面の構造を観察した。第二の海島構造のゲル電解質シー
トの断面には平均粒径２〜３μｍの粒子状のイオン伝導
性ポリマー相が分散した島構造とそれを取り囲む電解液
の海構造が観察された。この第二の海島構造の島構造を
形成するポリマー相の面積比は全体の６４％であった。
一方、第一の海島構造の領域には平均粒径５〜８μｍの
電解液が島構造となり、イオン伝導性ポリマー相が海構
造を形成していることがわかった。この領域の海の部分
を形成するポリマー相の面積比は全体の９１％であっ
た。従って、第一、第二の複合ゲル電解質シートの全断
面にしめるイオン伝導性ポリマー相の面積比は８５％で
あることがわかった。The laminate was cooled with liquid nitrogen, frozen and cut to form a cross section, and an electron microscope (SEM, manufactured by Hitachi, Ltd.)
(S570 type), and observed in a cooling state of the observation stage to observe the cross-sectional structure. In the cross section of the gel electrolyte sheet having the second sea-island structure, an island structure in which a particulate ion-conductive polymer phase having an average particle size of 2 to 3 μm was dispersed, and a sea structure of the electrolyte surrounding the island structure were observed. The area ratio of the polymer phase forming the island structure of the second sea-island structure was 64% of the whole.
On the other hand, in the region of the first sea-island structure, the electrolyte having an average particle size of 5 to 8 μm became an island structure, and it was found that the ion-conductive polymer phase formed a sea structure. The area ratio of the polymer phase forming the sea portion of this region was 91% of the whole. Therefore, it was found that the area ratio of the ion conductive polymer phase in the entire cross section of the first and second composite gel electrolyte sheets was 85%.
【００３２】[0032]
【実施例２】実施例１で作製した第一の海島構造のゲル
電解質シートを幅５３ｍｍに切断した。次に、このゲル
電解質シートをポリ（フッ化ビニリデン−ヘキサフルオ
ロプロピレン）共重合体（ヘキサフルオロプロピレン含
量３重量％、エルフアトケム社製カイナ−ル２８５０）
をポリマーが５重量％、電解液９５重量％（エチレンカ
ーボネート／γブチルラクトン＝１、ＬｉＢＦ4 を１．
０モル／リットルに溶解した均一溶液）の組成で６０℃
の均一溶液とした溶液中に浸積して引き上げた後冷却し
て第一の海島構造のゲル電解質シートの表面に平均厚さ
６μｍの第二の海島構造のゲル電解質シートが形成され
た複合構造ゲル電解質シート積層体を得た。Example 2 The gel electrolyte sheet having the first sea-island structure produced in Example 1 was cut to a width of 53 mm. Next, this gel electrolyte sheet was treated with a poly (vinylidene fluoride-hexafluoropropylene) copolymer (hexafluoropropylene content 3% by weight, Kynal 2850 manufactured by Elphatochem Co.).
The polymer is 5% by weight, the electrolyte solution 95 wt% (ethylene carbonate / gamma -butyrolactone = 1, LiBF 4 to 1.
0 ° C / homogeneous solution)
A composite structure in which a gel electrolyte sheet having an average thickness of 6 μm is formed on the surface of a gel electrolyte sheet having a first sea-island structure, which is immersed in a solution prepared as a uniform solution, and then cooled. A gel electrolyte sheet laminate was obtained.
【００３３】次に、平均粒径５μｍのＬｉＣｏＯ2を１
００重量部、バインダーにポリフッ化ビニリデン３重量
部およびアセチレンブラック３重量部をＮ−メチルピロ
リドンに分散し、厚み１５μｍ幅１００ｍｍのアルミ箔
集電体上に塗工後乾燥し、さらに加熱プレスして厚み１
１０μｍ片面塗工の正極電極シ−トを得た。また、平均
粒径１０μｍのグラファイトＭＣＭＢ（大阪ガス製）１
００重量部にスチレン−ブタジエンラテックスの水分散
スラリ−を固形分換算で２重量部およびカルボキシメチ
ルセルロ−スの水溶液を固形分換算で０．８重量部の割
合で水に均一分散したスラリ−を厚み１２μｍ幅１００
ｍｍの銅集電体箔上に塗工後乾燥し、さらに加熱プレス
して厚み８５μｍ片面塗工の負極電極シ−トを得た。こ
れらの電極表面に実施例１で用いた電解液（エチレンカ
ーボネート／γブチルラクトン＝１の混合溶媒に、Ｌｉ
ＢＦ4 の１．５モル／リットル溶液）を正極に３１ｇ／
ｍ 2、負極に４１ｇ／ｍ2になるように塗工した。Next, LiCoO having an average particle size of 5 μm is used.Two1
00 parts by weight, 3 parts by weight of polyvinylidene fluoride as binder
Parts and 3 parts by weight of acetylene black are
Aluminum foil with a thickness of 15 μm and a width of 100 mm dispersed in lidon
After coating on the current collector, it is dried and then hot pressed to a thickness of 1
A 10 μm single-sided coated positive electrode sheet was obtained. Also the average
Graphite MCMB with a particle size of 10 μm (Osaka Gas) 1
Water dispersion of styrene-butadiene latex in 00 parts by weight
2 parts by weight of slurry and carboxymethyl
The aqueous solution of rucellulose is divided into 0.8 parts by weight in terms of solid content.
The slurry, which is uniformly dispersed in water, is 12 μm thick and 100 mm wide.
mm on a copper current collector foil, dried and heated
As a result, a negative electrode sheet having a thickness of 85 μm and coated on one side was obtained. This
The electrolytic solution (ethylene glycol) used in Example 1 was applied to these electrode surfaces.
Libonate / γ-butyllactone = 1 in a mixed solvent
BFFourOf a 1.5 mol / liter solution of
m Two, 41g / m for negative electrodeTwoIt was coated so that it becomes.
【００３４】次に、この正極および負極の電極シートを
幅６０ｍｍに切断し、さらに各電極シートの長手方向に
片側に幅１０ｍｍで活物質層を剥離して集電体が露出し
た構造を形成した。そして、この電極シートの塗工面が
前記複合ゲル電解質シートを挟んで対向するように加熱
ロールラミネーション（加熱ロール温度１２５℃、速度
１ｍ／ｍｉｎ、圧１ｋｇ／ｃｍ）して積層一体化した。
次いで、ロールカッターで長手方向に垂直方向に幅３０
ｍｍで切断して電池要素を作製した。この電池要素は片
側から銅集電体、反対側からアルミ集電体がはみだした
構造であり、これを１２枚正極と正極、負極と負極が対
向するように重ねて片側から銅集電体がはみだし、反対
側からアルミ集電体がはみ出した構成の電池要素集合体
とした。次いで、集電体の端部を重ね、超音波溶接して
束ね、さらに、ニッケルシート（幅１０ｍｍ、長さ５０
ｍｍ、厚さ３０μｍ）を電極端子として端部に超音波溶
接した。Next, the positive and negative electrode sheets were cut to a width of 60 mm, and the active material layer was peeled off at a width of 10 mm on one side in the longitudinal direction of each electrode sheet to form a structure in which the current collector was exposed. . Then, heating roll lamination (heating roll temperature: 125 ° C., speed: 1 m / min, pressure: 1 kg / cm) was performed so that the coated surfaces of the electrode sheets faced each other with the composite gel electrolyte sheet interposed therebetween.
Then, the width 30 in the vertical direction in the longitudinal direction with a roll cutter.
mm to produce a battery element. The battery element has a structure in which a copper current collector protrudes from one side and an aluminum current collector protrudes from the opposite side. The battery element assembly was configured to protrude and the aluminum current collector protruded from the opposite side. Next, the ends of the current collector were overlapped, bundled by ultrasonic welding, and furthermore, a nickel sheet (width 10 mm, length 50
(mm, thickness 30 μm) was used as an electrode terminal and ultrasonically welded to the end.
【００３５】ポリマーシート積層体（ポリイミド（２５
μｍカプトンシート）／ポリエチレン（２０μｍ）／ア
ルミ（２０μｍ、但しアルミが一部ストライプ状に欠損
している）／ポリフェニレンスルフィド（１２μｍ）／
ポリプロピレン（６０μｍ））を７０ｍｍ×８０ｍｍに
切断、７０ｍｍの辺の中央で折り曲げポリプロピレン面
が対向する構造で端部を重ね加熱融着（融着幅２ｍｍ）
して筒状（３５ｍｍ×８０ｍｍ）とした。この筒に先の
電池要素集合体を入れ、電極端子が筒からはみ出る構造
で開口部を加熱融着（融着幅５ｍｍ）して電池を作製し
た。Polymer sheet laminate (polyimide (25
μm Kapton sheet) / Polyethylene (20 μm) / Aluminum (20 μm, but aluminum is partially stripped) / Polyphenylene sulfide (12 μm) /
Polypropylene (60 μm)) is cut into 70 mm x 80 mm, bent at the center of the 70 mm side, and the ends are overlapped with a structure in which the polypropylene surfaces face each other and heated and fused (fused width 2 mm)
To form a cylinder (35 mm x 80 mm). The battery element assembly was placed in this tube, and the opening was heated and fused (fused width: 5 mm) in a structure in which the electrode terminals protruded from the tube to produce a battery.
【００３６】電池を充放電機に接続して、定電流（２５
０ｍＡ）・定電位（４．２Ｖ）充電および定電流（２５
０ｍＡ、カット電圧３Ｖ）放電して充放電させた。初回
放電量は５８０ｍＡｈであり平均電圧３．７Ｖであっ
た。また、充放電を繰り返し１００回サイクル後の放電
量は５４５ｍＡｈであり繰り返し性に優れていることが
わかった。When the battery is connected to a charger / discharger, a constant current (25
0 mA), constant potential (4.2 V) charging and constant current (25
(0 mA, cut voltage 3 V) to discharge and charge. The initial discharge amount was 580 mAh, and the average voltage was 3.7 V. In addition, the discharge amount after 100 cycles of repeated charge / discharge was 545 mAh, indicating that the repetition was excellent.
【００３７】一方、前記の電池要素から集電体を剥離
後、凍結割断して断面を形成し、実施例１と同様にステ
ージ温度を−２０℃に維持しながら電子顕微鏡観察を行
った。電極に接合している界面側に厚さ約８μｍでポリ
マー粒子（平均粒径約２μｍ）が島状に配置した第二の
海島構造領域（島部分の面積比４３％）が形成され、ゲ
ル電解質シート層の内部領域に海構造のイオン伝導性ポ
リマー相、平均粒径５μｍの島構造の電解液からなる第
一の海島構造（海部分の面積比８２％）が厚さ約４５μ
ｍで形成されていることがわかった。このことからゲル
電解質シート積層体全体の断面に対するイオン伝導性ポ
リマー部分の面積比は７２％であることがわかった。On the other hand, after the current collector was peeled off from the above-mentioned battery element, it was frozen and cut to form a cross section, and observed with an electron microscope while maintaining the stage temperature at -20 ° C. as in Example 1. A second sea-island structure region (43% area ratio of island portions) in which polymer particles (average particle size of about 2 μm) are arranged in an island shape at a thickness of about 8 μm on the interface side joined to the electrode is formed, and the gel electrolyte is formed. In the inner region of the sheet layer, a first sea-island structure (area ratio of sea portion: 82%) composed of an ion-conductive polymer phase having a sea structure and an electrolyte having an island structure having an average particle size of 5 μm is about 45 μm thick.
m was formed. From this, it was found that the area ratio of the ion-conductive polymer portion to the entire cross section of the gel electrolyte sheet laminate was 72%.
【００３８】[0038]
【実施例３】実施例１で作製した第一の海島構造のゲル
電解質シートを幅５３ｍｍに切断した後に第二の海島構
造を形成しない以外は実施例２と同様の方法で作製した
電池を充放電機に接続して、定電流（２５０ｍＡ）・定
電位（４．２Ｖ）充電および定電流（２５０ｍＡ、カッ
ト電圧３Ｖ）放電して充放電させた。初回放電量は５７
８ｍＡｈであり平均電圧３．７Ｖであった。また、充放
電を繰り返し１００回サイクル後の放電量は５４３ｍＡ
ｈであり繰り返し性に優れていることがわかった。Example 3 A battery prepared in the same manner as in Example 2 except that the second sea-island structure was not formed after the gel electrolyte sheet having the first sea-island structure prepared in Example 1 was cut to a width of 53 mm. The battery was connected to a discharger and charged and discharged by charging at a constant current (250 mA) / constant potential (4.2 V) and discharging at a constant current (250 mA, cut voltage 3 V). Initial discharge amount is 57
It was 8 mAh and the average voltage was 3.7 V. Further, the discharge amount after 100 cycles of repeated charge / discharge was 543 mA.
h was found to be excellent in repeatability.
【００３９】一方、電池要素から集電体を剥離後、凍結
割断して断面を形成し、実施例１と同様にステージ温度
を−２０℃に維持しながら電子顕微鏡観察を行った。電
極に接合している界面側に厚さ約５μｍでポリマー粒子
（平均粒径約０．８μｍ）が島状に配置した第二の海島
構造領域（島部分の面積比約５０％）が形成され、ゲル
電解質シート層の内部領域に海構造のイオン伝導性ポリ
マー相、平均粒径７μｍの島構造の電解液からなる第一
の海島構造（海部分の面積比約８０％）が厚さ約４０μ
ｍで形成されていることがわかった。On the other hand, after the current collector was peeled off from the battery element, it was frozen and cut to form a cross section, and observed with an electron microscope while maintaining the stage temperature at -20 ° C. as in Example 1. A second sea-island structure region (approximately 50% of the area ratio of the island portion) in which polymer particles (average particle size of approximately 0.8 μm) are arranged in an island shape at a thickness of approximately 5 μm is formed on the interface side bonded to the electrode. A first sea-island structure (about 80% area ratio of sea portion) comprising an ion-conductive polymer phase having a sea structure and an electrolyte having an island structure having an average particle diameter of 7 μm is formed in an inner region of the gel electrolyte sheet layer with a thickness of about 40 μm.
m was formed.
【００４０】[0040]
【発明の効果】本発明の複合構造ゲル電解質シート積層
体は、高いイオン伝導度、機械的強度を有し、電極積層
後の切断加工で短絡を起こさず、これを用いて構成した
電池は電池特性および安全性に優れた性能を提供する。The composite gel electrolyte sheet laminate of the present invention has high ionic conductivity and mechanical strength, does not cause a short circuit in the cutting process after lamination of the electrodes, and the battery constituted by using this is a battery. Offers excellent performance in properties and safety.
【図１】本発明、第一の海島構造のゲル電解質シートの
断面の電子顕微鏡写真。FIG. 1 is an electron micrograph of a cross section of a gel electrolyte sheet having a first sea-island structure according to the present invention.
【図２】本発明、第二の海島構造のゲル電解質シートの
断面の電子顕微鏡写真。FIG. 2 is an electron micrograph of a cross section of a gel electrolyte sheet having a second sea-island structure according to the present invention.
【図３】本発明、第一の海島構造と第二の海島構造のゲ
ル電解質シートの積層体の断面の電子顕微鏡写真。FIG. 3 is an electron micrograph of a cross section of a laminate of a gel electrolyte sheet having a first sea-island structure and a second sea-island structure according to the present invention.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年８月７日（１９９８．８．７）[Submission date] August 7, 1998 (1998.8.7)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図１[Correction target item name] Fig. 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図１】 FIG.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図２[Correction target item name] Figure 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図２】 FIG. 2
【手続補正３】[Procedure amendment 3]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図３[Correction target item name] Figure 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図３】 FIG. 3
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山崎 悟 静岡県富士市鮫島２番地の１ 旭化成工業 株式会社内 Ｆターム(参考） 5H021 AA06 BB12 CC04 CC05 EE10 EE23 HH06 5H024 AA01 AA02 BB00 BB10 CC08 CC19 DD09 EE09 HH11 5H029 AJ02 AJ05 AJ12 AK03 AL07 AM03 AM05 AM06 BJ12 CJ13 DJ04 DJ09 DJ12 EJ12 HJ14 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoru Yamazaki 1 of 2 Samejima, Fuji City, Shizuoka Prefecture Asahi Kasei Kogyo Co., Ltd. F-term (reference) 5H021 AA06 BB12 CC04 CC05 EE10 EE23 HH06 5H024 AA01 AA02 BB00 BB10 CC08 CC19 DD09 EE09 HH11 5H029 AJ02 AJ05 AJ12 AK03 AL07 AM03 AM05 AM06 BJ12 CJ13 DJ04 DJ09 DJ12 EJ12 HJ14
Claims (4)
よび（ＩＩ）の海島構造を有するゲル電解質シートが積
層されていることを特徴とする複合構造ゲル電解質シー
ト積層体。 （Ｉ） 海が電解質を溶解した電解質溶媒からなる電解
液を含浸したポリマー相、および島が該電解液からなる
海島構造。 （ＩＩ）島が電解質を溶解した電解質溶媒からなる電解
液を含浸したポリマー相、および海が該電解液からなる
海島構造。1. A gel electrolyte sheet laminate having a composite structure, wherein gel electrolyte sheets having the following sea-island structure (I) and (II) are laminated in a state of being frozen by liquid nitrogen. (I) A polymer phase in which the sea is impregnated with an electrolyte solution containing an electrolyte solvent in which an electrolyte is dissolved, and a sea-island structure in which islands are made of the electrolyte solution. (II) A polymer phase in which islands are impregnated with an electrolytic solution composed of an electrolyte solvent in which an electrolyte is dissolved, and a sea-island structure in which the sea is composed of the electrolytic solution.
あることを特徴とする請求項１記載の複合構造ゲル電解
質シート積層体。2. The composite gel electrolyte sheet laminate according to claim 1, wherein at least one surface has a structure of (II).
マーであることを特徴とする請求項１または２の複合構
造ゲル電解質シート積層体。3. The composite gel electrolyte sheet laminate according to claim 1, wherein the polymer is a polyvinylidene fluoride-based polymer.
解質シート積層体が電極に接合した電気化学素子。4. An electrochemical device wherein the composite structure gel electrolyte sheet laminate according to claim 1 is joined to an electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10214275A JP2000048639A (en) | 1998-07-29 | 1998-07-29 | Composite structure gel electrolyte sheet laminated body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10214275A JP2000048639A (en) | 1998-07-29 | 1998-07-29 | Composite structure gel electrolyte sheet laminated body |
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|---|---|
| JP2000048639A true JP2000048639A (en) | 2000-02-18 |
Family
ID=16653046
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10214275A Withdrawn JP2000048639A (en) | 1998-07-29 | 1998-07-29 | Composite structure gel electrolyte sheet laminated body |
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| Country | Link |
|---|---|
| JP (1) | JP2000048639A (en) |
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