540175 五、 發明說明 ( 1 ) 技 術 領 域 本 發 明 係 關 於 具 有 高 度 離 子 傳 導性之高 分子電解質凝膠 及其 製 法 〇 背 景 技 術 在使 用 以 有 機 溶 劑 爲 主 體 的 電 解液之鋰 離子二次電池、 電 容 器 冷 凝 器 等 中 爲 防止 液 漏或短路 事故等引起火災 ， 必 須 封 入 電 解 液 ， 或 設 有 可 防止因衝擊 引起事故的堅固 外 殻 故 難 以 輕 量 化 〇 爲 改 進 其 缺 點 亟 需 將 電 解 液 固體化。 固體化策略之一 是 進 行 開 發 局 分 子 電 解 質 凝 膠 。在開發 初期，如特開平 6- 68906或特開平 Ί-‘ 4527 1號公報所揭示ί ，係以高分子彼 此 物 理 性相 互 作 用 所形成 之 凝 膠 (物理凝膠）爲中心加以檢 討 0 然 而 因 物 理 凝 膠 有 熱 可 逆 性，高溫 時凝膠會液化等 等 y 使 耐 熱 性大有 問 題 〇 改 善 此 耐 熱 性 之 方法 5 可 有 效 利用具有 因共有鍵形成三 次 元 構 造 之交 聯 高 分 子 〇 例 如 特 開平1 0-74526和特開平 11 -214038 ， 特願2000- 80138 ί 號' 公報等，= 有許多報告。然 而 此 等 局 分子 電 解 質 凝 膠 在 離 子傳導性和安全性方面仍 然 不 足 〇 即 迄 今 報 告 雖 然 記 載 具 有複數乙 烯基的高分子或 低分 子 j 經 加 熱 以 白 由 基 聚 合成 爲交聯高 分子之凝膠化方 法 ， 但 因 使 用 過 氧 化 物 化合 物 或 偶氮化合 物爲觸媒，在生 成 之 局 分 子 電 解 質 凝 膠 中 不 免 殘 存有未反 應觸媒或觸媒分 解 生 成 物 0 此 等 殘 存 物 在 凝 膠 中 變化，成 爲高分子電解質 凝 膠 的 離 子 傳 導 性 降 低的 原 因 •3 之 -- 〇 540175 五、發明說明（2) 使用偶氮化合物等，會因分解時發生氮氣’故在凝膠中 發生難以脫泡的氣泡，以致離子傳導性降低。另外，離子 流動會偏移，而有過熱之虞。使用過氧化物化合物時，由 於使凝膠化，在自由基聚合之際，有衝擊或摩擦引起*** 之虞，處理時必須小心注意。過氧化物化合物若未反應即 原般殘留凝膠中，在製品使用上亦有安全性的問題。 在同樣利用自由基聚合形成交聯高分子之凝膠化方法中 ，如特願2000-80 1 3 8號公報所載，使用苄基二甲基縮醛 等光引發劑，利用光照射成爲交聯高分子時，不會因分解 而產生氣體或***之危險，因此無前述問題。可是，利用 光照射成爲交聯高分子之凝膠化方法適用於鋰離子二次電 池或電容器等時，由於下述製造步驟的限制，產生不利的 層面。 即，利用加熱成爲交聯高分子之凝膠化方法，可先在組 合的電池注入高分子電解質凝膠之母質溶液，然後凝膠化 。以此方法凝膠化時，高分子電解質凝膠與電極接觸良好 ，界面電阻亦受到抑制。然而，利用光照射的凝膠化方法 ，光無法照射到電池內，注入後無法凝膠化。必須把預先 製成的凝膠與電極貼合，結果，高分子電解質凝膠和電極 間之界面電阻加入，致使離子傳導性下降。 另外，上述凝膠化方法造.成離子傳導性降低，在0°C以 下低溫時更爲明顯，適用此等方法的鋰離子二次電池或電 谷益’在寒冷地區則使用困難。 如上所述，利用加熱進行自由基聚合之凝膠化方法，來 540175 五、 發明說明（3) 白 局 分 子 電解質凝 膠中殘留 解 媒之雜質 5 對離 子傳導性或 安全性有 不良影響 。而利用 光 照射的自 由 基聚 合之凝膠化 方 法 基 於光照射 的限制， 在 電池的界面 電阻 會加大，以 致 離 子 傳 導性降低 。本發明 人 等爲克服 習 知高 分子電解質 凝 膠 之 缺 點，進行 潛心硏究 結 果，發現 以 特定 觸媒令特定 局 分 子 交 聯於材料 ，即可得 缺 點消除之 凝 膠， 而完成本發 明 〇 本 發 明之目的 ，在於提 供 離子傳導 性 較習 知高分子電 解 質 凝 膠 更爲優異 之高分子電解質凝膠 ，及該凝膠之製法。 發 明 槪 述 本 發 明 之第一發 明，係由 — 分子中具 有 二個 以上環氧基 的 筒 分 子 (以下稱含環氧基高分子），以: 支持電] 解質爲觸媒 進 行 xm 壞 氧 環的開環 交聯反應 所 得交聯高 分 子（以下稱環氧 交 聯 高 分 子），以及前述支持電解質和有機溶劑組成之高 分 子 電 解 質凝膠。 第 二 發 明係第一 發明所載 咼 分子電解 質 凝膠 ，其中含環 氧 基 高 分子係一分 子中含有 乙 烯基和環 氧 基之 單體爲必要 成份 聚 合所得，不 含有鋰以 外 之金屬離 子 者。 第 二 發 明係第一 和第二發 明 中任一所 載 之高 分子電解質 凝 膠 其 中支持電 解質係含 L iBF4和/或 ；LiPF6 的離子性化 合 物 〇 第 四 發 明係第一 、第一、 第 三發明中 任 一所 載之高分子 電 解 質 凝 膠，其中 環氧交聯 局 分子佔高 分 子電 解質凝膠之 2- 、20 ； 重: 量％者。 第 五 發 明係第一 /φτ 一 ~弟一' 第 -5 三、第四 發 明中 任一所載之 540175 五、 發明說明 ( 4 ) 局 分 子 電 解 質 凝 膠 之 製 法 ，:/其特 徵 爲 y 含有 機 溶 劑 內 以 含 TOT 氧 基 局 分 子 和 支持 電 解 質爲 必 要 成份 溶 解 而 得 的 溶 液 中 之 該 含 rsa 氧 基 高 分 子 以 支持 電 解 質 爲 觸 媒 進 行 四 氧 的 開 環 交 聯 反 應 形 成 氧 交聯 高 分 子 者 〇 茲 就 本 發 明之高分子電解質凝膠中實施具 ：m 例 詳 述 如下 〇 本 案 所 稱 含 TBS. 氧 基 高 分 子， 必 須 在 — 分 子 中 含有 二 個 以 上 環 氧 基 表 示 其 必 要 條 件爲 該 局 分 子 利用 氧 壞 的 開 rsa 鍵 之 局 分子反 應 可 形成環 氧 交 聯 尚 分 子 只 要 一 分 子 中 有 二 個 以 上 對 於 其 數 量、 結 合位 置 以 及 該 高 分 子 主 鏈 種 類 等 均 Μ j \ \\ 特 別 限 制 〇 而且 不 限 一 種 5 亦 可 爲 含有 二 種 以 上 含 氧 基 筒 分 子 之 混 合物 〇 其 數 平 均分 子 量 亦 Μ j \\\ 特別 限 制 大 槪 在 500 1，000,000 左右 〇 此 等 含 環 氧 基 局 分 子 5 可在不 飽 和 烴 系 聚 合 物 、 或 聚 醚 、 聚 酯 > 聚 胺 、甲 酸 酯 、 乙 烯基 聚 合 物 等 具 有反 m hllx、 性官 能 基 之 局 分 子 引 起 氧 基 而 得。 例 如在 聚 合 物 中 具 有 雙 鍵 的 聚 丁 二 烯 或 聚 異 戊 二 烯 等 ，可 藉 過 乙 酸 對 雙 鍵 反 應 而 導 入 m 氧 基 5 而在 聚 合 物 中 具有 羥 基 的 環 氧 乙 院 或 氧 丙 院 等 5 可在 羥 基 附 加 表 氯 院 ，用 氫 氧 化 鈉 脫 鹽 酸 而 導 入 XES. 氧 基 〇 如 上 所 述 在 現 有 聚 合 物導 入 環 氧 基 之 方 法 以 外 亦 可 採 取利 用 乙 烯 基 聚 合 ， 直 接合成含 環 氧 基 筒 分 子 之 方 法 〇 乙 烯 基 聚 合 是 利 用 各 種 乙 烯基 單 體 爲 共 聚 合成份 藉 其 共 聚 合成 份 的 變 化 > 容 易 對 應所 需 特 性 y 應 用 廣 泛 5 非常 適 用 〇 茲 就 下 述 情 況加 以 說 明。 -6540175 V. Description of the Invention (1) Technical Field The present invention relates to a polymer electrolyte gel having a high ion conductivity and a method for preparing the same. BACKGROUND ART Lithium ion secondary batteries and capacitors that use an electrolyte mainly composed of an organic solvent are condensed. In order to prevent a fire caused by a liquid leakage or a short circuit accident in an appliance, it is necessary to seal the electrolyte, or it is difficult to reduce the weight by providing a sturdy case to prevent accidents due to shock. To improve its shortcomings, the electrolyte must be solidified. One of the solidification strategies is to carry out the development of local molecular electrocoagulation gels. In the early stages of development, as disclosed in Japanese Patent Application Laid-Open No. 6-68906 or Japanese Patent Application Laid-Open No.-4527 1, the review was centered on gels (physical gels) formed by the physical interaction of polymers. 0 However, Physical gels are thermally reversible, gels liquefy at high temperatures, etc. y makes heat resistance problematic. Methods to improve this heat resistance 5 Effective use of crosslinked polymers with a three-dimensional structure formed by common bonds Kaiping 1 0-74526 and JP-A 11-214038, Japanese Patent No. 2000-80138 ′, etc., have many reports. However, these local molecular electrolyte gels are still inadequate in terms of ion conductivity and safety. That is to say, although it has been reported so far, polymers with a plurality of vinyl groups or low molecules j have been heated to polymerize to form crosslinked polymers. Method, but because of the use of peroxide compounds or azo compounds as catalysts, unreacted catalysts or catalyst decomposition products will inevitably remain in the generated local molecular electrolyte gel. 0 These residues change in the gel. It is the cause of the decrease in ion conductivity of polymer electrolyte gels. • 3 of them-〇540175 V. Description of the invention (2) The use of azo compounds, etc., causes nitrogen to occur during decomposition, so it is difficult to defoam in the gel. Bubbles, so that the ion conductivity is reduced. In addition, the ion flow is shifted and there is a risk of overheating. When a peroxide compound is used, it may cause an explosion due to impact or friction during the radical polymerization due to gelation, so care must be taken during handling. If the peroxide compound is left unreacted, it remains as it is in the gel, and there is also a safety problem in the use of the product. In the gelation method for forming a crosslinked polymer by free radical polymerization, as described in Japanese Patent Application No. 2000-80 1 38, a photoinitiator such as benzyl dimethyl acetal is used, and the cross-linking is performed by light irradiation. When linked to polymers, there is no danger of gas or explosion due to decomposition, so there is no such problem. However, when a gelation method that becomes a crosslinked polymer by light irradiation is applied to a lithium ion secondary battery, a capacitor, or the like, it is disadvantageous due to the limitation of the following manufacturing steps. That is, by using the gelation method of heating to become a crosslinked polymer, the mother cell solution of the polymer electrolyte gel can be injected into the combined battery, and then gelled. When gelatinized in this way, the polymer electrolyte gel is in good contact with the electrode, and the interface resistance is also suppressed. However, with the gelation method using light irradiation, light cannot be irradiated into the battery, and it cannot be gelled after injection. The gel prepared in advance must be bonded to the electrode. As a result, the interface resistance between the polymer electrolyte gel and the electrode is added, resulting in a decrease in ion conductivity. In addition, the above-mentioned gelation method results in a decrease in ion conductivity, which is more pronounced at a low temperature of 0 ° C or lower, and a lithium ion secondary battery or a battery that uses these methods is difficult to use in cold regions. As mentioned above, the gelation method of radical polymerization by heating is used to 540175. V. Description of the Invention (3) Residual solvent impurities in the white gel electrolyte gel 5 have an adverse effect on ion conductivity or safety. The gelation method of free radical polymerization using light irradiation is based on the limitation of light irradiation, and the interface resistance at the battery will increase, resulting in a decrease in ion conductivity. In order to overcome the shortcomings of the conventional polymer electrolyte gels, the present inventors conducted diligent research and found that a specific catalyst can be used to crosslink specific local molecules to the material, and a gel with the defects eliminated can be obtained, and the present invention has been completed. An object of the present invention is to provide a polymer electrolyte gel having better ion conductivity than a conventional polymer electrolyte gel, and a method for manufacturing the gel. Description of the invention The first invention of the present invention is based on-tube molecules with more than two epoxy groups in the molecule (hereinafter referred to as epoxy-containing polymers), to: support electricity] decomposition of the catalyst for xm bad oxygen A crosslinked polymer obtained from a ring-opening crosslinking reaction (hereinafter referred to as an epoxy crosslinked polymer), and a polymer electrolyte gel composed of the aforementioned supporting electrolyte and an organic solvent. The second invention is the tritium molecular electrolyte gel contained in the first invention, in which an epoxy-containing polymer is a monomer obtained by polymerizing vinyl and epoxy monomers as essential components, and does not contain metal ions other than lithium . The second invention is the polymer electrolyte gel according to any of the first and second inventions. The supporting electrolyte is an ionic compound containing LiBF4 and / or; LiPF6. The fourth invention is the first, first, and third. The polymer electrolyte gel contained in any one of the inventions, in which the epoxy crosslinked molecules account for 2 to 20 of the polymer electrolyte gel; the weight: the amount%. The fifth invention is the first / φτ a ~ brother one '-5-the third and fourth inventions 540175 contained in any of the fifth and fifth invention description (4) the method of preparing a local molecular electrolyte gel: / its characteristic is y contains The rsa oxygen-containing polymer in a solution obtained by dissolving a TOT-containing oxygen-containing molecule and a supporting electrolyte in an organic solvent as a necessary component is subjected to a ring-opening cross-linking reaction of tetraoxygen with a supporting electrolyte as a catalyst to form a high oxygen crosslinking The molecule holder 〇 implements the polymer electrolyte gel of the present invention: The example is detailed as follows. The TBS. Oxygen-containing polymer referred to in this case must contain two or more epoxy groups in the molecule to indicate its necessary conditions. For the molecule of the molecule, the molecular reaction of opening the rsa bond using oxygen bad can form an epoxy crosslinked molecule as long as there are more than two molecules in a molecule, the number, the binding position, and the type of the polymer main chain are all M j \ \ \ Special Restriction 〇 And not limited to one 5 can also be a mixture containing two or more oxygen-containing cylinder molecules 〇 The number average molecular weight is also M j \\\ Specially limited to about 500 1,000,000 〇 These epoxy-containing bureaus Molecule 5 can be obtained from a local molecule having a reverse m hllx and a sexual functional group such as an unsaturated hydrocarbon polymer, or a polyether, polyester > polyamine, formate, or vinyl polymer. For example, polybutadiene or polyisoprene, which has a double bond in the polymer, can be introduced by the reaction of acetic acid to the double bond to introduce m-oxy group 5 and have ethylene oxide or oxypropylene in the polymer. 5 and so on. The hydroxyl group can be added to the epichlorine compound, and XES can be introduced by dehydrochloric acid with sodium hydroxide. The oxygen group can be directly synthesized by using vinyl polymerization in addition to the method of introducing an epoxy group into the existing polymer as described above. Method for oxygen cylinder molecule. 0 Vinyl polymerization is the use of various vinyl monomers as the copolymerization component and changes in the copolymerization component. It is easy to respond to the required characteristics. It is widely used. 5 It is very applicable. The following will be described. -6
540175 五、發明說明（5) (爲由乙烯基聚合所得之乙烯基聚合物，直接用作含環氧 基高分子，該乙烯基聚合物必須爲含乙烯基和環氧基的單 體之均聚物，或以該單體爲共聚合成份之一的共聚物I) ^含 乙烯基和環氧基的單體，有例如甲基丙烯酸縮水甘油酯、 丙烯酸縮水甘油酯、丙烯酸2-甲基縮水甘油酯、1，2-環氧 基-3-丁烯、異戊二烯氧化物、1，2-環氧基-2-甲基-3-丁烯 、1，2 -環氧-5-己儲、3_乙烯基_7、嗜一環[4·1·0]庚烯、嫌 丙基縮水甘油醚、[(2-丙烯氧基）甲基]環氧乙烷等j 可與含乙烯基和環氧基的單體共聚合之其他單體，只要 是乙烯基單體，即無特別限定。而且不限一種，亦可使用 二種以上的乙烯基單體。此等乙烯基單體有例如丙烯腈、 甲基丙烯腈、丙烯酸酯類、甲基丙烯酸酯類、乙烯醚類等 。此等可共聚合之乙烯基單體，可考慮高分子電解質 膠所用有機溶劑種類或標的高分子電解質凝膠所要求特性 ，適當選擇。 乙細基聚合物中，含乙烯基和環氧基的單體，與其他共 聚性單體之比率，考慮高分子電解質凝膠所要求硬度之其 他特性而決定，惟通常含乙烯基和環氧基的單體/其他共 聚性乙細基卓體之旲耳比’爲5/95〜100/0，而以20/80〜 8 5/15爲佳。該乙烯基聚合物中，含乙烯基和環氧基的單 體比率、在5莫耳％以下時，爲了呈現後續的凝膠化狀態 ，有時難以良好效率進行環氧基彼此的開環交聯反應，以 形成環氧交聯高分子。另外，該比率爲1 〇 〇莫耳％，即單 獨時，可以良好效率進行形成環氧基交聯高分子，但因交540175 V. Description of the invention (5) (It is a vinyl polymer obtained by the polymerization of vinyl. It is used directly as an epoxy-containing polymer. The vinyl polymer must be the same as the monomer containing vinyl and epoxy groups. Polymer, or copolymer containing the monomer as one of the copolymerization components I) ^ vinyl and epoxy-containing monomers, such as glycidyl methacrylate, glycidyl acrylate, 2-methyl acrylate Glycidyl ester, 1,2-epoxy-3-butene, isoprene oxide, 1,2-epoxy-2-methyl-3-butene, 1,2-epoxy-5 -Hexyl, 3-vinyl_7, cyclic [4 · 1 · 0] heptene, propyl glycidyl ether, [(2-propenyloxy) methyl] ethylene oxide, etc. Other monomers in which a vinyl and epoxy-based monomer are copolymerized are not particularly limited as long as they are vinyl monomers. Moreover, it is not limited to one type, and two or more types of vinyl monomers may be used. Such vinyl monomers are, for example, acrylonitrile, methacrylonitrile, acrylates, methacrylates, vinyl ethers, and the like. These copolymerizable vinyl monomers may be appropriately selected in consideration of the type of organic solvent used in the polymer electrolyte gel or the characteristics required of the target polymer electrolyte gel. The ratio of monomers containing vinyl and epoxy groups to other copolymerizable monomers in ethylene-based polymers is determined by considering other characteristics of the hardness required for polymer electrolyte gels, but usually contains vinyl and epoxy The ratio of the monomers of other monomers / other copolymerizable ethylene-based polymers is 5/95 to 100/0, and preferably 20/80 to 8 5/15. In this vinyl polymer, when the ratio of a vinyl group and an epoxy group-containing monomer is 5 mol% or less, it may be difficult to perform ring-opening cross-linking of epoxy groups with good efficiency in order to exhibit a subsequent gelation state. Crosslinking reaction to form an epoxy crosslinked polymer. In addition, the ratio is 100 mol%, that is, the epoxy-based crosslinked polymer can be formed with good efficiency alone.
540175 五、發明說明（6) 聯緊密，可保持的有機溶劑量減少。又，此等乙烯基聚合 物的分子量，由於最後會形成交聯體，故不特別重要，只 要可溶解於有機溶劑/支持電解質系的程度即可，槪略數 平均分子量爲1，〇〇〇〜1，000,000左右。 又，製成此等乙烯基聚合物時，聚合重點爲不使環氧基 反應，且不引入鋰以外的金屬離子。此等聚合方法一般爲 自由基聚合法。離子聚合時，在聚合中環氧基會引起開環 結合反應，所得聚合物在後續步驟中不可能交聯凝膠化， 反之，會在聚合中交聯，而有成爲不溶於有機溶劑的聚合 物之虞。利用自由基聚合合成時，視聚合觸媒的種類，可 能使高分子電解質凝膠降低電化特性，故聚合觸媒的選擇 重要。 例如，在使用亞硫酸鈉和過硫酸鈉的氧化還原聚合中， 聚合物末辆基是由來自聚合觸媒自由基之礦酸納所形成， 結果在聚合物中有大量鈉離子存在。使用鋰離子二次電池 用高分子電解質凝膠時，鋰離子以外的鹼金屬離子或鹼土 類金屬離子等金屬離子雜質，會增加界面阻力，如此可望 極度減少鈉離子等。 無論如何必須採用上述氧化還原聚合時，爲除去高分子 中夾帶的金屬離子雜質，可用強酸性水溶液加以洗淨，惟 在工業生產上難謂有效率的方法。因此，爲使上述聚合物 不含鋰以外的金屬離子，要極力減少聚合觸媒的使用量， 或避免使用爲宜。基於此觀點，合成該乙烯基聚合物時， 工業上推荐以有機過氧化物或偶氮化合物等不產生金屬離 540175 五、發明說明（7 ) 子的聚合觸媒，或以紫外線照射，電子射束照射等手段加 以聚合。 本發明中所謂含環氧基高分子「不含」鋰以外的金屬離 子’並非意味「絕對無」如此雜質金屬離子存在。即。在 後述含環氧基高分子之有用製法，除了本發明推荐的溶液 聚合法所用有機溶劑外，即使爲L.B.級，目前不會絕對無 雜質金屬離子。於此，在本發明最終產物之高分子電解質 凝膠中，來自含環氧基高分子之雜質金屬離子量，只要不 超過共存的支持電解質或有機溶劑由來的雜質金屬離子量 ，即可比照「不含」處理。 本發明推荐之溶液聚合法，係在L.B.級有機溶劑內，將 不產生金屬離子之自由基聚合觸媒，含乙烯基和環氧基之 單體，以及視情況添加的共聚性乙烯基單體，按重量比大 約略爲有機溶劑6，聚合觸媒0.2，單體4的比例溶解， 製成溶液，利用加熱或光照射，而製成溶解含環氧基高分 子之乙烯基聚合物所得高分子溶液。所得高分子溶液原樣 可用作高分子電解質凝膠之母質，可對高分子實施除去雜 質之純化，不再經乾燥•溶解之步驟’可以簡化步驟’對 工業生產有利。 上述含環氧基高分子之乙烯基聚合物’在本發明高分子 電解質凝膠中，該聚合物所含環氧基成爲開環交聯反應之 環氧交聯高分子，使全系呈凝膠狀態’惟以高分子電解質 凝膠全體爲100重量。/。時，相對於如此環氧交聯高分子之 高分子電解質凝膠之比例爲2〜20重量°/°，以2〜10重量540175 V. Description of the invention (6) Closely linked, the amount of organic solvents that can be maintained is reduced. In addition, the molecular weight of these vinyl polymers is not particularly important because they will eventually form crosslinked bodies, as long as they can dissolve in organic solvents / supporting electrolytes, and the approximate molecular weight is 1,000,000. ~ 1,000,000. In the production of these vinyl polymers, the emphasis of polymerization is not to react epoxy groups, and to not introduce metal ions other than lithium. These polymerization methods are generally radical polymerization methods. In ionic polymerization, epoxy groups will cause a ring-opening binding reaction during polymerization. The resulting polymer cannot be cross-linked and gelled in the subsequent steps. On the contrary, it will cross-link during polymerization and become insoluble in organic solvents. Worry of things. When synthesizing by radical polymerization, depending on the type of the polymerization catalyst, the electrochemical properties of the polymer electrolyte gel may be reduced. Therefore, the selection of the polymerization catalyst is important. For example, in redox polymerization using sodium sulfite and sodium persulfate, the polymer terminal group is formed from sodium mineral acid derived from the polymerization catalyst free radicals. As a result, a large amount of sodium ions are present in the polymer. When a polymer electrolyte gel for a lithium ion secondary battery is used, metal ion impurities such as alkali metal ions or alkaline earth metal ions other than lithium ions may increase interfacial resistance, and it is expected that sodium ions and the like may be extremely reduced. In any case, when the above-mentioned redox polymerization is necessary, in order to remove the metal ion impurities entrained in the polymer, it can be washed with a strongly acidic aqueous solution, but it is difficult to say that it is an efficient method in industrial production. Therefore, in order to prevent the polymer from containing metal ions other than lithium, it is best to reduce the amount of polymerization catalyst used or to avoid using it. Based on this viewpoint, when synthesizing the vinyl polymer, it is industrially recommended to use organic peroxides or azo compounds, which do not generate metal ion 540175. V. Polymerization catalyst of the invention (7), or ultraviolet irradiation, electron emission Beam irradiation and other means to polymerize. In the present invention, the term "epoxy-containing polymer" does not contain "metal ions other than lithium" does not mean that "absolutely no" such impurity metal ions are present. which is. In the useful production method of the epoxy group-containing polymer described later, in addition to the organic solvent used in the solution polymerization method recommended by the present invention, even at the L.B. level, there are currently absolutely no impurity metal ions. Here, in the polymer electrolyte gel of the final product of the present invention, as long as the amount of impurity metal ions from the epoxy-containing polymer does not exceed the amount of impurity metal ions derived from the coexisting supporting electrolyte or organic solvent, it can be compared with " Exclude "processing. The solution polymerization method recommended in the present invention is based on a LB-grade organic solvent, a radical polymerization catalyst that does not generate metal ions, a monomer containing a vinyl group and an epoxy group, and a copolymerizable vinyl monomer that is optionally added. According to the weight ratio, it is approximately organic solvent 6, the polymerization catalyst 0.2, and the monomer 4 is dissolved. The solution is prepared and heated or light irradiated to prepare a vinyl polymer containing epoxy polymer. Molecular solution. The obtained polymer solution can be used as the mother material of the polymer electrolyte gel as it is. Purification of impurities can be performed on the polymer, and the step of drying and dissolving is no longer necessary. The process can be simplified, which is beneficial to industrial production. In the polymer electrolyte gel of the present invention, the above-mentioned vinyl polymer containing an epoxy-based polymer becomes an epoxy-crosslinked polymer having a ring-opening cross-linking reaction, so that the whole system is coagulated. The gel state is 100 weight based on the entire polymer electrolyte gel. /. The ratio of the polymer electrolyte gel to the epoxy-crosslinked polymer is 2 to 20 weight ° / °, and the weight is 2 to 10 weight.
540175 五、發明說明（8) %爲佳。比例低於2重量％時，難以形成凝膠，超過20重 量％時，有發生離子傳導性明顯降低的情況。而含有含環 氧基高分子的環氧環在開環交聯反應之際，副產品會脫離 ，且不會附加其他分子，故環氧交聯高分子對高分子電解 質凝膠之比例，與對含環氧基高分子開環交聯反應前的溶 液之比例相等。 其次，本發明所採用之支持電解質，宜使用LiC104、 LiBF4、LiPF6、LiAsF6 等無機化合物，或 LiS03CF3、 LiN(S02CF3)2、LiC(S02CF3)3等含氟之鋰鹽，四乙基四 氟硼酸銨、四乙基六氟磷酸銨、單甲基三乙基四氟硼酸銨 、單甲基三乙基六氟磷酸銨等溶於有機溶劑者，而以 LiBF4、LiPF6，或倂用二者尤佳。 其次，本發明所採用之有機溶劑，指含水量在0.1重量 %以下，得以溶解含環氧基高分子和支持電解質之溶劑， 此等有機溶劑除碳酸伸乙酯（簡稱FC)、碳酸伸丙酯（簡稱 PC)、碳酸伸丁酯（簡稱BC)、碳酸二乙酯（簡稱DEC)、碳 酸二甲酯（簡稱DMC)、碳酸乙甲酯（簡稱EMC)等碳酸酯， 乙二醇、丙二醇、甲基溶纖素、乙基溶纖素等醚化合物外 ，可推荐γ-丁內酯（簡稱GBL)、四氫噻吩-1，1-二氧化物、 二甲亞楓、己二腈、戊二腈、N-甲基四氫吡略酮、三甲基 磷酸酯等單獨或二種以上之混合溶劑。 此等有機溶劑在含環氧基高分子和支持電解質溶解能力 優異情況下，以沸點高者爲佳。沸點90 °C以下的有機溶 劑容易蒸發，且蒸氣壓高，因而產生不便。 -10- 540175 五、發明說明（9) 上述含環氧基高分子經開環交聯反應所得之環氧交聯高 分子、支持電解質和有機溶劑，爲本案所稱之高分子電解 質凝膠的必要成份，亦可添加不形成交聯的高分子化合物 或導電性添加物，作爲其他成份。 此等各成份在高分子電解質凝膠中所佔比例，依標的電 化特性和物性斟酌決定，惟通常如前述所述，環氧交聯高 分子爲2〜2 0重量％、支持電解質爲1〜3〇重量％、其餘爲 有機溶劑和其他成份者爲適當。 本發明高分子電解質凝膠，係由含環氧基高分子和支持 電解質等爲必要成份，溶於有機溶劑所得之溶液，以該支 持電解質爲觸媒，令該含環氧基高分子反應，使環氧基彼 此開環交聯，形成環氧交聯高分子，將該溶液交聯凝膠化 而得。而上述溶液調配之際，亦可添加不形成交聯之高分 子化合物或導電性添加物等爲其他成分。又，此等製造步 驟爲防止吸濕致使含水率增加，其重點爲要在大氣阻絕狀 態，或以露點在-5 (TC以下的乾燥氛圍氣體中進行。 該溶液由溶液態變成凝膠狀態（凝膠化），係按照上述， 由具有含環氧基高分子的環氧基彼此藉開環交聯反應，形 成交聯構造（發生交聯凝膠化）而成。此種交聯凝膠化反應 通常所用之觸媒，可用三級胺、路易氏酸、質子酸等，在 數十°C加熱數小時，而生成凝膠。然而，此時在交聯凝膠 化後，此等觸媒隨時均呈雜質殘留凝膠中，妨礙離子移動 ’而增加界面阻力，造成高分子電解質凝膠的離子傳導性 降低’故不能採用。於此，本發明推荐在此反應中使用支 -11- 540175 五、發明說明（1〇) 持電解質爲觸媒，尤其是LiBF4和LiPF6。使用支持電解 質爲觸媒之本發明，可以交聯凝膠化，且在凝膠中不殘留 雜質，可克服上述問題，故極爲優異。 溶解上述必要成份之溶液的調配方法並無特別限制，惟 因支持電解質亦具有交聯凝膠化觸媒的功能，以最後混合 爲佳。例如在有機溶劑溶有含環氧基高分子的高分子溶液 內，溶解支持電解質之方法，或把預先溶解支持電解質的 有機溶劑，加於高分子溶液之方法等。 於此所用之有機溶劑溶解含環氧基高分子之高分子溶液 ’可爲由預先聚合所得含環氧基高分子溶解於有機溶劑， 或在有機溶劑中由單體反應之溶液聚合法所製成之含環氧 基高分子溶液。在工業上，以後者爲特別値得推荐之方法 ，由於可從聚合系取出高分子加以精製，省略乾燥或溶解 之步驟，故提高生產效率，且易得均質之高分子溶液。可 是，形成含環氧基高分子時採用之觸媒，必須充分注意， 極力不殘留雜質，或不容許鋰離子以外的金屬離子進入。 視情況，對溶液聚合法所得高分子溶液，宜實施觸媒殘餘 物的除去處理。 本發明環氧環開環交聯反應，按前述方法將混合，溶解 之含環氧基高分子、有機溶劑和支持電解質溶液，直接加 熱，可得標的高分子電解質凝膠。大略條件是在50〜70°C 維持0.5〜3小時爲例。所用支持電解質，即觸媒係LiBF4 或LiPF6，其觸媒能力高，反應快。視支持電解質的種類 ，必須在高溫長時間呈現交聯凝膠化，但添加微量LiBF4 -12- 540175 五、發明說明（1〇 或LiPF6，即可促進反應。另外，即使環氧環的反應性高 ，在此開環交聯反應中，含環氧基高分子內存在的環氧環 ，可視爲大槪都參與反應，但因立體性阻礙，可當作有部 份環氧環未交聯。 以上詳述之本發明優良特徵，在於選用含環氧基高分子 爲起始物質，實質上不用觸媒，也可獲得高分子電解質凝 膠。由於無觸媒可以交聯凝膠化，即可不需要迄今廣用作 凝膠化觸媒之偶氮化合物或過氧化物，在生成的凝膠中不 會殘留觸媒分解或未反應觸媒。雖無需要特殊順序，但若 含環氧基高分子本身經精製使用時，亦可得完全無雜質之 凝膠。即，本發明高分子電解質凝膠係減少雜質之凝膠， 因此顯示優異之離子傳導性。 實施例 以下藉代表性實施例和比較例具體說明本發明，惟本發 明不限於此等實施例。以下實施例所載「份」，若無特別 註明，即指重量份，％爲重量％。實施例所得電解質凝膠 ’係製成以下所示電池，就其電池評估電化特性。 電化特性評估用雷池之製作方法 在不銹鋼製品皿底部，放置厚0.2mm的平板狀鋰箔（電 極）。上面定置厚0.2mm的鐵氟隆製角型隔體，在其中適 量塡入以下實施例和比較例製成的含環氧基高分子溶液’ 與支持電解質溶液預先混合製成之溶液，上面放置厚 0.2 mm的鋰箔（電極）作爲覆蓋，使隔體和鋰箔間不留間隙 後，在6(TC加熱1小時，使環氧基彼此進行開環交聯反 -13 - 540175 五、發明說明（12) 應，加以交聯凝膠化，製成厚度200μηι的高分子電解質 凝膠之凝膠膜。此鋰箔夾持之凝膠膜，用附設引線的 0.3mm厚鎳板夾持，***二玻璃板間，用夾具固定，製成 電化特性評估用之電池。 電化特性的評估 上述電化特性評估用電池，連接至交流阻抗測量裝置（ 索拉同公司製（音譯）1 286+ 1 25 0)，在25 t測量100仟赫至 1赫的交流阻抗，以在測量頻率1 00仟赫和1 00赫的阻抗 ，分別爲容體電阻値和界面電阻値。由此容體電阻値，以 及電池厚度和面積，可算出離子傳導率。 上述交流阻抗測定在25 °C繼續測量24小時後，把該評 估用電池連接到電化測量裝置（索拉同公司製品S 1 - 1 280 B) ，在25°C以反相電壓±0.5V，電位掃拂速度l〇mV/s的循 環重量計進行分極電解，測量第三次+0.5V的分極電流値 ，是成爲對鋰負極C V分極電流値。此成對鋰負極c V分 極電流値，以下簡稱分極電流。 再者，於此分極電流測量後，再進行測量交流阻抗，電 池製成24小時後，求得界面電阻値。由此測量結果，求 出剛測量開始後的界面電阻値與24小時後的界面電阻値 之比率，是爲界面電阻値增加率。又，凝膠膜之製作，電 池之製成，特性之評估，均使用露點-5 0°C的氬氣氛圍手 套箱實施。 比較例1 於水20克中溶解氫氧化鈉0.22克的水溶液，添加聚乙 -14- 540175 五、發明說明（13) 二醇單甲醚（數平均分子量2000)10克。在45 °C加熱，於 激烈攪拌中快速添加0.46克表氯烷，加溫至95 °C，繼續 攪混8 0分鐘。所得溶液以甲苯萃取，利用冷凍乾燥法， 由萃取液獲得一分子中具有一個環氧基的含單環氧基高分 子，在縮水甘油基經聚乙二醇單甲醚末端之羥基部份取代 修飾。 於碳酸伸乙酯（簡稱EC)和碳酸伸丙酯（簡稱PC)按容量 比2/1混合所得混合溶劑6克，溶解上述高分子4克，成 爲含單環氧基高分子溶液。另此上述混合溶劑9.22克溶 解LiBF4 0.78克，製成支持電解質溶液。使用該含單環氧 基高分子溶液2.0克和該支持電解質溶液8.0克，按上述 方法製成凝膠膜，但無法凝膠化。 實施例1 於水2 0克溶解氫氧化鈉0 · 9克的水溶液，添加聚乙二 醇（數平均分子量1〇〇〇)1〇克，加熱至45 °C，激烈攪拌中 快速添加1.85克表氯烷，加溫至95°C，繼續攪混80分鐘 。所得溶液用本卒取，利用冷凍乾燥法’從萃取液得一分 子中具有二個環氧基之含環氧基高分子，在縮水甘油基有 聚乙二醇兩末端的羥基部份取代修飾。使用以此高分子比 較例1同樣方法製成之含環氧基高分子溶液2.0克，和比 較例1同樣的支持電解質溶液8.0克，按上述方法製成電 池，進行測量。 實施例2 於比較例1之混合溶劑6.0克，溶解兩端爲縮水甘油基 -15- 540175 五、發明說明（Μ) 的雙酣 A -表氯院共聚物（p〇iy(Bisphenol A-co-epichlorohgdrin) ，gly-cidyl end-capped，數平均分子量 1 075)4.0 克，形成 含乙氧基高分子溶液。使用此溶液2.0和比較例1同樣的 支持電解質溶液8.0克，按上述方法製成電池，進行測量。 實施例3 在比較例1相同的混合溶劑6克，添加丙烯腈（以下簡 稱ΑΝ)2·0克，乙酸乙烯酯（以下簡稱VAc)〇.4克，甲基丙 烯酸縮水甘油酯（以下簡稱GMA) 1.6克，聚合觸媒苄基二 甲基縮醛（以下簡稱BDK)0.2克，加以溶解。其在3 60nm 具有高峰波長，在此波長的光度爲l〇mW/cm2的紫外線， 對此照射10分鐘，聚合後，在50°C塡入錶壓〇.〇9MPa的 減壓容器內，除去未反應單體，製成含環氧基高分子的高 分子溶液。使用該含環氧基高分子溶液2.0克和比較例1 之支持電解質溶液8.0克，按上述方法製成電池，進行測 量。 實施例4 除GMA改用烯丙基縮水甘油醚外，以實施例3同樣方 法製成電池，進行測量。 實施例5 在2公升燒瓶內裝水800毫升，於此分別經2小時連續 供應AN50克、VAclO克、GMA40克的混合溶液，聚合 觸媒焦亞硫酸鈉0.6克和過硫酸銨〇.2克分別溶解於水 120毫升之溶液。供應結束後，再於65 °C繼續聚合2小時 。聚合結果，把燒瓶水冷至常溫後，重複三次內容物之過 -16- 540175 五、發明說明（15) 濾、水洗、除去未反應單體和聚合觸媒殘渣，所得含環氧 基高分子在7 0 °C減壓乾燥器乾燥一夜，除去水份。在此 高分子中導入來自聚合觸媒之磺基，由於不進行離子交換 ，磺基不與鈉形成鹽。 使用所得含環氧基高分子，以比較例1同樣方法，製成 含環氧基高分子溶液，使用此溶液和比較例1同樣支持電 解質溶液8.0克，按上述方法製成電池，進行測量。 實施例6 於EC和碳酸二乙酯（DEC)按容量比1/3混合所得混合 溶劑6克，添加AN 1.0克、甲基丙烯酸酯（以下簡稱SMA) 0.8克、GMA 2.2克、聚合觸媒BDK 0.2克，加以溶解後 ，以實施例3同樣方法進行紫外線聚合，除去未反應單體 ，製成含環氧基高分子之高分子溶液。另外於上述混合溶 劑8.6克中溶解LiPF61.4克，製成支持電解質溶液。使用 該含環氧基高分子溶液2.0克和該支持電解質溶液8.0克 ，在上述方法中加熱條件改爲在70°C 1 8小時，製成電池 ，進行測量。 實施例7 取實施例3含環氧基高分子溶液2.〇克，和在比較例1 的混合溶劑8.75克溶解Li S03CF3 1.25克而成的支持電解 質溶液8.0克，混合而成之溶液，溶解LiBF4 0.02克作爲 交聯凝膠化促進目的之支持電解質。使用此溶液，按照上 述方法，製成電池，進行測量。 -17- 540175 五、發明說明（16) 比較例2 取實施例3含環氧基高分子溶液2.0克，和在比較例1 的混合溶劑8.75克中溶解LiS03CF3 1.25克而成的支持電 解質8 · 0克，混合而成之溶液，溶解比交聯凝膠化觸媒的 電解質Li S03CF3更壓倒性強力的開環觸媒一種路易氏酸 之四氯化錫〇 . 〇 2克，使用此溶液按照上述方法製成電池 ，進行測量。 比較例3 於比較例1同樣的混合溶劑6克，添加AN 2.84克， VAc 1.16克，聚合溶劑BDK 0.2克，溶解後，以實施例 3同樣方法進行紫外線聚合，除去未反應單體，製成AN/ V Ac共聚物溶液。另於上述混合溶劑6.0克，溶解聚合度 1 4的交聯性單體聚氧伸乙基二甲基丙烯酸酯4.0克，製成 交聯性單體溶液。使用該AN/V Ac共聚物溶液κο克、該 交聯性單體溶液1 · 〇克、比較例1之支持電解質溶液8.0 克、和偶氮雙異丁腈〇 · 04克混合溶解所得溶液，在上述 方法中，加熱條件改爲70°C、5小時，製成電池，進行測 量。此法製成的凝膠膜含有多數氣泡。 表1列出實施例1〜7和比較例1〜3的離子傳導率、界 面電阻增加率、分極電流之測量結果。由表1顯示本發明 高分子電解質凝膠的實施例1〜7均具有優異電化特性。 含環氧基高分子，在一分子中具有環氧基2個以上時，不 但實施例3或4之代表性乙烯基聚合物，連實施例1之聚 醚或實施例2的聚合物等均可使用’可以選用有機溶劑的 -18- 540175540175 V. Invention description (8)% is better. When the proportion is less than 2% by weight, it is difficult to form a gel, and when it exceeds 20% by weight, the ion conductivity may be significantly reduced. When the epoxy ring containing epoxy-containing polymer is undergoing a ring-opening cross-linking reaction, the by-products will be detached without adding other molecules. Therefore, the ratio of the epoxy cross-linked polymer to the polymer electrolyte gel is The proportion of the solution before the epoxy-containing polymer ring-opening crosslinking reaction is equal. Secondly, the supporting electrolyte used in the present invention is preferably an inorganic compound such as LiC104, LiBF4, LiPF6, LiAsF6, or a fluorine-containing lithium salt such as LiS03CF3, LiN (S02CF3) 2, LiC (S02CF3) 3, or tetraethyltetrafluoroborate. Those who dissolve in organic solvents such as ammonium, tetraethylammonium hexafluorophosphate, monomethyltriethylammonium tetrafluoroborate, monomethyltriethylammonium fluorofluorophosphate, etc., and LiBF4, LiPF6, or a combination of both good. Secondly, the organic solvent used in the present invention refers to a solvent having a water content of less than 0.1% by weight, which can dissolve epoxy-containing polymers and supporting electrolytes. These organic solvents except ethylene carbonate (FC) and propylene carbonate Esters (abbreviated as PC), butylene carbonate (abbreviated as BC), diethyl carbonate (abbreviated as DEC), dimethyl carbonate (abbreviated as DMC), ethyl methyl carbonate (abbreviated as EMC), etc., ethylene glycol, propylene glycol In addition to ether compounds such as methyl lysinolysin and ethyl lysinolysin, γ-butyrolactone (GBL for short), tetrahydrothiophene-1,1-dioxide, dimethylamorphine, adiponitrile, Glutaronitrile, N-methyltetrahydropyrrolidone, trimethyl phosphate, etc. alone or in a mixture of two or more solvents. In the case where these organic solvents are excellent in the ability to dissolve epoxy-containing polymers and supporting electrolytes, those having a high boiling point are preferred. Organic solvents with a boiling point below 90 ° C are easy to evaporate and have high vapor pressure, which causes inconvenience. -10- 540175 V. Description of the invention (9) The epoxy cross-linked polymer, supporting electrolyte and organic solvent obtained through the ring-opening cross-linking reaction of the above epoxy-containing polymer are the polymer electrolyte gels referred to in this case. As an essential component, a high-molecular compound or a conductive additive that does not form a cross-link may be added as other components. The proportion of these components in the polymer electrolyte gel is determined according to the standard electrochemical characteristics and physical properties, but generally, as mentioned above, the epoxy crosslinked polymer is 2 to 20% by weight and the supporting electrolyte is 1 to 30% by weight and the balance of organic solvents and other components are suitable. The polymer electrolyte gel of the present invention is a solution obtained by dissolving an epoxy-containing polymer and a supporting electrolyte in an organic solvent, and using the supporting electrolyte as a catalyst to react the epoxy-containing polymer. The epoxy groups are ring-opened and cross-linked to form an epoxy cross-linked polymer, which is obtained by cross-linking and gelling the solution. When the solution is prepared, a polymer compound or a conductive additive which does not form a cross-linking may be added as another component. In addition, in order to prevent moisture absorption from increasing moisture content in these manufacturing steps, the focus is to be carried out in an air-blocked state or in a dry atmosphere with a dew point of -5 (TC or lower). Gelation) is formed by the above-mentioned epoxy groups having an epoxy group-containing polymer through a ring-opening cross-linking reaction to form a cross-linked structure (cross-linked gelation). This cross-linked gel The catalyst usually used in the chemical reaction can be tertiary amine, Lewis acid, protonic acid, etc., and heated at tens of ° C for several hours to form a gel. However, after crosslinking gelation at this time, these catalysts The medium is present in the residual gel of impurities at any time, which hinders the movement of ions and increases the interface resistance, which reduces the ionic conductivity of the polymer electrolyte gel. Therefore, it cannot be used. Here, the present invention recommends the use of branch-11- 540175 V. Description of the invention (1) Support electrolytes as catalysts, especially LiBF4 and LiPF6. The present invention using supporting electrolytes as catalysts can be crosslinked and gelled, and no impurities remain in the gel, which can overcome the above. Problem, so extreme Excellent. There is no particular limitation on the method for preparing the solution in which the above-mentioned essential ingredients are dissolved, but the supporting electrolyte also has the function of cross-linking the gelation catalyst, and it is better to mix it finally. For example, an epoxy-containing polymer is dissolved in an organic solvent The method of dissolving the supporting electrolyte in the polymer solution, or the method of adding an organic solvent in which the supporting electrolyte is dissolved in advance to the polymer solution, etc. The organic solvent used here dissolves the polymer solution containing an epoxy-based polymer. It is an epoxy group-containing polymer solution prepared by a solution polymerization method in which an epoxy group-containing polymer obtained by prior polymerization is dissolved in an organic solvent, or a monomer is reacted in an organic solvent. In the industry, the latter is particularly important. The recommended method is to take out the polymer from the polymerization system and refine it, omitting the steps of drying or dissolving, so the production efficiency is improved, and a homogeneous polymer solution is easily obtained. However, the contact used when forming an epoxy-containing polymer is Care must be taken to ensure that impurities do not remain or metal ions other than lithium ions are not allowed to enter. In order to obtain a polymer solution, it is suitable to perform a catalyst residue removal treatment. In the epoxy ring ring-opening cross-linking reaction of the present invention, the epoxy group-containing polymer, the organic solvent and the supporting electrolyte solution which are mixed and dissolved according to the aforementioned method are directly heated The standard polymer electrolyte gel can be obtained. The approximate condition is to maintain it at 50 ~ 70 ° C for 0.5 ~ 3 hours as an example. The supporting electrolyte used is the catalyst system LiBF4 or LiPF6, which has high catalyst capacity and fast response. Depending on the support The type of electrolyte must be cross-linked and gelled at high temperature for a long time, but a small amount of LiBF4 -12-540175 is added. 5. Description of the invention (10 or LiPF6 can promote the reaction. In addition, even if the epoxy ring is highly reactive, In this ring-opening cross-linking reaction, the epoxy ring existing in the epoxy-containing polymer can be regarded as all of the osmiums participating in the reaction, but due to steric hindrance, it can be regarded as a part of the epoxy ring not cross-linked. The excellent feature of the present invention detailed above is that an epoxy-containing polymer is selected as a starting material, and a polymer electrolyte gel can be obtained without substantially using a catalyst. Since the catalyst can be cross-linked and gelled, azo compounds or peroxides which have hitherto been widely used as gelation catalysts are not required, and no catalyst decomposition or unreacted catalyst remains in the resulting gel. Although no special order is required, if the epoxy-containing polymer itself is purified and used, a gel completely free of impurities can also be obtained. That is, the polymer electrolyte gel of the present invention is a gel that reduces impurities, and therefore exhibits excellent ion conductivity. Examples The present invention will be specifically described below with reference to representative examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, the "parts" in the following examples means parts by weight, and% is% by weight. The electrolyte gels obtained in the examples were prepared as batteries shown below, and the electrochemical characteristics of the batteries were evaluated. How to make a thunder cell for evaluating the electrochemical characteristics A 0.2 mm thick flat lithium foil (electrode) is placed on the bottom of a stainless steel product dish. An angle type spacer made of Teflon with a thickness of 0.2 mm was set thereon, and an appropriate amount of the epoxy group-containing polymer solution prepared in the following Examples and Comparative Examples was mixed with a solution prepared in advance by mixing with a supporting electrolyte solution, and placed on top. 0.2 mm thick lithium foil (electrode) as a cover, so that there is no gap between the separator and the lithium foil, and then heated at 6 (TC for 1 hour to make the epoxy groups ring-open and cross-link each other-13-540175) V. Invention Explanation (12) Should be cross-linked and gelated to make a gel film of polymer electrolyte gel with a thickness of 200 μm. The gel film held by the lithium foil was held by a 0.3 mm thick nickel plate with leads. It was inserted between two glass plates and fixed with a jig to make a battery for evaluating the electrochemical characteristics. The evaluation of the electrochemical characteristics was connected to an AC impedance measuring device (solatong company (transliteration) 1 286+ 1 25 0). Measure the AC impedance from 100 Hz to 1 Hz at 25 t. The impedances at the frequencies of 100 Hz and 100 Hz are the volume resistance 値 and the interface resistance 分别. From this, the volume resistance 値, And the thickness and area of the battery. Conductivity: After the above-mentioned AC impedance measurement was continued at 25 ° C for 24 hours, the evaluation battery was connected to an electrochemical measurement device (Solatong Company Product S 1-1 280 B) and the reverse voltage was applied at 25 ° C ± Cyclic weight meter with 0.5V and potential sweep speed of 10mV / s performs polarized electrolysis, and the third polarized current 値 of + 0.5V is measured, which becomes the polarized current of lithium negative CV 値. This paired lithium negative electrode cV polarized The current 値 is hereinafter referred to as the polarized current. Furthermore, after this polarized current measurement, the AC impedance is measured. After the battery is made for 24 hours, the interface resistance 値 is obtained. From the measurement results, the interface immediately after the measurement is started is obtained. The ratio of the resistance 値 to the interface resistance 24 after 24 hours is the increase rate of the interface resistance 又. In addition, the production of gel films, the production of batteries, and the evaluation of characteristics all use an argon atmosphere with a dew point of 50 ° C. The glove box is implemented. Comparative Example 1 In 20 g of water, 0.22 g of an aqueous solution of sodium hydroxide was added, and polyethylene-14-540175 was added. V. Description of the invention (13) 10 g of glycol monomethyl ether (number average molecular weight 2000). Heat at 45 ° C, quickly under vigorous stirring Add 0.46 g of epichlorohydrin, heat to 95 ° C, and continue mixing for 80 minutes. The resulting solution was extracted with toluene and the freeze-drying method was used to obtain a monoepoxy group-containing monoepoxy group with one epoxy group in one molecule from the extract. Molecule, the glycidyl group is modified by the substitution of the hydroxyl group at the end of the polyethylene glycol monomethyl ether. The mixed solvent is obtained by mixing the ethyl carbonate (EC) and the propyl carbonate (PC) at a volume ratio of 2/1. 6 g, dissolve 4 g of the above polymer to become a monoepoxide-containing polymer solution. In addition, 9.22 g of the above mixed solvent dissolve 0.78 g of LiBF4 to prepare a supporting electrolyte solution. A gel film was produced in the above-mentioned manner using 2.0 g of the monoepoxide-containing polymer solution and 8.0 g of the supporting electrolyte solution, but gelation was not possible. Example 1 An aqueous solution of 0.9 g of sodium hydroxide dissolved in 20 g of water was added, 10 g of polyethylene glycol (number average molecular weight 1000) was added, and heated to 45 ° C, and 1.85 g was quickly added during vigorous stirring. Epichlorohydrin, warm to 95 ° C and continue mixing for 80 minutes. The obtained solution was taken by this method, and an epoxy-containing polymer having two epoxy groups in one molecule was obtained from the extract by freeze-drying method, and the glycidyl group was substituted with hydroxyl groups at both ends of polyethylene glycol. . Using 2.0 g of an epoxy-group-containing polymer solution prepared in the same manner as in Comparative Example 1 and 8.0 g of a supporting electrolyte solution as in Comparative Example 1, a battery was prepared in the same manner as described above and measured. Example 2 6.0 g of a mixed solvent in Comparative Example 1 with glycidyl-15-540175 at both ends of dissolution 5. Bis (A) -epichlorin copolymer (p0iy (Bisphenol A-co) -epichlorohgdrin), gly-cidyl end-capped, number average molecular weight 1 075) 4.0 g, to form an ethoxy-containing polymer solution. Using this solution 2.0 and 8.0 g of the same supporting electrolyte solution as in Comparative Example 1, a battery was fabricated as described above and measured. Example 3 6 g of the same mixed solvent of Comparative Example 1 was added with 2.0 g of acrylonitrile (hereinafter referred to as AN), 0.4 g of vinyl acetate (hereinafter referred to as Vac), and glycidyl methacrylate (hereinafter referred to as GMA ) 1.6 grams, 0.2 grams of polymerization catalyst benzyldimethylacetal (hereinafter referred to as BDK), and dissolved. It has a peak wavelength at 3 to 60 nm, and the ultraviolet light at this wavelength is 10 mW / cm2. This is irradiated for 10 minutes. After polymerization, it is poured into a decompression container with a gauge pressure of 0.9 MPa at 50 ° C and removed. Unreacted monomers are made into polymer solutions containing epoxy-based polymers. Using 2.0 g of the epoxy-group-containing polymer solution and 8.0 g of the supporting electrolyte solution of Comparative Example 1, a battery was fabricated according to the method described above and measured. Example 4 A battery was produced in the same manner as in Example 3 except that GMA was changed to allyl glycidyl ether and measured. Example 5 In a 2 liter flask, 800 ml of water was charged, and a mixed solution of AN50 g, VAclO, and GMA 40 g was continuously supplied over 2 hours, respectively. Polymerization catalyst 0.6 g of sodium metabisulfite and 0.2 g of ammonium persulfate were dissolved separately. A solution in 120 ml of water. After the supply was completed, the polymerization was continued for another 2 hours at 65 ° C. After polymerization, the flask was cooled to room temperature, and the contents were repeated three times. -16- 540175 V. Description of the invention (15) Filtration, washing, removal of unreacted monomers and polymerization catalyst residues, the obtained epoxy-containing polymer was Dry overnight at 70 ° C under reduced pressure to remove water. A sulfo group derived from a polymerization catalyst is introduced into this polymer, and since ion exchange is not performed, the sulfo group does not form a salt with sodium. Using the obtained epoxy group-containing polymer, an epoxy group-containing polymer solution was prepared in the same manner as in Comparative Example 1. Using this solution, 8.0 g of an electrolytic solution was supported in the same manner as in Comparative Example 1. A battery was prepared according to the above method and measured. Example 6 6 g of a mixed solvent obtained by mixing EC and diethyl carbonate (DEC) in a volume ratio of 1/3, adding 1.0 g of AN, 0.8 g of methacrylate (hereinafter referred to as SMA), 2.2 g of GMA, and a polymerization catalyst After 0.2 g of BDK was dissolved, ultraviolet polymerization was performed in the same manner as in Example 3 to remove unreacted monomers, thereby preparing a polymer solution containing an epoxy-based polymer. In addition, 61.4 g of LiPF was dissolved in 8.6 g of the above mixed solvent to prepare a supporting electrolyte solution. Using 2.0 g of the epoxy-containing polymer solution and 8.0 g of the supporting electrolyte solution, the heating conditions were changed to 70 ° C. for 18 hours in the above method to make a battery for measurement. Example 7 Take 2.0 g of the epoxy group-containing polymer solution of Example 3 and 8.75 g of Li S03CF3 dissolved in 1.25 g of the mixed solvent of Comparative Example 1 and 8.0 g of a supporting electrolyte solution, and mix the solution to dissolve LiBF4 0.02 g is used as a supporting electrolyte for the purpose of crosslinking gelation. Using this solution, a battery was made according to the method described above and measured. -17- 540175 V. Description of the invention (16) Comparative Example 2 Supporting electrolyte obtained by dissolving 1.25 g of LiS03CF3 in 8.75 g of the mixed solvent of Comparative Example 1 in Example 3 and 2.0 g of the epoxy group-containing polymer solution 8 · 0g, a mixed solution that dissolves a more overwhelmingly stronger ring-opening catalyst than the cross-linked gelled catalyst electrolyte Li S03CF3, a tin acid of tin tetrachloride of 0.20 g, using this solution according to A battery was made by the above method and measured. Comparative Example 3 6 g of the same mixed solvent as Comparative Example 1 was added with AN 2.84 g, VAc 1.16 g, and polymerization solvent BDK 0.2 g. After dissolving, UV polymerization was performed in the same manner as in Example 3 to remove unreacted monomers. AN / V Ac copolymer solution. In addition, 4.0 g of the cross-linkable monomer polyoxyethylene dimethacrylate having a polymerization degree of 14 was dissolved in 6.0 g of the above mixed solvent to prepare a cross-linkable monomer solution. Using the AN / V Ac copolymer solution κοg, the crosslinkable monomer solution 1.0 g, the supporting electrolyte solution of Comparative Example 1 8.0 g, and azobisisobutyronitrile 0.04 g, the resulting solution was mixed and dissolved, In the above method, the heating conditions were changed to 70 ° C for 5 hours, and a battery was made and measured. The gel film produced by this method contains many air bubbles. Table 1 shows the measurement results of ion conductivity, interface resistance increase rate, and polarization current of Examples 1 to 7 and Comparative Examples 1 to 3. Table 1 shows that Examples 1 to 7 of the polymer electrolyte gel of the present invention have excellent electrochemical properties. When the epoxy-containing polymer has two or more epoxy groups in one molecule, not only the representative vinyl polymer of Example 3 or 4, but also the polyether of Example 1 or the polymer of Example 2 Can be used '-18-540175 with optional organic solvents
五、發明說明（17) 種類（實施例3和6)或支持電解質的種類（實施例3 ’ 6和 7)。然而，如實施例5在含環氧基高分子中含有鋰以外的 金屬離子時，雖特性比習知爲優’但較其他實施例稍遜° /相對於本發明高分子電解質凝膠，在比較例1使用含單 環氧基高分子，一分子中只有一個環氧基，即使環氧環發 生開環反應，因只生成直鏈狀高分子，故不會凝膠化>。另 外，比較例2有對LiS03CF3優先作用來自四氯化錫之大 量金屬離子存在，比較例3環氧環不藉以支持電解質爲觸 媒的開環交聯反應形成交聯凝膠，但由於偶氮雙異丁腈的 分解氣體，而在凝膠中發生無法除去的氣泡，以致電化特 性降低。） 表1 離子傳導率 (m S/cm) 界面電阻增加率 (倍） 分極電流 (m A / c m) _實施例1 4.1 1.2 7.8 __實施例2 3.9 1.4 7.5 實施例3 4.3 1.1 9.0 實施例4 4.0 1.1 8.8 實施例5 2.9 1.9 5.9 實施例6 5.2 1.0 10.6 實施例7 4.2 1.2 8.9 比較例1 _製成凝膠膜 比較例2 1.1 3.1 _比較例3 1.2 —.— 2.2 -19- 540175 五、發明說明（18 ) 實施例8 使用實施例3的含環氧基高分子溶液0.5克，和比較例 1在混合溶劑9.3克溶解LiBF4 0.7克的支持電解質溶液 9.5克，按上述方法製成電池，進行測量。 實施例9 使用實施例3的含環氧基高分子溶液3.5克，和比較例 1在混合溶劑9.1克溶解LiBF4 0.9克的支持電解質溶液 6.5克，按上述方法製成電池，進行測量。 實施例1 0 使用實施例3的含環氧基高分子溶液0.5克及比較例1 在混合溶劑8.91克溶解1.09克LiBF4的支持電解質溶液 5 . 〇克，按上述方法製成電池，進行測量。 表2列有實施例3和實施例8〜1 0凝膠或環氧交聯高分 子濃度、離子傳導率、界面電阻增加率、分極電流之測量 結果。本發明高分子電解質凝膠之環氧交聯高分子濃度爲 2 · 0〜2 0 · 〇重量％，證實均顯示優異特性。再詳究之下，環 氧父聯高分子濃度愈低，顯示特性愈佳，但環氧交聯高分 子少日寸’要顧及離子容易移動。然而，環氧交聯高分子濃 度太低時，有時不會形成凝膠。 -20- 540175 五、發明說明（19) 表2 環氧交聯高分子濃度 (重量％) 離子傳導率 (mS//cm) 界面電阻增 加率 (倍） 分極電流 (mA/cm2) 實施例8 2.0 5.0 1.1 10.2 實施例3 8.0 4.3 1.1 9.0 實施例9 14.0 4.1 1.2 8.8 實施例10 20.0 3.9 1.3 8.2 發明效果 本發明高分子電解質凝膠，不但常溫，即使低溫，亦顯 示優良離子傳導性，對鋰聚合物二次電池或雙層電容器等 電化元件，非常有用，可期待優異的電化特性。 -21 -5. Description of the invention (17) Kind (Examples 3 and 6) or Kind of supporting electrolyte (Examples 3 '6 and 7). However, when Example 5 contains metal ions other than lithium in the epoxy-containing polymer, although the characteristics are better than conventional ones, it is slightly inferior to other examples. / Compared to the polymer electrolyte gel of the present invention, Comparative Example 1 uses a single-epoxy-containing polymer, and there is only one epoxy group in one molecule. Even if the epoxy ring undergoes a ring-opening reaction, only a linear polymer is generated, so it does not gel>. In addition, Comparative Example 2 has a large amount of metal ions that preferentially act on LiS03CF3 from tin tetrachloride. In Comparative Example 3, the epoxy ring does not form a crosslinked gel by the ring-opening crosslinking reaction using the supporting electrolyte as a catalyst, but due to the azo Decomposition gas of bisisobutyronitrile causes irremovable air bubbles in the gel, which reduces the electrochemical characteristics. ) Table 1 Ionic conductivity (m S / cm) Interface resistance increase rate (times) Dipole current (m A / cm) _ Example 1 4.1 1.2 7.8 __ Example 2 3.9 1.4 7.5 Example 3 4.3 1.1 9.0 Example 4 4.0 1.1 8.8 Example 5 2.9 1.9 5.9 Example 6 5.2 1.0 10.6 Example 7 4.2 1.2 8.9 Comparative Example 1 _ Preparation of a gel film Comparative Example 2 1.1 3.1 _ Comparative Example 3 1.2 —. — 2.2 -19- 540175 5 Explanation of the invention (18) Example 8 Using 0.5 g of the epoxy group-containing polymer solution of Example 3 and Comparative Example 1 dissolving 0.7 g of LiBF4 in a mixed solvent of 9.3 g and a supporting electrolyte solution of 9.5 g of LiBF4, a battery was prepared according to the method described above. To make a measurement. Example 9 Using 3.5 g of the epoxy-group-containing polymer solution of Example 3 and Comparative Example 1 with 6.5 g of a supporting electrolyte solution of 0.9 g of LiBF4 dissolved in 9.1 g of a mixed solvent, a battery was prepared according to the method described above and measured. Example 10 Using 0.5 g of the epoxy-group-containing polymer solution of Example 3 and Comparative Example 1 dissolving 1.09 g of LiBF4 supporting electrolyte solution 5.0 g in a mixed solvent of 8.91 g, a battery was prepared according to the above method, and measurement was performed. Table 2 shows the measurement results of the gel or epoxy crosslinked polymer concentration, ion conductivity, interface resistance increase rate, and polarizing current of Examples 3 and 8-10. The concentration of the epoxy-crosslinked polymer of the polymer electrolyte gel of the present invention is 2.0 to 20% by weight, and it is confirmed that all of them exhibit excellent characteristics. After further investigation, the lower the concentration of the epoxy parent polymer, the better the display characteristics. However, the epoxy crosslinked polymer has fewer molecules. It must take into account that the ions are easy to move. However, when the concentration of the epoxy crosslinked polymer is too low, a gel may not be formed. -20- 540175 V. Description of the invention (19) Table 2 Concentration of epoxy crosslinked polymer (% by weight) Ionic conductivity (mS // cm) Increase rate of interface resistance (times) Dipole current (mA / cm2) Example 8 2.0 5.0 1.1 10.2 Example 3 8.0 4.3 1.1 9.0 Example 9 14.0 4.1 1.2 8.8 Example 10 20.0 3.9 1.3 8.2 Effect of the Invention The polymer electrolyte gel of the present invention has excellent ion conductivity not only at normal temperature, but also at low temperature, and has a good effect on lithium. Electrochemical elements such as polymer secondary batteries and double-layer capacitors are very useful, and excellent electrochemical characteristics can be expected. -twenty one -