1295306 A7 B7 五、發明說明（ 電池係利用化學活性物質產生電化學反應的祕，其性能受到材料特性而 有所左右’材料科學當然是研究的基礎。目前％電子產品均有朝輕、薄、短、 小的趨勢，但其受限的條件，主要受制於電力的來源一電池，如果能夠發展出既 薄、電谷量大且不佔空間的電池，在市場上定會具有—定的競爭力。高分子材 料原本是絕·，但是經過適當的處理後，高分何能魏導電㈣材料係 近年來高分子材料科技上之突破性發展。高分子電解質材料具有化學構造上的 特徵·，尚分子電解質中含有某些元素如〇、N、F，其具有局部化的冗電子密度， 基於雙鍵的共振效果，可呈現載體的作用，因局部化的結果而產生游離基離子。 加上7Γ-軌道的幾何形態將容許執道的重疊，更促進分子間的載體輸送。由於分 子鏈長比實際材料試片尺寸為短甚多，故高分子電解質的電荷傳導主要須靠分 子鏈間的輸送。1953年M.B.Armand等人提出以聚夸化乙烷（p〇iyethylene oxide, ΡΕ0)與驗金屬的高分子錯合物可以應用於鐘電池當作固態電解質之後， 可以發展既薄且導電性高的高分子電解質便成為一個相當熱門的研究與發展的 主題。經過國内、外長期的研究與發展，發現傳統的聚環氧乙烷系高分子電解 貝’其在常溫下的導電度介於1〇_7〜l〇-5S/cm之間，這樣的性質限制了電池無法 承受較大電流的負載，降低了固態電解質在電池上的應用性。對於提昇高分子 電解質之常溫下的導電度就成為此領域最重要的研究目標之一。一般能應用於 電池的固態電解質應具備以下條件： 1·常溫下導電度在1〇_3 S/Cm以上，導電度愈高，有助於增加電池所能承受的大 電流放電，對於應用在附加功能繁多的3C電子產品有很大的助益。 2·有較寬的電化學穩定範圍（ffind〇ws 〇f electrochemical stability)，可 以增加電極與電解質介面間的穩定性，提昇電池的電化學特性。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I --------^---------- (請先閱讀背面之注意事項再填寫本頁) 1295306 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（2 ) 3·較低的反應活化能(Activation energy, Ea)，可降低電池對於溫度的敏感度。 雖然近來有人提出將不同種類的高分子以共聚合方式，可製造出結構較強 之固態電解質，但實際的成本及反應機制過於複雜，應用於電池的生產的成本 過高，不合乎經濟成本且生產過程太複雜。有鑑於此，本專利提出新的鹼性固 態電解質，其導電度(σ)在常溫下可達l(T2 (S/cm)逼近於液態驗性水溶液，提 升了常溫型高分子電解質電池的實用性。 開發以PE0高分子為主的驗性固態電解質(SPE)，聚氧化乙晞(p〇iyethyiene oxide，PE0)是一種線性結晶性高分子，在主鏈上有陰電性較大的元素，如s、〇、 F，可以幫助解離鹽類，增加導電度。在結晶性peo高分中摻合pVA高分子，可 以提咼電解質的導電度’主要是降低其Tg，使非結晶區增加，因而增加了 κ+和 0ΙΓ在非結晶區的傳導。本研究開發以聚氧化乙烯為主”鹼性固態電解質（s〇lid polymer electrolyte，SPE)，加入PVA親水性高分子（因含〇h~基)可以增加K〇H 在PEO非結晶區的含量，而有助於導電性的提昇。 另共聚合物為聚乙烯醇(polyvinyl alcohol, PVA)，以共價鍵及氫鍵所結合的 高分子是一種無定型具低結晶性的高分子且為具旋轉結構的高分子鏈，可阻隔 電子的傳導，是一種柔軟性相當高的高分子材料。由於聚乙烯醇具有氫氧根 (Hydroxyl groups，〇}〇，是一親水性相當高的高分子，與同樣具有氫氧基的水 及氫氧化鉀，具有相當好的相容性。金屬離子在聚氧化乙烯/聚乙烯醇共聚合高 分子中内傳導，是利用金屬離子與高分子鏈（backbone)的強偶合作用力 (coupling interaction)產生暫時性的配位結合，再利用高分子鏈的柔軟性將 金屬離子傳輸出去。聚氧化乙烯及聚乙烯醇高分子其用途相當的普遍、價位低 廉且無任何環保問題的高分子材料，將其應用於鋅空氣電池鹼性電池、燃料 I紙張尺度適用中國國家標準（CNS)A4規格⑽x 297公髮） - -~ --------------------訂--------- Φ (請先閱讀背面之注意事項再填寫本頁) 1295306 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 A7 B7 五、發明說明（3 ) 電池、鎳氫電池取代現有的PP/PE不織布及纖維素含鹼液的隔離膜，將成為未 來的新趨勢& 此聚氧化乙稀/聚乙烯醇共聚合高分子電解質，具有高氧氣阻斷性，若將其 應用於驗性鋅/空氣電池上，可隔絕空氣中的氧氣透過隔離膜進入到負極與鋅反 應產生氧化作用，增加電池壽命。且由於電解液被含入於高分子膜中保持凝膠 (gel)狀態，可解決電解液於一般隔離膜滲出造成電池漏液的問題，且置於高溫 亦有很高的導電度及電化學穩定性。 本專利係提供利用聚氧化乙稀/聚乙烯醇共聚合高分子電解質每特定的反 應條件下，與氫氧化鉀及水反應，即可製造出高導電度之鹼性固態電解質，在 常溫下導電度可達1〇_2 (S/cm)以上，經實際的應用於鎳氫電池、鎳鎘電池、鋅 空氣電池上，效果比市面上使用PP/PE隔離膜效果好/且依照不同使用、應用 場合不同，電解質膜厚可在50〜500#m之間變化，製造成本亦非常的便宜，對 於開發高分子驗性電池生產，可以往薄型化方向發展，以滿足3(：產品之要求。 兹將本發明之固態高分子電解質之製造方法敘述如次： 第一先選擇適當之聚氧化乙烯、聚乙烯醇、氫氧化鉀原物料及並分別將聚 氧化乙烯及聚乙烯醇及氫氧化鉀溶於水中；第二是聚氧化乙烯/聚乙烯醇的水溶 液加入氫氧化鉀水溶液，並控制在一定的反應溫度、時間條件下；第三是視反 應之時間及混合溶液之溶解情形將反應予以結束，並依照不同量的高分子液加 入培養皿中，依重量的不同來控制所需的膜厚。第四是控制高分子膜之成膜時 間、溫度及濕度，以維持高分子膜内的適當含水量。第五是高分子膜的電化學 的特性測試。 為進一步揭示本案之具體技術内容，首先請參閲圖式，其中， L-----I----*------"訂---- ----- (請先閱讀背面之注意事項再填寫本頁) 1295306 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（4 ) 圖一係以本發明之驗性固態PEO/PVA高分子電解質之製作流程圖。 圖二⑷係以本發明之驗性PEO/PVA高分子電解質導電度(σ )與溫度(T) 變化之阿瑞尼式圖(Arrhenius Plot)。 (b)係以本發明之驗性peo/PVA高分子電解質在不同溫度(τ)下， 電化學阻抗分析圖(Nyquist Plot) 〇 圖三係以本發明之驗性pE0/pVA高分子電解質在-15〜15伏特之間， 一極式電極的循環伏安圖，其電位掃瞒速率為1 mV/s，工作電極為 316 不鏽鋼平板電锋（SS-316 stainless steel)。 圖四係以本發明之驗性PEO/PVA高分子電解質應用在鋅·空氣電池之放 電電壓變化曲線圖並比較市面上傳統隔離膜做一比較。 ， 圖五⑻係以本發明之驗性PE0/PVA高分子電解質應用在鎳氫電池時之 充/放電電壓循環壽命曲線圖。 (b)係以本發明之鹼性PEO/pVA高分子電解質之鎳氫電池之單電池 一次充/放電電壓曲線圖。 1 1·原料之選擇及前處理 聚氧化乙烯（PEO)原料需純度90%以上，平均分子量範圍為 10,000〜100,000，最好其平均分子量在2，_〜50_範圍内者；聚乙烤醇(pvA) 原料需純度80〜90%，平均分子量範圍為2,〇〇〇〜120,000，最好其平均分子量在 2,000〜50,000棚内者，無論其為粒狀或粉狀均能參與反應。氮氧化卸(k〇h) 原料為純度為85%，分子量為56g/mde，無論其為粒狀或粉狀均能參與反應。 2·反應物之反應礪序 反應物之反應_及反應順序會直接的影_高分子膜的組成及成膜與 否的關鍵，如絲氧化乙職聚乙刺重量百分比過祕會導致溶朗難及導 電度下降，重量百分比過低將無法成膜。如果氫氧化鉀重量百分比過高，將導 • Γ」-------------- (請先閱讀背面之注意事項再填寫本頁) 訂ί Φ 1295306 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（5 ) 致結構變差甚至無法成膜。如果將兩者同時進料將導致兩者皆無法溶解。所以 反應物之比例及反應物之溶解順序，對於高分子膜的製造相當的重要。本專利 係將選擇聚氧化乙烯和聚乙烯醇依照反應物之20%〜30%重量百分比進料，在常 溫下密閉環境下與50%〜60%重量百分比之水攪拌混合，約兩小時即可全部溶 解’同時將15%〜25%重量百分比之氫氧化鉀，在常溫下密閉環境下與重量百分 比約10%之水混合溶解。 3·聚合反應之條件控制 聚合反應之溫度、時間控制將會影響高分子膜的水份組成，水份含量愈高 導電度也會愈高，但是必須要在一定的反應溫度下才會產生聚合反應，所以要 控制較短的聚合時間以及減少水份的散失，將會是非常的重要。本專利係將兩 完全溶解的聚氧化乙稀及聚乙婦醇高分子溶液及氫氧化钟溶液在常溫下混合， 此時會有白色固體物產生，將其與溶液充分攪拌，並於密閉容器内加熱兩混合 溶液於50〜80°C，反應約30分鐘使固體物完全溶解即+將溶液於大氣中冷卻1〇 分鐘。將冷卻之高分子液依照培養JHL的面積及高度，並確定所需膜厚的大小， 控制倒入培養皿中之高分手溶液之量。 4·成膜條件之控制 將裝有高分子液之培養皿放進恆溫怪濕箱中，控制溫度在4〇°c〜60°C，濕 度在30〜50%RH，最適條件為溫度50°C及濕度30 %RH下，將其置放3〇〜6〇分 鐘，使成固態高分子膜。取出培養皿於大氣中，平衡30分鐘使薄膜與玻璃界面 產生分離，即可將薄膜輕易的取下，並將薄膜置放於密閉之Pvc夾鏈袋中可保 存達一年以上。 5·高分子膜導電性之測試 A·導電度之測試： 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂--- Φ 1295306 A7 B7 五、發明說明（6 ) 在將固態高分子電解質以Eco Chemie公司所製之Autolab FRA交流阻抗分 析儀，並以兩極式不銹鋼電極測量電阻(即Blockionelectr〇de)。頻率掃瞄範圍在 100kHz〜0.1Hz 間，頻率振幅(amplitude)為 10mV。 B·電化學穩定度測試： 以Eco Chemie公司所製之Autolab GPES系統掃瞄包含聚乙烯醇高分子電解 質之不同種類隔離膜的循環伏安圖，以二極式方法進行電位掃描，電位範圍為 -1·5 V〜1.5 V，掃瞄速率1 mv/s，同樣以不鏽鋼電極(SS316)為工作電極。 C·電池電性測試： 將合成之PEO/PVA高分子電解質應用在鋅-空氣電極上，此電解質搭配鋅極 (-)與空氣極(+)組裝成鋅-空氣電池，並以50 mA電g進行放電（電極面積6 cm2) ’同時比較市售不同的隔離膜進行電性測試。另外將本發明之固態高分子電 解質也應用在鎳氫電池上，PEO/PVA固態高分子電解質搭配吸氫合金(MH)的負 極與正極氫氧化鎳(Ni(OH)2)電極組裝成鎳氫電池，以50mA電流進行充放電測 試0 -------Ψ------ (請先閱讀背面之注意事項再填寫本頁) 訂--- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1295306 經濟部智慧財產局員工消費合作社印製 A7 ___ B7__ 五、發明說明（7 ) 實施例(一）： 將依照不同比例配方，精稱各4· Og之PEO和PVA至裝有40g ΗζΟ之反應器 中。將其連同反應器PVA、水以及授拌子稱重並記錄之。在常溫下反應一小時， 使其完全溶解。將12· 5g之Κ0Η溶於10g &0中，並將其倒至反應器中。將反 應器升溫至70°C，並控制聚合時間在30分鐘以内。將反應完之反應器連同 在内之聚合物稱重記錄之，並將黏稠高分子液倒入培養皿中，固定重量（約 5g〜10g之高分子溶液），並置於恆溫恆濕箱中（控制於濕度在3〇%RH，溫度在50T) 一小時。取出置放於大氣中一小時，將高分子薄膜取下並稱重計算其乾燥後組 成成份比例，並放於夾鍊帶中。PE0/PVA固態高分子電解質製作流程如圖一所 示。 ’ 實施例(二）： 取合成所付PE0/PVA固態高分子電解質薄膜，以平】厚計測量膜厚並以Eco Chemie公司所製之電化學阻抗分析儀AUTOLAB FRA(兩極式不銹鋼電極)測量其 導電度及並以AUTOLAB GPESV4.0測量循環伏安圓。可得到如第二圖及第三圖 之結果，由圖二可知，此例所得PE0/PVA高分子電解質常溫導電度約為〇· 〇5 (S/cm) ’溫度變化下活化能約為3-7 kJ/mole，比較聚環氧乙燒高分子電解質 之活化能20kJ/mole以上來的非常低。結果如表一所示為peo/pva高分子電解 質在不同溫度的導電度變化。由圖三所掃瞄之循環伏安圖可知，此例所得 PE0/PVA高分子電解質在常溫下與PP/PE及纖維素(cellulose)隔離膜比較，發 現本發明之PE0/PVA高分子％解質在工作電壓範圍-1· 5〜1· 5V内都沒有任何氧 化及還原的法拉第電流（faradic current)產生，具有良好的電化學穩定性比 PP/PE隔離膜（電位範圍-l,〇V〜1·〇ν)及纖維素(cellui〇se)隔離膜（電位範圍 -1.2〜1.2V)來的更穩定。 X 297公釐） 丨丨丨--- 裝i_丨！丨—訂·1丨丨·丨|丨· (請先閱讀背面之注意事項再填寫本頁) 1295306 A7 B7 五、發明說明（8) 表一：PEO/PVA高分子電解質之導電度 溫度 CC) 25 30 35 40 45 50 60 導電度 (S/cm) 0.0577 0,0753 0.0838 0.0910 0.0959 0.0972 0.099 經濟部智慧財產局員工消費合作社印製 實施例㈢： 量稱3g含有65wt%鋅粉的鋅凝膠(zinc gei)當作負極，將pp/pE隔離膜與纖 維素隔離膜，搭配所製備的空氣極當作正極，組裝成鋅_空氣電池，同時取實施 例(一)之PEO/PVA高分子薄膜取代上述PP/PE及纖維备隔離膜，組裝成鋅_空氣 電池進行平行放電比較。其理論電容量皆為1600 mAh。在常溫25°C下以50mA 電流放電(電極面積6cm )’其結果如第四圖所示。由圖中可知，以ppypE當作 隔離膜的鋅空氣電池，放電時間為15.8小時，其利用率只有49.48%。而以纖維 素當作隔離膜的辞空氣電池，放電時間為18.2小時，其利用率亦只有57.18%， 但是以實施例(一)之PEO/PVA高分子薄膜當作隔離膜的鋅·空氣電池，其放電時 間為29.5小時，且利用率高達92.18%。利用率會有如此大的差異，這是由於市 面上鹼性電池所使用之ΡΡ/ΡΒ或是纖維素隔離膜，其孔洞大小約為2〇〜3〇μιη， 在電池放電時，由於鋅電極的膨脹，造成活性物質因為電極的膨脹擠壓，順著 隔離膜的孔洞進入到另一極形成短路。但如果是以PE〇/PVA高分子薄膜當作隔 離膜時，其是以高分子鏈與離子產生偶極作用力形成暫時性配位，由於 PEO/PVA高分子薄膜具有柔軟性，所以鋅電極放電膨脹時，目為固態薄膜的柔 軟彈性機械緣故，並不會造成短路，可使利用率較一般隔離膜來的高。 —裝---- (請先閱讀背面之注意事項再填寫本頁) 訂--------- 本紙張尺度週用中國國豕ί示準（CNS)A4規格（21〇 X 297公髮） 1295306 A7 B7 五、發明說明（9 ) 表二：鋅-空氣電池電性測試結果 (電極面積6 cm2) 項目'\ PP/PE 纖維素(Film) PEO/PVA 薄膜 理論電容 (mAh) 1600 1600 1600 放電電流 (mA) 50 50 50 放電時間 (hrs) 15.8 18.2 29.5 實際電容 (mAh) 792 915 1475 利用率 (%) 49.48 57.18 92.18 (請先閱讀背面之注意事項再填寫本頁) ----- 經濟部智慧財產局員工消費合作社印製 表三：鎳氫電池電性測試結果 (電極面積6 cm2) 1 2 3 4 5 6 7 8 | 9 10 理論電容 (mAh) 140 140 140 140 140 140 140 140 140 140 充電電流 (mA) 50 50 50 50 50 50 50 50 50 50 放電電流 (mA) 50 50 50 50 50 50 50 50 50 50 充電時間 (hrs) 2.2 2.5 2.8 2.4 3.0 2.4 3.1 3.4 3.0 3.0 放電時間 (hrs) 2.1 2.2 2.0 2.2 2.2 2.25 2.4 2.3 2.6 2.5 放電電容 (mAh) 105 125 100· 110 110 112.5 120 115 130 125 庫倫效率 (%) 95.4 88 71 92 73 94 77 68 87 83 利用率 (%) 75 89 71 79 79 80 86 82 93 89 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 訂_丨 Φ! 1295306 A7 __^____ 五、發明說明（10 ) 實施例(四)： 壓製〇.7g含有70wt%之氫氧化鎳粉末之糊狀混合物(paste)當作正極，取實 施例(一)之PEO/PVA膠態薄膜當作隔離膜，並搭配AB5吸氫合金當作負極，組 裝成鎳氫二次電池。其理涂電容置為140 mAh。以50 mA(電極面積6 cm2，約 C/3 rate)進行電池之充放電，其結果如圖五(a)及⑴)所示。由表三可知，在經過 1〇次的充放電循環後’其充放電效率亦可保持在8Q，率亦可達8〇% 以上。 1ί-------f —— (請先閱讀背面之注意事項再填寫本頁) 訂--- 4! 經濟部智慧財產局員工消費合作社印製1295306 A7 B7 V. INSTRUCTIONS (Batteries are secrets of electrochemical reactions using chemically active substances, and their performance is affected by material properties.) Materials science is of course the basis of research. At present, % of electronic products are light and thin. Short and small trends, but their limited conditions, mainly subject to the source of electricity, a battery, if you can develop a battery that is thin, large in electricity and does not occupy space, there will be a certain competition in the market. The polymer material was originally absolutely, but after proper treatment, the high-density He-Wei conductive (four) material system has made breakthroughs in the technology of polymer materials in recent years. The polymer electrolyte material has chemical structural characteristics. The molecular electrolyte also contains certain elements such as ruthenium, N, and F, which have a localized electron density. Based on the resonance effect of the double bond, it can exhibit the role of a carrier, and a radical ion is generated as a result of localization. The geometry of the 7Γ-orbit will allow overlapping of the orbital and promote the carrier transport between the molecules. Since the molecular chain length is much shorter than the actual material test piece size, Therefore, the charge conduction of polymer electrolytes mainly depends on the transport between molecular chains. In 1953, MBArmand et al. proposed that the polymer complexes of p〇iyethylene oxide (ΡΕ0) and metal can be applied to the clock. After the battery is used as a solid electrolyte, it is a very popular research and development subject to develop a polymer electrolyte that is thin and highly conductive. After long-term research and development at home and abroad, traditional polyethylene oxide is found. The polymer electrolysis shell's conductivity at room temperature is between 1〇_7~l〇-5S/cm. This property limits the load that the battery cannot withstand large currents, and reduces the solid electrolyte on the battery. The application of the polymer electrolyte at room temperature is one of the most important research goals in this field. The solid electrolyte generally used in batteries should have the following conditions: 1. Conductivity at room temperature is 1〇_ 3 S/Cm or more, the higher the conductivity, which helps to increase the high current discharge that the battery can withstand, which is of great benefit to the application of 3C electronic products with many additional functions. The wide electrochemical stability range (ffind〇ws 〇f electrochemical stability) can increase the stability between the electrode and the electrolyte interface and improve the electrochemical characteristics of the battery. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297). I)------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ (2) 3. Lower activation energy (Ea) can reduce the sensitivity of the battery to temperature. Although it has recently been proposed to synthesize different types of polymers by copolymerization. Strong solid electrolytes, but the actual cost and reaction mechanism are too complicated. The cost of producing batteries is too high, which is not economical and the production process is too complicated. In view of this, this patent proposes a new alkaline solid electrolyte whose conductivity (σ) can reach l at room temperature (T2 (S/cm) is close to the liquid aqueous solution, which improves the practicality of the normal temperature polymer electrolyte battery. Developed an inorganic solid electrolyte (SPE) based on PE0 polymer, and p〇iyethyiene oxide (PE0) is a linear crystalline polymer with a strong anion element in the main chain. Such as s, 〇, F, can help dissociate the salt and increase the conductivity. Blending the pVA polymer in the crystalline peo high score can improve the conductivity of the electrolyte 'mainly reduce its Tg, increase the amorphous area Therefore, the conduction of κ+ and 0ΙΓ in the amorphous region is increased. In this study, a polyoxyethylene-based "s〇lid polymer electrolyte (SPE) was added, and a PVA hydrophilic polymer was added (due to 〇h). ~Base) can increase the content of K〇H in the non-crystalline region of PEO, and contribute to the improvement of conductivity. The co-polymer is polyvinyl alcohol (PVA), which is combined by covalent bond and hydrogen bond. Polymer is an amorphous polymer with low crystallinity It is a polymer chain with a rotating structure, which can block the conduction of electrons, and is a highly flexible polymer material. Since polyvinyl alcohol has hydroxides (Hydroxyl groups, it is a relatively high hydrophilicity). The polymer has a relatively good compatibility with water and potassium hydroxide which also have a hydroxyl group. The metal ion is conducted in the polyethylene oxide/polyvinyl alcohol copolymer polymer, and the metal ion and the polymer chain are utilized. The strong coupling interaction of (backbone) produces a temporary coordination bond, and then the metal ion is transported out by the flexibility of the polymer chain. The use of polyethylene oxide and polyvinyl alcohol polymer is quite common and the price is relatively high. Low-cost polymer materials without any environmental problems, applied to zinc-air battery alkaline batteries, fuel I paper scale applicable to China National Standard (CNS) A4 specifications (10) x 297 public hair) - -~ ------- -------------Book--------- Φ (Please read the note on the back and fill out this page) 1295306 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Description of the invention (3) Replacement of existing PP/PE non-woven fabrics and cellulose lye-containing separators with batteries and nickel-hydrogen batteries will become a new trend in the future & This polyoxyethylene/polyvinyl alcohol copolymerized polymer electrolyte has a high Oxygen barrier property, if applied to an inspective zinc/air battery, can block the oxygen in the air from passing through the separator to enter the anode and react with zinc to produce oxidation, increasing battery life, and because the electrolyte is contained in the high Maintaining the gel state in the molecular film can solve the problem that the electrolyte leaks out due to the leakage of the common separator, and the high temperature and high electrochemical conductivity and electrochemical stability. The patent system provides a high-conductivity alkaline solid electrolyte by reacting with potassium hydroxide and water under the specific reaction conditions of polyethylene oxide/polyvinyl alcohol copolymerized polymer electrolyte, and is conductive at normal temperature. The degree can reach 1〇_2 (S/cm) or more. After being applied to nickel-hydrogen battery, nickel-cadmium battery and zinc-air battery, the effect is better than that of PP/PE isolation film on the market. Different applications, the electrolyte film thickness can be changed between 50~500#m, and the manufacturing cost is also very cheap. For the development of polymer inspection battery production, it can be developed in the direction of thinning to meet the requirements of 3 (: product. The manufacturing method of the solid polymer electrolyte of the present invention is described as follows: First, the appropriate polyoxyethylene, polyvinyl alcohol, potassium hydroxide raw materials and the respective polyethylene oxide, polyvinyl alcohol and potassium hydroxide are separately selected. Dissolved in water; the second is an aqueous solution of polyethylene oxide / polyvinyl alcohol added to the aqueous potassium hydroxide solution, and controlled at a certain reaction temperature and time conditions; the third is depending on the reaction time and mixed solution The dissolution of the liquid ends the reaction, and the different amount of the polymer liquid is added to the culture dish to control the required film thickness according to the weight. The fourth is to control the film formation time, temperature and humidity of the polymer film. In order to maintain the proper water content in the polymer film. The fifth is the electrochemical characteristic test of the polymer film. To further reveal the specific technical content of the case, first refer to the figure, where L-----I- ---*------"Book---- ----- (Please read the notes on the back and fill out this page) 1295306 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Print A7 V. Invention DESCRIPTION OF THE DRAWINGS (4) Figure 1 is a flow chart for the production of the intrinsic solid PEO/PVA polymer electrolyte of the present invention. Figure 2 (4) shows the conductivity (σ) and temperature (T) of the inspective PEO/PVA polymer electrolyte of the present invention. Arrhenius Plot (b) is based on the inspective peo/PVA polymer electrolyte of the present invention at different temperatures (τ), and the electrochemical impedance analysis chart (Nyquist Plot) According to the invention, the pE0/pVA polymer electrolyte is between -15 and 15 volts, and the one-electrode electrode is followed. The voltammogram has a potential broom rate of 1 mV/s and the working electrode is a 316 stainless steel flat steel front (SS-316 stainless steel). Figure 4 is an application of the inventive PEO/PVA polymer electrolyte in zinc. The discharge voltage variation curve of the air battery is compared with the conventional isolation film on the market. Figure 5 (8) shows the charge/discharge voltage cycle life curve of the inventive PE0/PVA polymer electrolyte of the invention applied to the nickel-hydrogen battery. (b) A graph of a single charge/discharge voltage of a single cell of a nickel-hydrogen battery using the alkaline PEO/pVA polymer electrolyte of the present invention. 1 1·Selection of raw materials and pretreatment Polyethylene oxide (PEO) raw materials need to be more than 90% pure, with an average molecular weight ranging from 10,000 to 100,000, preferably having an average molecular weight of 2, _~50_; (pvA) The raw material needs to have a purity of 80 to 90%, an average molecular weight range of 2, 〇〇〇~120,000, and preferably an average molecular weight of 2,000 to 50,000 sheds, whether it is in the form of granules or powders. Nitrogen Oxidation Unloading (k〇h) The raw material has a purity of 85% and a molecular weight of 56 g/mde, and it can participate in the reaction regardless of whether it is in the form of granules or powder. 2. The reaction of the reactants The reaction of the reaction reactants _ and the reaction sequence will directly affect the composition of the polymer membrane and the key to the formation of the film, such as the weight percentage of the silk oxidized B. It is difficult to reduce the conductivity, and the weight percentage is too low to form a film. If the weight percentage of potassium hydroxide is too high, it will lead to -"-------------- (please read the notes on the back and fill out this page) ί 1295306 Ministry of Economic Affairs Intellectual Property Bureau Employee consumption cooperatives printed A7 B7 V. Invention description (5) The structure is deteriorated and even film formation is impossible. Feeding both at the same time will result in both being insoluble. Therefore, the ratio of the reactants and the order of dissolution of the reactants are quite important for the production of the polymer film. The patent system selects polyethylene oxide and polyvinyl alcohol to be fed according to 20% to 30% by weight of the reactants, and mixes with 50%~60% by weight of water under a sealed environment at normal temperature for about two hours. All dissolved 'at the same time, 15% to 25% by weight of potassium hydroxide was mixed and dissolved in water at a normal temperature in a closed environment with about 10% by weight of water. 3. The conditions of the polymerization reaction The temperature and time control of the polymerization reaction will affect the moisture composition of the polymer membrane. The higher the moisture content, the higher the conductivity, but the polymerization must be generated at a certain reaction temperature. Reaction, so it is very important to control the shorter polymerization time and reduce the loss of water. The patent system combines two completely dissolved polyethylene oxide and polyglycolic acid polymer solution and a oxidized bell solution at room temperature, at which time a white solid is generated, which is thoroughly stirred with the solution and sealed in a closed container. The two mixed solutions were heated at 50 to 80 ° C for about 30 minutes to completely dissolve the solid matter, that is, the solution was cooled in the atmosphere for 1 minute. The amount of the high-part solution poured into the culture dish is controlled by adjusting the area and height of the JHL to the size of the desired film thickness. 4. Control of film forming conditions The culture dish containing the polymer liquid is placed in a constant temperature wetting box, the temperature is controlled at 4 ° ° C ~ 60 ° C, the humidity is 30 ~ 50% RH, the optimum condition is temperature 50 ° Under C and humidity of 30% RH, place it for 3 〇 to 6 〇 minutes to form a solid polymer film. The culture dish is taken out in the atmosphere and equilibrated for 30 minutes to separate the film from the glass interface. The film can be easily removed, and the film can be stored in a closed Pvc zipper bag for more than one year. 5. Test of Conductivity of Polymer Films A. Conductivity Test: This paper scale is applicable to China National Standard (CNS) A4 specification (21〇x 297 mm) (please read the notes on the back and fill out this page) - ------- Order --- Φ 1295306 A7 B7 V. Description of the invention (6) The solid polymer electrolyte is manufactured by Eco Chemie's Autolab FRA AC impedance analyzer, and the resistance is measured with a two-pole stainless steel electrode. (ie Blockionelectr〇de). The frequency sweep range is between 100kHz and 0.1Hz, and the frequency amplitude is 10mV. B. Electrochemical stability test: The cyclic voltammogram of different kinds of separators containing polyvinyl alcohol polymer electrolyte was scanned by AutoChem GPES system manufactured by Eco Chemie, and the potential range was measured by a two-pole method. -1·5 V~1.5 V, scan rate 1 mv/s, also using stainless steel electrode (SS316) as the working electrode. C. Battery electrical test: The synthesized PEO/PVA polymer electrolyte is applied to the zinc-air electrode. The electrolyte is assembled into a zinc-air battery with a zinc electrode (-) and an air electrode (+), and is charged at 50 mA. g discharge (electrode area 6 cm2) 'At the same time, compare different commercially available separators for electrical testing. In addition, the solid polymer electrolyte of the present invention is also applied to a nickel-hydrogen battery, and the PEO/PVA solid polymer electrolyte is combined with a negative electrode of a hydrogen absorbing alloy (MH) and a positive nickel hydroxide (Ni(OH)2) electrode to form nickel hydrogen. Battery, charge and discharge test with 50mA current 0 -------Ψ------ (Please read the note on the back and fill in this page) Order --- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm). 1295306 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 ___ B7__ V. Invention description (7) Example (1): Will be different Proportionally formulated, weighed 4·Og of PEO and PVA into a reactor containing 40 g of hydrazine. This was weighed together with the reactor PVA, water and the stirrer and recorded. The reaction was allowed to react at room temperature for one hour to completely dissolve it. 12 5 g of hydrazine was dissolved in 10 g & 0 and poured into the reactor. The reactor was warmed to 70 ° C and the polymerization time was controlled to within 30 minutes. The reactor after the reaction is weighed and recorded together, and the viscous polymer liquid is poured into the culture dish, and the weight (about 5 g to 10 g of the polymer solution) is fixed, and placed in a constant temperature and humidity chamber ( Control the humidity at 3〇% RH and the temperature at 50T) for one hour. After taking out and placing it in the atmosphere for one hour, the polymer film was taken out and weighed to calculate the composition ratio of the dried composition, and placed in a zipper tape. The production process of PE0/PVA solid polymer electrolyte is shown in Figure 1. Example (II): A PE0/PVA solid polymer electrolyte membrane was synthesized, and the film thickness was measured by a flat gauge and measured by an electrochemical impedance analyzer AUTOLAB FRA (two-pole stainless steel electrode) manufactured by Eco Chemie. Its conductivity and measurement of cyclic voltammetry circles with AUTOLAB GPESV4.0. The results of the second and third figures can be obtained. As can be seen from Fig. 2, the PE0/PVA polymer electrolyte obtained in this example has a normal temperature conductivity of about 〇· 〇5 (S/cm). The activation energy is about 3 under temperature change. -7 kJ/mole, the activation energy of the polyepoxyethylene polymer electrolyte is very low at 20 kJ/mole or more. The results are shown in Table 1. The conductivity of the peo/pva polymer electrolyte at different temperatures. According to the cyclic voltammogram scanned in Fig. 3, the PE0/PVA polymer electrolyte obtained in this example is compared with the PP/PE and cellulose (membrane) separator at room temperature, and the PE0/PVA polymer % solution of the present invention is found. The product has no oxidized and reduced Faraday current in the working voltage range -1·5~1·5V, and has good electrochemical stability than PP/PE isolation membrane (potential range -l, 〇V ~1·〇ν) and cellulose (cellui〇se) separators (potential range -1.2~1.2V) are more stable. X 297 mm) 丨丨丨--- Install i_丨!丨—订·1丨丨·丨|丨· (Please read the notes on the back and fill out this page) 1295306 A7 B7 V. INSTRUCTIONS (8) Table 1: Conductivity temperature of PEO/PVA polymer electrolyte CC) 25 30 35 40 45 50 60 Conductivity (S/cm) 0.0577 0,0753 0.0838 0.0910 0.0959 0.0972 0.099 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Example (3): 3g zinc gel containing 65wt% zinc powder Zinc gei) As a negative electrode, the pp/pE separator and the cellulose separator are used as the positive electrode to form a zinc-air battery, and the PEO/PVA polymer film of the embodiment (I) is taken. Instead of the above PP/PE and fiber backup membranes, assembled into a zinc-air battery for parallel discharge comparison. Its theoretical capacitance is 1600 mAh. The battery was discharged at a normal temperature of 25 ° C at a current of 50 mA (electrode area: 6 cm). The results are shown in the fourth figure. As can be seen from the figure, the zinc-air battery with ppypE as the separator has a discharge time of 15.8 hours and its utilization rate is only 49.48%. The air battery with cellulose as the separator has a discharge time of 18.2 hours, and its utilization rate is only 57.18%. However, the zinc/air battery using the PEO/PVA polymer film of the embodiment (I) as a separator is used. The discharge time is 29.5 hours, and the utilization rate is as high as 92.18%. There is such a big difference in the utilization rate. This is due to the ΡΡ/ΡΒ or cellulose separator used in alkaline batteries on the market. The pore size is about 2〇~3〇μιη, when the battery is discharged, due to the zinc electrode. The expansion causes the active material to be squeezed by the expansion of the electrode, and a short circuit is formed along the hole of the separator into the other pole. However, if a PE〇/PVA polymer film is used as the separator, it is a temporary coordination between the polymer chain and the ion-generated dipole force. Since the PEO/PVA polymer film has flexibility, the zinc electrode When the discharge is expanded, the solid mechanical film is soft and elastic, and does not cause a short circuit, which makes the utilization higher than that of the general separator. —装---- (Please read the notes on the back and fill out this page) Order --------- This paper is measured by the China National Standard CN 示 (CNS) A4 specification (21〇X 297 1) 2295306 A7 B7 V. Description of invention (9) Table 2: Electrochemical test results of zinc-air battery (electrode area 6 cm2) Item '\ PP/PE Cellulose (Film) PEO/PVA Film Theoretical Capacitance (mAh) 1600 1600 1600 Discharge current (mA) 50 50 50 Discharge time (hrs) 15.8 18.2 29.5 Actual capacitance (mAh) 792 915 1475 Utilization (%) 49.48 57.18 92.18 (Please read the notes on the back and fill out this page) --- -- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 3: Nickel-Hydrogen Battery Electrical Test Results (Electrode Area 6 cm2) 1 2 3 4 5 6 7 8 | 9 10 Theoretical Capacitance (mAh) 140 140 140 140 140 140 140 140 140 140 Charging current (mA) 50 50 50 50 50 50 50 50 50 50 Discharge current (mA) 50 50 50 50 50 50 50 50 50 50 Charging time (hrs) 2.2 2.5 2.8 2.4 3.0 2.4 3.1 3.4 3.0 3.0 Discharge Time (hrs) 2.1 2.2 2.0 2.2 2.2 2.25 2.4 2.3 2.6 2.5 Discharge Capacitance (mAh) 105 125 100· 110 110 112.5 120 115 130 125 Coulomb efficiency (%) 95.4 88 71 92 73 94 77 68 87 83 Utilization (%) 75 89 71 79 79 80 86 82 93 89 11 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 PCT) _丨Φ! 1295306 A7 __^____ V. INSTRUCTIONS (10) EXAMPLES (IV): Pressing 7. 7g of a paste mixture containing 70% by weight of nickel hydroxide powder as a positive electrode, The PEO/PVA colloidal film of the example (1) is used as a separator, and is combined with an AB5 hydrogen absorbing alloy as a negative electrode to be assembled into a nickel-hydrogen secondary battery. Its capacitance is set to 140 mAh. The battery was charged and discharged at 50 mA (electrode area: 6 cm2, approximately C/3 rate), and the results are shown in Fig. 5 (a) and (1). It can be seen from Table 3 that after 1 cycle of charge and discharge cycles, the charge and discharge efficiency can be maintained at 8Q, and the rate can reach 8〇% or more. 1ί-------f —— (Please read the notes on the back and fill out this page) Order--- 4! Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative