TWI316523B - Polybenzimidazole-benzamide copolymer, process for preparing the same, electrolyte membrane prepared therefrom and process for preparing the same - Google Patents

Polybenzimidazole-benzamide copolymer, process for preparing the same, electrolyte membrane prepared therefrom and process for preparing the same Download PDF

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TWI316523B
TWI316523B TW094138561A TW94138561A TWI316523B TW I316523 B TWI316523 B TW I316523B TW 094138561 A TW094138561 A TW 094138561A TW 94138561 A TW94138561 A TW 94138561A TW I316523 B TWI316523 B TW I316523B
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electrolyte membrane
copolymer
acid
film
polybenzimidazole
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TW200621855A (en
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Jong-Chan Lee
Yong-Su Park
Tae-Ho Kim
Bong-Keun Lee
Chong-Kyu Shin
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Lg Chemical Ltd
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Description

1316523 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種新穎的聚苯並咪唑-苯甲醯胺共聚合物，及 其製備方法’該共聚合物是由化學式1所代表之重複單元所組成， 其係可應驗㈣電池之電解質膜。本發明_於使用前述共聚 合物所製得之電解質膜，及其製備方法。本發明更進—步關於用 於含有前述之電解質膜的燃料電池之一種膜—電極單元 (membrane-electrode unit) ’以及一種包括該膜—電極 料電池系統。 … 【化學式1】
99.9 其中X係0. 1 【先前技術】 料電池係具有-電解質及由該 在-燃料電池内，如氫氣之揪 ^貝所^離之一對電極 而如 氧氣之氧化綱供應至另—極〗〜至兩電極中一者， 應的化學料可魅/如χ說明包括此i料之化~ 而反應氣體（即氫氣和氧氣） ㈣子）了穿越電解質， 池包括數個燃料電池嫩;電古通常，層疊式燃料電 祕電池具有一電解質及其所隔離 1316523 之 對電極 電池物電解⑽料電池、縣碳酸鹽燃料 解質為基礎二聚合物電解質膜燃料電池等，包括以電 膜之雷經Μ m質膜燃料電池，包括有聚合物電解質 快逮啟動^停==高電能密度及魏，及其侧低溫操作之 為了可被㈣在轉電财，—電解質必須要有高 Ϊ製透性及操作溫度時之穩定性。美國杜邦（此如^ 定物電解質膜’雖具有優越的機械、化學穩 及㈣子電¥率，但因其高單價及熱度穩定性低，並未能 ^泛採用m種克服上述缺失之聚合物電解質膜的研 九，已在大力進行中。 至今’該等研究已料·出—種碳氫聚合物、或氟/碳氫混 成聚合物電解質膜，而非僅一氟化聚合物電解質膜（Li等人，
Chemistry of materials ’ ACS ， 2003 ， 15 ， 4896-4915)。 最具代表性之碳氫聚合物電解質膜係藉由摻雜磷酸至鹼性聚 合物聚本並咪嗤，其具有低燃料滲透性、合宜的電解質價格、優 越的機械性質、抗氧化性及熱穩定性(Wainwright;等人，J〇urnal of the Electrochemical Society ， ECS ， 1995 ， 142 ， L121 ; Li 等人 ’ Solid State Ionics，（Elservier)，2004，168，177-185 ; Asensio 等人，Journal of Polymer Science，2002，40， 3703 3710 ’ Asensio 專人 ’ Journal of the Electrochemical Society ’ ECS ’ 2004 ’ 151，A304-A310 ; Kim 等人，Macromolecular Rapid Communications，（Wiley)，2004，25，894-897)。 然而，藉由摻雜磷酸製備的聚苯並咪唑聚合物電解質膜，其 1316523 質子導電率並不_而足以有效地取代Naf咖。 【發明内容】 確認，本發明人研究並完成本發明’此發明係 予八1代表之重覆單元之新穎聚苯並咪唑-笨曱醯 苯i呼^^製備之—聚合物電解質膜，而此膜具有比傳統聚 本並味錢合物電解質膜，相似或較高之質子導電率。 因此，本發明夕_ α u μ 目的係以提供一種新穎的聚笨並咪唑-苯甲 ==其，，該共聚合物是由化學式1所代表 ^ ”’成其係可應用於燃料電池之電解質膜。 的係以提供藉由本發明之聚苯並咪唾-笨甲 …口 t備之-聚合物電解質膜，及其製備方法。 本發月之X目的係以提供一用於燃 ::綱斷電極單元，及包括該膜-電極單元== 以下，為本發明之詳細說明。 本發明係·-含有化學式丨代表之域單元的 咪唑-笨曱醯胺共聚合物，及其製備方法。 、眾本並 【化學式1】
99.9 其中X係0. 1316523 _ ΛΚ笨並味峻-苯甲醯胺共聚合物，包括化學式【代表之重覆單 凡之0.1%〜99· 9%的聚苯並咪唾，及99. 9%〜1%的苯甲酸胺。 从a月之共聚合物係可賊為—燃料電池的聚合物電解質膜。此 ，，係由如下之方法所製備··在氮氣下、2齡~ 25叱純化 胺基笨曱’並將其溶於多碟酸中，與胺基苯甲酸混合，再擾 羊超過6小％。此時’當胺絲甲酸加人至二胺基苯情聚合化 溶液之時點’係以規娜證共聚合物之機械性質。 本發明係關域由使用本發明之共聚合物㈣備賴料電池 之聚合物電解質膜，及其製備方法。 本發明之聚合物電解_，係藉由直接自聚合化溶液產生電 :獏的直接賴法。本方法說明如下：在含化學式丨代表之重 將，有_之聚合化溶液置於玻璃 、_板上存放在50〜150 C之烘箱内1分鐘〜3天 2此溶液完全分散。使_墨观佩產襲的厚度。令此成 直Hi至溫或以下’並將其缝水中以洗去㈣酸。在G· 1刪取 =Γ下乾燥此膜，而形成—聚合物M。摻雜6 M養溶液於 酸:聚:物:Γ1 m•下乾燥24〜60小時以製備得-摻雜磷 地產1 f獏。直接魏法無需純化過程，且可快速簡便 發明之範/^f度的—電解_。—種改良的方法亦包括於本 外之硫酸及多二::之聚合物刪膜，可藉__ 化學法所製備得之電解質膜，具有優越的機械性質、 用。此i 而得以在室溫到2GirC之寬廣的溫度範圍内使 1 ，明自傳統之聚苯並咪唑聚合物，加入苯甲醯胺所 件之電解質膜，相較於聚苯並料電解質膜，具有 1316523 I · 〇 本發明又以提供一藉由使用摻雜酸之聚合物電解質膜，及含 有本發明之聚苯並咪唑一苯曱醯胺共聚合物所製備、用於燃料電池 的獏-電極單元（ΜΕΑ)，及一包括此單元之燃料電池系統。 【實施方式】 本發明實際及目前較佳之實施範例，說明於以下之實施例。 然而’基於本發明揭露之所慮，於本發明精神及範圍内所 做之修飾、改良係得為熟習此項技藝者所理解。 實施例 苯並咪唑-笨甲醯胺「95-5 (單位：書量％ 巷苹厶 物之合成 在本例中，胺基苯曱酸係由同時具有胺基群及羧酸群之二胺 φ 基笨曱酸’所共聚合化而成。此時’藉由再結晶純化二胺基苯曱 酸及胺基笨f酸。藉由加熱將5 g之二胺基苯甲酸溶於i〇〇mL之 蒸德水。溶解完成後，緩慢地冷卻此溶液至室溫，而得褐色針形 之結晶。以相同的方式純化胺基苯曱酸。真空乾燥此純化之單體 24小時，並使其於可使用之狀態。 將95 g多磷酸置於燒瓶中、22〇。〇下加熱，並加入5 g之5 rt% —胺基笨甲酸，再加以授拌。1〇分鐘後，加入〇. π g的5 重董％胺基苯甲酸。當聚合反應進行時，此溶液變成深紅色並 具高黏性。反應結束後，將此熱聚合化溶液置於一玻璃面板並平 1316523 ^之’然後置於烘箱内。存放於⑽。c之烘箱2天。具有— 二之膜層生成於玻璃面板±。鱗，使_墨刀規繼薄膜之 又將有1GG _厚之薄膜成形於上之玻璃面板浸置於2 l 水中，以洗好魏。於室溫下再加人4 L細水，以去除^ 膜内殘留之㈣酸。在薄膜内之多魏完全去除後，再將薄膜这 放於蒸餾水中3天。 犋，又 ，，備得之薄膜在1 mmHg下真空乾燥48小時。為能換雜此 已乾燥薄膜’將此薄膜置於6 Μ魏溶液6〇小時。6摻雜之薄 膜再置於1 mmHg、室溫下乾燥。 (箪位：重量％ )1共处 物之合i 、口 此共聚合化反應，除了使用〇.5 g之胺基苯甲酸外，係藉由 相同於實施例1之方式施行。 宜咪唑-笨甲醯胺[77-23 (單位：重量％ )1共兔 合物之合成 此共聚合化反應，除了使用1.5 g之胺基苯曱酸外，係藉由 相同於實施例1之方式施行。 試二驗實施例1 ·皙子導雷率的暑泪，丨 本發明之電解質膜的質子導電率，係使用ZAHNER IM-6阻抗 分析儀，在1 Hz〜1 MHz的頻率範圍内、〇. 〇〇1〜〇. 1 mA交流電幅 (AC current amplitude)恆電流模式（galvanostatic mode)、 在室溫到180°C之溫度範圍，及無濕度下所測得。於Nafion 115 10 1316523 之情況中，無濕度及100%濕度下，量測質子導電率兩次。此結果 顯示於圖一。 試驗實施例2.黏度的量測 本發明電解質膜黏度之量測’係藉由使用Ubbelohde黏度計 所測得。精確地，係將1 g之電解質膜溶於98%硫酸在50 mL 燒瓶内，使其體積形成0. 2 g/dL。然後，在3〇°C之恆溫器測量其 黏度。此結果顯示於表1。 試驗實施例3.機械強廣的量測 本發明電解質膜之機械強度，係以LloydLR-10K壓力試驗機 (universal testing machine，UTM)所測得。精確地，係再製 備每一個電解質膜為狗骨型（dog-bone)薄膜以滿足ASTMD638 V 变，在室溫下、25%濕度之要求。每一薄膜之機械強度測量5次。 平均拉力強度顯示於表1。 【表1】 共聚合物 拉力強度（MPa) 黏度(dL/g) ~ 3.76 聚笨並咪唑(ΑΒΡΒΙ) 99. 34 聚笨並咪唑-笨曱醯胺（95/5) 共聚合物 64.87 1. 78 聚笨並咪唑-笨曱醯胺（90/10) 共聚合物 114. 59 3. 22 聚笨並咪唑-苯曱醯胺（77/23) 共聚合物 101.84 2.36
試驗實施例 4.熱重分析（Thermogravimetrir analysis，ΤΓτΑ) 本發明合成之電解質膜的熱安定性’係以ΤΑ儀器公司之熱重 1316523 分析儀 2050(ΤΑ instruments thermogravimetirc analyzer 2050) 所測得。精確地’係在連續量測熱重期間’將每一 50mg之電解質 膜以10°C/min自5(TC加熱到800°C。此結果顯示於圖二。 一種由本發明之聚苯並咪唑—苯甲醯胺共聚合物所製備的聚 合物電解質膜。本發明之聚合物電解質膜較於僅含聚笨並咪唾之 聚合物電解質膜，已被證明有相同優良的機械性質，而同時也呈 現高的化學及熱力安定性（參表1及圖二）。此外，如圖一所示， 本發明之聚合物電解質膜具有改善之質子導電率。 熟習此項技藝者將理解，揭露於前揭敘述之觀念及特定實 施例，可被引為修飾或設計成其他實施例，以執行與本發明相 同目的之基礎。熟習此項技藝者亦將理解如此均等之實施例， 並未偏離如下申請專利範圍所表之本發明的範圍及精神。 【圖式簡單說明】 圖一係顯示本發明與傳統之聚合物電解質膜的質子導電率⑺ 度圖；及· ^ 圖二係顯示本發明與傳統之聚合物電解質膜的熱穩定性圖。 【主要元件符號說明】。

Claims (1)

  1. 严々月"_(氣)正本i 1316溢 094138561號專利案之說明書修正） 十、申請專利範圍： 1. 一種聚苯並咪唑-苯曱醯胺共聚合物，該共聚合物係由下列化 學式1所代表之重覆單元所組成， 【化學式1】 :O~r 100-ί 其中χ為0.1〜99. 9。 2. 一種如申請專利範圍第1項所述之聚苯並咪唑_苯曱醯胺共聚 合物的製備方法，其特徵在於下述之製備步驟： >谷解二胺基笨曱酸於多磷酸中，該二胺基苯曱酸係在氮氣存在 下，於200t〜250t下純化所得； 與胺基苯甲酸混合；及 稅動所得之混合物超過6小時。 3. 種U電解質膜’其特徵在於係由申請專利範圍第丄項之 共聚物所製備。 4.-種聚苯並料—苯？_共聚合物電鋪朗製備方法，盆 特徵在於下述之製備步驟： 、 在2申請專利範圍第i項所述之共聚合物的聚合反應完成 後’立即將-聚合溶紐置於面板或_不銹鋼板上； 存放該板於5(Tc〜15(Γγ夕、1 \ a在 〇 C之尤、相1分釭〜3天，以使該溶 液形成一薄膜；及 去除該薄膜中的多磷酸。 1316523 (案號第094138561號專利案之說明書修正） 5·如申請專利範圍第4項所述之製備方法，其中在去除該薄膜上 的多磷酸之步驟前，另外包括藉由在室溫下冷卻以硬化該薄膜 之步驟。 6.如申請專利範圍第4項所述之製備方法，其中在去除該薄膜上 :的多磷酸之步驟後，另外包括摻雜磷酸、硫酸或多磷酸之步驟。
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