TWI656684B - 製造具有優異鋪展特性之卷式氣體擴散層的方法 - Google Patents
製造具有優異鋪展特性之卷式氣體擴散層的方法 Download PDFInfo
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Abstract
本發明是於將使用具有低至10Gpa至100Gpa以下的
模數的碳纖維短纖製造的碳紙浸漬至酚樹脂後,以1,800℃至2,400℃進行碳化處理,之後於經碳化處理的碳紙的兩面中的一面形成具有微小多孔的聚四氟乙烯樹脂層而製造薄片狀的氣體擴散層後,將所製造的薄片狀的氣體擴散層捲取至輥而製造卷式氣體擴散層。由於本發明所製造的卷式氣體擴散層是由具有低模數的碳纖維短纖製造,因此自上述卷式氣體擴散層切割成薄片形態的氣體擴散層具有不翹曲而平坦地展開的優異鋪展性。
Description
本發明是關於一種鋪展性優異的卷式氣體擴散層(Gas
diffusion layer)的製造方法,具體而言,是關於一種於將由模數較低的碳纖維短纖(Chop)製造而捲取成輥形態的氣體擴散層切割成固定長度來製造成薄片形態的情形時,薄片形態的氣體擴散層不翹曲而平坦地展開的性質(以下,簡稱為「鋪展性」)優異的卷式氣體擴散層的製造方法。
氣體擴散層(Gas diffusion layer)作為燃料電池零件,是使於電極之間分解的氫離子及氧與氫結合而生成的水通過的膜片。
如韓國公開專利第10-2005-0054467號等中所記載,藉由如下方法製造氣體擴散層:將浸漬有酚樹脂等的碳紙(Carbon paper)碳化後,僅於兩面中的一面形成微小多孔性聚四氟乙烯樹
脂層。
於氣體擴散層商業化的初期,生產及供給薄片(sheet)形態的氣體擴散層。最近,為了運輸的容易性及量產等,主要是生產及供給捲取成輥(Roll)狀態的氣體擴散層(以下,簡稱為「卷式氣體擴散層」)。
製造卷式氣體擴散層的先前方法是依序經由如下製程而製造卷式氣體擴散層:(i)將強度為3.0Gpa以上、模數為230Gpa以上的聚丙烯腈類(PAN)碳纖維短纖(Chop)或瀝青類(Pitch base)碳纖維短纖(Chop)連同黏合劑纖維、界面活性劑、黏著劑及消泡劑一併投入至造紙用設備而製造薄片(Sheet)狀的碳紙(Carbon paper)的製程;(ii)於將如上所述般製造的碳紙浸漬至酚樹脂後,以1,800℃以上的溫度進行碳化,之後於經碳化處理的碳紙的兩面中的一面形成微小多孔性聚四氟乙烯樹脂層(PTFE layer)而製造薄片(Sheet)狀的氣體擴散層的製程;及(iii)將所製造的薄片(Sheet)狀的氣體擴散層捲取至輥(Roll)的製程。
藉由上述先前方法製造的卷式氣體擴散層是由模數高至230Gpa以上的碳纖維短纖(Chop)製造,故而於將捲繞於輥(Roll)的氣體擴散層切割成薄片(Sheet)形態的情形時,產生所切割的薄片狀的氣體擴散層不平坦地展開而翹曲的現象(即鋪展性(Spreading property)下降的現象),其結果存在如下問題:未徹底地密封(Sealing)所切割的薄片狀的氣體擴散層與燃料電池分離板之間而發生滲漏(Leak)或溢流(Flooding)等。
於為了解決如上所述的問題而另外使用黏合劑來密封(Sealing)如上所述般鋪展性(Spreading property)不良的薄片狀的氣體擴散層與燃料電池分離板之間的情形時,存在因使用黏合劑而導電性下降的問題。
本發明的課題在於提供一種製造於將捲繞於輥的氣體擴散層切割成所期望的固定長度而製成薄片形態時,薄片形態的氣體擴散層不翹曲而平坦地展開的性質、即鋪展性(Spreading property)卓越的卷式氣體擴散層的方法。
為了解決如上所述的課題,本發明是於將使用具有低至10Gpa至100Gpa以下的模數的碳纖維短纖(Chop)製造的碳紙浸漬至酚樹脂等後,以1,800℃至2,400℃進行碳化處理,之後於經碳化處理的碳紙的兩面中的一面形成具有微小多孔的聚四氟乙烯樹脂層而製造薄片狀的氣體擴散層後,將所製造的薄片狀的氣體擴散層捲取至輥(Roll)而製造卷式氣體擴散層。
本發明所製造的卷式氣體擴散層是由具有低模數的碳纖維短纖(Chop)製造,故而自上述卷式氣體擴散層切割成薄片形態的氣體擴散層具有不翹曲而平坦地展開的優異鋪展性
(Spreading property)。
因此,即便不另外使用黏合劑,亦可徹底地密封(Sealing)氣體擴散層與燃料電池分離板之間而不產生滲漏(Leak)或溢流(Flooding)等問題,亦防止因另外使用黏合劑而導電性下降的情形。
以下,詳細地對本發明進行說明。
本發明包括:(i)以1,750℃至2,450℃對作為纖維素類纖維的碳纖維用前驅物(Precursor)進行熱處理而製造強度為0.5Gpa至1.2Gpa、模數為10Gpa至100Gpa的碳纖維的製程;(ii)於將上述碳纖維切割成3mm至56mm而製造碳纖維短纖(Chop)後,將黏合劑纖維、界面活性劑、黏著劑及消泡劑連同上述碳纖維短纖(Chop)一併投入至造紙設備而製造薄片(sheet)狀的碳紙的製程;(iii)於將上述碳紙浸漬至樹脂後,以1,800℃至2,400℃進行碳化處理,之後於經碳化處理的碳紙的兩面中的一面形成具有微小多孔的聚四氟乙烯樹脂層而製造薄片(Sheet)狀的氣體擴散層(Gas diffusion layer)的製程;及(iv)將上述片狀氣體擴散層捲取至輥(Roll)的製程。
具體而言,本發明首先以最高1,750℃至2,450℃對作為纖維素類纖維的碳纖維用前驅物(Precursor)進行熱處理而製造強度為0.5Gpa至1.2Gpa、模數為10Gpa至100Gpa的碳纖維。
此時,使用乙酸纖維、嫘縈纖維、萊賽爾(Lyocell)纖維、棉纖維或木質素(Lignin)纖維等作為上述纖維素類纖維的碳纖維用前驅物。
若以未滿1,750℃的溫度對作為上述纖維素類纖維的碳纖維用前驅物進行熱處理,則碳纖維的模數變得低至未滿10Gpa,並且於碳纖維內部,除碳(C)以外殘留如氮(N)的成分而發揮雜質作用,從而作為最終製品的氣體擴散層的性能變差,若以超過2,450℃的溫度進行熱處理,則碳纖維用前驅物石墨化而對製程性及彎曲性產生不良影響。
如上所述般製造的碳纖維的強度為0.5Gpa至1.2Gpa,模數為10Gpa至100Gpa。
此時,若上述碳纖維的強度未滿0.5Gpa,則除碳以外的雜質較多而導熱度及導電度會下降,若超過1.2Gpa,則於進行熱處理時,過度地石墨化而容易碎裂等製程性會下降。而且,若模數未滿10Gpa,則碳纖維會容易撕裂,若超過100Gpa,則於捲取至輥時,會存在不易恢復而性能下降的問題。
如上所述般製造的碳纖維較佳為直徑為6μm至10μm,電阻率為0.0001Ω.cm至0.9Ω.cm,密度為1.4g/cm3至1.5g/cm3。
於碳纖維的直徑未滿6μm的情形時容易碎裂,於超過
10μm的情形時,難以均勻地碳化至碳纖維內部而會表現出不均勻的特性。而且,於電阻率脫離上述範圍的情形時,雜質較多或過度碳化而欠佳。
其次,於將上述碳纖維切割成3mm至56mm而製造碳纖維短纖(Chop)後,將黏合劑纖維、界面活性劑、黏著劑及消泡劑連同上述碳纖維短纖(Chop)一併投入至造紙設備而製造薄片(sheet)狀的碳紙。
此時,若將上述碳纖維切割成未滿3mm,則會難以製造成碳紙,需要多於碳纖維短纖的量的黏合劑的量而於碳化時黏合劑部分形成為中空,從而性能會急遽地下降。相反地,若將碳纖維切割成超過56mm,則分散性過度地下降而變得難以製造均勻狀態的碳紙,造紙濃度變低而會不具有經濟性。
如上所述般製造的碳紙的重量較佳為10g/m2至100g/m2。
其次,於將上述碳紙浸漬至樹脂後,再次於氮氣環境中以最高1,800℃至2,400℃進行碳化處理,之後於經碳化處理的碳紙的兩面中的一面形成具有微小多孔的聚四氟乙烯樹脂層而製造薄片(Sheet)狀的氣體擴散層(Gas diffusion layer)後,將所製造的薄片狀的氣體擴散層捲取至輥(Roll)而製造卷式氣體擴散層。
此時,使用酚樹脂或聚乙烯酚樹脂等作為浸漬碳紙的樹脂。
本發明所製造的卷式氣體擴散層是由具有低模數的碳
纖維短纖(Chop)製造,故而自上述卷式氣體擴散層切割成薄片形態的氣體擴散層具有不翹曲而平坦地展開的優異鋪展性(Spreading property)。
因此,即便不另外使用黏合劑,亦可徹底地密封(Sealing)氣體擴散層與燃料電池分離板之間而不產生滲漏(Leak)或溢流(Flooding)等問題,亦防止因另外使用黏合劑而導電性下降的情形。
以下,藉由實施例及比較實施例而更具體地對本發明進行說明。
然而,不應解釋為本發明的保護範圍僅限定於下述實施例。
實施例1
以1,800℃對作為乙酸纖維的碳纖維用前驅物(Precursor)進行熱處理而製造強度為0.7Gpa、模數為17Gpa、直徑為8μm、電阻率為0.1Ω.cm、密度為1.45g/cm3的碳纖維。
其次,於將上述碳纖維切割成20mm而製造碳纖維短纖(Chop)後,在500℃的溫度下對所製造的碳纖維短纖(Chop)進行3分鐘熱處理而去除殘留的上漿油。
其次,於混合經熱處理的上述碳纖維短纖(Chop)與聚乙烯醇纖維(黏合劑纖維)、界面活性劑、黏著劑及消泡劑而製成混合物後,將上述混合物投入至造紙用儲漿槽而製造重量為25g/m2的碳紙(Carbon paper)。
其次,於將如上所述般製造的碳紙浸漬至酚樹脂並進行乾燥後,以2,200℃的溫度進行碳化處理,之後以塗覆方式於如上所述般碳化處理的碳紙的兩面中的一面形成微小多孔性聚四氟乙烯樹脂層而製造薄片狀的氣體擴散層。
其次,縱切如上所述般製造的薄片狀的氣體擴散層的邊部而捲取至輥(Roll)來製造卷式氣體擴散層。
其次,按照300mm的長度鬆解切割如上所述般製造的捲繞於輥(Roll)的氣體擴散層而製造薄片狀的氣體擴散層,結果所製造的薄片狀的氣體擴散層具有不隨輥(Roll)的曲率半徑翹曲而平坦地展開的性質,即鋪展性優異。
實施例2
以2,000℃對作為嫘縈纖維的碳纖維用前驅物(Precursor)進行熱處理而製造強度為0.9Gpa、模數為60Gpa、直徑為6μm、電阻率為0.2Ω.cm、密度為1.45g/cm3的碳纖維。
其次,於將上述碳纖維切割成5mm而製造碳纖維短纖(Chop)後,在500℃的溫度下對所製造的碳纖維短纖(Chop)進行3分鐘熱處理而去除殘留的上漿油。
其次,於混合經熱處理的上述碳纖維短纖(Chop)與聚乙烯醇纖維(黏合劑纖維)、界面活性劑、黏著劑及消泡劑而製成混合物後,將上述混合物投入至造紙用儲漿槽而製造重量為40g/m2的碳紙(Carbon paper)。
其次,於將如上所述般製造的碳紙浸漬至酚樹脂並進行
乾燥後,以2,200℃的溫度進行碳化處理,之後以層壓方式於如上所述般碳化處理的碳紙的兩面中的一面形成微小多孔性聚四氟乙烯樹脂層而製造薄片狀的氣體擴散層。
其次,縱切如上所述般製造的薄片狀的氣體擴散層的邊部而捲取至輥(Roll)來製造卷式氣體擴散層。
其次,按照300mm的長度鬆解切割如上所述般製造的捲繞於輥(Roll)的氣體擴散層而製造薄片狀的氣體擴散層,結果所製造的薄片狀的氣體擴散層具有不隨輥(Roll)的曲率半徑翹曲而平坦地展開的性質,即鋪展性優異。
實施例3
以2,400℃對作為萊賽爾纖維的碳纖維用前驅物(Precursor)進行熱處理而製造強度為1.2Gpa、模數為90Gpa、直徑為10μm、電阻率為0.2Ω.cm、密度為1.45g/cm3的碳纖維。
其次,於將上述碳纖維切割成50mm而製造碳纖維短纖(Chop)後,在500℃的溫度下對所製造的碳纖維短纖(Chop)進行3分鐘熱處理而去除殘留的上漿油。
其次,於混合經熱處理的上述碳纖維短纖(Chop)與聚乙烯醇纖維(黏合劑纖維)、界面活性劑、黏著劑及消泡劑而製成混合物後,將上述混合物投入至造紙用儲漿槽而製造重量為60g/m2的碳紙(Carbon paper)。
其次,於將如上所述般製造的碳紙浸漬至酚樹脂並進行乾燥後,以2,200℃的溫度進行碳化處理,之後以塗覆方式於如上
所述般碳化處理的碳紙的兩面中的一面形成微小多孔性聚四氟乙烯樹脂層而製造片狀氣體擴散層。
其次,縱切如上所述般製造的薄片狀的氣體擴散層的邊部而捲取至輥(Roll)來製造卷式氣體擴散層。
其次,按照300mm的長度鬆解切割如上所述般製造的捲繞於輥(Roll)的氣體擴散層而製造薄片狀的氣體擴散層,結果所製造的薄片狀的氣體擴散層具有不隨輥(Roll)的曲率半徑翹曲而平坦地展開的性質,即鋪展性優異。
比較實施例1
以1,450℃對作為聚丙烯腈(PAN)纖維的碳纖維用前驅物(Precursor)進行熱處理而製造強度為3.5Gpa、模數為220Gpa的碳纖維。
其次,於將上述碳纖維切割成20mm而製造碳纖維短纖(Chop)後,在500℃的溫度下對所製造的碳纖維短纖(Chop)進行3分鐘熱處理而去除殘留的上漿油。
其次,於混合經熱處理的上述碳纖維短纖(Chop)與聚乙烯醇纖維(黏合劑纖維)、界面活性劑、黏著劑及消泡劑而製成混合物後,將上述混合物投入至造紙用儲漿槽而製造重量為25g/m2的碳紙(Carbon paper)。
其次,於將如上所述般製造的碳紙浸漬至酚樹脂並進行乾燥後,以2,200℃的溫度進行碳化處理,之後以塗覆方式於如上所述般碳化處理的碳紙的兩面中的一面形成微小多孔性聚四氟乙
烯樹脂層而製造片狀氣體擴散層。
其次,縱切如上所述般製造的薄片狀的氣體擴散層的邊部而捲取至輥(Roll)來製造卷式氣體擴散層。
其次,按照300mm的長度鬆解切割如上所述般製造的捲繞於輥(Roll)的氣體擴散層而製造薄片狀的氣體擴散層,結果所製造的薄片狀的氣體擴散層具有隨輥(Roll)的曲率半徑嚴重翹曲而平坦地展開的性質,即鋪展性不良。
Claims (3)
- 一種鋪展性優異的卷式氣體擴散層的製造方法,包括:(i)以1,750℃至2,450℃對作為纖維素類纖維的碳纖維用前驅物進行熱處理而製造強度為0.5Gpa至1.2Gpa、模數為10Gpa至100Gpa的碳纖維的製程;(ii)於將所述碳纖維切割成3mm至56mm而製造碳纖維短纖後,將黏合劑纖維、界面活性劑、黏著劑及消泡劑連同所述碳纖維短纖一併投入至造紙設備而製造薄片狀的碳紙的製程;(iii)於將所述碳紙浸漬至酚樹脂後,以1,800℃至2,400℃進行碳化處理,之後於經碳化處理的碳紙的兩面中的一面形成具有微小多孔的聚四氟乙烯樹脂層而製造薄片狀的氣體擴散層的製程;以及(iv)將所述薄片狀的氣體擴散層捲取至輥的製程,其中所述碳纖維的直徑為6μm至10μm,電阻率為0.1Ω.cm至0.9Ω.cm,密度為1.4g/cm3至1.5g/cm3。
- 如申請專利範圍第1項所述的鋪展性優異的卷式氣體擴散層的製造方法,其中所述碳紙的重量為15g/m2至100g/m2。
- 如申請專利範圍第1項所述的鋪展性優異的卷式氣體擴散層的製造方法,其中所述纖維素類纖維為選自乙酸纖維、嫘縈纖維、萊賽爾纖維、棉纖維及木質素纖維中的一種。
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