臺灣博碩士論文加值系統

增加Ni/YSZ陽極與YSZ反應界面表面積為提升固態氧化物燃料電池效率的有效方法之一。以規則性圖案製作方法應用在NiO/YSZ表面，具有快速及大面積化的應用潛力。

本研究以微影技術於P-type矽晶圓上建立不同尺寸之SU8負型光阻線陣圖案，再將圖案轉移到PDMS上，完成具規則圖案之PDMS模具。利用薄帶成形法及具規則圖案之PDMS模具製作具規則圖案之NiO-YSZ坯體基板，於1200℃燒成後完成具規則圖案之NiO-YSZ基板製作。將具規則圖案之NiO-YSZ基板於800℃及H2氣氛下進行還原處理後得到具規則圖案之Ni-YSZ基板。而Ni-YSZ/YSZ結構之製作，先以分散液鍍膜法於具規則圖案之NiO-YSZ基板上製備YSZ層，再於1400℃進行燒結，最後於800℃及H2氣氛下進行還原處理後得到。

研究結果顯示，利用具規則圖案之PDMS模具可將圖案有效地轉移，轉移的PDMS圖案深寬比最大可達2.77且不產生斷裂；於具規則圖案之NiO-YSZ坯體基材中，深寬比為1.57的圖案脫膜時會產生扭曲，而深寬比為2.19時圖案會由圖案基部斷裂；1200℃燒成後，具規則圖案之NiO-YSZ基板及圖案形狀保持完整且無發生裂縫或崩塌，表面積最大增加146％；經還原後，Ni-YSZ基板形成孔洞結構且圖案並不因為體積改變而發生破裂或崩塌的現象；Ni-YSZ/YSZ結構中，YSZ電解質緻密、與Ni-YSZ圖案接連良好且無間隙產生。經SEM顯微結構觀察，緻密YSZ薄膜也完整地被覆在NiO/YSZ規則圖案上。因此，藉NiO/YSZ規則圖案製作，預期將可有效地改善SOFC的轉換效率。

Increasing the interface area between Ni/YSZ (anode) and YSZ (electrolyte) is an effective way to enhance the performance of solid oxide fuel cells. Patterning on the surface of NiO/YSZ was proposed as a novel method to increase the surface area of NiO/YSZ. Patterned PDMS mold was first fabricated by replicating various SU8 patterns on Si wafers from photo-lithography technique. Patterned NiO-YSZ substrate was obtained after fabricating NiO-YSZ green tape from the PDMS mold. The pattern transfer of PDMS mold from SU8 patterns was successful. A fracture-free pattern with the maximum aspect ratio of 2.77 was obtained. However, after pattern transferring from PDMS mold, the patterns with aspect of 1.57 were significantly distorted. The patterns with aspect ratio of 2.19 were mostly damaged. These deformed and incomplete patterns were mainly caused by the friction between PDMS mold and ceramic green body during the mold releasing process. When the aspect ratio of the pattern reduced to below 0.91, patterns of PDMS could be completely transferred to the surface of NiO/YSZ. After firing at 1200℃, the shape of patterns on NiO/YSZ surface remained unchanged. Compared to the flat surface of un-patterned NiO/YSZ, 146％ increased surface area was observed in the patterns with aspect ratio of 1.57. Furthermore, a 17μm thick dense YSZ film was deposited on these patterned NiO/YSZ surface. A well-adhered YSZ film without any de-lamination was observed. In order to reduce NiO/YSZ to Ni/YSZ cermet, patterned NiO/YSZ samples were exposed to H2 at 800℃. Finally, desired electrolyte/electrode interface with a dense YSZ film covered on a patterned Ni/YSZ anode was obtained. It’s expected that the performance of SOFC would be enhanced when such a patterned structure is applied.

總目錄

中文摘要 I
英文摘要 II
誌謝 III
總目錄 IV
圖目錄 VII
表目錄 X

第一章 緒論 1

第二章 理論基礎與文獻回顧 3
2.1燃料電池簡介 3
2.1.1 燃料電池工作原理 3
2.1.2 燃料電池的優點 6
2.1.3 燃料電池種類及應用 6
2.2固態氧化物燃料電池 9
2.2.1固態氧化物燃料電池的結構 9
2.2.2固態氧化物燃料電池的型態 11
2.3陽極材料結構與工作原理 13
2.3.1鎳-釔安定氧化鋯(Ni-YSZ)材料 13
2.3.2鎳-釔安定氧化鋯(Ni-YSZ)陽極反應途徑 14
2.4薄帶成形技術 16
2.4.1薄帶成形製程步驟 16
2.4.2薄帶成形技術於SOFC的應用 20
2.5微影技術 20
2.5.1光阻 21
2.5.2微影製程步驟 21
2.5.3蝕刻 23

第三章 實驗方法與步驟 25
3.1實驗流程 25
3.2化學藥品選用 26
3.3具規則圖案之PDMS模具之製作 26
3.3.1矽晶片表面之SU8規則圖案之製作 26
3.3.2具SU8規則圖案之矽晶片及PDMS模具間之圖案轉移製程 29
3.4具規則圖案之NiO-YSZ基材之製作 33
3.4.1 NiO-YSZ粉末之製作 33
3.4.2具規則圖案之氧化鎳-釔安定氧化鋯(NiO-YSZ)基材之製作 33
3.5具規則圖案NiO-YSZ/YSZ之製作 33
3.5.1 YSZ電解質層之製備 33
3.5.2 NiO-YSZ/YSZ之還原處理 35
3.6材料特性分析 37
3.6.1掃瞄式電子顯微鏡分析 37
3.6.2 X射線繞射(XRD)分析 37
3.6.3熱重分析(TG)及熱差分析(DTA) 37
3.6.4 TMA分析 38
3.6.5 開孔孔隙率量測 38

第四章 結果與討論 39
4.1PDMS模具之製作 39
4.1.1曝光時間對於矽晶片表面SU8規則圖案型態之影響－圖案間距20μm 39
4.1.2曝光時間對於矽晶片表面SU8規則圖案型態之影響－圖案間距12μm 47
4.1.3 PDMS模具表面規則圖案之製作及觀察－圖案間距20μm 49
4.1.4 PDMS模具表面規則圖案之製作及觀察－圖案間隔12μm 55
4.2具規則圖案之NiＯ-YSZ基材之製作 58
4.2.1具規則圖案之NiO-YSZ坯體之SEM觀察 58
4.2.2具規則圖案之NiO-YSZ坯體之TG及DTA分析 65
4.2.3具規則圖案之NiO-YSZ胚體之TMA分析 67
4.2.4具規則圖案之NiO-YSZ基材之XRD分析 70
4.2.5具規則圖案之NiO-YSZ基材之SEM觀察 72
4.2.6不同尺寸之圖案其深寬比對於增加NiO-YSZ基材表面積之關係 76
4.3具規則圖案之NiO-YSZ基材於SOFC之應用 78
4.3.1具規則圖案之Ni-YSZ基板之XRD分析 79
4.3.2具規則圖案之Ni-YSZ基板之SEM觀察 82
4.3.3 Ni-YSZ陽極圖案與YSZ電解質接合情況之觀察 88

第五章 結論 90
參考文獻 92

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