磷酸燃料電池為現今最為普遍開發的燃料電池之一，磷酸作為電解質具有高電化學穩定特性，本實驗室使用聚苯並咪唑(PBI)作為磷酸的載體，扮演中間交換膜的角色，其操作溫度可高達200℃，此時白金觸媒便不容易被一氧化碳毒化，故磷酸燃料電池適合與甲醇重組氣整合使用。
欲將實驗成果商品化，長效性是非常重要的因素，在此前研究結果顯示，使用20wt%Pt商用觸媒製成的膜電極組在0.2A/cm2定電流密度、170℃操作溫度下，最高功率密度在100小時的長效時間內損失了27%，推測其中的原因是因為受酸性環境工作的影響，鉑會出現聚集、顆粒溶解、載體碳被腐蝕等現象造成。為了改善觸媒劣化的情形，選擇了兩種不同的方式。
方法一在碳球上佈植鎳後再從鎳顆粒上覆蓋鉑，形成外層鉑內層鎳的殼核形奈米粒子。鎳與鉑為同一族元素，同屬於面心立方結構，耐蝕性佳，是常用來與鉑混和作為合金觸媒的元素之一。而鎳與活性碳球間的吸附力較佳，較不易有剝落團聚的情形，且根據near surface effects，核元素與殼元素間接觸處會使殼元素之原子間距減少，且鍵結焓的變化能增進反應速率，以殼核結構之奈米粒子觸媒取代純鉑觸媒將提升觸媒穩定性與效能，長效性更加。
方法二使用鉑鎳合金於陰極觸媒，主要原因在於，鉑原子在二元合金中受到晶格扭曲，原子間收到拉伸應力的影響，使得合金表面對於氧中間體的吸附性降低，從而增進氧還原反應的進行，且合金奈米粒子因為是異相性的結構，與碳球間的吸附性佳，較不易有觸媒聚集、剝落的情形。結合以上兩因素，將能有效提升電池的效能與長效性。

Phosphoric acid fuel cell (PAFC) is one of the most commonly developed fuel cells for recent years. As an electrolyte, phosphoric acid has high electrochemical stability. We use polybenzimidazole (PBI) as a carrier of phosphoric acid, which acts as an intermediate exchange membrane. The operating temperature of PAFC can be as high as 200°C. It means that catalyst is not easily poisoned by carbon monoxide, so PAFC is suitable for integration with methanol reformer.
For the purpose of commercializing our research, durability is a very important factor. Previous research shows that peak power density of the membrane electrode assembly (MEA) made of 20wt% Pt commercial catalyst operating in the constant current density of 0.2A/cm2 and 170°C lost 27% in 100 hours. It is due to carbon carrier will be corroded makes platinum agglomeration and dissolution in acidic environment. In order to improve the situation, two different methods were selected.
Method One: planting nickel on carbon black before planting platinum. This method will generate a core-shell nanoparticle catalyst. Nickel is an element of the same group with platinum and both are face center cubic structure. It is the most commonly element mixing with platinum for alloy catalyst. Because the adsorption between nickel and carbon black is better, particle agglomeration will not be obvious. According to near surface effects, the contact in the core-shell interface will reduce the atomic distance of the shell element. Replacing pure platinum nanoparticle with core-shell nanoparticle will improve the durability and stability of the catalyst.
Method Two: using platinum-nickel alloy as the cathode catalyst. Because the distance between atomic Pt is shorter than pure platinum nanoparticle, catalyst has better absorption with oxygen. And the alloy nanoparticle is anisotropic material. The reason can lead to greater surface contact with the usual carbon support. With these two factors, the performance and durability of MEA will effectively improve.

摘要-----------------------------------------i
Abstract-----------------------------------iii
總目錄---------------------------------------v
表目錄--------------------------------------xii
第一章 緒論---------------------------------1
1-1 前言------------------------------------1
1-1-2 燃料電池市場應用------------------------2
1-2 燃料電池簡介------------------------------3
1-3 燃料電池種類原理--------------------------4
1-3-1質子交換膜燃料電池-----------------------5
1-3-2磷酸燃料電池-----------------------------6
1-3-3直接甲醇燃料電池--------------------------7
1-3-4鹼性燃料電池-----------------------------8
1-3-5固態氧化物燃料電池------------------------8
1-3-6熔融碳酸鹽燃料電池------------------------9
1-4 研究動機--------------------------------12
第二章 基本原理與文獻回顧----------------------13
2-1燃料電池基本結構---------------------------13
2-1-1 雙極板與集電板--------------------------13
2-1-2 氣體擴散層------------------------------14
2-2-2 微孔層----------------------------------15
2-1-3 觸媒層----------------------------------15
2-1-4 質子交換膜------------------------------16
2-2 燃料電池理論------------------------------17
2-2-1 電化學熱力學----------------------------17
2-2-2 電化學動力學----------------------------19
活性極化(activation polarization)-------------19
歐姆極化(ohmic polarization)------------------20
濃度極化(concentration polarization)----------20
2-3 燃料電池觸媒-----------------------------21
2-3-1 表面科學催化作用-------------------------21
2-3-2 結構敏感效應-----------------------------22
2-3-3 材料異向性(Anisotropy)的影響-------------22
2-3-4 Near Surface Effect--------------------22
2-3-5 d-Band Theory--------------------------23
2-4 各類型觸媒文獻回顧探討----------------------24
2-4-1 碳腐蝕與鉑團簇之關係與效能影響------------24
2-4-2 鉑鎳殼核觸媒研究-------------------------25
2-4-3 金屬氮化物之殼核研究----------------------26
2-4-4 鉑鎳合金與鉑鎳銥三元和金比較研究-----------29
2-4-5 奈米籠鉑鎳合金---------------------------31
2-5 儀器原理及操作-----------------------------33
2-5-1 掃描式電子微鏡---------------------------33
、能量色散光譜---------------------------------33
2-5-2 穿透式電子顯微鏡-------------------------33
2-5-3 化學分析電子能譜儀-----------------------33
2-5-4 感應耦合電漿原子發射光譜儀----------------34
2-5-5 X光繞射儀-------------------------------34
2-5-6 循環伏安法------------------------------34
2-5-7 單電池測試------------------------------35
第三章　實驗方法-------------------------------37
3-1 實驗流程----------------------------------37
3-2 實驗藥品與設備----------------------------38
3-2-1 藥品與耗材------------------------------38
3-2-2 實驗用氣體------------------------------39
3-2-3 實驗設備--------------------------------39
3-2-4 分析儀器--------------------------------40
3-3 燃料電池觸媒合成---------------------------40
3-3-1殼核觸媒製備-----------------------------40
3-3-2合金觸媒製備-----------------------------41
3-4 膜電極組製備與電池組裝---------------------42
3-4-1 電極製備--------------------------------42
3-4-2 膜電極組製備----------------------------42
3-4-3 電池測試--------------------------------43
第四章　結果與討論-----------------------------44
4-1 觸媒合成討論------------------------------44
4-1-1 商用觸媒長效形貌變化---------------------44
4-1-2 奈米鎳顆粒還原探討-----------------------45
4-1-3 殼核觸媒白金顆粒還原探討------------------47
4-1-4鉑鎳合金觸媒結果--------------------------53
第五章　結論-----------------------------------61
第六章　未來展望-------------------------------62
第七章 參考文獻--------------------------------63

[1]M. Mamlouk and K. Scott, "The effect of electrode parameters on performance of a phosphoric acid-doped PBI membrane fuel cell," International journal of hydrogen energy, vol. 35, no. 2, pp. 784-793, 2010.
[2]郭易宣, "一百瓦磷酸燃料電池系統及膜電極組優化," 國立清華大學碩士論文, 108年.
[3]N. Macauley et al., "Carbon corrosion in PEM fuel cells and the development of accelerated stress tests," Journal of The Electrochemical Society, vol. 165, no. 6, p. F3148, 2018.
[4]G. Diloyan, M. Sobel, K. Das, and P. Hutapea, "Effect of mechanical vibration on platinum particle agglomeration and growth in Polymer Electrolyte Membrane Fuel Cell catalyst layers," Journal of Power Sources, vol. 214, pp. 59-67, 2012.
[5]P. Ferreira, Y. Shao-Horn, D. Morgan, R. Makharia, S. Kocha, and H. Gasteiger, "Instability of Pt∕ C electrocatalysts in proton exchange membrane fuel cells: a mechanistic investigation," Journal of the Electrochemical Society, vol. 152, no. 11, p. A2256, 2005.
[6]Y. Zhai, H. Zhang, D. Xing, and Z.-G. Shao, "The stability of Pt/C catalyst in H3PO4/PBI PEMFC during high temperature life test," Journal of Power Sources, vol. 164, no. 1, pp. 126-133, 2007.
[7]M. L. Perry, T. Patterson, and C. Reiser, "Systems strategies to mitigate carbon corrosion in fuel cells," Ecs Transactions, vol. 3, no. 1, p. 783, 2006.
[8]G. Wang, H. Wu, D. Wexler, H. Liu, and O. Savadogo, "Ni@ Pt core–shell nanoparticles with enhanced catalytic activity for oxygen reduction reaction," Journal of Alloys and Compounds, vol. 503, no. 1, pp. L1-L4, 2010.
[9]K. A. Kuttiyiel, K. Sasaki, Y. Choi, D. Su, P. Liu, and R. R. Adzic, "Nitride stabilized PtNi core–shell nanocatalyst for high oxygen reduction activity," Nano letters, vol. 12, no. 12, pp. 6266-6271, 2012.
[10]F. Kong et al., "Active and stable Pt–Ni alloy octahedra catalyst for oxygen reduction via near-surface atomical engineering," ACS Catalysis, vol. 10, no. 7, pp. 4205-4214, 2020.
[11]V. R. Stamenkovic et al., "Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability," science, vol. 315, no. 5811, pp. 493-497, 2007.
[12]J. Greeley and M. Mavrikakis, "Near-surface alloys for hydrogen fuel cell applications," Catalysis Today, vol. 111, no. 1-2, pp. 52-58, 2006.
[13]P. Mani, R. Srivastava, and P. Strasser, "Dealloyed Pt− Cu core− shell nanoparticle electrocatalysts for use in PEM fuel cell cathodes," The Journal of Physical Chemistry C, vol. 112, no. 7, pp. 2770-2778, 2008.
[14]M.-k. Min, J. Cho, K. Cho, and H. Kim, "Particle size and alloying effects of Pt-based alloy catalysts for fuel cell applications," Electrochimica Acta, vol. 45, no. 25-26, pp. 4211-4217, 2000.
[15]A. Seo, J. Lee, K. Han, and H. Kim, "Performance and stability of Pt-based ternary alloy catalysts for PEMFC," Electrochimica Acta, vol. 52, no. 4, pp. 1603-1611, 2006.
[16]X. Tian et al., "Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells," Science, vol. 366, no. 6467, pp. 850-856, 2019.
[17]T. Toda, H. Igarashi, H. Uchida, and M. Watanabe, "Enhancement of the electroreduction of oxygen on Pt alloys with Fe, Ni, and Co," Journal of the Electrochemical Society, vol. 146, no. 10, p. 3750, 1999.
[18]IPHE, "Hydrogen and fuel cell global commercialization & development update," 2012.
[19]E. U. Ubong, "Safety issues in hydrogen transportation," in Proceedings: Electrical Insulation Conference and Electrical Manufacturing and Coil Winding Technology Conference (Cat. No. 03CH37480), 2003, pp. 395-401: IEEE.
[20]"維基百科Hydrogen station."
[21]楊雅筑, "燃料電池助無人機搶攻商用領域," 工業技術與資訊月刊, no. 339期, 民109 年4 月15 日.
[22]B. Viswanathan, "Fundamentals of Chemical Conversion Processes and Applications - Chapter 14 - Fuel Cells," Energy Source, pp. 329-356, 2017.
[23]R. He, Q. Li, G. Xiao, and N. J. Bjerrum, "Proton conductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic proton conductors," Journal of Membrane Science, vol. 226, no. 1-2, pp. 169-184, 2003.
[24]W. R. Grove, "XXIV. On voltaic series and the combination of gases by platinum," The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, vol. 14, no. 86-87, pp. 127-130, 1839/02/01 1839.
[25]J. Larminie, A. Dicks, and M. S. McDonald, Fuel cell systems explained. J. Wiley Chichester, UK, 2003.
[26]L. Burton, "Electrochemistry with DuPont’s Nafion membranes," in Tenth Int’l Symp on Electrosynthesis in the Chem Industry, 1996.
[27]本間琢也，上松宏吉, "燃料電池," 台灣:瑞昇文化, 2011.
[28]N. R. M.Muthukumar, C.Sasikumar, K.S.Kavin, M.Dharun, "A review on performance improvement of flow field design for PEM fuel cell," IJIAREC.
[29]王文琳、劉政宏, "低成本燃料電池雙極板技術發展現況," 工業材料雜誌328, 2014/04.
[30]P. L. Hentall, J. B. Lakeman, G. O. Mepsted, P. L. Adcock, and J. M. Moore, "New materials for polymer electrolyte membrane fuel cell current collectors," Journal of Power Sources, vol. 80, no. 1-2, pp. 235-241, 1999.
[31]J. Wind, R. Späh, W. Kaiser, and G. Böhm, "Metallic bipolar plates for PEM fuel cells," Journal of Power Sources, vol. 105, no. 2, pp. 256-260, 2002.
[32]M. Li, S. Luo, C. Zeng, J. Shen, and H. Lin, "Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments," Corrosion science, vol. 46, no. 6, pp. 1369-1380, 2004.
[33]Y. Ren and C. Zeng, "Corrosion protection of 304 stainless steel bipolar plates using TiC films produced by high-energy micro-arc alloying process," Journal of Power Sources, vol. 171, no. 2, pp. 778-782, 2007.
[34]L. Cindrella et al., "Gas diffusion layer for proton exchange membrane fuel cells—A review," Journal of Power Sources, vol. 194, no. 1, pp. 146-160, 2009.
[35]S. Park, J.-W. Lee, and B. N. Popov, "A review of gas diffusion layer in PEM fuel cells: Materials and designs," International Journal of Hydrogen Energy, vol. 37, no. 7, pp. 5850-5865, 2012.
[36]J. T. Gostick, M. A. Ioannidis, M. W. Fowler, and M. D. Pritzker, "On the role of the microporous layer in PEMFC operation," Electrochemistry Communications, vol. 11, no. 3, pp. 576-579, 2009.
[37]K.-D. Kreuer, S. J. Paddison, E. Spohr, and M. Schuster, "Transport in proton conductors for fuel-cell applications: simulations, elementary reactions, and phenomenology," Chemical reviews, vol. 104, no. 10, pp. 4637-4678, 2004.
[38]C. Marr and X. Li, "Composition and performance modelling of catalyst layer in a proton exchange membrane fuel cell," Journal of Power Sources, vol. 77, no. 1, pp. 17-27, 1999.
[39]SLADER.
[40]A. Chandan et al., "High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC)–A review," Journal of Power Sources, vol. 231, pp. 264-278, 2013.
[41]羅夢凡, "催化反應與表面科學," (Aug.12,2020) 2011.
[42]A. Wieckowski, Fuel cell catalysis: a surface science approach. John Wiley & Sons, 2009.
[43]G. A. Somorjai and J. Carrazza, "Structure sensitivity of catalytic reactions," Industrial & Engineering Chemistry Fundamentals, vol. 25, no. 1, pp. 63-69, 1986/02/01 1986.
[44]L. Bu et al., "Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis," Nature communications, vol. 7, no. 1, pp. 1-10, 2016.
[45]C. Koenigsmann, M. E. Scofield, H. Liu, and S. S. Wong, "Designing enhanced one-dimensional electrocatalysts for the oxygen reduction reaction: Probing size-and composition-dependent electrocatalytic behavior in noble metal nanowires," The Journal of Physical Chemistry Letters, vol. 3, no. 22, pp. 3385-3398, 2012.
[46]J. Witte, "ORR Catalysis with Pt-based CSNPs."
[47]H. Xin, A. Vojvodic, J. Voss, J. K. Nørskov, and F. Abild-Pedersen, "Effects of d-band shape on the surface reactivity of transition-metal alloys," Physical Review B, vol. 89, no. 11, p. 115114, 2014.
[48]M. G. Hosseini and R. Mahmoodi, "Preparation method of Ni@ Pt/C nanocatalyst affects the performance of direct borohydride-hydrogen peroxide fuel cell: Improved power density and increased catalytic oxidation of borohydride," Journal of colloid and interface science, vol. 500, pp. 264-275, 2017.
[49]K. A. Kuttiyiel et al., "Enhancement of the oxygen reduction on nitride stabilized pt-M (M= Fe, Co, and Ni) core–shell nanoparticle electrocatalysts," Nano Energy, vol. 13, pp. 442-449, 2015.
[50]R. Lin, L. Che, D. Shen, and X. Cai, "High durability of Pt-Ni-Ir/C ternary catalyst of PEMFC by stepwise reduction synthesis," Electrochimica Acta, vol. 330, p. 135251, 2020.
[51]李兰英, 肖英, 尚书勇, 戴晓雁, and 印永祥, "炭黑氧化改性的方法," 橡胶工业, vol. 51, no. 11, pp. 698-701, 2004.
[52]Z. Zhou, L. Han, and G. M. Bollas, "Kinetics of NiO reduction by H2 and Ni oxidation at conditions relevant to chemical-looping combustion and reforming," International Journal of Hydrogen Energy, vol. 39, no. 16, pp. 8535-8556, 2014.