質子交換膜燃料電池以其具有高能量轉換效率和低污染等特色，已成為倍受矚目的新能源技術。然而阻礙燃料電池的研發，除了功率密度的提升，昂貴的催化劑也限制了它的實用化。由於燃料電池為化學能直接轉換電能的裝置，電化學反應速率直接影響電池的發電效率，故針對電化學反應式中各反應物的傳遞現象進行分析，才能有效解決質量傳輸受阻問題，而電極結構為影響質量傳輸受阻的最大原因，因此若能藉由控制電極結構參數如電極孔隙率、氣體擴散層厚度及觸媒表面積等，使反應物的質量傳輸獲得改善，可望提高燃料電池的功率密度約10%。有鑑於此，本文將以質量傳輸的觀點來探討電極結構與電化學反應間的關係，建構一套以電化學反應為核心的理論模型，並進行燃料電池的性能分析。
　　
　　本研究以陰極反應為觀點，對各反應物之傳輸現象進行描述，首先根據電極內含水量變化，推估氧氣傳輸之有效擴散係數，並由Fick定律建立氧氣擴散方程。其次以交換電流密度、觸媒表面積和氧氣溶解濃度變化，對Butler-Volmer反應方程進行修正。最後利用歐姆定律描述電子與質子傳導，並透過物種守恆的觀念，推導出陰極過電位方程，以建構出電池內部質量傳輸、電化學反應及電子與質子傳導等估算方法，並整合為質子交換膜燃料電池理論模型。隨即將此理論模型進行電腦化，以系統化的方法快速求得電池輸出電壓。經由理論模擬結果與文獻實驗資料比對，證實本研究所建構之理論模型的正確性與可行性後，深入分析電極結構與外在控制參數對電池性能之關係。
　　
　　本研究以電化學反應為核心，並將質子交換膜含水量納入考量，建構出質子交換膜燃料電池理論模型。其Nafion含量與Pt載量理論估算值與文獻實驗值相互比對後，發現平均誤差為8.83%和8.16%，證實本文理論可精確預估燃料電池的電壓輸出。本文進一步針對電極結構進行分析，研究顯示增加電極孔隙率和觸媒表面積有助於提高氧氣的質量傳輸行為和電化學反應的進行，而氣體擴散層厚度對性能提升的影響甚微，故可根據此結果來改善電極結構並降低觸媒的使用量。在外在操作參數之影響方面，研究發現增加進氣壓力和工作溫度皆可提高功率密度，其中以壓力的影響最為顯著，可提供設計人員在應用上參考使用。最後藉由觸媒層結構最佳化與車輛電力供應等兩項應用，說明反應物之傳遞特性和電池堆設計流程，研究結果證實功率密度可提高7.98 %和單電池數目可減少3片，其中功率密度未能達成預期之目標，可能原因為電化學反應之生成水未能納入考量，導致氧氣質量傳輸不佳，但本文所提之理論模型仍具有實用價值。

　　PEMFC is now a noticeable energy technology with its high rate of energy transformation and low pollution properties. However, the research and development of the fuel cell, was hindered in many aspects except the improvement of the density of power. It is practically crucial that the expensive catalyst was the major limited obstacle. Because the fuel cell is the device that exchanges the electric energy directly for chemical energy. The electric speed of chemical reaction influences the power generating efficiency of the battery directly, so analyse to the transmission phenomenon of every reactant in the electric chemical equation, could solve quality effectively and is transmitted. In order to improve the quality to transmit the greatest obstructed, one can make the quality of the reactant transmitted and being improvedded by controlling the structure parameters of the electrodes. The improvement can also made on the density of power of the battery and utilization ratio of the catalyst. To clarify this problem, this study tries to explore the internal mass transfers, the electrochemical reactions, and their relationships with the electrode structure of the full cell, and also to construct a theoretical model and simulation package to further analyze, and to precisely control the real voltage output of the PEMFC.
　　
　　This study used the equation of cathode reaction to describe the transmission phenomenon of every reactant. Firstly, to estimate the effective diffusion coefficient of hydrogen transmitting rate by measuring the varying of water content in the electrode. Next, to correct the electrochemical reaction equation by referring to the varying of exchange current density, surface area of catalyst, and oxygen dissolution consistency. Finally, to describe the electron and proton conduction by the Ohm's law, followed the species conservation idea to derive the over-potential equation in order to estimate the mass transmission in battery, electrochemical reaction and electron/proton conduction, and integrate those inferences into a theory model for PEMFC. Following the construction of theoretical model, one can compute the output voltage of the battery quickly with the computer simulation program. By comparing simulated result of this study with experiment materials in references, proved the correctness and feasibility of the models constructed by this study. And, the effects of electrode structure that affects the performance, and the influence of the external control parameters on the system output can then be analyzed.
　　
　　By comparing the estimated value in PEMFC theory constructed by this study to which provided in the prevalent document, it is found that the average error falls within the engineering acceptable level, which verifies that the actual output voltage of fuel cell can be estimated accurately by the theory of this study. Through the verification by applying optimized catalyst layer structure and the supply of electric power of vehicle, the model constructed by this study is proved to be feasible and practical.

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