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研究生： 鄭欽獻
Chin-Hsien Cheng
論文名稱： 燃料電池電解質奈米尺度離子動態輸送模擬
Ionic Dynamics of Nano-Scale Transport Phenomena inside Fuel Cell Electrolytes
指導教授： 洪哲文
Che-Wun Hong
口試委員:
學位類別： 博士
Doctor
系所名稱： 工學院 - 動力機械工程學系
Department of Power Mechanical Engineering
論文出版年： 2007
畢業學年度： 95
語文別： 英文
論文頁數： 109
中文關鍵詞： 燃料電池 、奈米尺度 、輸送現象 、分子動力學 、多尺度模擬
外文關鍵詞： Fuel Cell, Nano-scale, Transport Phenomenon, Molecular Dynamics, Multi-scale Modelling
相關次數： 點閱：2  下載：0 
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    • 摘要

    本論文使用分子動力學模擬對燃料電池電解質內之離子動態輸送現象進行研究分析。本論文研究之燃料電池種類主要是固態氧化物燃料電池（SOFC）以及質子交換模式燃料電池（PEMFC）。質子交換模式燃料電池電解質所選用之材料為Nafion，此材料為一高分子材料，至於固態氧化物燃料電池之電解質則選用了Yttria stabilized zirconia (YSZ) and yttria doped ceria (YDC)這兩種材料。
    氧離子在固態氧化物燃料電池電解質內部之傳遞現象為一非連續之跳躍行為，不同的Y2O3添加濃度以及不同溫度對氧離子傳導率的影響在本論文中也有深入的探討。模擬結果顯示Y2O3添加濃度對氧離子的傳導來說有一最佳的濃度（YSZ: 8.0 mol%以及YDC: 10.2 mol%）且溫度越高氧離子的傳導率越好。
    同時本論文也利用了分子動力學研究質子在不同的電解質(Nafion)水含量以及不同溫度下所展現的不同動態行為，這四個不同的水含量分別為3、 6.125、9以及 15.375 H2O/SO3-），三個不同的操作溫度分別為333K、343K和353K。研究結果顯示碳原子以及氟原子表現出了疏水的特性，而磺酸根(SO3-)的部分則表現出親水性的特性。質子在電解質內的傳遞效果隨著水含量以及溫度的增加而增加，因為磺酸根和水分子所形成的親水性傳遞區域會隨著水含量和溫度增加而變大。由模擬可以算出在不同操作條件下的質子擴散係數，所得到的值與實驗值的趨勢相當吻合。

    Nano-scale analyses were performed to investigate the ion transport phenomena inside fuel cell electrolytes. Molecular dynamics (MD) techniques were employed to carry out the ionic dynamics simulation. Example fuel cells involved in this thesis are solid oxide fuel cells (SOFCs) and proton exchange membrane fuel cells (PEMFCs). The chosen electrolytes for the SOFC are the traditional yttria stabilized zirconia (YSZ) and the modern yttria doped ceria (YDC), while the Nafion® polymer is for the PEMFC.
    The transport mechanism of oxygen ions inside the SOFC electrolyte is proved to be through non-continuous hopping between oxygen vacancies. Influences of Y2O3 concentrations and operation temperatures on the ionic conductivity were studied. Simulation results show that there exists an optimal concentration (8.0 mol% for YSZ and 10.2 mol% for YDC) for the nano-scale transport. Also higher operation temperature promotes the oxygen ion move-ability that increases the ionic conductivity.
    An investigation of proton dynamics at various hydration levels and thermal conditions inside the Nafion membrane has been carried out also based on the molecular dynamics technique. Semi-empirical quantum mechanics calculations were performed to optimize the complex molecular structure of the polymer. The atomistic simulation was conducted at four different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) and three different thermal conditions (333 K, 343 K and 353 K). Simulation results show that different ionic segregations toward the hydrophobic (near fluorocarbon) and hydrophilic (sulfonate acid groups) regions. It is also found that higher temperature enhances the size of the hydrophilic phase. The diffusion coefficients of protons (or hydroniums) at various conditions have been evaluated and the comparison with experimental data shows good agreements.

    TABLE OF CONTENT Abstract I Table of Content II List of figures IV List of Tables IX Nomenclature…………………………………………………………………...……IX Chapter 1 Introduction 1 1.1 Background 1 1.2 Introduction: PEMFC and SOFC 5 1.3 Motivation 7 1.4 Literature Survey 8 1.4.1 Computer Simulation about SOFC electrolyte 8 1.4.2 Computer Simulation about PEMFC electrolyte 11 Chapter 2 Molecular Dynamics Simulation of High Temperature and Low Temperature SOFC electrolytes (YSZ and YDC) 13 2.1 Atomistic Model…………………………………………………………….13 2.2 Interaction Potential Function 16 2.3 Simulation Process and Numerical Scheme 18 2.4 Results and Discussion 22 2.4.1 Monitoring equilibrium-YSZ 22 2.4.2 Ionic transport process-YSZ 26 2.4.3 Mean square displacement and ionic conductivity 30 2.4.5 Molecular structure-YSZ………… 34 2.4.6 System energies and ionic transport process-YDC………… 39 2.4.7 Mean square displacement and ionic conductivity-YDC 45 2.4.8 Molecular structure-YDC………… 50 Chapter 3 Molecular Dynamics Simulation of PEMFC electrolyte (Nafion®) 55 3.1 Atomistic Model………… 55 3.2 Interaction Potential Function 58 3.2.1 Intermolecular potential function 60 3.2.2 Intramolecular potential function …………………………………..61 3.3 Details of the Simulation……………….. 63 3.4 Results and Discussion………………… 65 3.4.1 System equilibrium………………………………………………….65 3.4.2 Dynamics of hydroniums and water molecules….………………....70 3.4.3 Molecular structure 74 3.4.4 Water clusters and aggregation analysis………… 81 3.4.5 Temperature effect analysis 83 Chapter 4 The Concept of Multi-scale Modeling 86 4.1. Semi-Empirical Relation 86 4.2. Implement into CFD Model with Electrochemistry Kinetics 88 4.2.1 CFD model………….……………………………………………….88 4.2.2 Results of the multi-scale modeling...……………………………….90 Chapter 5 Conclusions 96 5.1 MD Simulation of SOFC 96 5.2 MD Simulation of PEMFC 97 5.3 Concept of the Multi-Scale Modeling………………………………………98 5.4 Contributions 98 5.5 Future Work 100 References……………………………………………………………………..…102 LIST OF FIGURES Fig 1.1 Energy consumption tendency of the world 1 Fig 1.2 Annual energy consumption per person of selected Asia country 2 Fig 1.3 Carbon emission per person of selected Asia country 3 Fig 1.4 Different kinds of fuel cells and their characteristics 4 Fig 1.5 Schematic diagram of how fuel cell works 4 Fig 1.6 Schematic diagram of the Nafion® structure 6 Fig 1.7 Schematic diagram of the YSZ fluorite structure (single unit cell) 7 Fig 2.1 (a) System arrangement of the single unit cell (b) illustration of tetrahedral geometry (c) illustration of octahedral geometry………………...…………14 Fig 2.2 Initial positions of all atoms (8.0 mol%) (a) 3D view (b) XY plane view (c) YZ plane view (d) XZ plane view……...…………………….…………….15 Fig 2.3 Total potential energies of the simulation system for (a) different Y2O3 concentrations at 1273K and (b) different temperatures at 8.0 mol% 24 Fig 2.4 Temperature distributions of the simulation system for different Y2O3 concentrations at 1273K (a) 5.9 (b) 8.0 (c) 10.2 and (d) 12.5 mol% 25 Fig 2.5 Temperature distributions of the simulation system for different temperatures at 8 mol% of Y2O3………………………………………………………........26 Fig 2.6 (a)Three-dimensional trajectories of cations (Y3+ and Zr4+) and projections at (b)X-Y plane (c) X-Z plane and (d) Y-Z plane 28 Fig 2.7 Discrete hopping transport of an oxygen ion at (a) 1273K (b) 1759K (c) 2057K 29 Fig 2.8 (a) Mean square displacements of the simulation system and (b) the comparison of calculated oxygen ionic conductivities and experimental data [60] for 5.9 mol%, 8.0 mol%,10.2 mol% and 12.5 mol% at 1273K………32 32 Fig 2.9 Mean square displacements at different temperatures (a) 973k, 1073K, 173K and 1273K (b) 1759 and 2057k at 8.0 mol% 33 Fig 2.10 Comparison of calculated oxygen ionic conductivities and experimental data [60] for 973K, 1073K, 1173K, 1273K, 1759K and 2057K 34 Fig 2.11 Radial distribution functions of (a) Zr-Zr and (b) Y-Y ion pair for different Y2O3 concentrations at 1273K ......................................................................36 Fig 2.12 Radial distribution functions of (a) Zr-O and (b) Y-O ion pair for different Y2O3 concentrations at 1273K……………………………………………..37 Fig 2.13 Radial distribution functions of O-O ion pair (a) for different Y2O3 concentrations at 1273K and (b) for different temperatures at 8 mol% 38 Fig 2.14 Total potential energies of the simulation system for (a) different Y2O3 concentrations at 1023K and (b) different temperatures at 10.2 mol%.........40 Fig 2.15 Temperature distributions of the simulation system for different Y2O3 concentrations at 1023K (a) 5.3 (b) 8.0 (c) 10.2 (d) and (d) 12.5 mol%.......41 Fig 2.16 Temperature distributions of the simulation system for different temperatures at 10.2 mol%.................................................................................................42 Fig 2.17 (a)Three-dimensional trajectories of cations (Y3+ and Ce4+) and projections at (b)X-Y plane (c) X-Z plane and (d) Y-Z plane……………………………..43 Fig 2.18 Discrete hopping transport of oxygen ion at (a) 873K (b) 1173K (c) 1273K and (d) 1473K………..……………………………………………………..44 Fig 2.19 (a) Mean square displacements of the simulation system and (b) the comparison of calculated oxygen ionic conductivities and experimental data [61] for 5.3 mol%, 8.0 mol%,10.2 mol%, 14.9 mol% and 19.9 mol% at 1023K………………………………………………………………………47 Fig 2.20 Relation between the mobility of vacancies and number of vacancies at 1023K………………………………………………………………………48 Fig 2.21 (a) Mean square displacements of the simulation system and (b) the comparison of calculated oxygen ionic conductivities and experimental data [60, 61] for 873K, 973K, 1173K, 1273K, 1373K and 1473K at 10.2 mol%.............................................................................................................49 Fig 2.22 Radial distribution functions of (a) Ce-Ce and (b) Y-Y ion pair for different Y2O3 concentrations at 1023K Fig 3.1 Structure formula of Nafion® 51 Fig 2.23 Radial distribution functions of (a) Zr-O and (b) Y-O ion pair for different Y2O3 concentrations at 1023K…………………………..…………………52 Fig 2.24 Radial distribution functions of O-O ion pair (a) for different Y2O3 concentrations at 1023K and (b) for different temperatures at 10.2 mol%...53 Fig 2.25 Radial distribution functions of Y-vacancy ion pair for different Y2O3 concentrations at 1023K……………………………………………………54 Fig 3.1 Structure formula of Nafion, the subscript x equals 5-10, y equals 1000 and z equals 1-2…………………………………………………………………56 Fig 3.2 Molecular structure of Nafion fragment used in the MD simulation (correspond to x=7, y=1 and z=1 of real Nafion chemical structure shown in Fig. 3.1).. 57 Fig 3.3 Charge distribution of a single Nafion fragment 57 Fig 3.4 Structure and charge distribution of the hydroxonium (H3O+) 58 Fig 3.5 Structure and charge distribution of the water molecule 59 Fig 3.6 Schematic diagram of the van der Waals interaction 60 Fig 3.7 Schematic diagram of the valence bond interaction 61 Fig 3.8 Schematic diagram of the valence angle interaction 62 Fig 3.9 Schematic diagram of the torsion interaction 63 Fig 3.10 Total potential energies of the simulation system for different hydration levels (a) 3 H2O/SO3- (b) 6.125 H2O/SO3- (c) 9 H2O/SO3- and (d) 15.375 H2O/SO3- at a fixed temperature of 353K…………………………………66 Fig 3.11 Temperature distributions of the simulation system for different hydration levels (a) 3 H2O/SO3- (b) 6.125 H2O/SO3- (c) 9 H2O/SO3- and (d) 15.375 H2O/SO3- at a fixed temperature of 353K 67 Fig 3.12 Total potential energies of the simulation system for different temperature (a) 333K (b) 343K at a fixed water content of 15.375 H2O/SO3- 68 Fig 3.13 Temperature distribution of the simulation system for different temperatures (a) 333K (b) 343K at a fixed water content of 15.375 H2O/SO3-…………69 Fig 3.14 Density and volume of the MD simulation cell at different water contents 70 Fig 3.15 Mean square displacements (MSD) of (a)hydroniums and (b)water molecules for different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) at 353K 72 Fig 3.16 Comparison of the predicted (a) hydronium and (b) water diffusion coefficients between MD simulation and Experiments [68, 69] for different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) at 353K 73 Fig 3.17 Three-dimensional trajectory of a specific hydronium during the MD simulation period (small cyan sphere: oxygen atom of H3O+, large multi-colored sphere: sulfur atoms of SO3-) 74 Fig 3.18 Radial distributions of (a) carbon- Owater (b) fluorine- Owater and (c) ether-like oxygen- Owater for different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) at 353K 77 Fig 3.19 Radial distributions of (a) OSulfur-OWater and (b) OSulfur-OHydronium for different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) at 353K 78 Fig 3.20 Radial distributions of (a) OWater-OWater and (b) OHydronium -OHydronium for different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) at 353K 79 Fig 3.21 Radial distributions of OHydronium -OWater for different hydration levels (3, 6.125, 9 and 15.375 H2O/SO3-) at 353K………………………...…………80 Fig 3.22 Distribution of water clusters inside the system for water contents of (a) 3 (b) 6.125 (c) 9 and (d) 15.375 H2O/SO3- 82 Fig 3.23 Mean square displacements (MSD) of (a) hydroniums and (b) water molecules for different temperatures (333, 343 and 353K) at the water content of 15.375 H2O/SO3-………………………………………………..84 Fig 3.24 Distribution of water clusters inside the system at (a) 333K (b) 343K and (c) 353K………………………………………………………………………..85 Fig 4.1 Power curve fitting of the MD simulation results (973K, 1073K, 1173K, 1273K, 1759K and 2057K)……………………..…………………………87 Fig 4.2 Geometry of the SOFC model……………………………………………….88 Fig 4.3 (a) Velocity distribution and (b) pressure distribution of the SOFC…………92 Fig 4.4 Concentration distribution of the (a) anode (b) cathode of the SOFC…….....93 Fig 4.5 Temperature distribution of the SOFC (a) slice at XY plane (b) slice at YZ plane…………………………………………………………………94 Fig 4.6 Temperature distribution of the Electrolyte surface (a) anode side (b) cathode side…………………………………………………………………………95 LIST OF TABLES Table 2.1 Parameters for the Meyer-Buckingham pair potential function –YSZ [56]. 17 Table 2.2 Parameters for the Meyer-Buckingham pair potential function –YDC [56]. 17 Table 2.3 Amount of atoms under different concentration-YSZ 19 Table 2.4 Amount of atoms under different concentration-YDC 19 Table 2.5 Values of parameter used for 5th order differential equations [25] 21 Table 3.1 Corresponding numbers of molecules in different simulation cases 58 Table 4.1 Source terms of governing equations……………………………………...90

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