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研究生: 羅濬辰
Chun-chen Lo
論文名稱: 鈉離子電池電化學與傳輸現象模擬分析
Numerical Analysis of Electrochemical and Transport Phenomenon in Sodium Ion Battery
指導教授: 曾重仁
Chung-jen Tseng
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 機械工程學系
Department of Mechanical Engineering
論文出版年: 2014
畢業學年度: 103
語文別: 中文
論文頁數: 234
中文關鍵詞: 鈉離子電池一維傳輸現象二維傳輸現象熱與電化學耦合數值模擬
外文關鍵詞: sodium-ion battery, one dimensional transport, two dimensional transport, coupled electrochemistry and heat transfer, numerical analysis
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  • 本研究利用鈉離子電池與鋰離子電池質傳機制的共通點,建立一維等溫鈉離子電池模型、二維等溫鈉離子電池模型及二維熱與電化學耦合鈉離子電池模型,並從以往文獻的實驗參數範圍做各項物理性質的參數測試,探討各項參數在各模型下對於鈉離子電池定電流放電下的影響性。
    本文建立的一維模型傳輸機制用來探討鈕扣型電池的傳輸現象,二維模型用來探討圓柱型電池的傳輸現象。本文的模型包含集電板、電極與隔膜,多孔電極模型預測則參考Newman學者所做的假設,利用許多球體結構堆疊排列作為電極多孔結構的模型。鈉離子的傳輸現象以擴散方式傳遞,電化學反應由多孔壁面鈉離子通量模擬嵌入或嵌出電極的濃度值。透過商用軟體COMSOL求解本研究的數值模型問題。
    研究結果顯示電化學反應愈劇烈,正極還原反應消耗的鈉離子速率愈快,當其速率大於由負極產生並傳遞至正極之鈉離子速率時,正極還原反應將受到影響而不穩定,故達截止電壓所放出的電容量愈低。因此放電速率、電極擴散係數、電解液體積分率及導電率皆對電池電容量及穩定性有很大的關係。定電流放電下,負極參數改變較正極影響來大,由於放電過程中,負極需進行氧化反應產生鈉離子與電子,並傳輸至正極,若負極產生鈉離子速率降低或是傳遞速率降低,正極必定因鈉離子濃度降低導致還原反應受到影響。
    螺旋纏繞式電池設計不但可節省電池體積,並聯的原理可以大幅提升電池之電容量,亦可承受較大的放電速率。電化學反應所產生的熱源包括焦耳熱與熵變化產生的熱,由於鈉離子電池能承受的放電速率比鋰離子電池低,在各項條件下,除非放電時間較長,否則鈉離子電池的溫度變化都較鋰離子電池小。


    In this work, we consider the transport mechanism of sodium-ion battery, and build one dimensional, two dimensional models. With physical property values obtained from literature, we investigate the effects of various parameters on the electrical characteristics of sodium-ion batteries.
    The one dimensional sodium-ion battery model is for the simulation of coin cell. Two dimension sodium-ion battery model is for the simulation of cylinder battery. Computational domain includes current collectors, electrodes and separator. Porous electrode is assumed to be made up of spherical particles. Sodium-ion are transported by diffusion, insertion and de-insertion processes. Numerical calculation are performed using the COMSOL software.
    Results show that the more violent of the electrochemical reaction, the more rapidly sodium ion is consumed in the reduction reaction at the positive electrode. When the consumption rate is greater than the rate of sodium ion supply from the negative electrode, the reduction reaction at the positive electrode becomes unstable. Therefore, the discharge rate, electrode diffusion coefficient, the volume fraction of the electrolyte, and conductivity all affect the capacity and stability of a battery. For constant current discharge, properties of negative electrode have greater impact on battery performance than that of positive electrode. This is because sodium ions and electrons are generated at and supplied by the negative electrode.
    Spiral wound battery design not only saves battery size, but also significantly enhance the capacity of batteries by the principle of parallel connection. In addition, it can withstand higher discharge rates. Heat released during a chemical reaction comes from the Joule heat and heat transfer associated with entropy change. Because the chemical reaction rate of a sodium ion battery is lower than that of a lithium ion battery, the heat release rate is smaller for the former. Therefore, the temperature change in a sodium-ion battery is smaller than that in a lithium-ion battery for the same discharging time.

    中文摘要 I 英文摘要 III 誌謝 V 目錄 VI 圖目錄 X 表目錄 XXIX 符號說明 XXX 一、緒論 1 1-1研究動機與背景 1 1-2鈉離子電池原理與結構 2 1-2-1基本原理 2 1-2-2基本結構 3 1-3文獻回顧 6 1-3-1鋰離子電池模型研究 6 1-3-2鈉離子電池特性研究 10 1-4研究目的 14 二、理論分析 15 2-1模型幾何外型 15 2-2鈉離子電池之數學模型 16 2-2-1基本假設 16 2-2-2基本方程式 16 2-2-3統御方程式 18 2-4邊界條件與初始條件 24 2-4-1邊界條件 24 2-4-2初始條件 29 三、數值方法 30 3-1有限元素法 30 3-2程式驗證 30 3-3網格驗證 31 四、結果與討論 35 4-1一維等溫鈉離子電池傳輸現象與放電性能分析 35 4-1-1放電速率對電池放電性能之影響 35 4-1-2電解液中鈉離子擴散係數對電池放電性能之影響 37 4-1-3鈉離子遷移數對電池放電性能之影響 38 4-1-4正極材料中鈉離子擴散係數對電池放電性能之影響 39 4-1-5負極材料中鈉離子擴散係數對電池放電性能之影響 40 4-1-6正極材料球體半徑對電池放電性能之影響 41 4-1-7負極材料球體半徑對電池放電性能之影響 42 4-1-8正極材料中電解液體積分率對電池放電性能之影響 42 4-1-9負極材料中電解液體積分率對電池放電性能之影響 43 4-1-10正極材料導電率對電池放電性能之影響 44 4-1-11負極材料導電率對電池放電性能之影響 45 4-2二維等溫鈉離子電池傳輸現象與放電性能分析 46 4-2-1放電速率對電池放電性能之影響 47 4-2-2電解液中鈉離子擴散係數對電池放電性能之影響 48 4-2-3鈉離子遷移數對電池放電性能之影響 49 4-2-4正極材料中鈉離子擴散係數對電池放電性能之影響 50 4-2-5負極材料中鈉離子擴散係數對電池放電性能之影響 51 4-2-6正極材料球體半徑對電池放電性能之影響 51 4-2-7負極材料球體半徑對電池放電性能之影響 52 4-2-8正極材料中電解液體積分率對電池放電性能之影響 53 4-2-9負極材料中電解液體積分率對電池放電性能之影響 54 4-2-10正極材料導電率對電池放電性能之影響 54 4-2-11負極材料導電率對電池放電性能之影響 55 4-3二維電化學與熱耦合鈉離子電池與二維等溫鈉離子電池比較 55 4-3-1熱物理性質參數分析 56 4-3-2電解液中鈉離子擴散係數對電池放電性能之影響 57 4-3-3鈉離子遷移數對電池放電性能之影響 58 4-3-4正極材料中鈉離子擴散係數對電池放電性能之影響 58 4-3-5負極材料中鈉離子擴散係數對電池放電性能之影響 59 4-3-6正極材料球體半徑對電池放電性能之影響 59 4-3-7負極材料球體半徑對電池放電性能之影響 60 4-3-8正極材料中電解液體積分率對電池放電性能之影響 60 4-3-9負極材料中電解液體積分率對電池放電性能之影響 61 4-3-10正極材料導電率對電池放電性能之影響 62 4-3-11負極材料導電率對電池放電性能之影響 62 五、結論與建議 64 5-1結論 64 5-1-1一維等溫鈉離子電池 64 5-1-2二維等溫鈉離子電池 65 5-1-3二維熱與電化學耦合鈉離子電池 65 5-2未來工作建議 65 參考文獻 67

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