氧化鎳助燒結技術應用於薄膜電解質固態氧化物燃料電池

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陳廷嘉(Ting-Chia Chen) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

氧化鎳助燒結技術應用於薄膜電解質固態氧化物燃料電池
(NiO-assisted sintering of thin-film BaCe0.6Zr0.2Y0.2O3-δ electrolyte for proton–conducting solid oxide fuel cells)

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摘要(中)

本研究以固相反應法合成質子傳導氧化物BaCe0.6Zr0.2Y0.2O3-δ (BCZY)電解質粉末，並將BCZY配置成電解質懸浮液以旋轉塗佈技術製備電解質薄膜，並探討添加助燒結劑於薄膜化電解質之影響。當添加3 wt% NiO至BCZY中，晶粒適當的成長且有效提升電解質燒結性質，使得電解質層數可從三層減少至兩層，進而縮短離子傳輸距離，且避免連通孔洞所造成之漏氣狀況。將添加NiO之兩層BCZY與三層BCZY之電池相比，於800 ℃下，最高功率密度可由61 mW/cm2提升至101 mW/cm2，除了有效減少質子傳輸之阻礙，由於電解質結構更為緻密使得電解質與陰、陽極有效反應面積將有所提升，於800 ℃下，總阻抗由5.81 Ωcm2降低至4.13 Ωcm2。於固相反應法中添加助燒結劑NiO，相較於溶膠-凝膠法、燃燒法等濕化學合成方法，其材料成本較低、製程方便且保持良好質子傳導性，因此更能實際應用於固態氧化物燃料電池之製程中。

摘要(英)

Small amounts of sintering agent NiO added to the calcined BCZY powders are known to promote the grain growth and to accelerate the densification of the NiO-modified BCZY at relatively low temperature. The purpose of this study is to investigate the effect of sintering agent NiO on the performance of proton-conducting SOFC single cell. Proton-conducting oxide (BaCe0.6Zr0.2Y0.2O3-δ, BCZY) powders were synthesized by solid-state reaction method. The electrolyte suspension was prepared by mixing 0-10 wt% with BCZY electrolyte powder and binder PVP in pure ethanol. The uniform suspension was spread onto NiO-BCZY composite anode support by spin coating. A thin, dense and crack free BCZY electrolyte film was successfully obtained after sintering at 1500 ℃. Single cells comprising of LSCF/BCZY(0-10 wt% NiO)/NiO-BCZY were then fabricated and tested for their electrochemical performance at 550-800 ℃. The results showed that cell performance was improved by addition of NiO to enhance the electrolyte sinterability in cells with reduced electrolyte layers. The maximum power density was increased from 61 mW/cm2 to 101 mW/cm2 at 800 ℃. The result of EIS measurement indicates that the addition of NiO can reduce ohmic resistance as well as polarization resistance for the cell, resulting in the improved cell performance.

關鍵字(中)

★ 助燒結劑
★ 固態氧化物燃料電池
★ 電解質
★ 旋轉塗佈

關鍵字(英)

★ SOFC
★ sintering agent
★ proton-conducting
★ spin coating

論文目次

摘要……………………………………………………………………………………………………………………………i
Abstract………………………………………………………………………………………………………………ii
致謝……………………………………………………………………………………………………………………………iv
目錄……………………………………………………………………………………………………………………………v
圖目錄…………………………………………………………………………………………………………………viii
表目錄………………………………………………………………………………………………………………………xi
前言………………………………………………………………………………………………………………………………1
第一章、實驗原理與文獻回顧…………………………………………………………………………3
1.1. 固態氧化物燃料電池(SOFC)………………………………………………………………3
1.1.1. SOFC之原理……………………………………………………………………………………………3
1.1.2. SOFC之優點……………………………………………………………………………………………5
1.1.3. SOFC之結構……………………………………………………………………………………………6
1.2. SOFC電解質材料…………………………………………………………………………………………8
1.2.1. 螢石(Fluorite)結構…………………………………………………………………………9
1.2.2. 鈣鈦礦(Perovskite)結構及性質………………………………………………11
1.2.3. 質子傳輸型電解質………………………………………………………………………………11
1.2.4. 質子傳輸機制…………………………………………………………………………………………13
1.3. 電解質粉末合成方法………………………………………………………………………………14
1.3.1. 固態反應法(Solid-state reaction method)…………………14
1.3.2. 水熱法(Hydrothermal method)…………………………………………………15
1.3.3. 溶膠-凝膠法(Sol-gel method)…………………………………………………15
1.3.4. 燃燒法(Combustion)…………………………………………………………………………16
1.3.5. 共沉澱法(Co-precipitation method)…………………………………16
1.4. SOFC電解質製備方法………………………………………………………………………………16
1.4.1. 乾壓成型技術(Dry pressing technique)……………………………16
1.4.2. 刮刀成型技術(Tape casting technique)……………………………17
1.4.3. 旋轉塗佈技術(Spin coating technique)……………………………18
1.4.4. 電子束蒸鍍(Electron beam coating technique)……………19
1.4.5. 雷射脈衝沉積(Pulse laser deposition technique)…………19
1.5. 粉末燒結理論………………………………………………………………………………………………………20
1.5.1. 燒結過程……………………………………………………………………………………………………………20
1.5.2. 燒結擴散機制…………………………………………………………………………………………………21
1.6. 電化學分析原理………………………………………………………………………………………………24
1.6.1. 極化曲線(I-V curve)之原理………………………………………………………………24
1.6.2. 電化學交流阻抗頻譜之原理……………………………………………………………………27
1.6.3. 等效電路之簡介………………………………………………………………………………………………28
第二章、實驗方法……………………………………………………………………………………………………………31
2.1. 實驗藥品………………………………………………………………………………………………………………31
2.2. 實驗方法與流程………………………………………………………………………………………………31
2.2.1. BaCe0.6Zr0.2Y0.2O3-δ粉末合成……………………………………………………31
2.2.2. 刮刀成型技術製備陽極基板………………………………………………………………32
2.2.3. 單電池製備………………………………………………………………………………………………………32
2.3. 材料性質分析…………………………………………………………………………………………………………33
2.3.1. X光粉末繞射儀…………………………………………………………………………………………………33
2.3.2. 掃描式電子顯微鏡…………………………………………………………………………………………33
2.4. 單電池I-V性能量測……………………………………………………………………………………………33
2.5. 電化學交流阻抗分析…………………………………………………………………………………………34
第三章、結果與討論…………………………………………………………………………………………………………35
3.1. 材料性質分析…………………………………………………………………………………………………………35
3.1.1. 煆燒粉末形貌分析…………………………………………………………………………………………35
3.1.2. 微結構分析…………………………………………………………………………………………………………37
3.1.3. 低掠角XRD相鑑定分析…………………………………………………………………………………45
3.2. 單電池I-V性能曲線測量與分析……………………………………………………………………45
3.3. 單電池之EIS測量與分析…………………………………………………………………………………48
第四章、結論………………………………………………………………………………………………………………… 50
參考文獻………………………………………………………………………………………………………………………………51

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指導教授

李勝偉(Sheng-Wei Lee)

審核日期

2018-7-30

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