國立臺灣師範大學博碩士論文全文系統

簡易檢索 / 詳目顯示

回結果列表

研究生：	張軒誌 hsuan chih Chang
論文名稱：	三價離子摻雜於電解質BaZrO3的導電趨勢 Trends of the Ionic Conductivity of Cation-Doped Barium Zirconates
指導教授：	王禎翰 Wang, Jeng-Han
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	136
中文關鍵詞：	電解質、固態氧化物燃料電池、BaZrO3
英文關鍵詞：	electrolyte, SOFC, barium zircornate
論文種類：	學術論文
相關次數：	點閱：175 下載：4
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

本實驗為探討BaZr1-xMxO3， (M = In3+、Y3+、 Yb3+、 Dy3+、 Gd3+、 Sm3+、 Nd3+、 La3+)不同摻雜金屬的導電趨勢，並利用計算的結果去解釋。實驗部分為使用燃燒法合成不同濃度的摻雜金屬，並使用XRD、SEM、EDX、ICP-MS來確認物理及化學性質。再把粉末壓錠，並燒結於1250、1450、1600 ℃，持溫5、10、40小時，形成BaZr1-xMxO3 試片，進行導電度測試，通入氣氛為濕-空氣、濕-氫氣、乾-氮氣、乾-氫氣。
　　計算部分為使用密度泛涵理論(DFT)計算摻雜於BaZrO3的氧空缺(V_o^(..))及氫缺陷的形成能以及氧空缺、氫缺陷、氫氧空缺移動的反應熱。
　　由實驗及計算的結果顯示，導電率會隨著摻雜的濃度增加或持溫時間降低而上升，燒結溫度對導電率的影響則不大。從化學的觀點來看，導電率會受到摻雜金屬的離子半徑所影響，較小的離子半徑，導電率佳，且計算出來的反應熱低。

Trends of the ionic conductivity of BaZr1-xMxO3, (M = In3+, Y3+, Yb3+, Dy3+, Gd3+, Sm3+, Nd3+, La3+) have been experimentally and computationally examined in this work. Experimentally, the powder with different dopant ratios , 2%, 5%, 10% and 20%, has been initially synthesized by GNP (glycine nitrate process) method, and it physical and chemical properties have been examined by XRD, SEM, EDX and ICP-Mass (Inductively coupled plasma mass spectrometry). The synthesized powder is further pressurized and sintered at different temperatures, 1250, 1450 and 1600 oC and heating period, 5, 10 and 40 hours, to form BaZr1-xMxO3 pellets for the conductivity tests in various atomspheres: dry N2, dry H2, wet air and wet H2. Computationally, formation energies of oxygen vacancy V_o^(..) and proton defect OH_o^' and enthalpy of V_o^(..) migration, proton hopping and OH_o^' diffusion of the doped BaZrO3 have been systematically examine by the means of density functional theory (DFT) calculation.
　　Based on the experimental and computational works, the results show that the ionic conductivity will increase as the dopant ratio raises and the sinter period decreases. The sinter temperature has limited effect on the conductivity. From the chemical aspect, the conductivity is systematically influenced by the ionic radius of the doped cation. The small radius of the dopant results a better conductivity from the experimental measurement and lower enthapy in the DFT calculation.

誌謝    2
中文摘要    3
英文摘要    4
目錄    6
圖表目錄    10

第一章    固態氧化物燃料電池介紹    14
    1-0 緒論    14
    1-1燃料電池    15
       1-1-1 燃料電池原理    15
       1-1-2 燃料電池種類    17
    1-2固態氧化物燃料電池(SOFC)    19
       1-2-1固態氧化物燃料電池簡介    19
       1-2-2固態氧化物燃料電池結構    19
    1-3固態電解質    21
       1-3-1 螢石結構    22
       1-3-2 鈣鈦礦結構    23
       1-3-3 電解質傳導機制    24
    1-4 文獻回顧    25
第二章    實驗與計算方法    28
    2-0實驗藥品列表    28
    2-1 粉末製備    29
       2-1-1 燃燒法    29
       2-1-2 溶膠-凝膠法(sol-gel)    32
       2-1-3 水熱法    34
    2-2 BaZr1-xMxO3-α試片與導電測量裝置    36
       2-2-1 試片成型與燒結條件    36
       2-2-2 導電度測量裝置    36
    2-3 儀器介紹    38
       2-3-1 X光繞射分析    38
       2-3-2 顯微結構分析(SEM)    38
       2-3-3 能量散射光譜儀(EDX)    39
       2-3-4 感應耦合電漿質譜儀(ICP-MS)    39
       2-3-5 導電率分析(conductivity)    40
       2-3-6 活化能分析(activity)    41
    2-4 計算方法介紹    42
       2-4-1 DFT原理    42
       2-4-2 計算方法    47
第三章    結果與討論    51
    3-1  實驗部分    51
    3-1-1合成粉末與燒結體的結構分析    51
       3-1-1-1以燃燒法合成BaZr1-xMxO3-α粉末結構分析    51
       3-1-1-2 燒結1450 ℃持溫5小時結構分析    53
    3-1-2 BaZr1-xMxO3-α粉末EDX分析及ICP-MS分析    54
       3-1-2-1 BaZr1-xMxO3-α粉末EDX分析    54
       3-1-2-2 BaZr1-xMxO3-α粉末ICP-MS分析    60
    3-1-3 BaZr1-xMxO3-α燒結前後的顯微結構分析    61
       3-1-3-1 比較以燃燒法及溶膠凝膠法的顯微結構差異    61
       3-1-3-2 BaZr1-xMxO3-α燒結後顯微結溝分析    62
    3-1-4導電性質分析    74
       3-1-4-1 1450℃下不同摻雜濃度對導電度影響    74
       3-1-4-2 不同溫度對導電度影響    84
       3-1-4-3持溫時間對導電度影響(1450 ℃)    94
       3-1-4-4同一條件不同摻雜離子比較    104
    3-1-5交流阻抗分析    113
    3-2 計算部分    116
       3-2-1 氧離子移動活化能，反應熱和氧空缺形成能    117
       3-2-2 氫離子移動活化能,反應熱和氧空缺形成能    119
       3-2-3 氫氧根離子移動活化能和反應熱    121
    3-3 實驗和計算的比較    123
第四章    結論    126
第五章    未來展望    127

文獻    128
                                

1. Gorte, S. M. a. R. J., Direct Hydrocarbon Solid Oxide Fuel Cells. Chem. Rev 2004, 104, 4845-4865.
2. Hsin-Lung Lin *, R.-K. C., Chun-Lin Kuo, Chih-Wei Chang, Synthesis of BaCeO3 powders by a fast aqueous citrate–nitrate process. Journal of Non-Crystalline Solids 2007, 353, 1188-1194.
3. M. D. Gross, J. M. V. a. R. J. G., Recent progress in SOFC anodes for directutilization of hydrocarbons. J. Mater. Chem 2007, 17, 3071-3077.
4. C. Brahim a, A. R. a., M. Cassir a,*, M. Putkonen b, L. Niinisto¨ b, Electrical properties of thin yttria-stabilized zirconia overlayers produced by atomic layer deposition for solid oxide fuel cell applications. Applied Surface Science 2007, 253, 3962-3968.
5. David A. Andersson*†, S. I. S., Natalia V. Skorodumova§, Igor A. Abrikosov‡, and Bo¨ rje Johansson*, Optimization of ionic conductivity in doped ceria. PNAS 2006, 103, 3518-3521.
6. R.O. Fuentesa, b., R.T. Bakerb, Synthesis and properties of Gadolinium-doped ceria solid solutions for IT-SOFC electrolytes. I NTERNATI ONAL JOURNAL OF HYDROGEN ENERGY 2008, 33, 3480-3484.
7. Embs, A. B. Æ. S. D. Æ. P. R. Æ. J., Proton diffusivity in the BaZr0.9Y0.1O3-δ proton conductor. J Appl Electrochem 2009, 39, 471-475.
8. Fumitada Iguchi a, Noriko Sata a, Takao Tsurui b, Hiroo Yugami, Microstructures and grain boundary conductivity of BaZr1-xYxO3 (x=0.05, 0.10, 0.15) ceramics. 2007.
9. Katsuhiro Nomura , H. K., Transport properties of Ba(Zr0.8Y0.2)O3-δ perovskite. Solid State Ionics 2007, 178, 661-665.
10. Peter Babilo, T. U., Sossina M. Haile, Processing of yttrium-doped barium zirconate for high proton conductivity. J. Mater. Res 2007, 22, 1322-1330.
11. Schober, H. G. B. a. T., Electrical Conductivity of the High-Temperature Proton Conductor BaZr0.9Y0.1O2.95. J. Am. Ceram. Soc 2000, 83, 768-772.
12. T. Schnellera, T. Schoberb, Chemical solution deposition prepared dense proton conducting Y-doped BaZrO3 thin films for SOFC and sensor devices. Solid State Ionics 2003, 164, 131-136.
13. V. P. Gorelov*, V. B. B., Yu. N. Kleshchev**, and V. P. Brusentsov**, Preparation and Electrical Conductivity of BaZr1-xRxO3–δ(R = Sc, Y, Ho, Dy, Gd, In). INORGANIC MATERIALS 2001, 37, 636-640.
14. Wensheng Wang, A. V. V., Ionic and electron–hole conduction in BaZr0.93Y0.07O3-δ by 4-probe dc measurements. Journal of Power Sources 2005, 142, 1-9.
15. Cristian D. Savaniu, J. C.-V. a. J. T. S. I., Investigation of proton conducting BaZr0.9Y0.1O2.95 : BaCe0.9Y0.1O2.95
core–shell structures. J. Mater. Chem 2005, 15, 598-604.
16. E. Gorbova a, V. M., D. Medvedev a, A. Demina,1, P. Tsiakaras b, Investigation of the protonic conduction in Sm doped BaCeO3. Journal of Power Sources 2008, 181, 207–213.
17. Gaetano Chiodellia, L. M. a., b,∗, Cristina Tealdi b, Simona Barisonc, Marino Battagliarin c, Lioudmila; Doubovac, M. F., Cecilia Mortalo` c, Rosalba Gerbasi d, Role of synthetic route on the transport properties of BaCe1-xYxO3 proton conductor. Journal of Alloys and Compounds 2009, 470, 477-485.
18. Guilin Ma*, H. M., Hiroyasu Iwahara, Ionic conduction and nonstoichiometry in non-doped BaxCeO 3-α. Solid State Ionics 1999, 122, 237-247.
19. Hee Jung Park ∗, C. K., Kyu Hyoung Lee, Sang Mock Lee, Eun Sung Lee, Interfacial protonic conduction in ceramics. Journal of the European Ceramic Society 2009, 29, 2429-2437.
20. Jin-Xia Wang a, L.-P. L. b., ∗, Branton J. Campbell b, Zhe Lvc,; Yuan Ji a, Y.-F. X., Wen-Hui Sua,c, Structure, thermal expansion and transport properties of BaCe1-xEuxO3-δ oxides. Materials Chemistry and Physics 2004, 86, 150–155.
21. Kui Xiea, R. Y., Xiaorui Chena, SonglinWanga, Yinzhu Jiangc,; Xingqin Liua, Guangyao Menga, A stable and easily sintering BaCeO3-based proton-conductive electrolyte. Journal of Alloys and Compounds 2009, 473, 323–329.
22. P. Pasierb∗, M. W., S. Komornicki, M. Rekas, Electrochemical impedance spectroscopy of BaCeO3 modified by Ti and Y. Journal of Power Sources 2009, 194, 31–37.
23. Robert C.T. Slade a~* , S. D. F. a., Narendra Singh a,b, Investigation of protonic conduction in Yb- and Y-doped barium zirconates. Solid State Ionics 1995, 82, 135-141.
24. T. Hea**, K. D. K., Yu.M. Baikovb, J. Maiera, Impedance spectroscopic study of thermodynamics and kinetics of a Gd-doped BaCeO3, single crystal. Solid State Ionics 1997, 95, 301-308.
25. W. Suksamai, I. S. M., Measurement of proton and oxide ion fluxes in a working Y-doped BaCeO3 SOFC. Solid State Ionics 2007, 178, 627–634.
26. He Wang, R. P., w Xinfeng Wu, Jinlin Hu, and Changrong Xia, Sintering Behavior and Conductivity Study of Yttrium-Doped BaCeO3–BaZrO3 Solid Solutions Using ZnO Additives. J. Am. Ceram. Soc 2009, 92, 2623-2629.
27. Jinxia Li, J.-L. L., Karl T. Chuang, Alan R. Sanger, Chemical stability of Y-doped Ba(Ce,Zr)O3 perovskites in H2S-containing H2. Electrochimica Acta 2008, 53, 3701-3707.
28. J. Wu, R. A. D., ‡ M. S. Islam,*,‡ and S. M. Haile*,†, Atomistic Study of Doped BaCeO3: Dopant Site-Selectivity and Cation Nonstoichiometry. Chem. Mater. 2005, 17, 846-851.
29. Tor S. Bjørheim a, A. K. b., Istaq Ahmed c, Reidar Haugsrud a, Svein Stølen a, Truls Norby a, A combined conductivity and DFT study of protons in PbZrO3 and alkaline earth zirconate perovskites. Solid State Ionics 2010, 181, 130-137.
30. M. E. Arroyo y de Dompablo, ‡ Yueh-Lin Lee,§ and D. Morgan§, First Principles Investigation of Oxygen Vacancies in ColumbiteMNb2O6(M=Mn, Fe, Co, Ni, Cu). Chem. Mater. 2010, 22, 906-913.
31. Thangadurai, F. T. a. V., Transformation of Proton-Conducting Perovskite-Type into Fluorite-Type Fast Oxide Ion Electrolytes Using a CO2 Capture Technique and Their Electrical Properties. Inorg. Chem. 2008, 47, 8972-8984.
32. Wei Wei, Y. D., * Meng Guo, Lin Yu, and Baibiao Huang, Density Functional Characterization of the Electronic Structure and Optical Properties of N-Doped, La-Doped, and N/La-Codoped SrTiO3. J. Phys. Chem 2009, 113, 15046–15050.

簡易檢索 / 詳目顯示

相關論文