臺灣博碩士論文加值系統

全釩氧化還原液流電池（Vanadium Redox Flow Battery,VRFB）為目前最有潛力的儲能系統之一。VRFB的內部阻抗為影響電池充放電效率的重要因素。其中主要影響到釩電池內部阻抗的組件之一是雙極板。本論文使用金屬雙極板（Metallic Bi-polar Plate）來替代石墨雙極板，金屬雙極板有高導電度與良好機械物性，可以降低內部阻抗與提高電池體積功率密度。但金屬雙極板應用在VRFB中會有腐蝕的問題，因此本研究實驗不同的導電膠（Conductive Adhesive）的抗腐蝕性與導電性。結果發現以熱固膠摻石墨烯之導電膠與商用石墨導電膠的性能為較佳；但在抗腐蝕性方面含石墨烯重量百分比25％之石墨烯熱固膠為最佳。所以本研究將此導電膠塗佈至鎳金屬板上並測試各種單電池組合、電解液組成、充放電條件下的電池充放電特性。最佳狀況是在電流密度為40 mA/cm2 時的單電池充放電效率為67 ％。此外也用線性掃描伏安法與交流阻抗法等電化學技術測量單電池特性。結果顯示單電池內部阻抗沒有因導電膠與金屬雙極板的使用而明顯的降低。以體積功率密度來看本研究的金屬雙極板單電池可達20W/L已經接近商業化石墨雙極板的全釩氧化還原液流電池水準。

All-vanadium redox flow battery（VRFB） is one of the most promising energy storage system. Internal resistance of the VRFB is an important factor affecting the efficiency of battery charge/discharge. Bipolar plate is one of the components affects the internal resistance of VRFB. This study used the metallic bipolar plate instead of using the graphite bipolar plates. Metal bipolar plate has good electrical conductivity and mechanical properties. It can reduce the internal resistance and increase the volumetric power density of VRFB. Metallic bipolar plate has corrosion problem for VRFB applications. Therefore, this study tested electrical conductivity and corrosion resistance of various conductive adhesives. We found that graphene thermosetting adhesive and commercial graphite conductive adhesive have good performance among all the adhesives tested. Corrosion resistance of the thermosetting adhesive containing 25% graphene was the best. This conductive adhesive was coated on the nickel bi-polar plate. The charge/discharge characteristics of this single cell were tested at various cell configurations, electrolytes, and charge/discharge conditions. The best charge/discharge efficiency of this single cell was 66.8 ％ at current density of 40 mA/cm2. In addition, their single cell characteristics was measured by linear scan voltammetry and electrochemical impedance spectroscopy. Results suggested that the internal impedance did not significantly reduced by applying conductive adhesive and metallic bi-polar plate. The volumetric power density of this cell was 20 W/L. It was near the volumetric power density of commercial all vanadium redox flow battery.

口試委員會審定書 i
致謝 ii
摘要 iv
Abstract v
目錄 vii
圖目錄 x
表目錄 xiv
第一章　緒論 1
1.1前言 1
1.2研究動機與目的 6
第二章　文獻回顧 7
2.1氧化還原液流電池 7
2.1.1 氧化還原液流電池介紹 7
2.1.2 氧化還原液流電池種類 9
2.2全釩氧化還原液流電池 13
2.2.1 全釩氧化還原液流電池原理與特性 13
2.2.2 全釩氧化還原液流電池應用 16
2.3全釩氧化還原液流電池雙極板 18
2.3.1 雙極板簡介 18
2.3.2 雙極板改質 20
2.4電化學特性 23
2.4.1線性掃描伏安法 23
2.4.2 電化學交流阻抗法 26
第三章　實驗步驟與方法 28
3.1實驗藥品、物品 28
3.2實驗儀器 29
3.3實驗架構 30
3.4實驗內容 32
3.4.1耗材前處理與電解液製備 32
3.4.2製備導電膠 33
3.4.3單電池結構 35
3.4.4單電池組裝步驟 37
3.5電化學測試 42
3.5.1單電池充放電測試 42
3.5.2充放電循環測試 45
3.5.3線性掃描伏安與交流阻抗測試 47
第四章　實驗結果與討論 48
4.1 單電池充電量測結果 48
4.1.1 不同雙極板單電池充電曲線分析 48
4.1.2 塗上導電膠的金屬雙極板單電池充電曲線分析 53
4.1.2.1碳粉混合熱溶膠 53
4.1.2.2碳粉混合保利龍膠 54
4.1.2.3碳粉混合AB膠 56
4.1.2.4商用石墨導電膠 60
4.1.2.5石墨烯熱固膠 67
4.1.3塗上導電膠的石墨雙極板單電池充電曲線分析 75
4.2 充放電循環測試與充放電效率 77
4.2.1 深度充放電測試 77
4.2.2 淺充淺放循環測試 79
4.3線性掃描伏安分析 83
4.4交流阻抗分析 86
4.5 體積功率密度比較 90
第五章　結論與未來展望 91
5.1結論 91
5.2未來展望 93
參考資料 94

[1]BP, Energy Outlook 2035, Retrieved from
http://www.bp.com/content/dam/bp/pdf/Energy-economics/energy-outlook-2015/Energy_Outlook_2035_booklet.pdf
[2]能源教育知識網。儲能科技。
取自http://www.enedu.org.tw/Technology/
[3]鍾岳霖(2014)。全釩液流電池儲電系統模擬計算與電池充放電用LabView介面控制設計(未出版之碩士論文)。國立聯合大學。
[4]馬振基、謝曉峰、江仁吉、蕭閔謙、楊士賢、張立學(2012)。新型儲能電池--全釩液流電池的原理與發展現況。化學，70(3)，237-246。
[5]Skyllas-Kazacos, M., Chakrabarti, M. H., Hajimolana, S. A., Mjalli, F. S., ＆ Saleem, M. (2011). Progress in Flow Battery Research and Development. Journal of The Electrochemical Society, 158 (8) R55-R79.
[6]Weber, A. Z., Mench, M. M., Meyers, J. P., Ross, P. N., Gostick, J. T., ＆ Liu,Q. (2011). Redox flow batteries: a review. Journal of Appl Electrochem, 41, 1137-1164.
[7]Leon, C. P., Ferrer, A. F, Garcia, J. G., Szanto, D. A., ＆ Walsh, F.C. (2006). Redox flow cells for energy conversion. Journal of Power Sources,160, 716-732.
[8]Thaller, L. H. (1974). Electrically rechargeable redox flow cells. NASATM-X-71540.
[9]張華民、張宇、劉宗浩、王曉麗(2009)。液流儲能電池技術研究進展。化學進展，21(11)。
[10]Skyllas-Kazacos, M. (2003). Novel vanadium chloride/polyhalide redox flow battery. Journal of Power Sources, 124, 299–302
[11]Rychcil, M., ＆ Skyllas-Kazacos, M. (1988). Characteristics of a new all-vanadium redox flow battery. Journal of Power Sources, 22 .59-67.
[12]Tokuda,N. et. Al., (2000). Development of a Redox Flow Battery System. SEI technical review, N. 50, 88-95.
[13]H2, Inc,“What is VRFB（Vanadium Redox Flow Battery） ?”, Retrieved from http://www.h2aec.com/english/product/vrfb.asp
[14]桑玉(2006)。釩電池用電解液的製備極負極電解液穩定性研究(未出版之碩士論文)。中南大學。
[15]Perrin, M., Malbranche, P., Potteau, E. L., Willer, B., Soria, M.L., Jossen, A., Dahlen, M., Ruddell, A., Cyphelly, I., Semrau, G., Sauer, D.U., ＆ Sarre, G. (2006). Temperature behaviour: Comparison for nine storage technologies Results from the INVESTIRE Network. Journal of Power Sources,154, 545–549.
[16]Energy Globe, “Energy Globe Austria Award 2009” Retrieved from http://www.energyglobe.at/de_at/award/press-room/pressefotos/aktuell/nominierte-energy-globe-austria-award-2009/
[17]Sumitomo Electric,“Development of Micro Smart-Grid Demonstration System Sumitomo Electric” Retrieved from http://global-sei.com/news/press/11/11_21.html
[18]Caglar, B., Richards, J., Fischer, P., ＆ Tuebke , J. (2014). Conductive polymer composites and coated metals as alternative bipolar plate materials for all-vanadium redox-flow batteries. Advanced Materials Letters, 5(6), 299-308. doi:10.5185/amlett.2014.amwc.1023
[19]Liao, S. H., Yen, C. Y., Weng, C. C., Lin, Y. F., Ma, C. C., Yang, C. H., Tsai, M. C., Yen, M. Y., Hsiao, M. C., Lee, S. J., Xie, X. F., ＆ Hsiao, Y. H. (2008). Preparation and properties of carbon nanotube/polypropylene nanocomposite bipolar plates for polymer electrolyte membrane fuel cells. Journal of Power Sources,185 ,1225–1232.
[20]元智大學燃料電池中心。新型替代性雙極板研究室。取自
http://www.fuelcells.org.tw/equipment-detail.php?id=17
[21]李平惠、廖威量、林明俊(2012)。PPS複合填充材料雙極板成行品導電品質之研究。桃園創新學報， 32， 33-43。
[22]Qian, P., Zhang, H., Chen, J., Wen, Y., Luo, Q., Liu, Z., You, D., ＆ Y, B. (2008). A novel electrode-bipolar plate assembly for vanadium redox flow battery applications. Journal of Power Sources ,175, 613–620.
[23]Bontempelli, G. ＆ Toniolo, R. (2009). Electrochemical: Linear Sweep and Cyclic Voltammetry . Elsevier B.V.
[24]胡啟章(2011)。 電化學原理與方法。五南圖書出版公司。
[25]何為、唐先忠、王守緒、王磊(2005)。線性掃描伏安法與循環伏安法實驗技術。Experiment Science & Technology。
[26]SciMedia Ltd., “Linear Sweep Voltammetry”, Retrieved from https://www.uam.es/docencia/quimcursos/Scimedia/chem-ed/echem/linsweep.htm
[27]Ciucci, F., ＆ Chen, C. (2015). Analysis of Electrochemical Impedance Spectroscopy Data Using the Distribution of Relaxation Times: A Bayesian and Hierarchical Bayesian Approach. Electrochimica Acta,167,439–454.
[28]Orazem, M. E., ＆ Tribollet, B. (2008). Electrochemical Impedance Spectroscopy. Wiley Interscience.
[29]Barsoukov, E., ＆ Macdonald, J.R. (2005). Impedance Spectroscopy: Theory, Experiment, and Applications. Wiley-Interscience.
[30]曹楚南、張鑑清(2002)。電化學阻抗譜導論。科學出版社。
[31]Lai, W., ＆ Haile, S.M. (2005). Impedance Spectroscopy as a Tool for Chemical and Electrochemical Analysis of Mixed Conductors: A Case Study of Ceria. Journal of the American Ceramic Society,88,2979–2997.
[32] 劉彥廷(2014)。應用於電網儲能之釩基液流電池特性分析(未出版之碩士論文)。國立聯合大學。