臺灣博碩士論文加值系統

本文為以石墨氈電極改質與電解液流場改良其對全釩氧化還原液流電池(Vanadium Redox Flow Battery, VRFB)性能之影響，進行實驗探討，本研究先更改實驗配置改善電池電容量快速衰退的問題，藉由離子交換膜改質中性能最佳者做後續實驗，在固定電解液、電流密度、離子交換膜對前處理、硝酸改質、混酸改質、王水改質4種不同石墨氈在電流密度40mA/cm2做20次充放電循環實驗。實驗結果發現以Nafion/SiO2改質離子交換膜配合王水改質石墨氈有最佳的性能。同樣的參數比較在電流密度20mA/cm2、80mA/cm2對電池效能的影響，以40mA/cm2為最佳電流密度，由結果可知以Nafion/SiO2改質離子交換膜配合王水改質石墨氈在電流密度40mA/cm2有最高的電容量、約80%的能量效率。
再以上述離子交換膜改質以及石墨氈改質方式對具有螺旋環狀(Spiral Patten)、交叉蛇狀(Serpentine Patterns)流道傳電石墨板之電池做20次充放電循環，但結果不如預期理想，估計原因為流道減少石墨板和石墨氈的接觸面積提高了局部區域的電流密度，進而提高極化程度，後續在流道石墨板中填充碳紙，雖有改善電池性能但仍低於使用無流道石墨板。
最後利用硫酸-鹽酸混合液調配高濃度電解液(3M V4+)，配合Nafion/SiO2改質膜、王水改質石墨氈在電流密度40mA/cm2做20次充放電循環實驗，相較於使用一般濃度電解液(1.5M V4+)，可提高1.86倍的電容量和小幅度的能量效率。

關鍵字: 全釩氧化還原液流電池、石墨氈改質、王水、電容量、能量效率。

In this study, effect of electrode modification on the vanadium redox flow battery (VRFB) performance was experimentally investigated. The material used for the electrode is graphite felt (GF) which was modified using chemical method. Three types of acidic solutions, nitric acid, dual acid (solution of nitric and sulfuric acids), and aqua regia (solution of nitric acid and Hydrochloric acids), were used to chemically modifying the electrode surface electrochemical activity by soaking the GF in these solutions. The VRFB performance with pretreated electrode (simply removing impurity) was used as the comparison basis. With the current density of 40 mA/cm2, SiO2 modified Nafion 117 as the membrane, and 1.5M VOSO4 as electrolyte, it was found that the aqua regia soaked GF has the optimal performance with lower electric capacity decay rate and energy efficiency as high as 80%.
Using the aqua regia soaked GF as electrodes, VRFB performance was studied under various current densities, electrolyte flow patterns, and electrolyte concentrations. For the current density varied in the range of 20~80 mA/cm2, it was found that current density of 40 mA/cm2 produces the best results. With electrolyte flow pattern modified by using serpentine and spiral channels, it was found that the flow pattern did not play a significant role in enhancing the VRFB performance. With carbon papers filled in these channels, no improvement in VRFB performance can be found. The reason may be attributed to the reduction in contact area between the electrode and electrolyte. With the electrolyte concentration increased from 1.5M VOSO4 to 3.0M VOSO4, it was found that the electric capacity was doubled while the energy efficiency kept unchanged.

Keywords: Vanadium redox flow battery, Graphite felt modification, Aqua regia, Electric capacity, Energy efficiency

摘要 i
Abstract ii
目錄 iii
表目錄 v
圖目錄 v
第一章緒論 1
1.1前言 1
1.2儲能系統簡介 1
1.2.1 超級電容儲能簡介 2
1.2.2 熱能儲存簡介 2
1.2.3 鋰電池簡介 3
1.2.4 氧化還原液流電池簡介 4
1.３ 文獻回顧 5
1.4研究動機與目的 8
第二章 理論基礎 9
2.1 全釩氧化還原液流電池原理 9
2.2電池常用性能指標 9
第三章 研究方法與實驗步驟 11
3.1 研究方法 11
3.2 電池設計與組成 11
3.3 石墨氈改質 13
3.4 流道設計 14
3.5 電解液的製備 14
3.6 實驗步驟 15
第四章 結果與討論 23
4.1 基礎電池操作參數 23
4.2電解液儲存槽改良對電池效能的影響 23
4.3 離子交換膜之選用 24
4.4 石墨氈改質對電池性能之影響 25
4.5流道對電池效能之影響 26
4.6高濃度電解液對電池效能之影響 27
第五章 總結與未來研究方向 42
5.1 總結 42
5.2 未來研究方向 43
參考文獻 44
附錄 47
附錄1.實驗藥品 47
附錄2.實驗器材 47

[1] 韋光華 “綠色能源—發電與儲能” 科學發展 (2010)
[2] 袁國輝 “電化學電容器” 化學工業出版社(2006)
[3] T. Kousksou, P. Bruel, A. Jamil, T. El Rhafiki, Y. Zeraouli, “Energy storage: Applications and challenges,” Solar Energy Materials & Solar Cells 120 (2014) 59¬¬-80
[4] 台灣區冷凍空調工程工業同業公會工程技術暨業務發展委員會編輯 “空調儲冰系統簡介”
[5] 程新群 “化學電源” 化學工業出版社 (2008)
[6] F. Diaz-Gonzaleza, A.Sumper, O. Gomis-Bellmunta, R.Villafafila-Roblesb, “A review of energy storage technologies for wind power applications,” Renewable and Sustainable Energy Reviews 16 (2012) 2154-2171
[7] M. Skyllas-Kazacos, M. Rychcik, R.G. Robins, A.G. Fane, “New all- vanadium redox cell,” Journal of the Electrochemical Society 133 (1986) 1057-1058
[8] S.S. Hosseiny, M. Saakes, M. Wessling, “A polyelectrolyte membrane - based vanadium/air redox flow battery,” Electrochemistry Communications 13 (2011) 751-754
[9] F. Rahman, M. Skyllas-Kazacos, “Vanadium redox battery: positive half-cell electrolyte studies,” Journal of Power Sources 189 (2009) 1212–1219
[10] L. Li, S. Kim, W. Wang, M. Vijayakumar, Z. Nie, B. Zhang, G. Xia, J. Hu, G. Graff, J. Liu, Z. Yang, “A Stable vanadium redox-flow battery with High energy density for large-scale energy storage,” Advanced Energy Materials 1 (2011) 394- 400
[11] S.K. Park, J. Shim, J. Yang, C.S. Jin, B. Lee, Y.S. Lee, K.H. Shin, J.D. Jeon, “Effect of inorganic additive sodium pyrophosphate tetrabasic on positive electrolytes for a vanadium redox flow battery,” Electrochimica Acta 121 (2014) 321-327
[12] J. Liu, S. Liu, Z. He, H. Han, Y. Chen, “Effects of organic additives with oxygen- and nitrogen-containing functional groups on the negative electrolyte of vanadium redox flow battery,” Electrochimica Acta 130 (2014) 314-321
[13] J. Xi, Z. Wu, X. Qiu, L. Chen, “Nafion/SiO2 hybrid membrane for vanadium redox flow battery,” J. Power Sources 166 (2007) 531–536
[14] J. Qiu, M. Zhai, J. Chen, Y. Wang, J. Peng, L. Xu, J. Li, G. Wei, “Performance of vanadium redox flow battery with a novel amphoteric ion exchange membrane synthesized by two-step grafting method,” Journal of Membrane Science 342 (2009) 215-220
[15] D. Chen, S. Kim, V. Sprenkle, M.A. Hickner, “Composite blend polymer membranes with increased proton selectivity and lifetime for vanadium redox flow batteries,” Journal of Power Sources 231 (2013) 301-306
[16] K.J. Kim, Y.J. Kim, J.H. Kim, M.S. Park, “The effects of surface modification on carbon felt electrodes for use in vanadium redox flow batteries,” Materials Chemistry and Physics 131(2011) 547-553
[17] L. Yue , W. Li, F. Sun , L. Zhao , L. Xing, “Highly hydroxylated carbon fibres as electrode materials of all-vanadium redox flow battery,” Carbon 48 (2010) 3079-3090
[18] W. Zhang, J. Xi, Z. Li, H. Zhou, Le Liu, Z. Wua, X. Qiu, “Electrochemical activation of graphite felt electrode for VO2+/VO2+ redox couple application,” Electrochimica Acta 89 (2013) 429-435
[19] C. Flox, J. Rubio-Garcı´a, M. Skoumal, T. Andreu, J.R. Morante, “Thermo-chemical treatments based on NH3/O2 for improved graphite-based fiber electrodes in vanadium redox flow batteries,” Carbon 60 (2013) 280-288
[20] Z. Wei, J. Zhao, M. Skyllas-Kazacos, B. Xiong, “Dynamic thermal-hydraulic modeling and stack flow pattern analysis for all-vanadium redox flow battery,” Journal of Power Sources 260 (2014) 89-99
[21] 吳政益 “電解液靈動型態對全釩氧化還原電池效能影響之實驗探討” 碩士論文,中興大學機械工程學系(2011)
[22] 龔盈瑝 “電解液與碳氈改良對全釩氧化還原電池性能改善之實驗探討” 碩士論文, 中興大學機械工程學系 (2012)
[23] 劉柏彥 “薄膜改良對全釩氧化還原電池性能改善之實驗探討” 碩士論文, 中興大學機械工程學系 (2013)
[24] N. Zhu, X. Chen, T. Zhang, P. Wu, P. Li, J. Wu, “Improved performance of membrane free single-chamber air-cathode microbial fuel cells with nitric acid and ethylenediamine surface modified activated carbon fiber felt anodes,” Bioresource Technology 102 (2011) 422–426.
[25] A. Di Blasi, O. Di Blasi, N. Briguglio, A.S. Aricò, D. Sebastián, M.J. Lázaro, G. Monforte, V. Antonucci, “Investigation of several graphite-based electrodes for vanadium redox flow cell,” J. Power Sources 227 (2013) 15-23