臺灣博碩士論文加值系統

全釩液流電池(VRFB，vanadium redox flow battery)是目前最為成熟的MW級儲電技術。於含再生能源的電網中，VRFB要發揮儲電的功能，電池的電解液充電程度(SOC，state-of-charge)必須即時精確估算。現以量測電解液開路電壓(OCV，open circuit voltage)再估算電池SOC的狀態。透過理論模擬的方式驗證無法透過OCV檢測手法得知SOC和電解液濃度間的正確變化。
本研究將發展以吸收光譜與氧化還原電位滴定等這兩種電解液分析方法並評估計算電解液SOC的可行性。電解液分為釩電解液3.5(外購)和釩電解液4.0(自行配製)兩種。在電解液不同SOC下，結果發現在UV-VIS吸收光譜有幾個主要吸收峰。利用這些吸收峰可以判斷釩離子種類與濃度。釩電解液4.0中正極SOC = 10 %與SOC = 50 %的主峰波長為420 nm與615 nm，SOC = 90 %波長為765 nm。負極SOC = 10 %與SOC = 50 %波長為770 nm，SOC = 90 %波長為420與610 nm。
釩電解液3.5中的正極SOC = 10 %與SOC = 50 %波長為765nm，SOC = 90 %波長無法檢測。負極SOC = 10 %與SOC = 50 %波長為410 nm與770 nm，SOC = 90 %波長為610 nm。電解液中各種釩離子會交互影響，造成吸收峰波長的偏移。此外，實驗發現電池正、負極電解液中的釩離子皆有相互摻混的現象。數學模式可以模擬出各別的SOC下UV的結果，最終仍要以氧化還原電位滴定來補強各別SOC下的精確度。
氧化還原電位滴定分析先以V2+、V3+、VO2+純釩電解液測試。結果驗證電位滴定可以偵測到各價釩離子的濃度。接著以釩電解液3.5與釩電解液4.0在SOC= 10%、50%、90%測試。釩電解液4.0的各個SOC狀態下的正、負極電解液測定結果與理論預期有相同的趨勢。驗證電解液SOC可以使用電位滴定技術分析。電解液分析發現電解液在電池充放電時會有相互摻混的現象。這與UV-Vis光譜分析結果相似。釩電解液3.5因取樣問題，沒有特定結論。V2+離子滴定終點電位範圍在118-309 mV vs. AgCl/Ag、V3+離子滴定終點電位範圍在645-703 mV、VO2+離子滴定終點電位範圍在865-941 mV。
在金屬雙極板實驗上，導電膠製程將以高溫爐烘烤已塗佈導電膠金屬雙極板，避免產生氣泡式結構出現。導電膠製成雙極板的電池充放電性能效果雖然不佳，但可以降低碳氈燒焦的損耗。單電池體積功率密度可達22 W dm-3，充放電效率69%。

Vanadium redox flow battery (VRFB) is currently the most mature technology of MW-level electricity storage. In order for VRFB to play a vital function as energy storage in the power grid containing renewable energy, the battery SOC (state-of-charge) must be in-situ and accurately estimated. At present, the open circuit voltage of the electrolyte (OCV) is used to estimate the SOC. From theoretical calculation result, the battery SOC cannot be estimated by measuring battery OCV along.
This project develops two analytical methods to assess the electrolyte SOC and to evaluate their technical feasibility. They are absorption spectroscopy and redox electrode potential titration. Two electrolytes, electrolyte 3.5 is purchased from commercial vendor and electrolyte 4.0 is lab-prepared electrolyte are used for this purpose.
With the electrolyte at different SOC, we found that there are several major absorption peaks in the UV-VIS absorption spectrum. Using these peaks can determine the type and concentration of vanadium ions. For electrolyte 4.0, electrolyte sampled from positive electrode at SOC = 10% and SOC = 50%, major absorption peak at wavelength of 420 nm and 615 nm were observed. At SOC = 90%, peak wavelength of 765 nm was observed. Electrolyte sampled from the negative electrode at SOC = 10% and SOC = 50%, major peak at wavelength of 770 nm was observed. At SOC = 90%, at wavelength of 420 to 610 nm were observed.
For electrolyte 3.5, sampled from the positive electrode at SOC = 10% SOC = 50%, peak at wavelength of 765 nm was observed. At SOC = 90%, no peak can be detected. Sampled from the negative electrode, at SOC = 10% SOC = 50%, peak at the wavelength of 410 nm and 770 nm were observed. At SOC = 90%, peak at the wavelength of 610 nm was observed. The wave length of major peak are shift due to the interaction among vanadium ions in the electrolyte. In addition, experiments found that vanadium ions in the positive electrode and in the negative electrode are crossover each other. Mathematical models can simulated the UV-Vis spectra at different SOC. However, spectra results at different SOC need the redox potentiometric titration result to enhance its accuracy.
Redox potential titration analysis is tested with electrolyte containing pure V2+, V3+, VO2+ ions. The test results verify that the potentiometric titration can detect concentrations and types of various vanadium ions. Then this method is tested with electrolyte 3.5 and electrolytic 4.0 sampled from positive electrode and negative electrode at SOC = 10%, 50%, 90%, respectively. Tested results shown that experimental measurement is consisted with theoretical predictions. The battery SOC can be analyzed using the potentiometric titration techniques. The titration result also indicated that there is a crossover phenomenon between positive and negative electrolyte during battery charge and discharge. This is similar to the observed results of UV-Vis spectroscopy. Due to sampling problem, titration of electrolyte 3.5 has no specific conclusions. V2+ ion end point potential range is 118-309 mV vs. AgCl/Ag. V3+ ion end point potential range is 645-703 mV. VO2+ ion end point potential range is 865-941 mV.
In the metal bipolar plate experiment, the baking of metal bipolar plate coated with conductive adhesive is carried out in high-temperature furnace to avoid air bubbles formation. The charge/discharge performance of battery with various conductive adhesive metal bipolar plates is less that we expected. The single cell volumetric power density reach 22 W dm-3 and charge-discharge efficiency of 69%.

誌謝 I
摘要 II
ABSTRACT IV
目錄 VI
圖目錄 X
表目錄 XV
符號表 XVII
第一章　緒論 1
1.1前言 1
1.2 電池電量的評估 8
1.3 研究動機與目的 9
第二章　文獻回顧 10
2.1氧化還原液流電池 10
2.1.1氧化還原液流電池介紹(原理與特性) 10
2.1.2 氧化還原液流電池種類 12
(1) 鐵/鉻氧化還原液流電池 12
(2) 溴/聚硫化物氧化還原液流電池 12
(3) 釩/溴氧化還原液流電池 12
(4) 鋅/溴氧化還原液流電池 13
(5) 鐵/釩氧化還原液流電池 13
(6) 鹼性離子陰極氧化還原液流電池 13
2.2 全釩氧化還原液流電池 14
2.2.1 全釩氧化還原液流電池原理與特性 14
2.2.2 全釩氧化還原液流電池優點及應用 17
2.3 電解液分析 19
2.3.1 UV-VIS吸收光譜介紹(原理與特性) 19
2.3.2 UV-VIS吸收光譜分析 21
2.3.3 氧化還原電位滴定法介紹(原理與特性) 23
2.3.4氧化還原電位滴定釩離子 25
2.4 石墨烯熱固導電膠 28
第三章　實驗步驟與方法 31
實驗藥品及耗材 31
實驗儀器 32
3.1 整體實驗步驟 33
3.2 耗材前處理與電解液製備 34
3.3 單電池元件備製與組裝 35
3.3.1鎳金屬集電板 35
3.3.2石墨雙極板 36
3.4 電池充電SOC推估與取樣方法 37
3.5 UV-VIS吸收光譜 38
3.6 UV-VIS吸收光譜模擬計算 39
3.7 氧化還原電位滴定 40
3.8 氧化還原電位滴定模擬計算 41
3.9 石墨烯熱固導電膠 43
第四章　實驗結果與討論 44
4.1單電池充放電OCV與SOC的關係量測結果 44
4.2 UV-VIS吸收光譜分析 47
4.2.1 UV-VIS吸收光譜分析-純價位 47
4.2.2 UV-VIS吸收光譜分析-電解液3.5 51
4.2.2.1 UV-VIS吸收光譜分析-電解液3.5 SOC = 10 % 51
4.2.2.2 UV-VIS吸收光譜分析-電解液3.5 SOC = 50 % 54
4.2.2.3 UV-VIS吸收光譜分析-電解液3.5 SOC = 90 % 57
4.2.3 UV-VIS吸收光譜分析-電解液4.0 62
4.2.3.1 UV-VIS吸收光譜分析-電解液4.0 SOC = 10 % 62
4.2.3.2 UV-VIS吸收光譜分析-電解液4.0 SOC = 50 % 64
4.2.3.3 UV-VIS吸收光譜分析-電解液4.0 SOC = 90 % 66
4.3. 氧化還原電位滴定法 71
4.3.1 氧化還原電位滴定法-純價位 71
4.3.2 氧化還原電位滴定法-電解液3.5 75
4.3.2.1 氧化還原電位滴定法-電解液3.5 SOC = 10 % 77
4.3.2.2 氧化還原電位滴定法-電解液3.5 SOC = 50 % 80
4.3.2.3 氧化還原電位滴定法-電解液3.5 SOC = 90 % 83
4.3.3 氧化還原電位滴定法-電解液4.0 87
4.3.3.1 氧化還原電位滴定法-電解液4.0 SOC = 10 % 87
4.3.3.2 氧化還原電位滴定法-電解液4.0 SOC = 50 % 90
4.3.3.3 氧化還原電位滴定法-電解液4.0 SOC = 90 % 93
4.3.4 氧化還原電位滴定法-滴定結果計算 97
4.3.4 氧化還原電位滴定法-滴定曲線模擬 101
4.4 石墨烯熱固膠製程 104
第五章　結論與未來展望 109
5.1結論 109
5.2未來展望 110
附錄 111
1 氧化還原電位滴定法-電解液4.0 SOC = 10 % 111
2 氧化還原電位滴定法-電解液4.0 SOC = 50 % 114
3 氧化還原電位滴定法-電解液4.0 SOC = 90 % 117
參考資料 121

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