臺灣博碩士論文加值系統

傳統鉛酸電化學電池在連續快速充放電過程中會產生不可逆之硫酸鉛，造成電極硫化電池壽命減短，最終導致電池失效，因此，常見於鉛膏中添加碳材，再塗佈於鉛格子體，抑制硫化現象，增加電池效能。但是，鉛和碳無法接合，通常利用物理方式接合，隨電池電化學反應進行，鉛膏中的活性材料容易脫落，常導致電極衰竭電池失效。所以，本論文希望藉由酸氧化及化學含浸法在碳材表面沉積鉛，以提高碳材與鉛的潤濕性。
本論文共選用六種碳粉，由中油提供的A、B、C、D與E粉，及市售AC碳粉，先以鉛片與碳粉熱壓的方式確認鉛碳潤濕性，與鉛接合效果不好的碳粉則是以不同方式進行鉛修飾，提升鉛碳接合性。其中E粉與鉛接合效果最佳，鉛液可以完全包覆E粉形成鉛碳複合材；A、B、C與D粉和鉛接合性不佳，先後嘗試硝酸氧化、Hummers氧化、化學含浸法等方式，改善鉛碳潤濕性。同時透過TGA、FTIR及XPS分析瞭解E粉的化學性質，推斷其與鉛潤濕的機制，並由AC碳粉驗證。
A、B與C三種粉的比表面積在1~5m^2/g之間，即使經改質後鉛修飾的成功率仍然不高，D粉與E粉同樣具有高比表面積且氧含量高，D粉鉛修飾成功率高。透過TGA、FTIR及XPS分析可知E粉具有C-O-C、C-OH、C=O、COOH等基團且均在8~10at.%，TGA分析顯示COOH基團在100~400℃快速裂解，鉛碳熱壓溫度只到350℃，因此，推判COOH官能團促進鉛碳熱壓的接合度。驗證組AC粉因此選擇硝酸氧化促進COOH基團，AC經氧化後C-OH、C-O-C、COOH官能團增加，C=O減少，TGA分析結果，COOH基團在200℃明顯裂解，AC粉經硝酸氧化後與鉛熱壓也成功形成鉛碳複合材料。
電化學循環伏安(CV)測試結果，純鉛片經50次循環，Pb/PbSO_4氧化電流峰值不超過50mA/cm2。六種碳粉以及粉材經鉛修飾後與鉛熱壓組成鉛碳電極，其Pb/PbSO_4氧化還原電流皆提升，除了B粉外，其餘粉材經鉛修飾後，Pb/PbSO_4氧化電流更高，其中D粉原材與鉛修飾後最高(氧化電流最高可達180 mA/cm2)。C粉和AC粉則發現其較活潑，鉛修飾前後水解產氫電流皆很高(C和AC粉水解產氫電流最高分別達-720、-645mA/cm2)。E粉與鉛潤濕性佳， 鉛碳(E粉)鉛碳電極經50圈循環後，氧化電流最高可達116 mA/cm2。

The conventional lead-acid battery failed due to sulfation of the negative electrode during the continuous and quickly charge-discharge process. Carbon materials are added to electrode paste to improve battery efficiency. But, lead and carbon cannot be combined, and they are usually combined by physical contact. And the active material in the electrode paste is easy to fall off with the battery cycle, which often leads to battery failure. Therefore, in this study lead materials were deposited on the surface of active carbon powders by acid oxidation and chemical impregnation, to improve the wettability between active carbon powders and liquid lead.
Six kinds of active carbon powders are selected, A~ E active carbon powders provided by Chinese Petroleum Corporation(CPC) and agent active carbon(AC). First, the wetting of carbon powders by liquid lead was tested by hot pressing lead sheets and six kinds of carbon powders, respectively. Besides E powder, the other powders can’t be fully covered by liquid lead, which was modified until most areas of powders were wetted by liquid lead. The modification included nitric acid oxidation, modified Hummers’ oxidation, and chemical impregnation Pb method. And the chemical characterization of E powders is based on the TGA, FTIR, and XPS analysis of E powders to infer the mechanism of its binding with lead. The AC carbon powder was modified to verify the mechanism.

摘要...i
Abstract...iii
誌謝...iv
目錄...v
表目錄...viii
圖目錄...ix
第一章 緒論...1
1.1 前言...1
1.2 實驗目的...1
第二章 文獻回顧...2
2.1 綠色能源...2
2.1.1 再生能源...2
2.2 儲能系統...3
2.2.1 儲能裝置成本...4
2.3 鉛酸電池介紹...6
2.3.1 鉛酸電池內部構造與機制...8
2.4 鉛酸電池組成...9
2.4.1 正極板...9
2.4.2 負極板...9
2.4.3 電解液...9
2.4.4 隔離板...9
2.5 鉛酸電池失效原因...10
2.5.1 硫酸鉛機制...10
2.6 添加碳材對鉛酸電池的影響...11
2.6.1 添加劑對鉛酸電池的影響...13
2.7 鉛碳電極與超級電池...15
2.8 碳材介紹...16
2.8.1 活性碳...16
2.8.2 碳纖維...18
2.8.3 石墨烯...18
2.8.4 碳黑...19
2.8.5 奈米碳管...19
2.9 碳材表面改質...20
2.9.1 石墨氧化法...20
2.9.2 硝酸氧化法...21
2.10 金屬觸媒與載體結合之常見製備方法...23
2.10.1 共沉澱法...23
2.10.2 多元醇法...23
2.10.3 含浸法...23
第三章 實驗材料與步驟...24
3.1 實驗藥品與設備...24
3.1.1實驗藥品...24
3.1.2實驗設備...24
3.2 實驗流程...24
3.2.1硝酸氧化法...25
3.2.2改良Hummers and Offeman氧化法...25
3.2.3化學溼式含浸法鉛修飾...26
3.2.4鉛碳潤濕性測試_鉛碳熱壓...26
3.2.5循環伏安法(CV)測試參數及條件...26
3.3 分析儀器...27
3.3.1掃描式電子顯微鏡...27
3.3.2能量散佈光譜儀...27
3.3.3 X-Ray繞射分析儀...28
3.3.4 傅立葉轉換顯微紅外線光譜...29
3.3.5 X射線光電子能譜儀...29
3.3.6 熱重分析儀...29
3.3.7 多功能電化學儀-循環伏安(CV)...30
第四章 結果與討論...31
4.1 中油碳粉(A粉)微觀結構分析(SEM)...31
4.1.1硝酸氧化A粉鉛修飾微觀結構分析...33
4.1.2改良Hummers氧化A粉鉛修飾微觀結構分析...35
4.2 中油碳粉(B粉)微觀結構分析(SEM)...37
4.2.1硝酸氧化B粉鉛修飾微觀結構分析...39
4.3 中油碳粉(C粉)微觀結構分析(SEM)...41
4.3.1化學濕式含浸法C粉鉛修飾微觀結構分析...43
4.4 中油碳粉(D粉)微觀結構分析(SEM)...45
4.4.1化學濕式含浸法D粉鉛修飾微觀結構分析...47
4.5 中油碳粉(E粉)微觀結構分析(SEM)...49
4.6 粉狀活性碳(AC)微觀結構分析(SEM)...51
4.6.1硝酸氧化粉狀活性碳AC微觀結構分析...53
4.6.2硝酸氧化粉狀活性碳AC鉛修飾微觀結構分析...55
4.7 X-Ray繞射儀(XRD)分析...57
4.8 鉛碳熱壓電極...63
4.9 熔煉鉛/E粉複合材剖面微觀結構分析(SEM)...66
4.10 傅立葉轉換顯微紅外線光譜分析(FTIR)...67
4.11 X射線光電子能譜儀分析(XPS)...69
4.12 熱重分析儀(TGA)...73
4.13 電化學分析(CV)...75
第五章 結論...83
參考文獻...85
Extended Abstract...89

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