臺灣博碩士論文加值系統

本研究主要以同步輻射X-ray吸收光譜、X-ray繞射、阻抗分析及拉曼光譜，進行溶膠-凝膠法製備之LiNiVO4陰極材料及PEO固態高分子電解質物性之研究，並輔以其充放電之結果，嘗試建立材料特性與其充放電特性之關係。XAS研究發現，pH=1條件下製備之LiNiVO4粉末，Ni-O鍵長最長，Li離子嵌入之阻力最小，組裝之電池性能最佳。由阻抗分析得知，當EO/Li值小於10，則鋰鹽在PEO之溶解達飽和，此值較文獻值之4~5高，顯示此類電解質膜有結晶相之產生。另外，由增強拉曼光譜之分析，發現LiClO4之935.6 cm-1及2930 cm-1峰及PEO之1474.5 cm-1及1487.5 cm-1有偏移或互為消長之現象，且在1420.8cm-1有新峰形成，說明Li離子與PEO間有新的作用產生。XAS研究中發現CuCl2+PEO電解質中，有Cl與O兩原子之貢獻，可作為Cu與O原子作用的依據。而在CuSO4+PEO及Cu(ClO4)+PEO中，其O之貢獻有來自鹽類及PEO。

The material properties LiNiVO4 cathode materials prepared by a sol-gel method and PEO polymer electrolytes were investigated by XAS, XRD, AC impedance and Raman spectroscopy in this study. The relation between the material properties and the charging-discharging performance of the cells was expected to be established. It was found that Ni-O radius of the LiNiVO4 powder prepared at pH 1 is the longest among the prepared LiNiVO4 powders from the XAS results. The resistance of Li ion intercalation is the lowest and the performance of the cell obtained from the LiNiVO4 powder prepared at pH 1 is the best. On the contrary, the coordination numbers of the Ni-Ni shell is the largest among the prepared LiNiVO4 powders from the XAS results. From AC impedance analysis, it indicated PEO becomes saturated with Li salt when the [EO]/[Li] ratio is less than 10 which is larger than the value of 4~5 reported in the literature. It implies that there are some crystalline phases produced in the PEO polymer electrolytes. From Enhanced Raman spectroscopy study, the peaks of LiClO4 at 935.6 cm-1and 2930 cm-1 and the peaks of PEO at 1474.5 cm-1 and 1487.5 cm-1 shift with changing the [EO]/[Li] ratio. Meanwhile, a new peak was found at 1420.8 cm-1. It means that there are some interactions between Li ions and PEO polymers. From the XAS study, the contributions of Cl and O atoms were observed in the surrounding of Cu in the CuCl2+PEO electrolytes. However, it is difficult to distinguish the contributions of different O atoms in the surrounding of Cu in the CuSO4 + PEO and Cu(ClO4)2 + PEO electrolytes.

中文摘要I
英文摘要II
致謝III
目錄IV
圖表索引VIII
符號說明XII
第一章緒 論1
1.1前 言1
1.1.1鋰電池發展現況1
1.1.2同步輻射光源4
1.2文獻回顧5
1.2.1鋰電池陰極材料5
1.2.1.1LiCoO26
1.2.1.2LiNiO27
1.2.1.3LiNiXCo1-XO27
1.2.1.4LiCo1-yAlyO27
1.2.1.5LiMn2O47
1.2.1.6LiNiVO4及LiCoVO48
1.2.2固態電解質8
1.2.3同步輻射X光吸收光譜10
1.3研究目的及動機13
第二章原理19
2.1EXAFS20
2.2XANES24
2.3交流阻抗分析之原理24
2.4數據分析30
2.4.1同步輻射EXAFS數據分析：30
第三章實驗35
3.1儀器設備35
3.2實驗藥品36
3.3實驗裝置37
3.3.1同步輻射X光吸收光譜術實驗配置圖38
3.3.2玻璃反應器裝置39
3.3.3電化學交流阻抗分析系統：Solartron 1260 & 128639
3.3.4交流阻抗量測反應器裝置39
3.4實驗程序42
3.4.1同步輻射X光吸收光譜術42
3.4.2PEO高分子固態電解質膜之製備43
3.4.3固態高分子電解質膜之交流阻抗量測44
3.4.4交流阻抗之分析44
3.4.5鹽類溶解於PEO高分子電解質之RAMAN光譜研究44
第四章結果與討論46
4.1LINIVO4陰極材料系統46
4.1.1XRD圖譜46
4.1.2電池充放電結果47
4.1.3XANES50
4.1.4EXAFS53
4.1.4.1Ni K-edge吸收光譜53
4.1.4.2V K-edge吸收光譜59
4.2固態高分子電解質63
4.2.1以XAS探討銅鹽類與PEO之作用63
4.2.2Raman 光譜67
4.2.3阻抗分析71
第五章結論84
第六章建議86
第七章參考文獻87

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