本論文是研究電解液添加劑對高電壓鋰離子電池的電化學效能影響。此研究是以Li|1.0 M LiPF6-EC/DEC (= 1/1, v/v)|LiNi0.5Mn1.5O4高電壓電池添加含磷有機化合物為添加劑，如: tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate, tris(2,2,2-trifluoro ethyl) phosphite, tris(4-fluorophenyl)phosphine, (perfluorophenyl)diphenylphosphine, (difluoromethyl)(diphenyl)phosphine oxide, tris(pentafluorophenyl)phosphine, tris(3,5-bis(trifluoromethyl)phenyl)phosphine, triphenylphosphine oxide和trio-tolylphosphine等。經由循環伏安法、電池充放電和循環壽命的測試發現電解液添加2 wt.% tris(4-fluorophenyl)phosphine的電池有較佳的循環壽命。以掃描式電子顯微鏡觀察此經充放電後的電極表面，發現添加劑可以抑制鈍化膜在LiNi0.5Mn1.5O4表面的生成。進一步地，以X-光電子能譜發現其可抑制LiF的生成。所以，可以提升Li|1.0 M LiPF6-EC/DEC (= 1/1, v/v)|LiNi0.5Mn1.5O4電池的循環壽命。

Effects of electrolyte additives for high-voltage lithium-ion batteries on electrochemical performance are studies. High voltage batteries, Li|1.0 M LiPF6-EC/DEC (= 1/1, v/v)|LiNi0.5Mn1.5O4, contain phosphorous additives, such as tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate, tris(2,2,2-trifluoro ethyl) phosphite, tris(4-fluorophenyl)phosphine, (perfluorophenyl)diphenylphosphine, (difluoromethyl)(diphenyl)phosphine oxide, tris(pentafluorophenyl)phosphine, tris(3,5-bis(trifluoromethyl)phenyl)phosphine, triphenylphosphine oxide, and trio-tolylphosphine. The electrochemical properties of the batteries were investigated by cyclic voltammetry, charge-discharge measurements, and cycle-life tests. The cycle-life result shows that the battery with 2 wt.% of tris(4-fluorophenyl)phosphine has improved cyclabilty. The observation of scanning electron microscopy indicates that the additive can suppress the formation of solid electrolyte interphase (SEI) film on the LiNi0.5Mn1.5O4 cathode electrode. Furthermore, the X-ray photoelectron spectroscopy (XPS) results show that the additive indeed inhibits the formation of LiF growing thick SEI. Therefore, the Li|1.0 M LiPF6-EC/DEC (= 1/1, v/v)|LiNi0.5Mn1.5O4 with 2 wt.% of tris(4-fluorophenyl)phosphine has enhanced cycle-life performance.

論文審定書 i
摘要 ii
Abstract iii
第一章 緒論 1
1-1前言 2
1-2鋰離子二次電池 3
1-3電解液(Electrolyte) 4
1-3.1常見的電解質種類 5
1-3.2高電壓電解液 7
1-4鈍化膜 (Solid Electrolyte Interface, SEI) 9
1-5密度泛函理論(Density Functional Theory) 10
第二章 實驗儀器原理 11
2-1場發射型掃描式電子顯微鏡(Field-emission Scanning Electron Microscope, FE-SEM) 12
2-2電子能譜化學分析儀(Electron Spectroscopy for Chemical Analyzer, ESCA) 13
第三章 實驗部分 15
3-1實驗材料 16
3-2實驗藥品 16
3-3實驗儀器 18
3-3.1電化學分析儀(Electrochemical Chromatography) 18
3-3.1.1循環伏安法(Cyclic Voltammetry) 19
3-3.1.2充放電(Charge-Discharge) 19
3-3.1.3循環壽命(Cycle Life) 19
3-3.2場發射型掃描式電子顯微鏡 20
3-3.3電子能譜化學分析儀 20
3-3.4密度泛函理論(Density Functional Theory) 20
3-4實驗流程與設計 21
3-4.1配置電解液 22
3-4.2組裝電池 22
3-4.3清洗極片 23
第四章 結果與討論 24
4-1 Li1.0Ni0.5Mn1.5O4高電壓極片與無添加劑電池(STD) 25
4-1.1循環伏安法(Cyclic Voltammetry) 26
4-1.2充放電 (Charge-Discharge) 26
4-1.3場發射型掃描式電子顯微鏡(SEM) 27
4-1.4光電子能譜儀(ESCA) 28
4-1.5循環壽命(Cycle Life) 29
4-1.6密度泛函理論(Density Functional Theory) 30
4-2 Tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite(THFPP) 32
4-3 Tris(2,2,2-trifluoroethyl) phosphite(TTFEP) 35
4-4 Tris(4-fluorophenyl) phosphine(TFPP) 39
4-5 (Pentafluorophenyl)diphenyl phosphine (PFPDPP) 43
4-6(Difluoromethyl)(diphenyl)phosphine oxide(DFDPPO) 45
4-7 Tris(perfluorophenyl)phosphine(TPFPP) 46
4-8 Tris[3,5-bis(trifluoromethyl)phenyl] phosphine(TTFMPP) 49
4-9 Triphenylphosphine oxide(TPPO) 53
4-10 Tri(o-tolyl)phosphine(TTP) 56
4-11 統整 59
第五章 結論 68
第六章 參考文獻 70

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