氧化亞錫鋰鈦氧複合材於高能鋰電池負極之應用

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研究生：	陳奕志 Yi-chih Chen
論文名稱：	氧化亞錫鋰鈦氧複合材於高能鋰電池負極之應用
指導教授：	諸柏仁 Po-jen Chu
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	112
中文關鍵詞：	金屬氧化物、負極材料、氧化亞錫、鋰鈦氧
相關次數：	點閱：10 下載：0
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金屬氧化物(Metal oxide)負極材料視為新鋰電世代鋰電池的發展趨勢，本研究結合兩種不同鋰離子嵌入/脫嵌機制的金屬氧化物，形成一新穎複合材料，達成抑制粉末化、改善速率電容以及循環壽命表現之目標。氧化亞錫(SnO)屬於合金/去合金(Alloying/de-alloying)系統，可擁有高比電容量(875 mAh.g-1)以及電化學活性；然而，修飾用的鋰鈦氧 (Li4Ti5O12) 屬於嵌入/脫嵌機制(Intercalation / de-intercalation)，充放電過程中具有體積零應變(Zero-strain)，並且展現出優異的速率電容。本研究使用溶膠─凝膠法(Sol-gel)，並以75/25、50/50、25/75等不同SnO / LTO重量比例，合成出一系列複合材，結合兩材料特性，達成穩定氧化亞錫的體積變化問題，其中SnO-LTO(75/25)樣本的速率電容表現最為優異，於1C變速率充放電測試中仍保有466.2 mAh g-1放電容量，在0.2C下進行充放電30圈後，SnO-LTO(75/25)樣品仍有423.3 mAh g-1的電容量，電容保持率仍有約53.0%。此結果可看出鋰鈦氧有助於氧化亞錫結構穩定，並同時可改善速率電容以及循環壽命表現。藉循環伏安法測試以及搭配充放電圖，發現LTO可能於首圈充放電過程中，與分散於Li2O中，有如孔道一般，於高電位中短暫儲存鋰離子後將其轉移給SnO，然而LTO則成為在於充放電過程當中可
緩衝SnO所造成之劇烈體積膨脹現象，同時於高倍率操作條件下，此轉移鋰離子的行為表現使複合材於高倍率充放電下仍可保有較高的放電容量，以及優異的穩定性。

Anode materials play a pivotal role for high power density lithium ion batteries applications. Graphite was the dominant materials of choice, but still fall short of the goal owing to low rate-capability and specific capacity (372 mAh g-1). Among other electrochemically active materials, Tin monoxide (SnO) appears promising to replace graphite and is widely explored due to its high specific capacity (875 mAh g-1).
However it suffered from pulverization problem and hampered its commercial implementation. In this study we have developed a novel composite anode material that combined two types of lithium ion insertion and exertion mechanisms with the purpose to reduce pulverization, improve rate capability and cycling performance. SnO is alloying/de-alloying system, which possess higher specific capability and electrochemical activity. On the other hand, Li4Ti5O12 (LTO) is an intercalation/de-intercalation system, which shows unique rate-capability and zero-strain ability. Combining the two features of the two materials we are able to stabilize the huge volume change of SnO. Pure SnO and the composite powder with SnO/LTO of 75/25, 50/50 and 25/75 wt% were successfully synthesized by sol-gel method. The decrease of capacity with increasing C-Rate was found to be slower in SnO-LTO (75/25) composite powders, and a high discharge capacity of 466.2 mAh.g-1 at 1Crate was observed, which is higher than that in commercial graphite anode materials. The presence of LTO appears to improve simultaneously the rate capability and cycle life through stabilizing the structure of whole active material. The observed cyclic voltammetry and galvanostatic cycling are reflected as lithium storage mechanism based on alloying-dealloying reaction of Sn in composite of Sn-LTO-Li2O, in which LTO acting as a buffer matrix, thus reducing pulverization. In addition, a flat plateau of LTO (1.55V) observed during charge cycle, but does not appear under discharge cycling of both samples, SnO-LTO (75/25) and SnO-LTO (50/50), represents that LTO could transport Li-ion to SnO from, accelerate alloying-dealloying reaction at higher C-Rate operation, and stabilize the pulverization during such reaction

摘要    I
Abstract    III
目錄    VI
圖目錄    X
表目錄    XV
第一章 緒論    1
1-1.    前言    1
1-1.    鋰離子電池發展史與現況    2
1-2.    鋰離子電池之工作原理    5
1-3.    研究動機    7
第二章 原理介紹與文獻回顧    10
2-1. 金屬氧化物負極材料特點與分類    10
2-2. 氧化亞錫 (SnO) 負極材料    12
2-2-1. 不同合成法對型態與結構之修飾    13
2-2-2. SnO 以其他材料進行複合之修飾    20
2-2-3. SnO以碳材進行表面修飾    27
2-3. 鋰鈦氧(Li4Ti5O12)負極材料    33
2-3-1. LTO與其他金屬氧化物進行複合之修飾    34
2-3-2. LTO對正極材料表面修飾    38
2-4. 研究動機和設計    40
第三章 實驗方法    42
3-1. 實驗藥品、器材與儀器設備    42
3-1-1. 實驗藥品    42
3-1-2. 實驗設備    45
3-1-3. 實驗器材    47
3-1-3. CR2032 Type 鈕扣式電池測試組件與儀器    47
3-2. 實驗步驟    48
3-2-1. 氧化亞錫鋰鈦氧複合材 (SnO-LTO)    48
3-2-2. 極片製作與半電池組裝    49
3-3. 物化性實驗儀器原理及介紹    50
3-3-1.  X光散射光譜儀(X-Ray Diffraction, XRD)    50
3-3-2. 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM)    50
3-3-3. 穿透式電子顯微鏡(Tunneling Electron Microscopy, TEM)    51
3-3-4. X-光電子能譜儀(X-ray Photoelectron Spectroscope XPS)    51
3-3-5. 氮氣吸脫附儀(N2 Adsorption Desorption Isotherm)    52
3-4. 半電池效能測試及電化學特性分析    55
3-4-1. 半電池之變速率與恆速率循環壽命測試    55
3-4-2. 循環伏安法分析(Cyclic Voltammetry)    55
3-4-3. 交流阻抗分析儀(AC Impedance)    56
第四章 結果與討論    58
4-1.SnO-Li4Ti5O12複合材之物理性質分析    58
4-1-1. 粉末結構鑑定─X光粉末繞射(XRD)    59
4-1-2. 粉末表面型態及剖面型態分析─ SEM與TEM微結構鑑定    61
4-1-3. 粉末表面氣體吸附特性─氮氣吸脫附(BET)比表面積鑑定    69
4-2. SnO-Li4Ti5O12複合材之化學性質與電化學性質分析    72
4-2-1. 活性物質之組成鑑定-XPS    72
4-2-2. 氧化還原 CV循環伏安測試    74
4-2-3. 循環壽命測試    76
4-2-4. 變速率充放電測試    80
4-2-5. 充放電過後極片表面變化    84
第五章 結論與未來展望    88
參考文獻    91

                                

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