臺灣博碩士論文加值系統

在全固態鋰電池的應用上，鋰離子導體是極關鍵的材料。然而，許多具有高離子導電率的結晶陶瓷體與鋰金屬陽極接觸時，會形成部分電子傳導特性，這使得具有高離子導電率的結晶陶瓷體無法作為全固態鋰電池之固態電解質。到目前為止只有極少的研究探討鋰金屬與離子導體間的界面反應，也僅用肉眼觀察試片變色的現象來判斷試片的反應，或藉著離子導體電性轉換後的結果推斷反應特性。本研究的目的即在於探討上述的反應機制與尋求可能的反應抑制方法，以進一步設計高穩定性的鋰離子導體。
本研究使用具鈣鈦礦(ABO3)結構的鈦酸鑭鋰氧化物(La2/3–xLi3xTiO3)做為模型材料進行界面反應。原因是此氧化物具有高達10–3 S cm–1的離子導電率，但卻無法作為固態鋰電池之電解質，且其晶體結構與離子傳導機制已較具定論。研究中發現當組成La0.56Li0.33TiO3試片與鋰金屬反應接觸24小時之後，X光光電子能譜儀分析結果指出位於B位置的12%的四價Ti4+離子被轉變成三價Ti3+離子；此價態的轉變受限於鈦酸鑭鋰的B位置空間大小(基質晶體結構剛性)。離子二次質譜儀分析結果顯示在靠近反應界面有局部電場存在，而且也顯示本研究所使用的同位素6Li追蹤劑是透過這個電場效應嵌入樣品中。因此，在室溫下，金屬活化的界面反應機制為Ti4+過渡金屬離子還原及局部電場引導的鋰離子嵌入試片行為有關。再者，雖然這個鋰金屬活化的施體摻雜步驟將試片表面半導體化，但整體試片的離子導電特性卻持續轉變成混合離子/電子導電特性，因此在這個過程中必定牽涉一個與界面反應不直接相關的自發性電子移動行為，而此行為屬於隨鋰離子移動的電子躍遷。會發生上述的界面反應及傳導機制的改變，主要是因為La2/3–xLi3xTiO3結構中同時具有Ti4+過渡金屬離子及高濃度陽離子空缺，所以具有高濃度陽離子空缺的La2/3–xLi3xTiO3(3x<0.27)與鋰金屬反應後的16分鐘內，氧化物的電子導電率會提升到ca. 10–2 S cm–1；具有最低陽離子空缺的La0.50Li0.50TiO3與鋰金屬反應90分鐘後，其電子導電率僅提升到ca. 10–3 S cm–1，亦即此組成會有較高的鋰金屬反應抑制性。此外，本研究取代La0.50 Li0.50TiO3的Ti4+過渡金屬離子進一步穩定此氧化物的化學及導電傳導性質。本研究發現鈣鈦礦結構的LaAlO3可以融入La0.50Li0.50TiO3而形成單一La0.50+0.50xLi0.50–0.50xTi1–xAlxO3固溶體，指出Al3+離子能夠完全地取代Ti4+離子以穩定離子導體的性質。然而僅有LaAlO3固溶量為0–40 mol%的試片具有鋰離子傳導特性。試片與鋰金屬反應的導電率轉變的過程顯示隨著LaAlO3固溶量的增加，電子導電率由1.23×10–2 S cm–1下降到4.33×10–4 S cm–1，表示試片的電子濃度隨著固溶量增加而下降。因此，Al3+離子取代Ti4+離子能夠抑制La0.50Li0.50TiO3與鋰金屬的界面反應。

Li+ conductors are key materials for technological applications as all- solid-state lithium batteries. Unfortunately, many crystalline phases having high Li+ conductivity are unstable in the presence of a metallic lithium anode. Although interfacial reactions between such conductors and the lithium anode are always inferred, very little effort has been devoted to studying this interfacial instability, which is usually examined by observing the coloration of sample with the naked eye. The scope of our study is, therefore, focused on the detailed reaction mechanism and its suppression.
Among the various ceramic Li+ conductors, we employed a perovskite-type La2/3–xLi3xTiO3 as a model material for our fundamental study into the interfacial instability. This selection stems from the availability of the crystal structure and the easily comprehensible ion-transport mechanism. In this study, we found that when this La0.56Li0.33TiO3 sample and lithium were placed in contact at room temperature for 24 h, the results of X-ray photoelectron spectrometry (XPS) indicate that 12% of the tetravalent Ti4+ ions were converted into trivalent Ti3+ ions and the valence conversion and degree of conversion were limited by the structural rigidity of the host crystal. The secondary ion mass spectrometry (SIMS) analyses suggests the existence of a local electric field near the contact surface and indicates that the 6Li+ isotope ions were inserted into the specimen through the effect of this field. The mechanism of the lithium-activated RT interfacial reaction is associated with the reduction of Ti4+ transition metal ions from tetravalent to trivalent states, which resulted in the increase of electronic conductivity, and the local-electric-field-induced Li+ insertion into La3+/Li+-site vacancies of La0.56Li0.33TiO3. Moreover, although this metallic-lithium- activated donor doping process semiconductorized the sample on its surface, the ionic conduction of bulk sample was altered to mixed ionic/electronic conduction, which includes a spontaneous electronic transition without directly depending on the interfacial instability. Through our identification, this transition is the lithium-ion- motion dependent electron hopping process. As a result, it was roughly found that the phenomena mentioned above were caused by the presence of Ti4+–transition metal ions and the highly vacant structure in La2/3–xLi3xTiO3 system. Thus, La0.50Li0.50TiO3 has higher reaction inhibition against metallic lithium, and we also found that the perovskite-type LaAlO3 can be incorporated into La0.50Li0.50TiO3 to form a xLaAlO3–(1–x)La0.50Li0.50TiO3 solid solution (0.0 ≤ x ≤ 1.0; i.e., La0.50+0.50xLi0.50–0.50x - Ti1–xAlxO3), indicating that the Al3+ ions can be completely substituted for the Ti4+ ions. However, the samples with 0–40 mol % LaAlO3 have the Li+ ion conduction properties to be used as solid electrolytes of electrochemical devices. After measuring its electrical transition by using metallic lithium electrodes and digital multimeter, the altered process indicate that the sample’s electron concentration decreased with the incorporated amount of LaAlO3, in accordance with the decrease in the resulting electronic conductivity form 1.23× 10–2 S cm–1 to 4.33×10–4 S cm–1. Consequently, Al3+ ions substituted for the Ti4+ ions can assist La0.50Li0.50TiO3 to suppress the interfacial reaction between solid electrolyte and metallic lithium.

中文摘要…………………………………………………………………I
英文摘要……………………………………………………………….II
致謝…………………………………………………………………… IV
總目錄………………………………………………………………… V
圖目錄…………………………………………………………………IX
表目錄………………………………………………………………..XIV
英漢名詞對照表…………………………………………………….. XV

第一章 緒論…………………………………………………………1
1-1 能源工業現況述……………………………………………1
1-2 全固態無機化合物鋰離子電池之潛力……………………1
1-3 動機及目的…………………………………………………2
第二章 理論基礎與文獻回顧………………………………………5
2-1 全固態鋰電池原理…………………………………………5
2-2 結晶氧化物固態電解質基本特性……………………… 10
2-2-1 具高離子導電率的陶瓷體所具備的結構特性……………10
2-2-2 滲透理論(Percolation theory)…………………………11
2-2-3 電解質的其他必需特性……………………………………15
2-3 離子傳導導電率定義及相關理論……………………….15
2-3-1 離子導電度—歐姆定律……………………………………15
2-3-2 離子移動活化能理論………………………………………16
2-4 穩定於室溫鋰金屬環境的一元及二元相系統氧化物… 18
2-4-1 鋰金屬基本物理化學性質…………………………………18
2-4-2 穩定的一元相及二元(Li2O–MxO)相系統氧化物……….18
2-5 鈣鈦礦結構(Perovskite)與傳統結晶化學理論……….21
2-5-1 鈣鈦礦結構………………………………………………. 21
2-5-2 穩定結構評估—容忍因子(Tolerance factor)…………22
2-6 鈣鈦礦鈦酸鑭鋰氧化物(La2/3–xLi3xTiO3)………….22
2-6-1 鈦酸鑭鋰氧化物之缺陷結構………………………………22
2-6-2 鈦酸鑭鋰氧化物化學組成與離子導電率的關係…………24
2-6-3 A位置離子的取代對離子傳導活化能所造成的效應…….27
2-6-4 鋰金屬與鈦酸鑭鋰氧化物之化學不穩定性相關研究……29
2-7 鈣鈦礦結構鋁酸鑭氧化物(LaAlO3)…………………….29
2-7-1 鋁酸鑭氧化物之結構………………………………………29
2-7-2 鋁酸鑭氧化物化學組成及離子導電率的關係……………31
2-8 X光光電子能譜儀(XPS)分析原理……………………….31
2-9 二次離子質譜儀(SIMS)分析原理……………………… 32
2-10 交流阻抗分析原理—離子傳導量測…………………… 32
第三章 實驗方法與步驟………………………………………… 36
3-1 La0.56Li0.33TiO3/Metallic-lithium界面反應………36
3-1-1 實驗流程……………………………………………………36
3-1-2 La0.56Li0.33TiO3合成及燒結步驟…………………… 36
3-1-3 La0.56Li0.33TiO3固態離子導體試片與鋰金屬反應步驟37
3-1-4 分析方法及性質量測……………………………………… 37
3-1-4-1 結構分析—X光繞射分析(X-ray diffractometer; XRD)…………………………………………………………………………37
3-1-4-2 掃描式電子顯微鏡(Scanning electron microscope;SEM)觀察……………………………………………………………………37
3-1-4-3 X光光電子能譜儀(X-ray photoelectron spectrometer; XPS)析…………………………………………………………………37
3-1-4-4 二次離子質譜儀(Secondary ion mass spectrometer; SIMS)分析…………………………………………………………… 38
3-1-4-5 導電性質測試—交流阻抗分析及直流數位電表量測……38
3-2 化學鋰化La2/3–xLi3xTiO3離子導體導電行為轉換研究………………………………………………………………………38
3-2-1 實驗流程………………………………………………………………………38
3-2-2 La2/3–xLi3xTiO3合成及燒結步驟…………………… 39
3-2-3 La2/3–xLi3xTiO3導電行為轉換的測試—導電率動態變化量測……………………………………………………………………39
3-2-4 La2/3–xLi3xTiO3與鋰金屬反應前後的離子與電子導電率量測………………………………………………………………………41

3-3 LaAlO3的添加對La0.50Li0.50TiO3性質與對鋰金屬反應抑制性之影響………………………………………………………………………41
3-3-1 實驗流程…………………………………………………41
3-3-2 LaAlO3–La0.50Li0.50TiO3固溶體合成及燒結步驟 41
3-3-3 性質量測……………………………………………………42
3-3-3-1 結構分析—X光繞射分析………………………………… 42
3-3-3-2 導電性質測試—交流阻抗分析……………………………42
3-3-3-3 LaAlO3–La0.50Li0.50TiO3固溶體與鋰金屬之間的穩定性測試……………………………………………………………………42
第四章 La0.56Li0.33TiO3與鋰金屬間之界面反應研究……… 43
4-1 前言……………………………………………………… 43
4-2 反應前後的La0.56Li0.33TiO3結晶相分析…………… 43
4-3 反應前後La、Li、Ti元素的XPS分析………………… 47
4-3-1 La與Li的XPS分析結果…………………………………… 47
4-3-2 Ti的XPS分析結果………………………………………… 47
4-4 四價鈦轉換為三價後的電荷補償—SIMS分析………… 51
4-5 La0.56Li0.33TiO3導電行為的轉變…………………… 55
4-5-1 界面反應對試片鋰離子傳導特性的影響—交流阻抗分析………………………………………………………………………55
4-5-1-1 界面反應對試片晶粒導電率的影響…………………… 59
4-5-1-2 界面反應對晶界導電率的影響………………………… 60
4-5-2 界面反應對試片電子傳導特性的影響……………… 62
4-6 La0.56Li0.33TiO3與鋰金屬的界面反應機制………… 62
4-7 小結……………………………………………………… 65
第五章 化學鋰化La2/3–xLi3xTiO3離子導體導電行為轉換研究………………………………………………………………………67
5-1 前言……………………………………………………… 67
5-2 化學鋰化La2/3–xLi3xTiO3的導電行為轉換的物理意涵…………………………………………………………………… 67
5-3 簡單現象模型的建立…………………………………… 70
5-4 定義化學鋰化後的試片導電率變化行為……………… 74
5-5 鋰化La2/3–xLi3xTiO3的導電行為轉換現象………… 81
5-5-1 La2/3–xLi3xTiO3的反應前後總導電率變化……………81
5-5-2 La2/3–xLi3xTiO3電傳導機制的轉換……………………84
5-6 小結……………………………………………………… 88

第六章 LaAlO3的添加對La0.50Li0.50TiO3性質與對鋰金屬反應抑制性之影響………………………………………………………… 90
6-1 前言……………………………………………………… 90
6-2 LaAlO3–La0.50Li0.50TiO3固溶體性質……………… 91
6-2-1 LaAlO3–La0.50Li0.50TiO3固溶體相發展………………91
6-2-1-1 固溶體的存在範圍…………………………………………91
6-2-1-2 xLaAlO3–(1−x)La0.50Li0.50TiO3固溶體晶體結構對稱性之改變……………………………………………………………… 92
6-2-1-3固溶體晶體結構資訊整理……………………………… 103
6-2-2 LaAlO3–La0.50Li0.50TiO3固溶體之導電性質……… 103
6-2-2-1 固溶體的離子傳導活化能……………………………… 106
6-2-2-2 固溶體的常溫離子導電率……………………………… 112

6-3 LaAlO3–La0.50Li0.50TiO3固溶體與鋰金屬之反應…114
6-4 小結…………………………………………………… 116
第七章 總結論……………………………………………………118
參考文獻………………………………………………………………120
自述……………………………………………………………………127

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