論文提要

在鋰錳尖晶石當做鋰離子二次電池中陰極材料的研究，大部分致力於了解其電化學的特性，對於結構的演化則缺乏直接的證據。本論文主要的研究課題則為研究電化學特性隨著充放電而變化時其微觀結構的演化(evolution)，而希望能找出其間的關係來解釋充、放電時鋰離子嵌入與淬出的機制。
鋰離子電池充、放電的電極反應可以由下列式子來表示:

反應向左時是放電(discharging)，往右時是充電(charging)。由此式可以說明鋰離子(Li+-ion)在陰陽兩極之間來回往返，當完全放電時，陰極理論上又回復到尖晶石的結構。可是這些鋰離子在嵌入(insertion)和淬出(extraction)於 LiMn2O4結構時，總有一部份拒絕再加入往返於兩極之間的行列，所以電池容量逐漸降低，直到完全沒有。
研究結果發現，要得到單一均質的 LiMn2O4粉體，最適當的煆繞溫度為 800°C。於鋰不足的情況，合成而得到的粉體會含有 LiMn2O4和第二相 Mn2O3；而鋰過量時，除了形成第二相 Li2MnO3外，生成的尖晶石相為具有相同空間群的 Li4Mn5O12或 Li2Mn4O9。鋰錳尖晶石(LixMn2O4)的晶格常數變化，在 x < 1時是介於 0.823~0.824 nm之間，但在 x = 1.0~1.8則由 0.824 nm迅速掉到 0.817 nm。
微差熱分析的結果顯示當溫度高於 935°C時，氧和氧化鋰會擴散損失而形成具有長方(tetragonal)對稱的 Mn3O4。當溫度升高超過 1045°C時，則會形成具有斜方晶系(orthorhombic)對稱的 LiMnO2。且發現當退火溫度超過 935°C，形成的殘留相為 Mn3O4。
平板狀晶粒(lamellae domain)和雙晶(twinned)結構在 LiMn2O4粉體中常可觀察到，且其界面大部分為 {111}面。起始合成的粉體中 {200}及 {420}等在 禁止出現的繞射面，及充放電後出現的超晶格 1/2{311}和 1/3{422}說明 LiMn2O4結構的空間群不屬於 。繞射面 {311}和 {111}的比值隨充電、放電循環而增加說明了經過充放電後，反尖晶石相增加了。
LiMn2O4結晶相經過燒結後，其構形像 {100}面被切掉的 cubo-octahedron。其明顯出現的結晶面為 {111}，{011}，{001}，{113}。具有最低表面能的結晶面為 {111}。
在充放電過程中結構的演化可分為可逆和不可逆兩部分。可逆部分包括(1)具有立方尖晶石結構，於 3.3~4.3 V之間充放電，晶格常數呈可逆變化(0.824~0.814 nm)，組成改變(如形成Li4Mn5O12，Li1-xMn2O4)，但仍保有尖晶石結構；(2)LiMn2O4表面形成的圓方形介穩定相亦在充放電過程中使鋰離子可來回淬出嵌入。不可逆部分(1)已扭曲成長方、斜方、三斜晶格的粉體；(2)高度不規則排列的奈米區域；(3)表面被可阻礙鋰離子進出的非結晶相包覆的粉體；(4)轉變成 Mn2O3的粉體；(5)結構內部或晶格界面已崩潰的粉體；(6)具反尖晶石結構的粉體。

Abstract

A vast majority of the studies devoted to Lithium manganese oxide deals with their electrochemical characteristics in lithium batteries. The main project of this study is to realize the structure evolution upon electrochemical cycling. The phase transformations under the charge and discharge testing are an interesting project.

Nitrate or oxide precursor calcined at 800°C can produce single phase stoichiometric LiMn2O4. The hypo-stoichiometric compositions (xLi2O×4MnO, x < 1) synthesized by Li-poor situation contain LiMn2O4 and Mn2O3. The hyper- stoichiometric compositions (xLi2O×4MnO, x > 1) synthesized by Li-rich situation contain non-stoichiometric spinel LixMn2O4 (such as Li4Mn5O12 or Li2Mn4O9) and Li2MnO3. The lattice parameter of LiMn2O4 increases slightly with increase of the lithium content at x < 1 (0.823 ~ 0.824 nm), but decreases sharply for x = 1.0 ~ 1.8 (0.824 to 0.817 nm).

Differential thermal analysis showed at temperature higher than 935&ordm;C, rocksalt phase (with tetragonal symmetry), Mn3O4 will be produced. Above 1045&ordm;C, the crystallite phases contain cubic LiMn2O3 spinel, tetragonal Mn3O4 and orthorhombic symmetry LiMnO2. After high temperature annealing (> 935&ordm;C), the residual phase is lithium-deficient structure, Mn3O4.

Apparent facets with {111}, {011}, and {001} (and {113}) planes are usually observed. The LiMn2O4 crystallite appears to be a truncated cubo-octahedron. The lowest surface energy gsv for LiMn2O4 spinel is located at the {111} planes.

Lamellae domain and twinned structure are usually observed in LiMn2O4 particles. The occurrence of domain boundary and twin plane are {111} mostly. Forbidden reflections {200}, {420} in the initial powder and 1/2{311} and 1/3{422} superlattice reflections occurred after charging and discharging test reveal LiMn2O4 structure is a violation of space group. [311]/[111] peak ratio in the XRD traces is increase after electrochemical cycling. Fraction of inverse phase increased upon electrochemical cycling.

The results for structure evolution under charging and discharging test can be divided into two parts for reversible and irreversible. First, unit cell of cubic spinel contracted upon charging and returned to original after discharging. The lattice constant varies back and forth between 0.824 nm to 0.814 nm for cycle between 3.3 and 4.3 V. LiMn2O4 transits to Li4Mn5O12 and l-MnO2 after fully charging to 4.3 V, which then recovers to cubic spinel LixMnyO4 after discharging to 3.3 V. The structure variations in the cycle of changing and discharging are LiMn2O4 – (Li4Mn5O12 + l-MnO2) – LixMnyO4. And metastable circular or rectangle LiMn2O4 particles observed in the surface can be extracted and inserted Li+ ion upon charging and discharging test. This process is reversible.

Second, (1) tetragonal, rhombohedral and triclinic distorted within cubic spinel particles; (2) nanoscale regions of highly disordered lattices observed; (3) amorphous film observed in the powder particle surface; (4) crystalline phase Mn2O3 increased; (5) structure collapse inside the particle and the domain boundary; (6) inverse spinel structure. The structure of LixMn2O4 had distorted upon electrochemical cycling. These results are irreversible.

Contents
Page
論文提要 …………………………………………………………………………….…...i
Abstract ……………………………………………………………...………...………ii
Contents ………………………………………………………………………………..iv
List of Tables ...………………………………………………………...……….…..viii
List of Figures ………………………………………………………………….…..…ix

Chapter 1 Introduction ………………………………………………...………………...1
1.1 Basic information of lithium ion batteries ………………………………..1
1.1.1 Developments of lithium ion battery ……………………………..1
1.1.2 Researches of cathode …………………………………………3
1.1.3 Researches of anode …………………………………………...5
1.1.4 Researches of electrolyte ………………………..……………..6
1.2 Objectives of research …………………………………………………7
1.3 Experimental approach ………………………………………………...7

Chapter 2 Literature survey ………………………………………………………….14
2.1 Background knowledge ………………………………………………14
2.1.1 Crystal structure …………………………………………...…14
2.1.2 Chemical bonding in lithium intercalation compound ………….18
2.2 Phase diagram of Li-Mn-O system …………………………………..19
2.3 Lithium manganese spinel ……………………………………………20
2.3.1 Powder preparation …………………………………………..20
2.4 Surface energy - general description …………………………………22
2.4.1 Definition of surface energy ………………………………….23
2.4.2 Surface energy from chemical bonding ………………………25
2.4.3 Surface energy from thermodynamic view ……………………..25
2.4.4 Anisotropic surface energy ……………………………………...26
2.4.5 Wulff theorem - the equilibrium shape of a crystal ……………..28
2.4.6 Thermodynamic basis of Wulff plot ……………………………29
2.4.7 Determination of equilibrium crystal shape ……………………..30
2.5 Intercalation mechanism ……………………..……………………....30
2.5.1 Charging and discharging mechanisms …………………………34
2.5.2 LiMn2O4 cathode ………………………………………………..35
2.6 Capacity fading for LixMn2O4 …………………………………………..35
2.7 Phase transformations for LixMn2O4 ……………………………………37
2.8 Defect structure in LiMn2O4 spinels ……………………………………38
2.8.1 Oxygen deficient spinels; LiMn2O4-d …………………………...39
2.8.2 Extracted forms of Li1-xMn2O4 ………………………………….39
2.9 The Jahn-Teller effect ………………….….……………………………39

Chapter 3 Experimental Procedures …………………………………………………....74
3.1 Powder preparation …………………………………………………......74
3.1.1 Thermogravimetric and differential thermal analysis …………..75
3.1.2 Particle size distribution ……………………………….…..……76
3.2 Test cell assembly ………………………………………………………76
3.3 Charging and discharging cycles ………………………………………..78
3.4 Density measurements …………………………………………………..80
3.5 X-ray diffractometry …………………………………………………….81
3.6 Microstructure observations ………………………………………...…..81
3.6.1 Scanning electron microscopy ……………………………...…..81
3.6.2 Transmission electron microscopy …………………………...…82
3.6.2.1 Kikuchi map for cubic spinel ………………...……..83
3.6.2.2 Convergent beam electron diffraction ……………....84

Chapter 4 Experimental Results ………………………………………………………..91
4.1 As-prepared LixMn2O4 powders ………………………………………...91
4.1.1 Chemical reactions for synthesized powder …………………….91
4.1.2 Particle size distribution ……………………………………...…91
4.1.3 Crystalline phases ……………………………………………….92
4.1.4 Lattice parameters ……………………………………………....95
4.1.5 Chemical bonding of LiMn2O4 ………………………………....95
4.1.6 Ionic structures …………………………………………………97
4.1.7 Microstructure observations ……………………………………98
4.1.8 The thermal stability of LiMn2O4 ……………………………...100
4.2 Crystallographic facetting in solid-state-reacted LiMn2O4 spinel powder 101
4.2.1 As-calcined powder ……………………………………………102
4.2.2 Annealed powder ………………………………………………104
4.3 Microstructural analysis of powders from charging-discharging cycles 108
4.3.1 Phase transformations upon electrochemical cycling ………....108
4.3.2 Microstructural observations of cathode ……………………....110
4.3.3 Structure evolution for spinel LixMn2O4 under cycling ……….111
4.3.3.1 Region “1” (before charge and discharge) ………….111
4.3.3.2 Region “2” (as the first charge plateau) …………….112
4.3.3.3 Region “3” (as the second charge plateau) …………113
4.3.3.4 Region “4” (after charge test) ……………………….114
4.3.3.5 Region “5” (as first discharge plateau) ……………...116
4.3.3.6 Region “6” (as secondary discharge plateau) ……….117
4.3.3.7 Region “7” (end of one electrochemical cycle) ……..117
4.3.3.8 Region “8” (dead cell) ………………………………117
4.3.3.9 Summary of microstructure observations …………..118
4.3.4 Microstructural observations of particle surface ………………118
4.4 Microstructural observations of sintered LiMn2O4 ceramics ………….119
4.4.1 X-ray diffraction …………………………………………...…..120
4.4.2 Microstructure observations ……………………..…………….120
4.5 Defect reaction equations ……………………………………...………122

Chapter 5 Discussion of Results ………………………………………………………217
5.1 As-prepared LixMn2O4 powders ……………………………………….217
5.1.1 Chemical reactions for synthesized powder ……………...…....217
5.1.2 Particle size distribution ……………...………………………..217
5.1.3 Crystalline phases ……………………………………………...218
5.1.4 Lattice parameters …………………………………...………...219
5.1.5 Chemical bonding of LiMn2O4 …………………………...…...220
5.1.6 Ionic structures …………………………………………...……221
5.1.7 Microstructure observations ……………………………...……223
5.1.8 The thermal stability of LiMn2O4 ……………………………...225
5.2 Crystallographic facetting in solid-state-reacted LiMn2O4 spinel powder 227
5.2.1 Surface energy anisotropy ……………………………………..227
5.2.2 Crystal form ……………………………………………………230
5.3 Microstructural analysis of powders from charging-discharging cycles 232
5.3.1 Phase transformations upon electrochemical cycling …...…….232
5.3.2 Structure evolution for spinel LixMn2O4 under cycling ……….233
5.3.3 Microstructural observations of particle surface ……………....242
5.3.3.1 Interface chemistry of LixMn2O4 electrodes ………….243
5.4 Microstructural observations of sintered LiMn2O4 ceramics ……...…..244
5.4.1 X-ray diffraction ……………………………………………….244
5.4.2 Microstructure observations …………………………………...244

Chapter 6 Conclusions ……………………………...………………………………...257

Chapter 7 Suggestions to Future Work ……………………………...………………..259

Appendices
Appendix 1 …………………………………………………………………….260
Appendix 2 ……………………………………………………………….……267
Appendix 3 ……………………………………………………………….……269
Appendix 4 ……………………………………………………………….……272
Appendix 5 ……………………………………………………………….……274
Appendix 6 ……………………………………………………………….……278
Appendix 7 ……………………………………………………………….……279
Appendix 8 ……………………………………………………………….……285
Appendix 9 ……………………………………………………………….……286
Appendix 10 ....…………………………………………………………….…..287
Appendix 11 ………………………………………………………...…….…...289
Appendix 12 ……………………………………………………………….…..292

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