現今，全固態鋰離子電池展現出十足發展潛力成為下世代的能源
儲存裝置，尤其是在電動車上的應用備受關注。在所有型態的固態鋰
電池中，石榴石型固態電解質有望可達成所有電動車上必要的應用條
件。本研究之目標為開發具奈米網狀結構的鋰鑭鋯鋁氧氧化物(石榴
石型電解質)作為鋰電池之固態電解質。首先藉由溶凝膠法製備石榴
石型電解質前驅物過程之交連誘發相分離行為，獲得奈米網狀之結構。
反應中，可經由反應物酸鹼值與溫度的調控，有效達到溶凝膠反應中
水解及縮合速率之最佳化條件，即可在無模板的條件下，生成溶凝膠
雙連續相，待移除溶液後，成功獲得可控制孔洞大小以及孔隙率的奈
米網狀鋰鑭鋯鋁氧氧化物前驅物。若於反應中摻入鋰與鋁進行摻雜再
經研磨形成奈米多孔鋰鑭鋯鋁氧氧化物微米粉末，與星狀聚乙二醇混
合後，可成功製備混成固態電解質，相比於傳統的高分子固態電解質，
於室溫下，將擁有更高的離子傳導率，同時，將具備更高的硬度模數，
以期形成全固態鋰電池的所需之電解質層。

Among all kinds of solid state lithium ion battery (LIB) for
next-generation energy storage, the one with garnet-type electrolytes provides the feasibility to fulfill the criteria for the EV applications. Herein, we aim to fabricate nanonetwork-structured Li6.06La3Zr2Al0.196O12 (LLAZO) (a Garnet-type electrolyte) through a template-free sol-gel reaction to give nanoporous LLAZO spheres after milling. Subsequently, those nanoporous spheres will bind with star-shape polyethylene glycol
(s-PEG) to create a new-type solid electrolytes with excellent toughness and high output performances. By taking advantage of gelation-induced phase separation, network-structured LLAZO precursors (i.e., La2Zr2O7) could be successfully fabricated through spinodal decomposition from sol-gel reaction. With precise temperature and pH value control for the sol-gel reaction through hydrolysis and condensation, a spontaneous phase separation of LLAZO precursor gels from solution during sol-gel reaction leads to the formation of co-continuous texture through morphological evolution. After removal of the residual solution, free-standing nanonetwork-structured LLAZO precursors could be formed to give nanoporous LLAZO precursors with controlled pore size and porosity. By introducing Li and Al ions into the sol-gel reaction, the aimed phase separation could also be achieved to give the formation of nanoporous cubic-type LLAZO spheres followed by milling. With blending of the fabricated spheres and s-PEG, the hybrid electrolytes fabricated exhibits high ion conductivity and theoretical high modulus under ambient conditions, giving appealing properties as solid state
electrolytes for LIB applications.

Abstract……………………………………………………….……..…..I
List of Tables………………………………..……………...…………. VI
Figure Caption……………………………………………….......……VII
Chapter 1 Introduction………………………………………..………..1
1.1 All Solid-State lithium Ion Battery…………………......…..…..1
1.2 Solid Electrolytes…………….…………………….…………...3
1.2.1 Polymer Electrolytes……...…………………..…………..4
1.2.2 Inorganic Electrolytes……………………………….……8
1.2.3 Nanohybrid Solid Electrolytes…………………………..10
1.3 Nanonetwork Materials for SSBs..…………………….……...13
1.3.1 Nanonetwork Structures for Solid Electrolytes...…...…..14
1.3.2 Recent Development of Nanonetwork Electrolytes……..16
1.4 Fabrication of Nanostructured Materials……………………...19
1.4.1 Templated Synthesis from Hard Template…………........19
1.4.2 Templated synthesis from Soft Template………...….…..21
1.4.3 Polymerization-Induced Microphase Separation……..…23
1.4.4 Gelation-Induced Phase Separation…………...……...…25
Chapter 2 Objectives……………………………………..………...…32
Chapter 3 Experimental……………………………………..…...…...34
3.1 Sample Preparation…………………………………………....34
3.1.1 Synthesis of LLAZO precursors…………………...……34
3.1.2 Doping of lithium and aluminum ions……….………….35
3.1.3 Calcination for Cubic-type LLAZO……………….…....36
3.2 Electrochemical Testing…………………………………….…37
3.2.1 Membrane Preparation……………………………….….37
3.2.2 Lithium Ion Conductivity Measurements…………….....40
3.3 Instrumentation………………….…………………….....……40
Chapter 4 Results and Discussion………...……………………..……42
4.1 Sol-Gel Reaction of LLAZO Precursors………………………42
4.1.1 pH Effects…………………………………….……...….42
4.1.2 Chelating Effects…………………...………….…...……45
4.1.3 Temperature Effects…………………………………..…47
4.2 Morphologies and Characterization of Forming LLAZO.….....50
4.2.1 Morphological evolution from Spinodal decomposition...50
4.2.2 Mechanisms for Gelation-Induced Phase Separation…....53
4.2.3 Characterization of Porous LLAZO spheres.....……...…57
4.3 Network Electrolytes for SSBs………………………………..61
Chapter 5 Conclusions and Perspectives…………………….….…...67
References………………………………..…………………...….….....69

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