Synthesis, structure, and electrochemical intercalation mechanism of new electrode materials for next-generation batteries
- Title
- Synthesis, structure, and electrochemical intercalation mechanism of new electrode materials for next-generation batteries
- Alternative Title
- 차세대 배터리를 위한 새로운 양극 소재의 합성, 구조, 그리고 전기화학적 메커니즘의 분석
- Author(s)
- Hyeri Bu
- DGIST Authors
- Hyeri Bu ; Seung-Tae Hong ; Hochun Lee
- Advisor
- 홍승태
- Co-Advisor(s)
- Hochun Lee
- Issued Date
- 2023
- Awarded Date
- 2023-08-01
- Type
- Thesis
- Description
- Rechargeable batteries; Ca-ion batteries; intercalation mechanism; crystal structure; X-ray diffraction.
- Table Of Contents
-
Ⅰ. Introduction 1
1.1 From Sony to Today: LIBs and the Quest for Sustainable Energy Storage 1
1.2 Emerging Multivalent-ion Battery Technologies, with a Focus on Calcium-ion Batteries 2
1.3 The recent accomplishments of calcium-ion cathode materials 3
1.4 The remained challenges for calcium-ion battery systems 5
1.5 References 6
Ⅱ. THEORY 11
2.1 Crystallography 11
2.1.1 X-ray diffraction 11
2.1.2 Ab-initio structure determination 12
2.1.3 SAED(Selected area diffraction) pattern 14
2.2 Bond valence sum mapping and Bond valence energy landscape calculation 15
2.2.1 bond valence sum 15
2.3 Electrochemistry 18
2.3.1 Rechargeable battery 17
2.3.2 Electrochemical techniques 18
2.4 References 20
Ⅲ. Crystal structure of calcium perchlorate anhydrate, Ca(ClO4)2, from laboratory powder X-ray diffraction data 23
3.1 Introduction 23
3.2 Synthesis and crystallization 23
3.3 Description of structures 23
3.4 Refinement details 24
3.5 References 29
Ⅳ. Exploring Three-dimensional modeling of Icosahedral Quasicrystal Zn-Mg-Y Structures : Beyond HD Crystallography 31
4.1 Introduction 31
4.2 Experimental 32
4.3 Results and discussion 33
4.4 Conclusions 38
4.5 References 53
Ⅴ. A New Ammonium Vanadium Bronze as a Li-ion host materials: Unveiling the Unprecedented Stoichiometry and Insight into Reaction Mechanisms 56
5.1 Introduction 56
5.2 Experimental 57
5.2.1 Materials Synthesis 57
5.2.2 Materials Characterization 57
5.2.3 Structure Determination 57
5.2.4 Powder Diffraction and Refinement 58
5.2.5 Electrochemical Characterization 58
5.3 Results and discussion 59
5.3.1 Characterization of (NH4)2V7O16 59
5.3.2 Electrochemical Characterization of (NH4)2V7O16 61
5.4 Conclusions 63
5.5 References 77
ⅤI. (NH4)2V7O16 as Cathode Material for Rechargeable Calcium-ion Batteries : Structural Transformation and Co-intercalation of Ammonium and Calcium Ions. 83
6.1 Introduction 83
6.2 Experimental 85
6.2.1 Synthesis and materials characterization 85
6.2.2 Electrochemical characterization 85
6.2.3 Quantitative analysis of the intercalation properties 87
6.2.4 Structural analysis 87
6.2.5 Chemical Preparation of (NH4)2−xV7O16 and Ca0.8V7O16 88
6.2.6 BVEL calculation 88
6.3 Results and discussion 88
6.3.1 Characterization of the synthesized material 88
6.3.2 Electrochemical characterization 89
6.3.3 Evidence of co-intercalation of ammonium and calcium ions 90
6.3.4 From irreversible to robust reversible structural changes 91
6.3.5 Reaction mechanism in the first charging process 92
6.3.6 BVEL calculations 93
6.3.7 Importance of co-intercalation of calcium and ammonium to stable cycling 94
6.3.8 Full-cell test using Ca-metal anode 94
6.4 Conclusions 94
6.5 References 108
Ⅶ. Novel Calcium Vanadium Bronze, Ca0.7V7O16·4H2O, as a Cathode Material for Calcium-Ion Batteries : Activation-Induced Structural Rearrangement 112
7.1 Introduction 112
7.2 Experimental 113
7.2.1 Synthesis and materials characterization 113
7.2.2 Electrochemical characterization 114
7.2.3 Quantitative analysis of the intercalation properties 115
7.2.4 Structural analysis 116
7.2.5 BVEL calculation 116
7.3 Results and discussion 116
7.3.1 Synthesis and structure determination for Ca0.7V7O16·4H2O 116
7.3.2 Electrochemical performance of Ca0.7V7O16·4H2O 118
7.3.3 Ca-ion storage mechanism of Ca0.7V7O16·4H2O 119
7.3.4 Structural transformation of Ca0.7V7O16·4H2O : Activated-structure, Ca0.25V7O16·2H2O 121
7.4 Conclusions 122
7.5 References 139
Ⅷ. Aluminum Vanadium Oxide, Al0.7V3O8∙2.3H2O : A New Laminar-structure Cathode Material for Calcium-Ion Batteries 144
8.1 Introduction 144
8.2 Experimental 146
8.2.1 Synthesis and materials characterization 146
8.2.2 Electrochemical characterization 147
8.2.3 Quantitative analysis of the intercalation properties 148
8.2.4 Structural analysis 148
8.2.5 BVEL calculation 149
8.3 Results and discussion 149
8.3.1 Synthesis and structure determination of Al0.7V3O8·2.6H2O 149
8.3.2 Electrochemical performance of Al0.7V3O8·2.6H2O 150
8.3.3 Intercalation mechanism for Ca-ion storage of Al0.7V3O8·2.6H2O 151
8.4 Conclusions 155
8.5 References 171
Ⅸ. Comparative Analysis based on decoding intercalation mechanism: Ca0.5VOPO4·2H2O Outperforms VOPO4·2H2O in Calcium-Ion Batteries 175
9.1 Introduction 175
9.2 Experimental 177
9.2.1 Synthesis and materials characterization 177
9.2.2 Electrochemical characterization 178
9.2.3 Quantitative analysis of the intercalation properties 179
9.2.4 Structural analysis 179
9.2.5 BVEL calculation 180
9.3 Results and discussion 180
9.3.1 Synthesis of Ca0.5VOPO4∙2H2O and VOPO4∙2H2O 180
9.3.2 Electrochemical performance of Ca0.5VOPO4∙2H2O 181
9.2.3 The role of pre-intercalated Ca ions for Ca-ion intercalation process : Comparing Ca0.5VOPO4∙2H2O and VOPO4∙2H2O 182
9.3.4 The Ca-ion intercalation mechanism of Ca0.5VOPO4∙2H2O focusing on structural transformation 184
9.4 Conclusions 185
9.5 References 202
Ⅹ. Structural Evolution of NaV1.5Cr0.5(PO4)3 during Calcium Ion Intercalation: Enhanced Electrochemical Properties and Distinct Diffusion Mechanism 204
10.1 Introduction 204
10.2 Experimental 206
10.2.1 Synthesis of Na3V1.5Cr0.5(PO4)3 206
10.2.2 Material characterization 207
10.2.3 Electrochemical characterization 207
10.2.4 Structural analysis 209
10.3 Results and discussion 209
10.3.1 Synthesis and characterization of monoclinic structure, Na3V1.5Cr0.5(PO4)3 209
10.3.2 Electrochemical characterization of Na3V1.5Cr0.5(PO4)3 210
10.3.3 Understanding V4+/5+ Activation and Other Reactions: Elemental Analysis Insights 212
10.3.4 Effect of Cr Substitution on Phase Separation and Diffusion Pathway: XRD Analysis 213
10.3.5 Structural Models and Diffusion pathways : Investigating the Ca/Na ion sites for Ca0.7Na1V1.5Cr0.5(PO4)3 214
10.3.5 Ca metal anode cell test 216
10.4 Conclusions 217
10.5 References 240
Summary (in Korean) 245
- URI
-
http://hdl.handle.net/20.500.11750/46404
http://dgist.dcollection.net/common/orgView/200000686229
- Degree
- Doctor
- Department
- Department of Energy Science and Engineering
- Publisher
- DGIST
- Related Researcher
-
-
Hong, Seung-Tae
- Research Interests Magnesium; calcium; and zinc ion batteries; lithium all-solid-state batteries; Inorganic materials discovery; Solid state chemistry; Crystallography; Mg; Ca; Zn 이온 이차전지; 리튬 전고체전지; 신 무기재료 합성; 고체화학; 결정화학
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