臺灣博碩士論文加值系統

本研究以硼氮摻雜之石墨烯做為鋁離子電池之陰極材料，使用VASP軟體搭配密度泛函理論中廣義梯度近似（GGA）之Perdew-Burke-Ernzerhof（PBE）方法，計算硼氮摻雜濃度、硼氮摻雜之石墨烯及四氯化鋁離子結構、總自由能、共聚能、嵌入行為、遷移能障、疊層數以及理論電壓。四氯化鋁離子以tetrahedron lying結構嵌入硼氮摻雜石墨烯，且四氯化鋁離子之所有原子皆嵌入在硼氮摻雜石墨烯之中空位點。四氯化鋁離子遷移最小能障為0.2 電子伏特。最佳之疊層數為1，理論電壓為3.9 伏特。

In this work, first-principles calculations were performed to examine (B, N)-doped graphene as cathode materials of aluminum-ion batteries. Stacking mode, geometry and intercalation sites of intercalant, intercalation configuration, migration path, stage number and theoretical voltage are determined. It is revealed that BN3G possess larger cohesive energy than B3N6G and B12N12G. For geometry of intercalant, tetrahedron lying AlCl4⁻ has the lowest total free energy. As for intercalation sites of intercalant, all atoms intercalated at hollow sites of (B, N)-doped graphene. For migration path, Path PA1 has lowest migration energy barriers with 0.20 eV. Stage-1 is most favorable with the theoretical voltage 3.9 V.

Acknowledgement I
Contents II
Content of Figures IV
Content of Tables V
摘要 VI
Abstract VII
Chapter 1 Introduction 1
Chapter 2 Computational Methods 4
2.1 Details of the calculations 4
2.2 Density Functional Theory 5
2.2.1 Hohenberg-Kohn theorem 5
2.2.2 Kohn and Sham approach 6
2.2.3 Generalized gradient approximation 8
2.3 Vienna Ab Initio Simulation Package (VASP) 13
2.4 Plane-wave Pseudopotential Method 16
2.4.1 Projector Augmented Wave (PAW) Method 17
2.5 Bloch's theorem 19
2.6 Atomic positions and Wyckoff positions 21
2.7 Calculation of Binding Energy ( Ebinding ) and Cohesive energy ( Ecoh ) 26
2.8 Calculation of Voltage 28
Chapter 3 Results and discussion 29
3.1 The optimized structure of (B, N)-doped graphene 29
3.2 Stacking of (B, N)-doped zigzag graphene 34
3.2.1 Optimized configuration of AA Stacking of (B, N)-doped zigzag graphene 36
3.2.2 Optimized configurations of AB Stacking of (B, N)-doped zigzag graphene 38
3.2.3 Summary of stacking of (B, N)-doped zigzag graphene 42
3.3 The geometry of AlCl4- intercalated in (B, N)-doped graphene 44
3.4 The intercalating configuration with AlCl4⁻ intercalated in (B, N)-doped graphene 48
3.4 Migration pathways of AlCl4- on (B, N)-graphene 63
3.4.1 Migration pathways along polyacenic direction 64
3.4.2 Migration paths along polyphenylic direction 67
3.4.3 Summary of migration paths along polyacenic and polyphenylic direction 70
3.5 The stacking stage and theoretical voltage of AlCl4⁻ intercalated in (B, N)-doped graphene 72
Chapter 4 Conclusion 78
Reference 79

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