臺灣博碩士論文加值系統

β12 borophene是一個新型的二維材料，在超真空的環境下，在銀表面上成功合成出來。然而，如果要使其從銀表面分離出，β12 borophene會變得非常不穩定。所以我們用加入雜質的方式來破壞原本晶格的週期，改變其電子性質。
本研究以氮摻雜的β12 borophene當鋰/鈉離子電池的陽極材料，使用VASP軟體搭配密度泛函數理論中的Perdew-Burke-Ernzerhof (PBE) 廣義梯度近似法(GGA)方法，計算了結構、總能量、共聚能、電子性質、吸附行為、遷移能障和最大電容量。結構方面，氮摻雜的β12 borophene比純的β12 borophene還要來得穩定；吸附方面，鋰/鈉離子在氮摻雜的β12 borophene最穩定的吸附位點為中空位點，吸附能分別為-2.315 e和-1.710 eV；電子性質方面，純的β12 borophene為金屬性質，加氮之後的β12 borophene，由於能帶沒有交雜在費米能階，所以轉變為半導體性質；遷移方面，鋰/鈉離子在氮摻雜的β12 borophene遷移能障比純的β12 borophene還要來得小，分別為0.239 eV和0.089 eV；最後，電容量方面，鋰/鈉離子在氮摻雜的β12 borophene最大電容量分別為602和482 mA h/g。
因此，我們的計算結果指出，氮摻雜的β12 borophene比純的β12 borophene充放電速率還要來得高。

β12 Borophene is a new type of two-dimensional material which has been successfully synthesized on Ag (111) surface under ultrahigh-vacuum conditions. Borophenes are unstable when they are separated from Ag(111) substrates, but it can be improved by doping nitrogen to change the electronic properties by breaking the lattice periodicity.
In this work, N-doped β12 borophenes were considered as the anode material of Li-ion and Na-ion batteries. Theoretical methods were adopted to calculate the structures, total energies, cohesive energies, electronic properties, adsorption behavior, migration barrier and maximal capacity at GGA-PBE level based on first-principle calculations using Vienna ab initio simulation package (VASP). N4-doped β12 borophene is more stable than primitive β12 borophene. The most favorable adsorption sites for Li-ion and Na-ion on N4-doped β12 borophene are hole sites with the adsorption energy of -2.315 eV and -1.710 eV, respectively. Comparing to primitive β12 borophene, the band structure converts from metallic into semiconducting due to the non-crossing band on Fermi level and thus lower adsorption energy. The migration barrier of Li and Na are 0.239 eV and 0.089 eV, much lower than that of primitive β12 borophene. Finally, the maximum capacity for Li and Na cations on N4-doped β12 borophene are 602 and 482 mA h/g, respectively.
Therefore, our results suggest that N-doped β12 borophene has a higher charge-discharge performance than primitive borophene.

Abstract...................................................................V
中文摘要..................................................................VII
Chapter 1. Introduction....................................................1
Chapter 2. Computational Methods...........................................5
2-1. Details of the calculation............................................5
2-2. Density Functional Theory.............................................6
2-2-1. Hohenberg-Kohn theorem..............................................6
2-2-2 Kohn and Sham approach...............................................7
2-2-3. Generalized gradient approximation..................................9
2-3. Vienna ab initio simulation package (VASP)...........................14
2-4. Plane-wave Pseudopotential Method....................................17
2-4-1.Projector Augmented Wave (PAW) Method...............................18
2-5. Bloch's theorem......................................................20
2-5-1. Band structure.....................................................21
2.6 Atomic positions and Wyckoff positions................................24
2.6 Calculation of Adsorption Energy (Ead) and Cohesive energy (Ecoh).....28
Chapter 3. Results and discussion.........................................30
3-1. The optimized structure of β12 borophene and N-doped β12 borophene unit cell......................................................................30
3-2. The stability of β12 borophene and N-doped β12 borophene.............38
3-3. The electronic band structures of primitive β12 borophene and N-doped β12 borophenes............................................................40
3-4. Adsorption for Li/Na cation on the N4-doped β12 borophene............43
3-5. Migration of Li/Na cations on the N4-doped and primitive β12 borophene ..........................................................................49
3-5-1. Migration pathways along polyacenic direction......................50
3-5-2. Migration pathway along polyphenylic direction.....................57
3-5-3. Summary of migration pathways along polyacenic and polyphenylic direction.................................................................61
3-6. Maximal capacity for Li/Na on the N4-doped and β12 primitive borophene ..........................................................................64
Chapter4. Conclusion......................................................67
References................................................................69
Supplementary information.................................................74

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