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为了加快镁离子电池的开发与应用,寻找合适的镁离子电池阳极材料势在必行。此外,具有较低摩尔质量的阳极材料有利于获得较高的理论存储容量。因此,本文采用基于密度泛函理论的第一性原理计算系统地研究了BeB2单层材料作为镁离子电池阳极的潜力。计算结果表明,基于声子谱检测,BeB2结构展现了优异的动力学稳定性。此外我们从BeB2的能带结构可以看到清晰的狄拉克锥,表明其具有良好的导电性能。BeB2可以稳定吸附镁离子,并且镁离子在该材料上表现了较低的扩散势垒 (0.04 eV),这意味着更快的充放电速率。重要的是,BeB2展现了超高的理论容量 (5250 mA h g-1)、较低平均开路电压 (0.33 V)以及较小的体积膨胀 (2%)。此外,Mg离子在双层BeB2结构中的吸附能为-1.38~-2.24 eV,扩散势垒为0.134~0.84 eV。综合以上性能,我们相信BeB2可以作为一种优秀的镁离子电池阳极材料。Rechargeable lithium-ion batteries as the main energy storage equipment should possess high power density, excellent reversible capacity, and long cycle life. However, due to the high cost and dendrites growth of Li, searching for non-Li-ion batteries is urgent. Compared to lithium, magnesium has abundant resources, smaller ionic radius, and high energy density. Therefore, magnesium-ion batteries (MIBs) can act as the next generation metal-ion batteries. Two-dimensional materials based on Be or B element acting as the anode of metal-ion batteries always exhibit high theoretical storage capacity. Using first-principles calculations, we systematically explore the potential of BeB2 as MIBs anode. The optimized BeB2 monolayer structure shown in Fig. 1a consists of two atomic layers, where each Be atom is coordinated with six B atoms, and each B atom is coordinated with three Be atoms. The lattice constants are a = b = 3.037 Å with a thickness of 0.554 Å. From the phonon spectrum calculations, the absence of imaginary modes indicates the dynamic stability of BeB2 monolayer. The presence of a Dirac cone further suggests the excellent conductivity (Fig. 1b). Three stable adsorption sites (Be1: Top of Be atoms. Be2 and B2: Bottom of Be and B atoms) are labeled in the Fig. 1a. Taking symmetry into account, we consider three pathways to evaluate the migration of Mg atom on BeB2 monolayer (Fig. 1c). The corresponding lowest diffusion energy barrier is 0.04 eV along Path III. The stable configuration with the maximum adsorption Mg concentration is shown in Fig. 1d, which generates a theoretical capacity of 5696 mAhg-1. The calculated average open-circuit voltage is 0.33V. Based on ab initio molecular dynamics simulations, the total energy of BeB2 with Mg adsorbed fluctuates within a narrow range, suggesting that BeB2 can sustain structural stability after the storage of Mg at room temperature (Fig.1e). Finally, for practical application, we investigate the adsorption and diffusion behavior of Mg on bilayer BeB2. Three configurations are considered: AA stacking (overlapping of Be atoms in upper layer with Be atoms in lower layer), AB stacking (overlapping of Be atoms in upper layer with B atoms in lower layer), and AC stacking (overlapping of Be atoms in upper layer with B-B bonds in lower layer). The most stable configuration is AB stacking (shown in Fig. 1f) with the interlayer space of 3.12 Å and the binding energies of -120.97 meV/atom. Compared to the BeB2 monolayer structure, the adsorption energy of Mg is -2.24 eV for Be1, -1.38 eV for B5 site, and -1.90 eV for B4 site, while the lowest diffusion energy barrier is 0.13 eV along the path of B5-Be3-B5. Therefore, based on the above-mentioned properties, we believe BeB2 monolayer can act as an excellent MIBs anode material.
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