Na在XC_3(X=B,N,P)掺杂石墨烯表面吸附与扩散行为的第一性原理研究
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摘要
采用基于密度泛函理论(DFT)的第一性原理方法,对Na在本征石墨烯(PG)和掺杂单层石墨烯(BC_3、NC_3、PC_3)表面的吸附结构、电子性质和扩散行为进行了详细的理论计算。结果表明,由于磷掺杂体系(PC_3)P-C键剧烈变化,PG中原有的平面结构消失;而硼、氮掺杂(BC_3和NC_3)对PG结构的影响很小,B-C键和N-C键变化不显著,BC_3和NC_3仍然能维持PG的平面结构,并且没有正反面之分。电子结构计算表明,PG、BC_3和NC_3体系分别呈现半金属、p型掺杂和n型掺杂特征,而PC_3表现出金属性;然而,在Na吸附后所有的材料都表现出金属性。进一步的吸附能计算发现磷、硼掺杂(PC_3和BC_3)能够有效改善石墨烯的储Na容量,从扩散机制的研究发现,Na在PC_3掺杂体系表面的扩散能垒较小,仅为0.081 5 eV,有利于Na在PC_3掺杂石墨烯表面的传输和扩散,是一种潜在的钠离子电池负极材料。
The firstprinciples calculations based on density functional theory(DFT) were conducted to explore the adsorption structures, electronic pro-perties, and diffusion behaviors of Na on pristine graphene(PG) and XC_3(X=B, N and P) doping graphene surfaces in detail. The computational results showed that the P-doping damaged the planar surface structure of PG due to the considerable elongation of P-C bond, while the impact of B-and N-doping on PG was slight, with imperceptible variations in B-C and N-C bond. Consequently, BC_3 and NC_3 could still maintain the plane structure of PG, and there was no difference between positive and negative sides. The electronic structure calculations presented that PG is a semi-metallic material, while BC_3 and NC_3 materials are p-and n-type semiconductors, respectively. The biggest difference lay in the metallic nature of PC_3 material. However, all the XC_3(X=B, N and P) doping graphene materials exhibit metallic characte-ristics after Na adsorption. It was discovered from further calculations that PC_3 and BC_3 doping could enlarge adsorption energy, which contributed to the Na storage capacity of graphene. In addition, the study of diffusion mechanism of Na on the PG and XC_3(X=B, N and P) indicated that the P-doping material(PC_3) possessed the lowest diffusion barrier of 0.081 5 eV. Therefore, PC_3 material is beneficial to the transference and diffusion of Na, and it is a potential anode material for sodium-ion batteries.
The firstprinciples calculations based on density functional theory(DFT) were conducted to explore the adsorption structures, electronic pro-perties, and diffusion behaviors of Na on pristine graphene(PG) and XC_3(X=B, N and P) doping graphene surfaces in detail. The computational results showed that the P-doping damaged the planar surface structure of PG due to the considerable elongation of P-C bond, while the impact of B-and N-doping on PG was slight, with imperceptible variations in B-C and N-C bond. Consequently, BC_3 and NC_3 could still maintain the plane structure of PG, and there was no difference between positive and negative sides. The electronic structure calculations presented that PG is a semi-metallic material, while BC_3 and NC_3 materials are p-and n-type semiconductors, respectively. The biggest difference lay in the metallic nature of PC_3 material. However, all the XC_3(X=B, N and P) doping graphene materials exhibit metallic characte-ristics after Na adsorption. It was discovered from further calculations that PC_3 and BC_3 doping could enlarge adsorption energy, which contributed to the Na storage capacity of graphene. In addition, the study of diffusion mechanism of Na on the PG and XC_3(X=B, N and P) indicated that the P-doping material(PC_3) possessed the lowest diffusion barrier of 0.081 5 eV. Therefore, PC_3 material is beneficial to the transference and diffusion of Na, and it is a potential anode material for sodium-ion batteries.
引文
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19 Vanderbilt D.Physical Review B,1990,41(11),7892.
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