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合理设计高容量的新型电极材料是进一步提高离子电池能量密度的关键. 石墨烯曾被认为是离子电池负极材料最有前景的候选者之一, 然而因纯的石墨烯与相应离子的相互作用较弱, 导致其理论容量都不高. 基于此, 本文通过第一性原理评估氮氧(N, O)锚定的单原子铜掺杂石墨烯的二维材料Cu/NO2G作为锂/钠/钾离子电池负极的可行性. 计算结果显示, Cu/NO2G在热力学和动力学上都是稳定的, 在吸附Li/Na/K前后均保持良好导电性, 并且Cu/NO2G储存Li/Na/K的理论容量分别高达1639.9 mAh/g, 2025.8 mAh/g, 1157.6 mAh/g, 在Li/Na/K嵌入的过程中, 其晶格常数变化微小(<1%), 这预示着其循环稳定性能佳. 此外, Li, Na, K在Cu/NO2G表面上的迁移势垒分别为0.339 eV, 0.209 eV和0.098 eV, 表明其具有优异的倍率性能. 综上所述, 本文结果为合理设计金属单原子掺杂石墨烯作为碱金属离子电池的新型负极材料奠定了坚实的理论基础. 本文数据集可在
https://doi.org/10.57760/sciencedb.j00213.00063 中访问获取.Reasonably designing high-capacity novel electrode materials is key to further enhancing the energy density of ion batteries. Graphene has been considered one of the most promising candidates for anodes in ion batteries. However, the weak interaction between pure graphene and the corresponding ions results in a low theoretical capacity. Based on this, in this work the first-principles calculation is used to assess the viability of two-dimensional Cu/NO2G, a single-atom copper-doped graphene anchored by nitrogen and oxygen, as an anode material for Li/Na/K-ion batteries. The results show that Cu/NO2G is stable in terms of thermodynamics and kinetics. It maintains good conductivity before and after the adsorption of Li/Na/K, with theoretical capacities of 1639.9 mAh/g for lithium, 2025.8 mAh/g for sodium, and 1157.6 mAh/g for potassium. In the embedding process of Li/Na/K, the lattice constant changes minimally (less than 1%), indicating excellent cycling stability. Additionally, the migration energy barriers for Li, Na, and K on the surface of Cu/NO2G are 0.339 eV, 0.209 eV, and 0.098 eV, respectively, demonstrating its superior rate performance. In summary, these results provide a solid theoretical foundation for rationally designing metal single-atom doped graphene as a novel anode material for alkali metal ion batteries. All the data presented in this paper are openly available athttps://doi.org/10.57760/sciencedb.j00213.00063 .-
Keywords:
- first-principles /
- ion batteries /
- graphene /
- doping
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图 1 (a) 结构优化后Cu/NO2G的俯视图; (b) 结构优化后Cu/NO2G的侧视图; (c) Cu/NO2G单层的声子色散曲线; (d) 300 K下AIMD模拟的结果, 插图为5 ps和10 ps时的原子结构俯视图
Fig. 1. (a) Top view of the optimized Cu/NO2G; (b) side view of the optimized Cu/NO2G; (c) phonon dispersion curves of Cu/NO2G monolayer; (d) results of AIMD simulations at 300 K, where insets are snapshots of atomic structures at 5 ps and 10 ps.
图 2 (a) Cu/NO2G上A面和B面所考虑的吸附位点俯视图; (b)—(d)分别为Li/Na/K在A面最稳定的吸附构型的俯视图和侧视图; (e)—(g) 分别为Li/Na/K在B面最稳定的吸附构型的俯视图和侧视图
Fig. 2. (a) Top view of adsorption sites on Cu/NO2G that we have considered on side A and side B; (b)–(d) the top and side views of the most stable adsorption configurations of Li/Na/K on the A side; (e)–(g) the top and side views of the most stable adsorption configurations of Li/Na/K on the B side.
图 3 (a) Li, (b) Na, (c) K吸附在Cu/NO2G的B面上的电荷密度差的侧视图, 蓝色和黄色分别代表电子耗尽区和积累区, 相应的等值面(isosurface level)的数值为0.0015 Bohr–3
Fig. 3. Side views of the charge density difference of (a) Li, (b) Na and (c) K atom adsorbed on B side of Cu/NO2G. The blue and the yellow colors represent regions with electron depletion and accumulation, respectively. The corresponding value of isosurface level is 0.0015 /Bohr–3.
图 4 (a) Cu/NO2G态密度图; (b) Cu/NO2G 中C和Cu的局部态密度图; (c) Cu/NO2G 中N和O的局部态密度图; (d) Cu/NO2G吸附Li原子后态密度图; (e) Cu/NO2G吸附Na原子后态密度图; (f) Cu/NO2G吸附K原子后态密度图
Fig. 4. (a) DOS of Cu/NO2G; (b) LDOS plots for C and Cu in Cu/NO2G; (c) LDOS plots for N and O in Cu/NO2G; (d) DOS of Cu/NO2G after Li adsorption; (e) DOS of Cu/NO2G after Na adsorption; (f) DOS of Cu/NO2G after K adsorption.
图 5 不同浓度Li/Na/K嵌入Cu/NO2G的$ {V}_{{\mathrm{o}}{\mathrm{c}}{\mathrm{v}}} $
Fig. 5. Vocv of different Li/Na/K concentrations intercalation in the Cu/NO2G.
图 6 Cu/NO2G与其他二维材料的理论比容量对比图
Fig. 6. Comparison of the theoretical specific capacities between Cu/NO2G monolayer and other 2D anode materials.
图 7 (a) Li/Na/K在Cu/NO2G的A面迁移路径; (b) Li/Na/K在Cu/NO2G的B面迁移路径; (c) Li/Na/K在Cu/NO2G的A面迁移路径上的扩散势垒; (d) Li/Na/K在Cu/NO2G的B面迁移路径上的扩散势垒
Fig. 7. (a) Migration pathways of Li/Na/K on side A of Cu/NO2G; (b) migration pathways of Li/Na/K on side B of Cu/NO2G; (c) diffusion barriers of Li/Na/K for the pathways on side A of Cu/NO2G; (d) diffusion barriers of Li/Na/K for the pathways on side B of Cu/NO2G.
表 1 Cu/NO2G 吸附Li/Na/K后的Bader电荷分析
Table 1. Bader charge analysis of Cu/NO2G Li/Na/K adsorbed states.
Average charge states Li Na K C N O Cu $ {{\mathrm{L}}{\mathrm{i}}{\mathrm{C}}{\mathrm{u}}{\mathrm{N}}{{\mathrm{O}}}_{2}{\mathrm{C}}}_{14} $ –0.845 — — –0.162 1.232 1.115 –0.355 $ {{\mathrm{N}}{\mathrm{a}}{\mathrm{C}}{\mathrm{u}}{\mathrm{N}}{{\mathrm{O}}}_{2}{\mathrm{C}}}_{14} $ — –0.835 — –0.154 1.206 1.097 –0.403 $ {{\mathrm{K}}{\mathrm{C}}{\mathrm{u}}{\mathrm{N}}{{\mathrm{O}}}_{2}{\mathrm{C}}}_{14} $ — — –0.842 –0.142 1.224 1.053 –0.503 
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