Theoretical prediction of nitrogen-oxygen-anchored monatomic copper-doped graphene as an anode for alkaline ion batteries

HU Junping; LIANG Sisi; DUAN Huixian; TIAN Juncheng; CHEN Shuo; DAI Boyang; HUANG Chunlai; LIU Yu; LV Ying; WAN Lijia; OUYANG Chuying

doi:10.7498/aps.74.20241461

Abstract
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 at https://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

Figure 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.

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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

Figure 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.

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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

Figure 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.

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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

Figure 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.

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图 5 不同浓度Li/Na/K嵌入Cu/NO₂G的$ {V}_{{\mathrm{o}}{\mathrm{c}}{\mathrm{v}}} $

Figure 5. V_ocv of different Li/Na/K concentrations intercalation in the Cu/NO₂G.

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图 6 Cu/NO₂G与其他二维材料的理论比容量对比图

Figure 6. Comparison of the theoretical specific capacities between Cu/NO₂G monolayer and other 2D anode materials.

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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

Figure 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.

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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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