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Magnesium-ion batteries (MIBs) are regarded as a promising alternative to lithium-ion batteries (LIBs) due to their material abundance, cost-effectiveness, and improved safety. The development of high-performance anode materials is crucial for the advancement of MIBs. In this work, the feasibility of boron-doped graphene/blue phosphorene heterojunctions BiGr/BP (i = 0, 1, 2, 3, 4) as potential anode materials for MIBs is systematically investigated using the density functional theory. Our results show that the average binding energies of BiGr/BP (i = 0, 1, 2, 3, 4) are negative, suggesting their suitability for experimental synthesis. The analyses of band structure and density of states reveal that BiGr/BP (i = 0, 1, 2, 3, 4) exhibit high conductivity, as the 2p orbitals of carbon and boron dominantly contribute to the density of states at the Fermi level. Magnesium (Mg) adsorption capacity rises with the increase of boron doping concentrations, indicating stronger interactions between the heterojunctions and Mg. At the highest doping concentration (i = 4), the adsorption energy of Mg adsorbed in the interlayer is –3.38 eV, demonstrating substantial potential for Mg storage. The ab initio molecular dynamics (AIMD) simulations at 300 K show minor fluctuations in total energy, confirming the thermal stability of B4Gr/BP. Climbing image nudged elastic band (CI-NEB) method is used to determine two diffusion pathways of Mg in the B4Gr/BP interlayer. Along Path II, the maximum diffusion barrier is 0.47 eV, suggesting rapid Mg diffusion in the B4Gr/BP interlayer. The average open-circuit voltage is 0.37 V, ensuring the safety of the charge-discharge process. The theoretical capacity is 286.04 mAh/g, which is twice that of the B4Gr/MoS2 system. In summary, boron doping significantly enhances the Mg storage capacity. Specifically, B4Gr/BP appears to be a promising candidate for high-performance anodes in MIBs, owing to its excellent stability, conductivity, Mg storage capacity, and electrochemical properties.
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Keywords:
- boron-doped Gr/BP /
- magnesium-ion batteries /
- first-principles
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图 1 (a) B0Gr/BP, (b) B1Gr/BP, (c) B2Gr/BP, (d) B3Gr/BP, (e) B4Gr/BP的几何结构图
Figure 1. Geometric structure of (a) B0Gr/BP, (b) B1Gr/BP, (c) B2Gr/BP, (d) B3Gr/BP, (e) B4Gr/BP.
图 2 AIMD模拟了300 K下的B4Gr/BP能量分布
Figure 2. AIMD simulations of the energy profiles of B4Gr/BP at 300 K.
图 3 (a) B0Gr/BP, (b) B1Gr/BP, (c) B2Gr/BP, (d) B3Gr/BP, (e) B4Gr/BP的能带图(左侧)和态密度图(右侧)
Figure 3. Band structures (left panel) and DOS (right panel) of (a) B0Gr/BP, (b) B1Gr/BP, (c) B2Gr/BP, (d) B3Gr/BP, (e) B4Gr/BP.
图 4 BiGr/BP(i = 0, 1, 2, 3, 4)上Mg的吸附位点俯视图(a)和侧视图(b)
Figure 4. Top (a) and side (b) views of the Mg adsorption sites on the BiGr/BP (i = 0, 1, 2, 3, 4).
图 5 (a) B0Gr/BP和(b) B4Gr/BP的差分电荷密度, 其中蓝色和黄色的区域分别代表电子耗尽和积累(等值面为 0.00015 e/Å3)
Figure 5. Charge density difference of (a) B0Gr/BP and (b) B4Gr/BP. The blue and yellow regions represent electron depletion and accumulation, respectively(the isosurface value is 0.00015 e/Å3).
图 6 (a) B0Gr/BP和(b) B4Gr/BP吸附Mg后的差分电荷密度, 其中蓝色和黄色的区域分别代表电子耗尽和积累(等值面为0.002 e/Å3)
Figure 6. Charge density difference of Mg adsorbed in (a) B0Gr/BP and (b) B4Gr/BP. The blue and yellow regions represent electron depletion and accumulation, respectively (the isosurface value is 0.002 e/Å3).
图 7 Mg在B4Gr/BP层间的扩散路径和扩散势垒 (a) 路径Ⅰ; (b) 路径Ⅱ
Figure 7. Diffusion pathways and diffusion barriers of Mg in the interlayer: (a) Path Ⅰ; (b) Path Ⅱ.
图 8 B4Gr/BP的开路电压
Figure 8. Open circuit voltage of B4Gr/BP.
表 1 BiGr/BP (i = 0, 1, 2, 3, 4)的平均结合能、晶格常数、层间距、键长和键角
Table 1. Average binding energies, lattice constants, interlayer distances, bond lengths and bond angles of BiGr/BP (i = 0, 1, 2, 3, 4).
Systems Eb/(meV·atom–1) A/Å d/Å Bondtype Distance/Å Type Angle/(°) B0Gr/BP –24.98 9.86 3.57 C—C
P—P1.42
2.26∠C—C—C
∠P—P—P119.98—120.01
93.06—93.11B1Gr/BP –24.55 9.90 3.59 C—C
C—B
P—P1.41—1.44
1.49
2.27∠C—C—C
∠C—B—C
∠P—P—P119.29—122.72
120.00
93.04—93.43B2Gr/BP –23.80 9.94 3.59 C—C
C—B
P—P1.41—1.45
1.50
2.27∠C—C—C
∠C—B—C
∠P—P—P119.66—123.58
119.96—119.99
93.49—93.72B3Gr/BP –24.33 9.99 3.58 C—C
C—B
P—P1.41—1.45
1.50—1.51
2.28∠C—C—C
∠C—B—C
∠P—P—P118.34—123.70
119.51—120.83
93.70—93.97B4Gr/BP –19.75 10.04 3.53 C—C
C—B
P—P1.40—1.44
1.50
2.28∠C—C—C
∠C—B—C
∠P—P—P117.47—124.64
119.85—120.04
93.85—94.39
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表 2 Mg在BiGr/BP (i = 0, 1, 2, 3, 4)层间和外表面不同吸附位点的吸附能(eV)
Table 2. Mg adsorption energies (eV) at the interlayer and outer surface of BiGr/BP (i = 0, 1, 2, 3, 4)
System Mg/BiGr/BP BiGr/BP/Mg BiGr/Mg/BlueP Hc Tp T1 T2 T3 T4 T5 B0Gr/BP –0.25 –0.44 –1.05 –1.00 –1.02 –1.02 –1.00 B1Gr/BP –0.88 –0.73 –2.52 –1.87 –2.19 –2.15 –1.87 B2Gr/BP –0.95 –0.85 –2.82 –2.22 –2.53 –2.53 –2.23 B3Gr/BP –1.06 –0.91 –3.08 –2.80 –2.84 –2.90 –3.02 B4Gr/BP –1.61 –1.04 –3.36 –3.33 –3.38 –3.17 –3.17
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