First principles study of two-dimensional boron antimony films as anchoring materials for lithium-sulfur batteries

doi:10.19799/j.cnki.2095-4239.2023.0354

Abstract

Abstract:

Lithium-sulphur batteries are receiving increasing attention in research into electrochemical energy storage technologies due to their higher theoretical energy density. However, long-chain polysulfides tend to dissolve into the electrolyte during charge and discharge, causing a "shuttle effect" that can impact the cycling stability of the sulfur electrodes and lithium-sulfur batteries. Based on first-principles calculations, this research investigated a two-dimensional boron antimony (BSb) monolayer to suppress the shuttle effect as an anchoring material for lithium-sulfur batteries. The adsorption process of Li₂S _n on BSb monolayer was systematically investigated by calculating the adsorption energy, physical and chemical adsorption, differential charge density, density of states (DOS), diffusion barrier, and Gibbs free energy of polysulfide on BSb monolayer. As the lithiation process proceeded, the adsorption energy of Li₂S _n molecules increased from 1.64 to 3.44 eV, effectively inhibiting the dissolution of polysulfides in the electrolyte. Chemisorption prevails at the early stage of the lithiation process, and chemical bonds can be formed at the Li₂S₆ stage, which ensures that higher-order Li₂S _n can be effectively adsorbed and suppress the shuttle effect. The calculation of the density of states showed that the band gap of the BSb monolayer is reduced from 0.51 to 0.24 eV after adsorption, effectively improving the conductivity. The optimal migration paths were obtained using CI-NEB method calculations. The good adsorption properties and electrical conductivity of BSb monolayers indicate their promise as anchoring materials for lithium-sulfur battery cathodes.

Key words: polysulfide, adsorption energy, first principles, two-dimensional materials, shuttle effect

CLC Number:

O 469

Yinchen YANG, Shanling REN, Zhihong YANG, Yunhui WANG. First principles study of two-dimensional boron antimony films as anchoring materials for lithium-sulfur batteries[J]. Energy Storage Science and Technology, 2023, 12(9): 2760-2766.

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References 23

1	THACKERAY M M, WOLVERTON C, ISAACS E D. Electrical energy storage for transportation-Approaching the limits of, and going beyond, lithium-ion batteries[J]. Energy & Environmental Science, 2012, 5(7): 7854-7863.
2	GOODENOUGH J B, PARK K S. The Li-ion rechargeable battery: A perspective[J]. Journal of the American Chemical Society, 2013, 135(4): 1167-1176.
3	ZHAO K J, WANG W L, GREGOIRE J, et al. Lithium-assisted plastic deformation of silicon electrodes in lithium-ion batteries: A first-principles theoretical study[J]. Nano Letters, 2011, 11(7): 2962-2967.
4	CAI Y M. The anchoring effect of 2D graphdiyne materials for lithium-sulfur batteries[J]. ACS Omega, 2020, 5(22): 13424-13429.
5	SONG X H, QU Y Y, ZHAO L L, et al. Monolayer Fe₃GeX₂ (X=S, Se, and Te) as highly efficient electrocatalysts for lithium-sulfur batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(10): 11845-11851.
6	SHAO Y F, WANG Q, HU L, et al. BC₂N monolayers as promising anchoring materials for lithium-sulfur batteries: First-principles insights[J]. Carbon, 2019, 149: 530-537.
7	GRIXTI S, MUKHERJEE S, SINGH C V. Two-dimensional boron as an impressive lithium-sulphur battery cathode material[J]. Energy Storage Materials, 2018, 13: 80-87.
8	SUN J, SUN Y M, PASTA M, et al. Entrapment of polysulfides by a black-phosphorus-modified separator for lithium-sulfur batteries[J]. Advanced Materials, 2016, 28(44): 9797-9803.
9	HE F, LI K, YIN C, et al. A combined theoretical and experimental study on the oxygenated graphitic carbon nitride as a promising sulfur host for lithium-sulfur batteries[J]. Journal of Power Sources, 2018, 373: 31-39.
10	KONG S Z, CAI D, LI G F, et al. Hydrogen-substituted graphdiyne/graphene as an sp/sp² hybridized carbon interlayer for lithium-sulfur batteries[J]. Nanoscale, 2021, 13(6): 3817-3826.
11	LI H X, MA S, CAI H Q, et al. Ultra-thin Fe₃C nanosheets promote the adsorption and conversion of polysulfides in lithium-sulfur batteries[J]. Energy Storage Materials, 2019, 18: 338-348.
12	LI Y J, XU P, CHEN G L, et al. Enhancing Li-S redox kinetics by fabrication of a three dimensional Co/CoP@nitrogen-doped carbon electrocatalyst[J]. Chemical Engineering Journal, 2020, 380: 122595.
13	KHOSSOSSI N, PANDA P K, SINGH D, et al. Rational design of 2D h-BAs monolayer as advanced sulfur host for high energy density Li-S batteries[J]. ACS Applied Energy Materials, 2020, 3(8): 7306-7317.
14	付宇, 崔玉福, 李志刚, 等. 三结砷化镓太阳电池-锂离子蓄电池的小卫星电源分系统仿真模型研究[J]. 空间电子技术, 2019, 16(4): 56-67, 88.
	FU Y, CUI Y F, LI Z G, et al. Study on simulation model of small satellite power subsystem of GaInP₂/GaAs/Ge solar array-Li-ion battery[J]. Space Electronic Technology, 2019, 16(4): 56-67, 88.
15	KRESSE G, FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Physical Review B, Condensed Matter, 1996, 54(16): 11169-11186.
16	GRIMME S, ANTONY J, EHRLICH S, et al. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu[J]. The Journal of Chemical Physics, 2010, 132(15): 154104.
17	YU T T, GAO P F, ZHANG Y, et al. Boron-phosphide monolayer as a potential anchoring material for lithium-sulfur batteries: A first-principles study[J]. Applied Surface Science, 2019, 486: 281-286.
18	RAO D W, WANG Y H, ZHANG L Y, et al. Mechanism of polysulfide immobilization on defective graphene sheets with N-substitution[J]. Carbon, 2016, 110: 207-214.
19	ZHANG Q F, WANG Y P, SEH Z W, et al. Understanding the anchoring effect of two-dimensional layered materials for lithium-sulfur batteries[J]. Nano Letters, 2015, 15(6): 3780-3786.
20	CHEN Q Y, WANG H C, LI H, et al. Two-dimensional MnC as a potential anode material for Na/K-ion batteries: A theoretical study[J]. Journal of Molecular Modeling, 2020, 26(4): 1-6.
21	WU W X, ZHANG Y M, GUO Y H, et al. Exploring anchoring performance of InP₃monolayer for lithium-sulfur batteries: A first-principles study[J]. Applied Surface Science, 2020, 526: 146717.
22	DU Z Z, CHEN X J, HU W, et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries[J]. Journal of the American Chemical Society, 2019, 141(9): 3977-3985.
23	SONG X H, QU Y Y, ZHAO L L, et al. Monolayer Fe₃GeX₂ (X=S, Se, and Te) as highly efficient electrocatalysts for lithium-sulfur batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(10): 11845-11851.

参数	S₈	Li₂S₈	Li₂S₆	Li₂S₄	Li₂S₂	Li₂S
E_ads/eV	0.69	1.64	1.45	1.76	2.65	3.44
d/Å	2.84	1.31	1.57	1.78	1.21	1.12
l_Li-S/Å	—	2.49	2.66	2.45	2.56	2.34
l_S-S/Å	2.07	2.13	2.10	2.11	2.11	－
ΔQ/e	0.06	0.18	0.22	0.41	0.49	0.56

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