Rational Design of a Ni3N0.85 Electrocatalyst to Accelerate Polysulfide Conversion in Lithium–Sulfur Batteries
Abstract
Slow kinetics of polysulfide conversion reactions lead to severe issues for lithium–sulfur (Li–S) batteries, for example, low rate capability, polysulfide migration, and low Coulombic efficiencies. These challenges hinder the practical applications of Li–S batteries. Here, we proposed a rational strategy of tuning the d-band of catalysts to accelerate the conversion of polysulfides. Nitrogen vacancies were engineered in hexagonal Ni3N (space group P6322) to tune its d-band center, leading to the strong interaction between polysulfides and Ni3N. Because of the greater electron population in the lowest occupied molecular orbital of Li2S4, the terminal S–S bonds were weakened for breaking. Temperature-dependent experiments confirm that Ni3N0.85 demonstrates a much low activation energy, thereby accelerating the conversion of polysulfides. A Li–S cell using Ni3N0.85 can deliver a high initial discharge capacity of 1445.9 mAh g–1 (at 0.02 C) and low decay per cycle (0.039%). The Ni3N0.85 cell can also demonstrate an initial capacity of 1200.4 mAh g–1 for up to 100 cycles at a high loading of 5.2 mg cm–2. The high efficiency of rationally designed Ni3N0.85 demonstrates the effectiveness of the d-band tuning strategy to develop low-activation-energy catalysts and to promote the atomic understanding of polysulfide conversion in Li–S batteries.
- Authors:
-
[1];
[2];
[1]
- Nanjing Univ. (China)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC)
- OSTI Identifier:
- 1660426
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 14; Journal Issue: 6; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Ni3N0.85; electrocatalyst; lithium-sulfur batteries; nanocubes; polysulfide conversion
Citation Formats
Shen, Zihan, Zhang, Zili, Li, Matthew, Yuan, Yifei, Zhao, Yue, Zhang, Shuo, Zhong, Chenglin, Zhu, Jia, Lu, Jun, and Zhang, Huigang. Rational Design of a Ni3N0.85 Electrocatalyst to Accelerate Polysulfide Conversion in Lithium–Sulfur Batteries. United States: N. p., 2020.
Web. doi:10.1021/acsnano.9b09371.
Shen, Zihan, Zhang, Zili, Li, Matthew, Yuan, Yifei, Zhao, Yue, Zhang, Shuo, Zhong, Chenglin, Zhu, Jia, Lu, Jun, & Zhang, Huigang. Rational Design of a Ni3N0.85 Electrocatalyst to Accelerate Polysulfide Conversion in Lithium–Sulfur Batteries. United States. https://doi.org/10.1021/acsnano.9b09371
Shen, Zihan, Zhang, Zili, Li, Matthew, Yuan, Yifei, Zhao, Yue, Zhang, Shuo, Zhong, Chenglin, Zhu, Jia, Lu, Jun, and Zhang, Huigang. Thu .
"Rational Design of a Ni3N0.85 Electrocatalyst to Accelerate Polysulfide Conversion in Lithium–Sulfur Batteries". United States. https://doi.org/10.1021/acsnano.9b09371. https://www.osti.gov/servlets/purl/1660426.
@article{osti_1660426,
title = {Rational Design of a Ni3N0.85 Electrocatalyst to Accelerate Polysulfide Conversion in Lithium–Sulfur Batteries},
author = {Shen, Zihan and Zhang, Zili and Li, Matthew and Yuan, Yifei and Zhao, Yue and Zhang, Shuo and Zhong, Chenglin and Zhu, Jia and Lu, Jun and Zhang, Huigang},
abstractNote = {Slow kinetics of polysulfide conversion reactions lead to severe issues for lithium–sulfur (Li–S) batteries, for example, low rate capability, polysulfide migration, and low Coulombic efficiencies. These challenges hinder the practical applications of Li–S batteries. Here, we proposed a rational strategy of tuning the d-band of catalysts to accelerate the conversion of polysulfides. Nitrogen vacancies were engineered in hexagonal Ni3N (space group P6322) to tune its d-band center, leading to the strong interaction between polysulfides and Ni3N. Because of the greater electron population in the lowest occupied molecular orbital of Li2S4, the terminal S–S bonds were weakened for breaking. Temperature-dependent experiments confirm that Ni3N0.85 demonstrates a much low activation energy, thereby accelerating the conversion of polysulfides. A Li–S cell using Ni3N0.85 can deliver a high initial discharge capacity of 1445.9 mAh g–1 (at 0.02 C) and low decay per cycle (0.039%). The Ni3N0.85 cell can also demonstrate an initial capacity of 1200.4 mAh g–1 for up to 100 cycles at a high loading of 5.2 mg cm–2. The high efficiency of rationally designed Ni3N0.85 demonstrates the effectiveness of the d-band tuning strategy to develop low-activation-energy catalysts and to promote the atomic understanding of polysulfide conversion in Li–S batteries.},
doi = {10.1021/acsnano.9b09371},
journal = {ACS Nano},
number = 6,
volume = 14,
place = {United States},
year = {Thu May 28 00:00:00 EDT 2020},
month = {Thu May 28 00:00:00 EDT 2020}
}
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