Phase Engineering of Defective Copper Selenide toward Robust Lithium-Sulfur Batteries

Dawei Yang; Mengyao Li; Xuejiao Zheng; Xu Han; Chaoqi Zhang; Jordi Jacas Biendicho; Jordi Llorca; Jiaao Wang; Hongchang Hao; Junshan Li; Graeme Henkelman; Jordi Arbiol; Joan Ramon Morante; David Mitlin; Shulei Chou; Andreu Cabot

doi:10.1021/acsnano.2c03788

Phase Engineering of Defective Copper Selenide toward Robust Lithium-Sulfur Batteries

ACS Nano. 2022 Jul 26;16(7):11102-11114. doi: 10.1021/acsnano.2c03788. Epub 2022 Jun 27.

Authors

Dawei Yang^{1

2

3}, Mengyao Li^{1

2

4}, Xuejiao Zheng⁵, Xu Han⁶, Chaoqi Zhang^{1

2}, Jordi Jacas Biendicho¹, Jordi Llorca⁷, Jiaao Wang⁸, Hongchang Hao⁹, Junshan Li¹⁰, Graeme Henkelman⁸, Jordi Arbiol^{6

11}, Joan Ramon Morante^{1

2}, David Mitlin⁹, Shulei Chou¹², Andreu Cabot^{1

11}

Affiliations

¹ Catalonia Institute for Energy Research - IREC, Sant Adrià de Besòs, 08930 Barcelona, Spain.
² Department of Electronic and Biomedical Engineering, Universitat de Barcelona, 08028 Barcelona, Spain.
³ Henan Key Laboratory of Photovoltaic Materials, Henan University, Kaifeng 475004, China.
⁴ School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China.
⁵ Nanjing Hydraulic Research Institute, Nanjing 210029, China.
⁶ Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST, Campus, UAB, Bellaterra, 08193 Barcelona, Spain.
⁷ Institute of Energy Technologies, Department of Chemical Engineering and Barcelona Research Center in Multiscale Science and Engineering, Universitat Politècnica de Catalunya, EEBE, 08019 Barcelona, Spain.
⁸ Department of Chemistry and the Oden Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712 United States.
⁹ Materials Science and Engineering Program & Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712, United States.
¹⁰ Institute of Advanced Study, Chengdu University, 610106 Chengdu, China.
¹¹ ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain.
¹² Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China.

PMID: 35758405
DOI: 10.1021/acsnano.2c03788

Abstract

The shuttling of soluble lithium polysulfides (LiPS) and the sluggish Li-S conversion kinetics are two main barriers toward the practical application of lithium-sulfur batteries (LSBs). Herein, we propose the addition of copper selenide nanoparticles at the cathode to trap LiPS and accelerate the Li-S reaction kinetics. Using both computational and experimental results, we demonstrate the crystal phase and concentration of copper vacancies to control the electronic structure of the copper selenide, its affinity toward LiPS chemisorption, and its electrical conductivity. The adjustment of the defect density also allows for tuning the electrochemically active sites for the catalytic conversion of polysulfide. The optimized S/Cu_1.8Se cathode efficiently promotes and stabilizes the sulfur electrochemistry, thus improving significantly the LSB performance, including an outstanding cyclability over 1000 cycles at 3 C with a capacity fading rate of just 0.029% per cycle, a superb rate capability up to 5 C, and a high areal capacity of 6.07 mAh cm^-2 under high sulfur loading. Overall, the present work proposes a crystal phase and defect engineering strategy toward fast and durable sulfur electrochemistry, demonstrating great potential in developing practical LSBs.

Keywords: copper selenide; copper vacancies; lithium polysulfide; lithium−sulfur battery; phase engineering.