Promoting Polysulfide Redox Reactions through Electronic Spin Manipulation

Catalytic additives able to accelerate the lithium-sulfur redox reaction are a key component of sulfur cathodes in lithium-sulfur batteries (LSBs). Their design focuses on optimizing the charge distribution within the energy spectra, which involves refinement of the distribution and occupancy of the...

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Bibliographic Details
Authors: Yu, Jing, Huang, Chen, Usoltsev, Oleg, Black, Ashley P., Gupta, Kapil, Spadaro, Maria Chiara, Pinto, Iván, Botifoll, Marc, Li, Canhuang, Herrero Martín, Javier, Zhou, Jinyuan, Ponrouch, Alexandre, Zhao, Ruirui, Balcells, Lluis, Zhang, Chao Yue, Cabot, Andreu, Arbiol, Jordi
Format: article
Status:Published version
Publication Date:2024
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/372220
Online Access:http://hdl.handle.net/10261/372220
https://api.elsevier.com/content/abstract/scopus_id/85198542312
Access Level:Open access
Keyword:Cobalt selenide
Lithium polysulfide
Lithium−sulfur battery
Spin polarization
Vacancy
Description
Summary:Catalytic additives able to accelerate the lithium-sulfur redox reaction are a key component of sulfur cathodes in lithium-sulfur batteries (LSBs). Their design focuses on optimizing the charge distribution within the energy spectra, which involves refinement of the distribution and occupancy of the electronic density of states. Herein, beyond charge distribution, we explore the role of the electronic spin configuration on the polysulfide adsorption properties and catalytic activity of the additive. We showcase the importance of this electronic parameter by generating spin polarization through a defect engineering approach based on the introduction of Co vacancies on the surface of CoSe nanosheets. We show vacancies change the electron spin state distribution, increasing the number of unpaired electrons with aligned spins. This local electronic rearrangement enhances the polysulfide adsorption, reducing the activation energy of the Li-S redox reactions. As a result, more uniform nucleation and growth of Li2S and an accelerated liquid-solid conversion in LSB cathodes are obtained. These translate into LSB cathodes exhibiting capacities up to 1089 mA h g-1 at 1 C with 0.017% average capacity loss after 1500 cycles, and up to 5.2 mA h cm-2, with 0.16% decay per cycle after 200 cycles in high sulfur loading cells.

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