Operando FTIR study on water additive in lithium-sulfur batteries to mitigate shuttle effect  

作　　者：Érick A.Santos Martim C.Policano Manuel J.Pinzón Isabela Galantini Vanessa A.Goncalves Francisco C.B.Maia Lucyano J.A.Macedo Gustavo Doubek Renato G.Freitas Hudson Zanin 

机构地区：[1]Advanced Energy Storage Division,Center for Innovation on New Energies,School of Electrical and Computer Engineering,University of Campinas,Av Albert Einstein 400,Campinas,SP 13083-852,Brazil [2]Catalytic Processes and Materials Group,Department of Chemical Engineering,Faculty of Science and Technology,MESA+Institute for Nanotechnology,University of Twente,PO Box 217,7500 AE Enschede,The Netherlands [3]Centre for Cooperative Research on Alternative Energies(CIC EnergiGUNE),Basque Research and Technology Alliance(BRTA),Vitoria-Gasteiz 01510,Spain [4]Institute of Physics&Institute of Chemistry,Laboratory of Computational Materials,Federal University of Mato Grosso,Cuiabá78060-900,MT,Brazil [5]Brazilian Synchrotron Light Laboratory,Brazilian Center for Research in Energy and Materials,Campinas 13083-970,SP,Brazil [6]Advanced Energy Storage Division,LAB,Center for Innovation on New Energies,School of Chemical Engineering,University of Campinas,Av Albert Einstein 500,Campinas 13083-852,SP,Brazil

出　　处：《Journal of Energy Chemistry》2024年第11期702-713,共12页能源化学（英文版）

基　　金：the financial support from the Brazilian funding agencies FAPESP. (2024/01031-1, 2022/022220, 2020/04281-8, 21/14442-1, 17/11986-5);support from FAPESP through the research project Pi (2022/02901-4);CAPES (1740195);CNPq through the research grant (313672/2021-0);support Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R & D levy regulation。

摘　　要：Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the use of water as an additive in the commonly used electrolyte,1.0 M LiTFSI/1.0%(w/w) LiNO_(3) and a 1:1 mixture of 1,3-dioxolane(DOL) and 1,2-dimethoxyethane(DME) was investigated.We used Co_(2)Mn_(0.5)Al_(0.5)O_(4)(CMA) as an electrocatalyst anchored on an activated carbon(AC) electrode with added sulfur via a melt-diffusion process.The structural analysis of CMA via Rietveld refinement showed interatomic spaces that can promote ionic conductivity,facilitating Li^(+) ion migration.Electrochemical tests determined 1600 ppm as the optimal water concentration,significantly reducing the shuttle effect.Post-mortem XPS analysis focused on the lithium metal anode revealed the formation of Li_(2)O layers in dry samples and LiOH in wet samples.Better capacity was observed in wet samples,which can be attributed to the superior ionic conductivity of LiOH at the electrode/electrolyte interface,surpassing that of Li_(2)O by 12 times.Finally,Operando FTIR experiments provided real-time insights into electrolyte degradation and SEI formation,elucidating the activity mechanisms of water and Li_(2)CO_(3) over the cycles.This work presents results that could aid future advancements in Li-S battery technology,offering possibilities to mitigate its challenges with inexpensive and scalable additives.

关 键 词：Diffusion Li-S Ionic conductivity Operando FTIR 

分 类 号：TM912[电气工程—电力电子与电力传动]