Unveiling the Reactivity and the Li‐Ion Exchange at the PEO‐Li6PS5Cl Interphase: Insights from Solid‐State NMR

Li6PS5Cl (LPSCl) argyrodites offer high room temperature ionic conductivity (>1 mS cm−1) and are among the most promising solid electrolytes. However, their chemical instability against Li metal compromises the long‐term cyclability. Using PEO‐LiTFSI as an interlayer or as a matrix for composite...

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Bibliographic Details
Published in:Small structures 2024-10, Vol.5 (10), p.n/a
Main Authors: Ghorbanzade, Pedram, Pesce, Arianna, Armand, Michel, Gómez, Kerman, Devaraj, Shanmukaraj, López‐Aranguren, Pedro, López del Amo, Juan Miguel
Format: Article
Language:English
Subjects:
argyrodite ion conductors
batteries
composite polymer electrolytes
Electrolytes
Interface reactions
Interface stability
Interlayers
interphases
Ion currents
Ion exchange
Ion transport
Molten salt electrolytes
NMR
Nuclear magnetic resonance
Nuclear reactions
Reaction products
Room temperature
Solid electrolytes
solid state NMR
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Summary:Li6PS5Cl (LPSCl) argyrodites offer high room temperature ionic conductivity (>1 mS cm−1) and are among the most promising solid electrolytes. However, their chemical instability against Li metal compromises the long‐term cyclability. Using PEO‐LiTFSI as an interlayer or as a matrix for composite electrolytes is a promising strategy to address this issue. Nevertheless, the interphase of PEO‐LiTFSI and LPSCl requires further detailed investigations. This work explores the interfacial reactions between these phases using solid‐state nuclear magnetic resonance. Results show that PEO facilitates the formation of a complex with LiCl and Li3PS4 from LPSCl, resulting in an interphase material with limited local mobility, thus impeding ion transport. Although the addition of Br as a dopant can improve the ionic conductivity of LPSCl by inducing disorder and generating the Li vacancies, it makes the LPSCl more susceptible to PEO and increases the extent of the interfacial reaction. 6Li–6Li EXSY experiments demonstrate spontaneous Li‐ion exchange between the PEO and the LPSCl, yet this exchange is significantly hindered by reaction products within the PEO‐LPSCl interphase, attributable to their sluggish local dynamics. This study sheds light on the complex interfacial interaction between PEO‐LiTFSI and sulfide argyrodite, providing insights into designing solid electrolytes for the new generation of electrochemical devices. The interactions at the interphase between PEO and Li6PS5Cl particles play a crucial role in Li+ transport within multilayer electrolytes and composite solid electrolyte membranes. In this work, a variety of solid‐state nuclear magnetic resonance experiments are applied to analyze the nature of this interphase and probe the Li exchange between the organic and the inorganic phases.
ISSN:2688-4062
2688-4062
DOI:10.1002/sstr.202400139