In Situ XPS Studies of Solid Electrolyte Electroreduction Through Graphene Electrode

Inozemtseva, Alina I.; Визгалов, В.А.; Kapitanova, Olesya O.; Panin, G. N.; Velasco‐Vélez, Juan‐Jesús; Itkis, Daniil M.; Usachov, Dmitry Yu.

doi:10.1149/1945-7111/aba370

Cited by 7 publications

(4 citation statements)

References 47 publications

(58 reference statements)

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“…An MCI was also observed for Li 1.6 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP), Li 1.6 Al 0.5 Ti 0.95 Ta 0.5 (PO 4 ) 3 (LATTP), and a commercial Ti- and Ge-containing material for the same reasons. 189,191 Similarly, Wenzel et al studied Li 7 P 3 S 11 . Performing time-resolved impedance spectroscopy on a Li/Li 7 P 3 S 11 /Li symmetrical cell, a resistance increase was seen, indicative of interphase formation.…”

Section: In Situ and Operando Xps Measurementsmentioning

confidence: 99%

Advances in studying interfacial reactions in rechargeable batteries by photoelectron spectroscopy

et al. 2022

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Section: In Situ and Operando Xps Measurementsmentioning

confidence: 99%

Advances in studying interfacial reactions in rechargeable batteries by photoelectron spectroscopy

et al. 2022

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“…Decomposition products upon reduction, especially against lithium metal, were widely investigated for LAGP (Paolella et al, 2020;Sun et al, 2020) and LATP (Hartmann et al, 2013;Chung and Kang, 2017;Inozemtseva et al, 2020;Zhu et al, 2020;Hou et al, 2020). However, experimental studies on their decomposition upon oxidation are nonexistent.…”

Section: O 2 Sensing Measurementsmentioning

confidence: 99%

Assessing the Electrochemical Stability Window of NASICON-Type Solid Electrolytes

et al. 2021

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All-Solid-State Lithium Batteries (ASSLBs) are promising since they may enable the use of high potential materials as positive electrode and lithium metal as negative electrode. This is only possible through solid electrolytes (SEs) stated large electrochemical stability window (ESW). Nevertheless, reported values for these ESWs are very divergent in the literature. Establishing a robust procedure to accurately determine SEs’ ESWs has therefore become crucial. Our work focuses on bringing together theoretical results and an original experimental set up to assess the electrochemical stability window of the two NASICON-type SEs Li1.3Al0.3Ti1.7(PO4)3 (LATP) and Li1.5Al0.5Ge1.5(PO4)3 (LAGP). Using first principles, we computed thermodynamic ESWs for LATP and LAGP and their decomposition products upon redox potentials. The experimental set-up consists of a sintered stack of a thin SE layer and a SE-Au composite electrode to allow a large contact surface between SE and conductive gold particles, which maximizes the redox currents. Using Potentiostatic Intermittent Titration Technique (PITT) measurements, we were able to accurately determine the ESW of LATP and LAGP solid electrolytes. They are found to be [2.65–4.6 V] and [1.85–4.9 V] for LATP and LAGP respectively. Finally, we attempted to characterize the decomposition products of both materials upon oxidation. The use of an O2 sensor coupled to the electrochemical setup enabled us to observe operando the production of O2 upon LAGP and LATP oxidations, in agreement with first-principles calculations. Transmission Electron Microscopy (TEM) allowed to observe the presence of an amorphous phase at the interface between the gold particles and LAGP after oxidation. Electrochemical Impedance Spectroscopy (EIS) measurements confirmed that the resulting phase increased the total resistance of LAGP. This work aims at providing a method for an accurate determination of ESWs, considered a key parameter to a successful material selection for ASSLBs.

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“…11 In this study, we adopt a different approach to investigate the electrochemical decomposition of LPSCl SE through an ultrathin metal film as electrode (and current collector) which is partially transparent to the photoelectrons. The idea of using electron-transparent films (e.g., graphene) for probing electrochemical processes has been demonstrated already in earlier studies, both in liquid [31][32][33][34] and solid phase 35 cell setups. These methodologies are not easily applicable to sulfide-based SEs due to their sensitivity to film transfer, cleaning or water exposure.…”

Section: Introductionmentioning

confidence: 96%

Operando Photoelectron Spectroscopy Analysis of Li6PS5Cl Electrochemical Decomposition Reactions in Solid-State Batteries

Aktekin,

Kataev,

Riegger

et al. 2024

Preprint

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Most solid electrolytes (SEs) which are promising for all-solid-state battery (ASSB) applications are known to have a narrow electrochemical stability window. Consequently, parasitic electrolyte reactions are observed when high-energy-density electrode materials such as lithium and silicon are employed, hindering their utilization in commercial battery systems. Therefore, it is crucial to understand at which potentials such reactions start, and which chemical species are present in the subsequently formed solid electrolyte interphase (SEI). Herein, a new operando experimental approach is introduced to investigate such reactions by employing hard X-ray photoelectron spectroscopy (HAXPES). This approach enables the examination of the SEI formed below a thin metal film (e.g., 6 nm nickel) acting as the working electrode. The feasibility of this approach is demonstrated using a sulfide-based Li6PS5Cl solid electrolyte (lithium argyrodite). It is shown that electrolyte reduction reactions start upon polarization of the working electrode to voltages below 1.75 V (vs. Li+/Li) and result in considerable Li2S formation, particularly in the voltage range of 1.5 – 1.0 V. The overall intensity trends confirm the heterogeneous/layered microstructure of the SEI (e.g., preferential Li2O and Li2S deposition near the current collector). The reversibility of side reactions is also observed, as Li2O and Li2S decompose in the 2–4 V potential window, generating oxidized sulfur species, sulfites and sulfates. The introduced experimental approach is promising for the spectroscopic investigation of electrolyte side reactions under dynamic conditions for various solid electrolyte and current collector combinations.

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In Situ XPS Studies of Solid Electrolyte Electroreduction Through Graphene Electrode

Cited by 7 publications

References 47 publications

Advances in studying interfacial reactions in rechargeable batteries by photoelectron spectroscopy

Advances in studying interfacial reactions in rechargeable batteries by photoelectron spectroscopy

Assessing the Electrochemical Stability Window of NASICON-Type Solid Electrolytes

Operando Photoelectron Spectroscopy Analysis of Li6PS5Cl Electrochemical Decomposition Reactions in Solid-State Batteries

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