Assessing the Electrochemical Stability Window of NASICON-Type Solid Electrolytes

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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Computational screening and first-principles investigations of NASICON-type LixM2(PO4)3 as solid electrolytes for Li batteries

Journal of Materials Chemistry A ◽

10.1039/c7ta08968f ◽

2018 ◽

Vol 6 (6) ◽

pp. 2625-2631 ◽

Cited By ~ 22

Author(s):

Xudong Zhao ◽

Zihe Zhang ◽

Xu Zhang ◽

Bin Tang ◽

Zhaojun Xie ◽

...

Keyword(s):

First Principles ◽

Solid Electrolytes ◽

Computational Screening ◽

Nasicon Type ◽

Li Batteries

Li-containing NASICONs were screened from the Materials Project database and seven kinds of LixM2(PO4)3 are proposed as solid electrolytes for Li batteries.

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(Battery Division Student Research Award sponsored by Mercedes-Benz Research & Development) Revisiting the Electrochemical Stability Window of Solid Electrolytes

ECS Meeting Abstracts ◽

10.1149/ma2018-02/1/36 ◽

2018 ◽

Keyword(s):

Solid Electrolytes ◽

Electrochemical Stability ◽

Research Development ◽

Student Research ◽

Research Award ◽

Electrochemical Stability Window

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The role of glass crystallization processes in preparation of high Li-conductive NASICON-type ceramics

CrystEngComm ◽

10.1039/c9ce00386j ◽

2019 ◽

Vol 21 (19) ◽

pp. 3106-3115 ◽

Cited By ~ 7

Author(s):

Victor A. Vizgalov ◽

Tina Nestler ◽

Anastasia Vyalikh ◽

Ivan A. Bobrikov ◽

Oleksandr I. Ivankov ◽

...

Keyword(s):

Solid Electrolytes ◽

Electrochemical Stability ◽

Glass Crystallization ◽

Storage Devices ◽

Nasicon Type ◽

Electrochemical Storage

One of the approaches to tackle the problem of limited electrolyte electrochemical stability, which controls the development of novel electrochemical storage devices, is the use of solid electrolytes.

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Study of nanostructured ultra-refractory Tantalum-Hafnium-Carbide electrodes with wide electrochemical stability window

Chemical Engineering Journal ◽

10.1016/j.cej.2021.128987 ◽

2021 ◽

Vol 415 ◽

pp. 128987

Author(s):

Emerson Coy ◽

Visnja Babacic ◽

Luis Yate ◽

Karol Załęski ◽

Yeonho Kim ◽

...

Keyword(s):

Electrochemical Stability ◽

Hafnium Carbide ◽

Electrochemical Stability Window

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A Critical Review for an Accurate Electrochemical Stability Window Measurement of Solid Polymer and Composite Electrolytes

Materials ◽

10.3390/ma14143840 ◽

2021 ◽

Vol 14 (14) ◽

pp. 3840

Author(s):

Adrien Méry ◽

Steeve Rousselot ◽

David Lepage ◽

Mickaël Dollé

Keyword(s):

Ionic Conductivity ◽

Energy Density ◽

High Performance ◽

Mechanical Stability ◽

Electrochemical Stability ◽

Solid Polymer Electrolytes ◽

Solid Polymer ◽

Composite Electrolytes ◽

Battery System ◽

Electrochemical Stability Window

All-solid-state lithium batteries (ASSLB) are very promising for the future development of next generation lithium battery systems due to their increased energy density and improved safety. ASSLB employing Solid Polymer Electrolytes (SPE) and Solid Composite Electrolytes (SCE) in particular have attracted significant attention. Among the several expected requirements for a battery system (high ionic conductivity, safety, mechanical stability), increasing the energy density and the cycle life relies on the electrochemical stability window of the SPE or SCE. Most published works target the importance of ionic conductivity (undoubtedly a crucial parameter) and often identify the Electrochemical Stability Window (ESW) of the electrolyte as a secondary parameter. In this review, we first present a summary of recent publications on SPE and SCE with a particular focus on the analysis of their electrochemical stability. The goal of the second part is to propose a review of optimized and improved electrochemical methods, leading to a better understanding and a better evaluation of the ESW of the SPE and the SCE which is, once again, a critical parameter for high stability and high performance ASSLB applications.

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First-Principles DFT Study on Inverse Ruddlesden–Popper Tetragonal Compounds as Solid Electrolytes for All-Solid-State Li+-Ion Batteries

Chemistry of Materials ◽

10.1021/acs.chemmater.1c00124 ◽

2021 ◽

Author(s):

Randy Jalem ◽

Yoshitaka Tateyama ◽

Kazunori Takada ◽

Masanobu Nakayama

Keyword(s):

Solid State ◽

First Principles ◽

Solid Electrolytes ◽

Dft Study ◽

Li Ion Batteries ◽

Li Ion

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The influence of the host–guest interaction on the oxidation of natural flavonoid dyes

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc2011106 ◽

2011 ◽

Vol 76 (12) ◽

pp. 1651-1667 ◽

Cited By ~ 5

Author(s):

Šárka Ramešová ◽

Romana Sokolová ◽

Ilaria Degano ◽

Magdaléna Hromadová ◽

Miroslav Gál ◽

...

Keyword(s):

Cyclic Voltammetry ◽

Inclusion Complex ◽

Fluorescence Intensity ◽

Oxidation Product ◽

Aqueous Media ◽

Electrochemical Methods ◽

Redox Potentials ◽

Decomposition Products ◽

Degradation Processes ◽

Bioorganic Compounds

The influence of the molecular cavity protection on degradation processes of bioorganic compounds quercetin and luteolin used as the original dyes in old tapestries was studied. The degradation processes were studied by electrochemical methods in aqueous media. The products of the exhaustive electrolysis were separated and identified by GC-MS analysis. Cyclic voltammetry characteristics indicate that the inclusion complex is formed. The inclusion affects the redox potentials of both oxidation waves related to the different dissociation forms of the flavonoid molecule. It was shown that decomposition products formed by the oxidation of quercetin are stabilized in the cavity of β-cyclodextrin, including the main oxidation product 2(3′,4′-dihydroxybenzoyl)-2,4,6-trihydroxybenzofuran-3(2H)-one. The formation of the 1:1 inclusion complex of luteolin with β-cyclodextrin is supported by the enhancement of fluorescence intensity. In the case of quercetin, a decrease of fluorescence intensity occurs when 1:1 inclusion complex with β-cyclodextrin is formed.

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Enhanced ionic conductivity and electrochemical stability of Indium doping Li1.3Al0.3Ti1.7(PO4)3 solid electrolytes for all-solid-state lithium-ion batteries

Ionics ◽

10.1007/s11581-021-04310-8 ◽

2021 ◽

Author(s):

Jieqiong Li ◽

Chengjin Liu ◽

Chang Miao ◽

Zhiyan Kou ◽

Wei Xiao

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Lithium Ion Batteries ◽

Solid Electrolytes ◽

Lithium Ion ◽

Electrochemical Stability ◽

Indium Doping

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Mono- and Bi-Molecular Adsorption of SF6 Decomposition Products on Pt Doped Graphene: A First-Principles Investigation

Applied Sciences ◽

10.3390/app8102010 ◽

2018 ◽

Vol 8 (10) ◽

pp. 2010 ◽

Cited By ~ 2

Author(s):

Yongqian Wu ◽

Shaojian Song ◽

Dachang Chen ◽

Xiaoxing Zhang

Keyword(s):

Single Molecule ◽

First Principles ◽

Density Functional ◽

Energy Gap ◽

Adsorption Parameters ◽

Functional Theory ◽

Decomposition Products ◽

Before And After ◽

Doped Graphene ◽

Sf6 Decomposition

Based on the first-principles of density functional theory, the SF6 decomposition products including single molecule (SO2F2, SOF2, SO2), double homogenous molecules (2SO2F2, 2SOF2, 2SO2) and double hetero molecules (SO2 and SOF2, SO2 and SO2F2, SOF2 and SO2F2) adsorbed on Pt doped graphene were discussed. The adsorption parameters, electron transfer, electronic properties and energy gap was investigated. The adsorption of SO2, SOF2 and SO2F2 on the surface of Pt-doped graphene was a strong chemisorption process. The intensity of chemical interactions between the molecule and the Pt-graphene for the above three molecules was SO2F2 > SOF2 > SO2. The change of energy gap was also studied and according to the value of energy gap, the conductivity of Pt-graphene before and after adsorbing different gas molecules can be evaluated.

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