The Hidden Side of Nanoporous β‐Li<sub>3</sub>PS<sub>4</sub> Solid Electrolyte

Marchini, Florencia; Porcheron, Benjamin; Rousse, Gwenaëlle; Blanquer, Laura Albero; Droguet, Léa; Foix, Dominique; Koç, Tuncay; Deschamps, Michaël; Tarascon, J. M.

doi:10.1002/aenm.202101111

Cited by 34 publications

(32 citation statements)

References 35 publications

(49 reference statements)

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“…After the first‐step milling with Li 2 S and P 2 S 5 powders at a molar ratio of 3:1 ( x = 0), only the diffraction peaks of the β ‐Li 3 PS 4 phase with Pnma space group were observed. [ 10 ] Although a broad background was detected suggesting the formation of amorphous phases, the sample prepared by the first‐step milling was denoted as Li 3 PS 4 . After the two‐step milling, the final samples were obtained (hereafter, referred to as (1− x )Li 3 PS 4 ·2 x LiBH 4 ).…”

Section: Resultsmentioning

confidence: 99%

Lithium Superionic Conduction in BH₄‐Substituted Thiophosphate Solid Electrolytes

et al. 2022

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Compared with conventional liquid electrolytes, solid electrolytes can better improve the safety properties and achieve high-energy-density Li-ion batteries. Sulfide-based solid electrolytes have attracted significant attention owing to their high ionic conductivities, which are comparable to those of their liquid counterparts. Among them, Li thiophosphates, including Li-argyrodites, are widely studied. In this study, Li thiophosphate solid electrolytes containing BH 4 − anions are prepared via a simple and fast milling method even without heat treatment. The synthesized materials exhibit a high ionic conductivity of up to 11 mS cm −1 at 25 °C, which is much higher than reported values. To elucidate the mechanism behind, the thiophosphate local structure, whose effect on the ionic conductivity remains unclear to date, is investigated. Raman and solid-state NMR spectroscopies are performed to identify the thiophosphate local structure in the sulfide samples. Based on the analysis results, the ratios of the different thiophosphate units in the prepared electrolyte samples are determined. It is found that the thiophosphate local structure can be varied by changing the amount of LiBH 4 and the milling conditions, which significantly impact the ionic conductivity. The all-solid-state cell with the prepared solid electrolyte exhibits superior cycle and rate performances.

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Section: Resultsmentioning

confidence: 99%

Lithium Superionic Conduction in BH₄‐Substituted Thiophosphate Solid Electrolytes

et al. 2022

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“…Its potential stability with lithium metal and high ionic conductivity in nanoporous form 19 have made it the subject of or prelude to many experimental and computational studies. 4 − 7 , 20 − 23 Li 3 PS 4 primarily exists as three main polymorphs: γ, β, and α, each with varying structural and physical properties. The γ polymorph ( Pmn 2 1 ) exhibits low room-temperature ionic conductivity (∼3 × 10 –7 S cm –1 ).…”

Section: Introductionmentioning

confidence: 99%

Disentangling Cation and Anion Dynamics in Li₃PS₄ Solid Electrolytes

et al. 2022

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A prerequisite for the realization of solid-state batteries is the development of highly conductive solid electrolytes. Li3PS4 is the archetypal member of the highly promising thiophosphate family of Li-ion conductors. Despite a multitude of investigations into this material, the underlying atomic-scale features governing the roles of and the relationships between cation and anion dynamics, in its various temperature-dependent polymorphs, are yet to be fully resolved. On this basis, we provide a comprehensive molecular dynamics study to probe the fundamental mechanisms underpinning fast Li-ion diffusion in this important solid electrolyte material. We first determine the Li-ion diffusion coefficients and corresponding activation energies in the temperature-dependent γ, β, and α polymorphs of Li3PS4 and relate them to the structural and chemical characteristics of each polymorph. The roles that both cation correlation and anion libration play in enhancing the Li-ion dynamics in Li3PS4 are then isolated and revealed. For γ- and β-Li3PS4, our simulations confirm that the interatomic Li–Li interaction is pivotal in determining (and restricting) their Li-ion diffusion. For α-Li3PS4, we quantify the significant role of Li–Li correlation and anion dynamics in dominating Li-ion transport in this polymorph for the first time. The fundamental understanding and analysis presented herein is expected to be highly applicable to other solid electrolytes where the interplay between cation and anion dynamics is crucial to enhancing ion transport.

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“…[27][28][29] However, in practice, such solution processes were shown to lead to phase contaminations or surficial remaining solvent species on solid ionic conductors. 30,31 Most of these aspects have already been addressed for most of ionic conductors independently and almost no cross-comparison between such studies have been made, with the exception of a recent study on halides that report their stability against argyrodite. 32 Thus to fill this gap, we decided to embark ourselves in a benchmarking study of solid-state batteries using coated-LiNi0.6Mn0.2Co0.2O2 as part of a composite positive electrodes also including β-Li3PS4, Li6PS5Cl and Li3InCl6 as solid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

In Search of the Best Solid Electrolyte-Layered Oxide Pairing for Assembling Practical All-Solid-State Batteries

Koç

Marchini

Rousse

et al. 2021

ACS Appl. Energy Mater.

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All-solid-state batteries (ASSBs) are the subject of large enthusiasm as they could boost by 50% the energy density of today's Li-ion batteries provided that several fundamental/practical roadblocks can be solved.Focusing on the interface between the solid electrolyte and cathode active material (CAM), we herein studied the chemical/electrochemical compatibility of coated-layered oxide LiNi0.6Mn0.2Co0.2O2 with the three main inorganic electrolytes contenders, these being lithium thiophosphate (β-Li3PS4), argyrodite (Li6PS5Cl), and halide (Li3InCl6). Such electrolytes were prepared by either solvent-free or solution chemistry and paired with the CAM to form a composite which was further tested by assembling solid-state batteries using Li0.5In as negative electrode. Amongst the electrolytes prepared by dry routes, the best performing was found to be Li6PS5Cl followed by β-Li3PS4 and lastly Li3InCl6. In contrast, no general trend of benefit or detriment was observed when switching to solution route as it resulted in either performance improvement or deterioration depending on the electrolyte. Additionally, we show a strong dependence of the battery performance upon the presence of carbon additives. Lastly, we unraveled a pronounced chemical/electrochemical incompatibility of Li3InCl6 towards Li6PS5Cl and β-Li3PS4, hence questioning the design of hetero-structural cell architectures. Altogether, we hope these findings to provide guidance in the proper pairing of electrode-electrolytes components for designing highly performing solid-state batteries.

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The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

Cited by 34 publications

References 35 publications

Lithium Superionic Conduction in BH₄‐Substituted Thiophosphate Solid Electrolytes

Lithium Superionic Conduction in BH₄‐Substituted Thiophosphate Solid Electrolytes

Disentangling Cation and Anion Dynamics in Li₃PS₄ Solid Electrolytes

In Search of the Best Solid Electrolyte-Layered Oxide Pairing for Assembling Practical All-Solid-State Batteries

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The Hidden Side of Nanoporous β‐Li3PS4 Solid Electrolyte

Cited by 34 publications

References 35 publications

Lithium Superionic Conduction in BH4‐Substituted Thiophosphate Solid Electrolytes

Lithium Superionic Conduction in BH4‐Substituted Thiophosphate Solid Electrolytes

Disentangling Cation and Anion Dynamics in Li3PS4 Solid Electrolytes

In Search of the Best Solid Electrolyte-Layered Oxide Pairing for Assembling Practical All-Solid-State Batteries

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Resources

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The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

Lithium Superionic Conduction in BH₄‐Substituted Thiophosphate Solid Electrolytes

Lithium Superionic Conduction in BH₄‐Substituted Thiophosphate Solid Electrolytes

Disentangling Cation and Anion Dynamics in Li₃PS₄ Solid Electrolytes