Impact of the Li substructure on the diffusion pathways in alpha and beta Li3PS4: an in situ high temperature neutron diffraction study

Kaup, Kavish; Zhou, Laidong; Huq, Ashfia; Nazar, Linda F.

doi:10.1039/d0ta02805c

Cited by 55 publications

(108 citation statements)

References 42 publications

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“…in 2010 for bulk β‐Li 3 PS 4 at high temperature, [ 27 ] but in agreement with the recently suggested by Nazar et al. [ 5 ] The activation energies for Li + conduction were also determined for LC, MC, and HC samples from the Arrhenius‐like fitting (Equation (12) in Experimental Section) of their temperature dependent EIS spectra, these being 0.35, 0.37, and 0.39 eV, respectively, in line with the trend found for the ionic conductivity in such samples (Figure 9d).…”

Section: Resultssupporting

confidence: 91%

“…[ 3,4 ] Further heating above 475 °C leads to the conversion into the highly conductive α‐phase, whose structure has been recently elucidated by neutron diffraction. [ 5 ]…”

Section: Introductionmentioning

confidence: 99%

“…[ 15–19 ] A higher level of complexity was revealed in a recent study claiming for the first time the presence of an amorphous H‐containing secondary phase as a promoter for the stabilization of the metastable β‐Li 3 PS 4 . [ 5 ]…”

Section: Introductionmentioning

confidence: 99%

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The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

Marchini

Porcheron

Rousse

et al. 2021

Advanced Energy Materials

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Solid‐state batteries are enjoying a regained interest owing to the discovery of sulfide‐based solid electrolytes with ionic conductivities comparable to their liquid counterparts. Among them, the metastable β‐Li3PS4 polymorph has attracted great attention given its high room temperature ionic conductivity (≈0.15 mS cm−1) when synthesized via a solvent‐mediated route. However, the origin of such a high conductivity together with its structural interplay remains unclear. Herein, an in‐depth study of the THF‐synthesized nanoporous β‐Li3PS4 is reported. Synchrotron X‐ray diffraction, NMR, and Raman spectroscopy confirm the presence of β‐Li3PS4 as the only crystalline phase and also reveal an additional amorphous phase and remnant THF. Moreover, a clear dependence of the ionic conductivity of the material on the relative content of its phases is found, the amorphous one being the most conductive. Lastly, high chemical reactivity is found for the nanoporous β‐Li3PS4 and other phosphosulfide electrolytes toward Li metal, evidenced in the spontaneous ignition when mixed together and further investigated by XRD and XPS. This study, which unveils a hidden side of the THF‐synthesized β‐Li3PS4 and other sulfide solid electrolytes, provides a new insight to the battery community when selecting a proper electrolyte for practical all‐solid state batteries.

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Section: Resultssupporting

confidence: 91%

“…[ 3,4 ] Further heating above 475 °C leads to the conversion into the highly conductive α‐phase, whose structure has been recently elucidated by neutron diffraction. [ 5 ]…”

Section: Introductionmentioning

confidence: 99%

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The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

Marchini

Porcheron

Rousse

et al. 2021

Advanced Energy Materials

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“…In situ XRD results show that α‐Li 3 PS 4 will directly generate γ‐Li 3 PS 4 without forming β phase during the cooling process, and its ion conductivity is only 3 × 10 −7 S cm −1 . Recently, Kaup et al 78 found that Si‐substituted Li 3.25 Si 0.25 P 0.75 S 4 can well stabilize the β‐phase structure and can still maintain β‐Li 3 PS 4 structure at 600°C (Figure 5(A)). In addition, Stöffler et al 79 found that some Li 4 P 2 S 6 phases will be formed during the heating process of Li 3 PS 4 , and the phenomenon of sulfur sublimation can be observed at ~660°C.…”

Section: Material‐level Thermal Stability Of Sesmentioning

confidence: 99%

Progress in thermal stability of all‐solid‐state‐Li‐ion‐batteries

Wang

et al. 2021

InfoMat

178

108

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Thermal safety is one of the major issues for lithium‐ion batteries (LIBs) used in electric vehicles. The thermal runaway mechanism and process of LIBs have been extensively studied, but the thermal problems of LIBs remain intractable due to the flammability, volatility and corrosiveness of organic liquid electrolytes. To ultimately solve the thermal problem, all‐solid‐state LIBs (ASSLIBs) are considered to be the most promising technology. However, research on the thermal stability of solid‐state electrolytes (SEs) is still in its initial stage, and the thermal safety of ASSLIBs still needs further validation. Moreover, the specified reviews summarizing the thermal stability of ASSLIBs and all types of SEs are still missing. To fill this gap, this review systematically discussed recent progress in the field of thermal properties investigation for ASSLIBs, form levels of materials and interface to the whole battery. The thermal properties of three major types of SEs, including polymer, oxide, and sulfide SEs are systematically reviewed here. This review aims to provide a comprehensive understanding of the thermal stability of SEs for the benign development of ASSLIBs and their promising application under practical operating conditions.

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“…In anti-perovskites, like Li 3 OCl, cation motion is largely vacancy driven(REFS), 45,46 with the displacement of a cation required before another cation can take its place and so, if the E a associated with a cation hop is large, very little transport occurs at all, correlated or otherwise. However, in Li 3 PS 4 (and other thiophosphate materials), a different mechanism has been proposed, namely, the so-called 'paddle-wheel effect', 47,48 which refers to the complex motion of polyanions that are able to undergo rotations that drive the concerted motion of cations. Even if the GBs have relatively little impact on the actual E a of cation transport, the change in the degree of correlation might lead one to assume that these polyanion rotations are inhibited in the vicinity of the boundary.…”

Section: Resultsmentioning

confidence: 99%

Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors

Dawson

Quirk

2022

Preprint

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Although polycrystalline solid electrolytes are central to the utilization of solid- state batteries with lithium metal anodes, lithium dendrite formation and reduced Li-ion conductivity at their grain boundaries remain primary concerns. Given that experimental studies on polycrystalline materials are notoriously difficult to perform and interpret, computational techniques are invaluable for providing insight at the atomic scale. Here, we carry out first-principles calculations on representative grain boundaries in three important Li-based solid electrolyte families, namely, an anti-perovskite oxide, Li3OCl, a thiophosphate, Li3PS4, and a halide, Li3InCl6, to demonstrate the significantly different impacts that grain boundaries have on their electronic structure, ion conductivity and correlated ion transport. Our results show that even when grain boundaries do not significantly impact ionic conductivity, they can still strongly perturb the electronic structure and contribute to undesirable electrical conductivity and potential lithium dendrite propagation. We also illustrate, for the first time, how cor- related motion, including the so-called paddle-wheel mechanism, which has so far only been considered for the bulk, can vary substantially at grain boundaries. Our findings reveal the dramatically different behaviour of solid electrolytes at the grain boundary compared to the bulk and its potential consequences and benefits for the design of solid-state batteries.

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Impact of the Li substructure on the diffusion pathways in alpha and beta Li₃PS₄: an in situ high temperature neutron diffraction study

Cited by 55 publications

References 42 publications

The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

Progress in thermal stability of all‐solid‐state‐Li‐ion‐batteries

Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors

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Impact of the Li substructure on the diffusion pathways in alpha and beta Li3PS4: an in situ high temperature neutron diffraction study

Cited by 55 publications

References 42 publications

The Hidden Side of Nanoporous β‐Li3PS4 Solid Electrolyte

The Hidden Side of Nanoporous β‐Li3PS4 Solid Electrolyte

Progress in thermal stability of all‐solid‐state‐Li‐ion‐batteries

Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors

Contact Info

Product

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Impact of the Li substructure on the diffusion pathways in alpha and beta Li₃PS₄: an in situ high temperature neutron diffraction study

The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte

The Hidden Side of Nanoporous β‐Li₃PS₄ Solid Electrolyte