Li7PS6 and Li6PS5X (X: Cl, Br, I): Possible Three‐dimensional Diffusion Pathways for Lithium Ions and Temperature Dependence of the Ionic Conductivity by Impedance Measurements

Deiseroth, H. J.; Maier, Joachim; Weichert, Katja; Nickel, Vera; Kong, Shiao‐Tong; Reiner, Christof

doi:10.1002/zaac.201100158

Cited by 154 publications

(190 citation statements)

References 17 publications

(26 reference statements)

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“…MD simulations also suggest 0.14 eV for a localized motion close to the BV prediction of E A for Li(1)-Li(2)-Li (1) pathways. This pathway model for Li 6 PS 5 I is essentially identical to the model proposed by Deiseroth et al [6] based on crystal-geometrical considerations, but it should be noted that in contrast to what the authors implied, we find that argyrodites containing different halide ions exhibit differences in their Li + ion transport pathways that may be traced back to the difference in the halide/sulphide anion size ratio as well as the difference in the degree of anion ordering.…”

Section: Resultsmentioning

confidence: 55%

“…With such high lithium mobilities, these materials may be ideal for use as solid electrolytes in lithium-ion batteries. Very recent impedance and DC polarization studies by the same group suggest significantly lower dc conductivities but high chemical diffusion coefficients for pressed pellets of various argyrodites [6]. Here, we prepare argyrodite-type Li 6 PS 5 X (X = Cl, Br, I) using mechanical milling followed by annealing of the samples.…”

Section: Introductionmentioning

confidence: 96%

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Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes

Rao

Sharma

Peterson

et al. 2011

J Solid State Electrochem

198

213

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All-solid-state rechargeable lithium-ion batteries (AS-LIBs) are attractive power sources for electrochemical applications due to their potentiality in improving safety and stability over conventional batteries with liquid electrolytes. Finding a solid electrolyte with high ionic conductivity and compatibility with other battery components is a key factor in raising the performance of AS-LIBs. In this work, we prepare argyrodite-type Li 6 PS 5 X (X = Cl, Br, I) using mechanical milling followed by annealing. X-ray diffraction characterization reveals the formation and growth of crystalline Li 6 PS 5 X in all cases. Ionic conductivity of the order of 7×10 −4 S cm −1 in Li 6 PS 5 Cl and Li 6 PS 5 Br renders these phases suitable for AS-LIBs. Joint structure refinements using high-resolution neutron and laboratory X-ray diffraction provide insight into the influence of disorder on the fast ionic conductivity. Besides the disorder in the lithium distribution, it is the disorder in the S 2− /Cl − or S 2− /Br − distribution that we find to promote ion mobility, whereas the large I − cannot be exchanged for S 2− and the resulting more ordered Li 6 PS 5 I exhibits only a moderate conductivity. Li + ion migration pathways in the crystalline compounds are modelled using the bond valence approach to interpret the differences between argyrodites containing different halide ions.

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Section: Resultsmentioning

confidence: 55%

Section: Introductionmentioning

confidence: 96%

Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes

Rao

Sharma

Peterson

et al. 2011

J Solid State Electrochem

198

213

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“…The structure of Li 7 Ge 3 PS 12 is featured by ordered arrangement of (P/Ge)S 4 3− tetrahedra, in contrary to the ordered PS 4 3− tetrahedra in Li 7 PS 6 and anion‐substituted Li 6 PS 5 X structure (Figure d). The ionic conductivity of Li 7 Ge 3 PS 12 was determined to be 1.1 × 10 −4 S cm −1 at 25 °C (with the presence of 2.4 wt% Li 4 P 2 S 6 impurities), which is higher than that of Li 7 PS 6 (10 −6 S cm −1 ) …”

Section: Sulfide‐based Solid‐state Electrolytesmentioning

confidence: 93%

Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries

et al. 2019

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Due to their high ionic conductivity and adeciduate mechanical features for lamination, sulfide composites have received increasing attention as solid electrolyte in all-solid-state batteries. Their smaller electronegativity and binding energy to Li ions and bigger atomic radius provide high ionic conductivity and make them attractive for practical applications. In recent years, noticeable efforts have been made to develop high-performance sulfide solid-state electrolytes. However, sulfide solid-state electrolytes still face numerous challenges including: 1) the need for a higher stability voltage window, 2) a better electrode-electrolyte interface and air stability, and 3) a cost-effective approach for large-scale manufacturing. Herein, a comprehensive update on the properties (structural and chemical), synthesis of sulfide solid-state electrolytes, and the development of sulfide-based all-solid-state batteries is provided, including electrochemical and chemical stability, interface stabilization, and their applications in high performance and safe energy storage.

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“…14,80,[84][85][86]117,118 Within this close-packed structure, phosphorus atoms fill tetrahedral interstices, forming a network of isolated PS 4 tetrahedron (similarly to the thio-LISICON structure), while lithium ions are randomly distributed over the remaining tetrahedral interstices (48h and 24g sites). Lithium-ion diffusion occurs through these partially occupied positions, forming hexagonal cages, which are connected to each other by an interstitial site around the halide ions in the case of Li 6 PS 5 Cl and around the sulfur anions in Li 6 PS 5 I.…”

Section: Argyroditementioning

confidence: 98%

Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction

Bachman¹,

Muy²,

Grimaud³

et al. 2015

Chem. Rev.

1,969

1,656

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This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochemical energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the conductivity through interfacial effects-specifically controlling grain boundaries and strain at the interfaces-is introduced. High-frequency dielectric constants and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Experimental studies and theoretical results are discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present Review aims to provide insight into the physical parameters affecting the diffusion process, to allow for more efficient and target-oriented research on improving solid-state ion conductors.

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Li₇PS₆ and Li₆PS₅X (X: Cl, Br, I): Possible Three‐dimensional Diffusion Pathways for Lithium Ions and Temperature Dependence of the Ionic Conductivity by Impedance Measurements

Cited by 154 publications

References 17 publications

Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes

Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes

Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries

Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction

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