Li10GeP2S12‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Kato, Yoshifumi; Hori, Shingo; Kanno, Ryoji

doi:10.1002/aenm.202002153

Cited by 122 publications

(99 citation statements)

References 120 publications

(306 reference statements)

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“…[38,40] As described in Figure 2c, in comparison to many different SSEs, thio-/LISICON-like SSE stand out because of their excellent ionic conductivity, which has attracted the attention of many researchers. [34,41] The crystalline structure of the thio-/LISICON compounds is consistent with that of γ-Li 3 PO 4 , with an orthorhombic unit cell and Pnma space group where all cations are tetrahedral coordination. [34] Since the 1980s, a significant amount of research effort has been conducted on LISICONs.…”

Section: Brief Development History Of Thio-/lisicon and Lgps-type Ele...supporting

confidence: 52%

Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

Tao

Ren²,

et al. 2022

Adv Funct Materials

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As an integral part of all‐solid‐state lithium (Li) batteries (ASSLBs), solid‐state electrolytes (SSEs) must meet requirements in high ionic conductivity, electrochemical/chemical stability toward the electrode. The ionic conductivity of the Li super ionic conductor (LISICON) is limited, and the thio‐LISICON is improved by replacing O2− in the LISICON with S2−. Currently, the ionic conductivity of Li10GeP2S12 (LGPS) has exceeded 10 mS cm−1, which meets the demands of commercial ASSLBs. However, poor stability of SSEs, baneful interfacial reactions, Li dendrite growth, and other factors have impeded the development of ASSLBs. Hence, this review first traces the development progress of thio‐/LISICON and LGPS‐type SSEs, analyzes the complicated ion transport mechanism, and summarizes the effective strategies for improving ionic conductivity. Moreover, exciting methods focusing on electrode interface engineering are outlined separately. As to SSE/anode interface, poor chemical or electrochemical compatibility, poor interfacial contact, and the mechanisms of dendrite formation are discussed. For the SSE/cathode interface, poor interfacial stability and non‐intimate solid–solid contact are daunting challenges. Then, effective methods to improve interface stability and electrochemical performance of ASSLBs with LGPS‐type SSEs are introduced. Finally, combined with the present chances and challenges, the possible future developing directions of LGPS‐based ASSLBs and the perspectives are proposed.

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Section: Brief Development History Of Thio-/lisicon and Lgps-type Ele...supporting

confidence: 52%

Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

Tao

Ren²,

et al. 2022

Adv Funct Materials

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“…However, we point out that the existence of highly correlated dynamics and hotspots-while common in many solid electrolytes-is not itself a necessary condition for superionic behaviour. This can be seen by comparing the spatiotemporal analysis of LLZO to that of the thiophosphate Li 10 GeP 2 S 12 (LGPS) [60,93,[122][123][124][125] in figure 4a. In contrast to LLZO, LGPS has almost liquidlike anisotropic diffusion along one-dimensional channels, with little clear evidence of hotspots.…”

Section: (B) Correlation and Local Fluctuations In Cation Mobilitymentioning

confidence: 97%

Paradigms of frustration in superionic solid electrolytes

Wood

Varley

Kweon

et al. 2021

Phil. Trans. R. Soc. A.

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Superionic solid electrolytes have widespread use in energy devices, but the fundamental motivations for fast ion conduction are often elusive. In this Perspective, we draw upon atomistic simulations of a wide range of superionic conductors to illustrate some ways frustration can lower diffusion cation barriers in solids. Based on our studies of halides, oxides, sulfides and hydroborates and a survey of published reports, we classify three types of frustration that create competition between different local atomic preferences, thereby flattening the diffusive energy landscape. These include chemical frustration, which derives from competing factors in the anion–cation interaction; structural frustration, which arises from lattice arrangements that induce site distortion or prevent cation ordering; and dynamical frustration, which is associated with temporary fluctuations in the energy landscape due to anion reorientation or cation reconfiguration. For each class of frustration, we provide detailed simulation analyses of various materials to show how ion mobility is facilitated, resulting in stabilizing factors that are both entropic and enthalpic in origin. We propose the use of these categories as a general construct for classifying frustration in superionic conductors and discuss implications for future development of suitable descriptors and improvement strategies. This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.

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“…[124][125][126] Wang et al have systematically studied the influences of the anion-host matrix on the ionic conductivity of solid-state Li-ion conductors, such as Li 10 GeP 2 S 12 and Li 7 P 3 S 11 . [111,127] As demonstrated in Figure 8, a structure matching algorithm was used to map the sulfur positions to the three most common lattices, namely, body-centered cubic one (bcc, Figure 8a), face-centered cubic one (fcc, Figure 8b), and hexagonal close-packed one (hcp, Figure 8c), and a comparison was given on the calculated Li-ion migration barriers in the absence of other cations. [111] It was found that the most stable Li sites were the tetrahedral sites in all the three crystal lattices.…”

Section: Electrolytesmentioning

confidence: 99%

Crystal Channel Engineering for Rapid Ion Transport: From Nature to Batteries

Mei

Liao

Sun

2021

Chemistry A European J

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Ion transport behaviours through cell membranes are commonly identified in biological systems, which are crucial for sustaining life for organisms. Similarly, ion transport is significant for electrochemical ion storage in rechargeable batteries, which has attracted much attention in recent years. Rapid ion transport can be well achieved by crystal channels engineering, such as creating pores or tailoring interlayer spacing down to the nanometre or even sub‐nanometre scale. Furthermore, some functional channels, such as ion selective channels and stimulus‐responsive channels, are developed for smart ion storage applications. In this review, the typical ion transport phenomena in the biological systems, including ion channels and pumps, are first introduced, and then ion transport mechanisms in solid and liquid crystals are comprehensively reviewed, particularly for the widely studied porous inorganic/organic hybrid crystals and ultrathin inorganic materials. Subsequently, recent progress on the ion transport properties in electrodes and electrolytes is reviewed for rechargeable batteries. Finally, current challenges in the ion transport behaviours in rechargeable batteries are analysed and some potential research approaches, such as bioinspired ultrafast ion transport structures and membranes, are proposed for future studies. It is expected that this review can give a comprehensive understanding on the ion transport mechanisms within crystals and provide some novel design concepts on promoting electrochemical ion storage capability in rechargeable batteries.

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Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Cited by 122 publications

References 120 publications

Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

Paradigms of frustration in superionic solid electrolytes

Crystal Channel Engineering for Rapid Ion Transport: From Nature to Batteries

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