Targeting Superionic Conductivity by Turning on Anion Rotation at Room Temperature in Fast Ion Conductors

Zhang, Zhizhen; Li, Hui; Kaup, Kavish; Zhou, Laidong; Roy, Pierre‐Nicholas; Nazar, Linda F.

doi:10.1016/j.matt.2020.04.027

Cited by 99 publications

(118 citation statements)

References 50 publications

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“…4d ). While similar behavior has been observed in lithium superionic conductors containing borohydride anions B 10 H 10 2− 32 , B 12 H 12 2− 33 , and BH 4 − 34 , and the sulfides β-Li 3 PS 4 and Li 3.25 Si 0.25 P 0.75 S 4 35 , this is the first observed instance of rotational motion of Cl − in a halide single ion conductor. It is important to note that while there is polyanionic rotation, there is no signature for Zr(Y)-Cl bond breaking (Supplementary Fig.…”

Section: Resultssupporting

confidence: 77%

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

et al. 2021

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Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na3-xY1-xZrxCl6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10−5 S cm−1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2 + NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room temperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.

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Section: Resultssupporting

confidence: 77%

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

et al. 2021

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“…4d). While similar behavior has been observed in lithium superionic conductors containing borohydride anions B10H10 2-, 29 B12H12 2-, 30 and BH4 -, 31 and the sulfides β-Li3PS4 and Li3.25Si0.25P0.75S4 32 , this is the first observed instance of rotational motion of Clin a halide single ion conductor. It is important to note that while there is polyanionic rotation, there is no signature for Zr(Y)-Cl bond breaking (Fig.…”

Section: Mechanism For Enhanced Conductivitysupporting

confidence: 77%

A Stable Cathode-Solid Electrolyte Composite for Long-Cycle-Life, High Voltage Solid-State Sodium-ion Batteries

Wu¹,

Banerjee²,

Tang³

et al. 2020

Preprint

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Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of Na3-xY1-xZrxCl6 (NYZC) as an ion conductor that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 x 10-5 S cm-1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2+NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room temperature and can cycle over 1000 cycles with 89.3% capacity retention at 40°C. These findings highlight the immense potential of halide ion conductors for SSSB applications.

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“…They found that [PX 4 ] 3− rotation transiently widens the bottlenecks in the migration pathways, introducing dynamical frustration that facilitates Na + diffusion. A similar mechanism has also been suggested in crystalline thiophosphates by several other authors, generally based on correlation between enhanced [PX 4 ] 3− rotational mobility and cation diffusion upon chemical or structural modification [84,[89][90][91][92][93][94]. In addition to the crystalline phases, Smith et al demonstrated that significant coupling between cation diffusion and the anion motion can be present in the Li 3 PS 4 glass at low temperature [95].…”

Section: (A) Soft Modes and Rotational Disordersupporting

confidence: 61%

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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Targeting Superionic Conductivity by Turning on Anion Rotation at Room Temperature in Fast Ion Conductors

Cited by 99 publications

References 50 publications

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

A Stable Cathode-Solid Electrolyte Composite for Long-Cycle-Life, High Voltage Solid-State Sodium-ion Batteries

Paradigms of frustration in superionic solid electrolytes

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