Hopping Rate and Migration Entropy as the Origin of Superionic Conduction within Solid-State Electrolytes

Li, Xiaona; Liu, Honggang; Zhao, Changtai; Kim, Jung Tae; Fu, Jiamin; Hao, Xiaoge; Li, Weihan; Li, Ruying; Chen, Ning; Cao, Duanyun; Wu, Zhenwei; Su, Yuefeng; Liang, Jianwen; Sun, Xueliang

doi:10.1021/jacs.3c01955

Cited by 15 publications

(2 citation statements)

References 44 publications

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“…For SS-synthesized Li–Y–Cl SEs, with the decrease in Li content, the Li + carrier concentration becomes more dependent on the thermal activation process along with more trapped Li + carriers in the lattice (as reflected by the increasing E f and C e values), resulting in the higher concentration of Li + carriers at near-RT ( Figure S9 ). Although the effective attempt frequency (ω e ) becomes lower as Li stoichiometry decreases (0 < x ≤ 0.13 in SS-Li 3–3 x Y 1+ x Cl 6 ), which may be caused by the smaller migration entropy in Li deficient SEs, 50 the energy barrier that hopping migration needs to overcome ( E m ) decreases from 0.409 to 0.213 eV. As a 0.2 eV decrease in E m leads to about a two-thousand-fold increase in exp(− E m / k B T ) at RT, much larger than the 2 orders of magnitude difference in ω e of SS-synthesized Li–Y–Cl SEs, the hopping frequency ω p is mainly determined by E m .…”

Section: Ionic Conductivity and LI + Carrier Analysismentioning

confidence: 99%

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity

Yang,

Kim,

Chen

2024

ACS Energy Lett.

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Owing to their high-voltage stabilities, halide superionic conductors such as Li 3 YCl 6 recently emerged as promising solid electrolyte (SE) materials for all-solid-state batteries (ASSBs). It has been shown that by either introducing off-stoichiometry in solid-state (SS) synthesis or using a mechanochemical (MC) synthesis method the ionic conductivities of Li 3−3x Y 1+x Cl 6 can increase up to an order of magnitude. The underlying mechanism, however, is unclear. In the present study, we adopt a hopping frequency analysis method of impedance spectra to reveal the correlations in stoichiometry, crystal structure, synthesis conditions, Li + carrier concentrations, hopping migration barriers, and ionic conductivity. We show that unlike the conventional Li 3 YCl 6 made by SS synthesis, mobile Li + carriers in the defect-containing SS-Li 3−3x Y 1+x Cl 6 (0 < x < 0.17) and MC-Li 3−3x Y 1+x Cl 6 are generated with an activation energy and their concentration is dependent on temperature. Higher ionic conductivities in these samples arise from a combination of a higher Li + carrier concentration and lower migration energy barriers. A new off-stoichiometric halide (Li 2.61 Y 1.13 Cl 6 ) with the highest ionic conductivity (0.47 mS cm −1 ) in the series is discovered, which delivers exceptional cycling performance (∼90% capacity retention after 1000 cycles) in ASSB cells equipped with an uncoated high-energy LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode. This work sheds light on the thermal activation process that releases trapped Li + ions in defect-containing halides and provides guidance for the future development of superionic conductors for all-solid-state batteries.

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Section: Ionic Conductivity and LI + Carrier Analysismentioning

confidence: 99%

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity

Yang,

Kim,

Chen

2024

ACS Energy Lett.

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“…To gain further insight into entropic contribution, the migration entropy of Na 1+x Ta 1−x Zr x Cl 6 was estimated by deconvoluting the prefactor contributions with the characteristic frequency of the migration processes. This estimation is conducted in a similar manner as the work on the halide solid solution of xLiCl-InCl 3 by Li et al 47 The detailed analysis is summarized in the Supporting Information and the comparison of the trends in prefactor and resulting migration entropy is displayed in Figure 5a.…”

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confidence: 99%

NaMCl₆ (M = Nb and Ta): A New Class of Sodium-Conducting Halide-Based Solid Electrolytes

Huang,

Yoshida,

Akamatsu

et al. 2024

ACS Materials Lett.

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Highly conductive solid electrolytes (SEs) are a prerequisite for developing all-solid-state batteries. Recently, Li-ion conducting halide-based SEs have attracted enormous attention owing to their electrochemical, mechanical, and transport properties. Despite the success of Li-ion conducting halides, the research on the Na analogue remains sparse, and the reported ionic conductivities are limited. In this study, we demonstrate the significantly improved ionic conductivity in NaM 5+ Cl 6 (M 5+ = Nb, Ta) by extending the existing structural framework of the Na-ion conducting halides Na 3 M 3+ Cl 6 (M 3+ = Y, Er) and Na 2 ZrCl 6 . Transport analysis reveals that the cation M rules the activation energies of the resulting phases. Given that M is pivotal, a further fine-tuning of M in NaMCl 6 leads to a high ionic conductivity of 0.1 mS cm −1 at 30 °C, owing to a beneficial inductive effect and enhanced migration entropy. These discoveries will provide more design strategies for Na-ion conducting halide-based SEs.

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From Liquid to Solid‐State Batteries: Li‐Rich Mn‐Based Layered Oxides as Emerging Cathodes with High Energy Density

Kong,

Zhao,

Sun

et al. 2023

Advanced Materials

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Li‐rich Mn‐based (LRMO) cathode materials have attracted widespread attention due to their high specific capacity, energy density, and cost‐effectiveness. However, challenges such as poor cycling stability, voltage deca,y and oxygen escape limit their commercial application in liquid Li‐ion batteries. Consequently, there is a growing interest in the development of safe and resilient all‐solid‐state batteries (ASSBs), driven by their remarkable safety features and superior energy density. ASSBs based on LRMO cathodes offer distinct advantages over conventional liquid Li‐ion batteries, including long‐term cycle stability, thermal and wider electrochemical windows stability, as well as the prevention of transition metal dissolution. This review aims to recapitulate the challenges and fundamental understanding associated with the application of LRMO cathodes in ASSBs. Additionally, it proposes the mechanisms of interfacial mechanical and chemical instability, introduces noteworthy strategies to enhance oxygen redox reversibility, enhances high‐voltage interfacial stability, and optimizes Li+ transfer kinetics. Furthermore, it suggests potential research approaches to facilitate the large‐scale implementation of LRMO cathodes in ASSBs.

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Hopping Rate and Migration Entropy as the Origin of Superionic Conduction within Solid-State Electrolytes

Cited by 15 publications

References 44 publications

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity

NaMCl₆ (M = Nb and Ta): A New Class of Sodium-Conducting Halide-Based Solid Electrolytes

From Liquid to Solid‐State Batteries: Li‐Rich Mn‐Based Layered Oxides as Emerging Cathodes with High Energy Density

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Hopping Rate and Migration Entropy as the Origin of Superionic Conduction within Solid-State Electrolytes

Cited by 15 publications

References 44 publications

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity

NaMCl6 (M = Nb and Ta): A New Class of Sodium-Conducting Halide-Based Solid Electrolytes

From Liquid to Solid‐State Batteries: Li‐Rich Mn‐Based Layered Oxides as Emerging Cathodes with High Energy Density

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NaMCl₆ (M = Nb and Ta): A New Class of Sodium-Conducting Halide-Based Solid Electrolytes