Interrupted anion-network enhanced Li+-ion conduction in Li3+yPO4Iy

Patel, Sawankumar; Truong, Erica; Liu, Haoyu; Yongkang, Jin; Chen, Benjamin; Wang, Yan; Lincoln, Miara; Kim, Ryoung-Hee; Hu, Yan‐Yan

doi:10.1016/j.ensm.2022.06.026

Cited by 6 publications

(5 citation statements)

References 36 publications

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“…Enhanced ion transport via anion diversification can be applied to other Li3PS4–LiX (X = Cl, I) systems. [ 16,49,73,74 ] A diversified anion sublattice prevents Li + trapping, yielding increased ion mobility. In addition, the introduced local disorder often leads to a frustrated energy landscape, producing lower energy barriers for ion migration.…”

Section: Discussionmentioning

confidence: 99%

Transforming Li₃PS₄ Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

Poudel,

Deck,

Wang

et al. 2023

Adv Funct Materials

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To enhance Li+ transport in all‐solid‐state batteries (ASSBs), harnessing localized nanoscale disorder can be instrumental, especially in sulfide‐based solid electrolytes (SEs). In this investigation, the transformation of the model SE, Li3PS4, is delved into via the introduction of LiBr. 31P nuclear magnetic resonance (NMR)unveils the emergence of a glassy PS43− network interspersed with Br−. 6Li NMR corroborates swift Li+ migration between PS43− and Br−, with increased Li+ mobility indicated by NMR relaxation measurements. A more than fourfold enhancement in ionic conductivity is observed upon LiBr incorporation into Li3PS4. Moreover, a notable decrease in activation energy underscores the pivotal role of Br− incorporation within the anionic lattice, effectively reducing the energy barrier for ion conduction and transitioning Li+ transport dimensionality from 2D to 3D. The compatibility of Li3PS4 with Li metal is improved through LiBr incorporation, alongside an increase in critical current density from 0.34 to 0.50 mA cm−2, while preserving the electrochemical stability window. ASSBs with 3Li3PS4:LiBr as the SE showcase robust high‐rate and long‐term cycling performance. These findings collectively indicate the potential of lithium halide incorporation as a promising avenue to enhance the ionic conductivity and stability of SEs.

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Section: Discussionmentioning

confidence: 99%

Transforming Li₃PS₄ Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

Poudel,

Deck,

Wang

et al. 2023

Adv Funct Materials

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“…[ 30,31 ] In the TMO SLE, however, only fast Li + ions can be identified. Furthermore, the increased mobility of Li + ions in TMO can be confirmed by its shorter T 1 relaxation time, [ 32,33 ] as shown in Figure S10, Supporting Information. The adsorption energy ( E ads ) of Li on the MOF hosts was calculated by density functional theory (DFT), and the predicted adsorption sites are shown in Figure S11, Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

A Fluoride‐Rich Solid‐Like Electrolyte Stabilizing Lithium Metal Batteries

Wang,

Huang,

Rao

et al. 2024

Advanced Materials

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To address the problems associated with Li metal anodes, we present a fluoride‐rich solid‐like electrolyte (SLE) that combines the benefits of solid‐state and liquid electrolytes. Its unique triflate‐group‐enhanced frame channels facilitate the formation of a functional inorganic‐rich solid electrolyte interphase (SEI), which not only improves the reversibility and interfacial charge transfer of Li anodes but also ensures uniform and compact Li deposition. Furthermore, these triflate groups contribute to the decoupling of Li+ and provide hopping sites for rapid Li+ transport, enabling a high room‐temperature ionic conductivity of 1.1 mS cm−1 and a low activation energy of 0.17 eV, making it comparable to conventional liquid electrolytes. Consequently, Li symmetric cells using such SLE achieve extremely stable plating/stripping cycling over 3500 h at 0.5 mA cm−2 and support a high critical current up to 2.0 mA cm−2. The assembled Li||LiFePO4 solid‐like batteries exhibit exceptional cyclability for over one year and a half, even outperforming liquid cells. Additionally, high‐voltage cylindrical cells and high‐capacity pouch cells are demonstrated, corroborating much simpler processibility in battery assembly compared to all solid‐state batteries. These findings highlight the potential of the SLE approach in building a desirable SEI, offering practical solutions for the widespread adoption of rechargeable LMBs.This article is protected by copyright. All rights reserved

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“…One reason for the trend is that many of the phosphates formed in Li 3 PS 4− x O x compositions with x > 0.31 are poor Li + conductors, such as Li 3 PO 4 (Figure S1, Supporting Information). [ 55 ]…”

Section: Resultsmentioning

confidence: 99%

“…As illustrated in Figure 4b, a minimum E a,DC of 0.34 eV, is reached for . [55] To study how x in Li 3 PS 4−x O x (x = 0, 0.1, 0.25, 0.31, 0.5, and 1) impacts Li + dynamics on different length scales and its effect on 𝜎 DC , we examine the real part of complex resistivity at a fixed frequency, 𝜌′ (𝜌′ = Μ″/𝜔; see Supporting Information), as a function of temperature (T) (Figure S8, Supporting Information). [48] The activation barriers obtained from the Arrhenius-type fit for the high-T (E a,𝜌'HT ) and low-T (E a,𝜌'LT ) regime of 𝜌'-peaks are shown in Table S5 (Supporting Information).…”

Section: Origin Of Fast-ion Conduction In LI 3 Ps 4−x O Xmentioning

confidence: 99%

Oxygen‐Induced Structural Disruption for Improved Li⁺ Transport and Electrochemical Stability of Li₃PS₄

Deck,

Chien,

Poudel

et al. 2023

Advanced Energy Materials

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The performance of all‐solid‐state batteries (ASSBs) relies on the Li+ transport and stability characteristics of solid electrolytes (SEs). Li3PS4 is notable for its stability against lithium metal, yet its ionic conductivity remains a limiting factor. This study leverages local structural disorder via O substitution to achieve an ionic conductivity of 1.38 mS cm−1 with an activation energy of 0.34 eV for Li3PS4−xOx (x = 0.31). Optimal O substitution transforms Li+ transport from 2D to 3D pathways with increased ion mobility. Li3PS3.69O0.31 exhibits improvements in the critical current density and stability against Li metal and retains its electrochemical stability window compared with Li3PS4. The practical implementation of Li3PS3.69O0.31 in ASSBs half‐cells, particularly when coupled with TiS2 as the cathode active material, demonstrates substantially enhanced capacity and rate performance. This work elucidates the utility of introducing local structural disorder to ameliorate SE properties and highlights the benefits of strategically combining the inherent strengths of sulfides and oxides via creating oxysulfide SEs.

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Interrupted anion-network enhanced Li+-ion conduction in Li3+yPO4Iy

Cited by 6 publications

References 36 publications

Transforming Li₃PS₄ Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

Transforming Li₃PS₄ Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

A Fluoride‐Rich Solid‐Like Electrolyte Stabilizing Lithium Metal Batteries

Oxygen‐Induced Structural Disruption for Improved Li⁺ Transport and Electrochemical Stability of Li₃PS₄

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Interrupted anion-network enhanced Li+-ion conduction in Li3+yPO4Iy

Cited by 6 publications

References 36 publications

Transforming Li3PS4 Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

Transforming Li3PS4 Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

A Fluoride‐Rich Solid‐Like Electrolyte Stabilizing Lithium Metal Batteries

Oxygen‐Induced Structural Disruption for Improved Li+ Transport and Electrochemical Stability of Li3PS4

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Product

Resources

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Transforming Li₃PS₄ Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

Transforming Li₃PS₄ Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries

Oxygen‐Induced Structural Disruption for Improved Li⁺ Transport and Electrochemical Stability of Li₃PS₄