skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Transforming Li 3 PS 4 Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries
Title: Transforming Li 3 PS 4 Via Halide Incorporation: a Path to Improved Ionic Conductivity and Stability in All‐Solid‐State Batteries
Abstract 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 Li3PS4with 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.  more » « less
Award ID(s):
1847038
PAR ID:
10490581
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
34
Issue:
4
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; (, Advanced Energy Materials)
    Abstract The performance of all‐solid‐state batteries (ASSBs) relies on the Li+transport and stability characteristics of solid electrolytes (SEs). Li3PS4is 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−1with 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. Li3PS3.69O0.31exhibits improvements in the critical current density and stability against Li metal and retains its electrochemical stability window compared with Li3PS4. The practical implementation of Li3PS3.69O0.31in ASSBs half‐cells, particularly when coupled with TiS2as 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. 
    more » « less
  2. ; ; ; ; ; ; ; ; ; ; et al (, Advanced Science)
    Abstract Localized atomistic disorder in halide‐based solid electrolytes (SEs) can be leveraged to boost Li+mobility. In this study, Li+transport in structurally modified Li3HoCl6, via Br−introduction and Li+deficiency, is explored. The optimized Li3‐3yHo1+yCl6‐xBrxachieves an ionic conductivity of 3.8 mS cm−1at 25 °C, the highest reported for holmium halide materials.6,7Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li+motional rate neighboring 116 MHz. X‐ray diffraction analyses reveal mixed‐anion‐induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho‐free planes with favorable energetics for Li+migration. Bond valence site energy analysis highlights preferred Li+transport pathways, particularly in structural planes devoid of Ho3+blocking effects. Molecular dynamics simulations corroborate enhanced Li+diffusion with Br−introduction into Li3HoCl6. Li‐Ho electrostatic repulsions in the (001) plane presumably drive Li+diffusion into the Ho‐free (002) layer, enabling rapid intraplanar Li+motion and exchange between the 2d and 4h sites. Li3‐3yHo1+yCl6‐xBrxalso demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high‐performance fast ion conductors for all‐solid‐state batteries. 
    more » « less
  3. ; ; (, Advanced Energy Materials)
    Abstract While significant efforts are being devoted to improving the ionic conductivity of lithium solid electrolytes (SEs), electronic transport, which has an important role in the calendar life, energy density, and cycling stability of solid‐state batteries (SSBs), is rarely studied. Here, the electronic conductivities of three representative SEs, including Li3PS4, Li7La3Zr2O12, and Li3YCl6, are reported. It is reported that the electronic conductivities of SEs are overestimated from the conventional measurements. By revisiting direct current polarizations using two‐blocking‐electrode cells and the Hebb‐Wagner approach, their sources of inaccuracy are provided and the anodic decomposition of SE is highlighted as the key source for the overestimated result. Modifications in the electrode selection and data interpretation are also proposed to approach the intrinsic electronic conductivity of SEs. A two‐step polarization method is also proposed to estimate the electronic conductivity of sulfides that decompose during measurement. Measured by the modified approach, the electronic conductivities of all SEs are one or two orders of magnitude lower than the reported value. Despite that, the electronic conductivity of sulfides seems to be still quite high to enable SSBs with a long calendar life of >10 years, highlighting the critical need for a more careful study of electronic transport in lithium SEs. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al (, Angewandte Chemie International Edition)
    Abstract All‐solid‐state potassium batteries emerge as promising alternatives to lithium batteries, leveraging their high natural abundance and cost‐effectiveness. Developing potassium solid electrolytes (SEs) with high room‐temperature ionic conductivity is critical for realizing efficient potassium batteries. In this study, we present the synthesis of K2.98Sb0.91S3.53Cl0.47, showcasing a room‐temperature ionic conductivity of 0.32 mS/cm and a low activation energy of 0.26 eV. This represents an increase of over two orders of magnitude compared to the parent compound K3SbS4, marking the highest reported ionic conductivity for non‐oxide potassium SEs. Solid‐state39K magic‐angle‐spinning nuclear magnetic resonance on K2.98Sb0.91S3.53Cl0.47reveals an increased population of mobile K+ions with fast dynamics. Ab initio molecular dynamics (AIMD) simulations further confirm a delocalized K+density and significantly enhanced K+diffusion. This work demonstrates diversification of the anion sublattice as an effective approach to enhance ion transport and highlights K2.98Sb0.91S3.53Cl0.47as a promising SE for all‐solid‐state potassium batteries. 
    more » « less
  5. ; ; ; ; ; ; ; ; (, Advanced Functional Materials)
    Abstract The correlation between lattice chemistry and cation migration in high‐entropy Li+conductors is not fully understood due to challenges in characterizing anion disorder. To address this issue, argyrodite family of Li+conductors, which enables structural engineering of the anion lattice, is investigated. Specifically, new argyrodites, Li5.3PS4.3Cl1.7−xBrx(0 ≤x≤ 1.7), with varying anion entropy are synthesized and X‐ray diffraction, neutron scattering, and multinuclear high‐resolution solid‐state nuclear magnetic resonance (NMR) are used to determine the resulting structures. Ion and lattice dynamics are determined using variable‐temperature multinuclear NMR relaxometry and maximum entropy method analysis of neutron scattering, aided by constrained ab initio molecular dynamics calculations. 15 atomic configurations of anion arrangements are identified, producing a wide range of local lattice dynamics. High entropy in the lattice structure, composition, and dynamics stabilize otherwise metastable Li‐deficient structures and flatten the energy landscape for cation migration. This resulted in the highest room‐temperature ionic conductivity of 26 mS cm−1and a low activation energy of 0.155 eV realized in Li5.3PS4.3Cl0.7Br, where anion disorder is maximized. This study sheds light on the complex structure–property relationships of high‐entropy superionic conductors, highlighting the significance of heterogeneity in lattice dynamics. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Text Encoded Conversion
  • XML
  • Save / Share this Record
  • Send to Email