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.

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 10:00 PM to 12:00 AM ET on Tuesday, March 25 due to maintenance. We apologize for the inconvenience.

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


Title: Charge-clustering induced fast ion conduction in 2LiX-GaF 3 : A strategy for electrolyte design
2LiX-GaF3(X = Cl, Br, I) electrolytes offer favorable features for solid-state batteries: mechanical pliability and high conductivities. However, understanding the origin of fast ion transport in 2LiX-GaF3has been challenging. The ionic conductivity order of 2LiCl-GaF3(3.20 mS/cm) > 2LiBr-GaF3(0.84 mS/cm) > 2LiI-GaF3(0.03 mS/cm) contradicts binary LiCl (10−12S/cm) < LiBr (10−10S/cm) < LiI (10−7S/cm). Using multinuclear7Li,71Ga,19F solid-state nuclear magnetic resonance and density functional theory simulations, we found that Ga(F,X)npolyanions boost Li+-ion transport by weakening Li+-X−interactions via charge clustering. In 2LiBr-GaF3and 2LiI-GaF3, Ga-X coordination is reduced with decreased F participation, compared to 2LiCl-GaF3. These insights will inform electrolyte design based on charge clustering, applicable to various ion conductors. This strategy could prove effective for producing highly conductive multivalent cation conductors such as Ca2+and Mg2+, as charge clustering of carboxylates in proteins is found to decrease their binding to Ca2+and Mg2+.  more » « less
Award ID(s):
1847038
PAR ID:
10490580
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
AAAS
Date Published:
Journal Name:
Science Advances
Volume:
9
Issue:
47
ISSN:
2375-2548
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. ; ; ; ; ; ; ; ; (, 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
  3. ; ; ; ; ; ; ; ; ; (, Small Methods)
    Abstract A thin solid electrolyte with a high Li+conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg2+stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li1.2Mg0.1Zr1.9(PO4)3(LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr2(PO4)3.7Li and6Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO4cell. The enhanced performance of these cells enabled by the Li1.2Mg0.1Zr1.9(PO4)3solid electrolyte is stable upon repeated charge/discharge cycling. 
    more » « less
  4. ; (, Journal of the American Ceramic Society)
    Abstract In this report, a facile wet chemical method using acetonitrile combined with thermal annealing was used to prepare Li2S‐P2S5(LPS) based glass‐ceramic electrolytes with (1 wt%, 3 wt%, and 5 wt% Ce2S3) and without Ce2S3doping. The crystal structure, ionic conductivity, and chemical stability of Li7P3S11glass‐ceramic electrolytes were examined at varying temperatures (250–350°C). The results indicated that the highest ionic conductivity of 3.15 × 10−4S cm−1for pure Li7P3S11was observed at a temperature of 325°C. By incorporating 1 wt% Ce2S3and subjecting it to a heat treatment at 250°C, the glass ceramic electrolyte attained a remarkable ionic conductivity of 7.7 × 10−4(S cm−1) at 25°C. Furthermore, it exhibited a stable and extensive electrochemical potential range, reaching up to 5 volts when compared to the Li/Li+reference electrode. By tuning the glass transition and crystallization temperature, cerium doping seems to make Li7P3S11more chemically stable, compared to its original 70Li2S‐30P2S5counterpart. According to Raman and X‐ray photoelectron spectroscopy analyses, cerium doping inhibits the decomposition of highly conductive P2S74‐(pyro‐thiophosphate) to PS43−and P2S64−. Doped LPS has a greater crystallinity and more uniform microstructure than pure LPS, according to XRD, Raman spectroscopy, and scanning electron microscopy analysis. Consequently, Li7P2.9Ce0.1S11electrolyte shows great potential as a solid‐state electrolyte for constructing high‐performance sulfide‐based all‐solid‐state batteries. 
    more » « less
  5. ; ; (, physica status solidi (b))
    Secondary‐ion mass spectrometry (SIMS) is used to determine impurity concentrations of carbon and oxygen in two scandium‐containing nitride semiconductor multilayer heterostructures: ScxGa1−xN/GaN and ScxAl1−xN/AlN grown by molecular beam epitaxy (MBE). In the ScxGa1−xN/GaN heterostructure grown in metal‐rich conditions on GaN–SiC template substrates with Sc contents up to 28 at%, the oxygen concentration is found to be below 1 × 1019 cm−3, with an increase directly correlated with the scandium content. In the ScxAl1−xN–AlN heterostructure grown in nitrogen‐rich conditions on AlN–Al2O3template substrates with Sc contents up to 26 at%, the oxygen concentration is found to be between 1019and 1021 cm−3, again directly correlated with the Sc content. The increase in oxygen and carbon takes place during the deposition of scandium‐alloyed layers. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email