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.


Title: Mo 3 S 13 Chalcogel: A High‐Capacity Electrode for Conversion‐Based Li‐Ion Batteries
Abstract Despite large theoretical energy densities, metal‐sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution‐processable, room temperature (RT) synthesis, local structures, and application of a sulfur‐rich Mo3S13chalcogel as a conversion‐based electrode for lithium‐sulfide batteries (LiSBs). The structure of the amorphous Mo3S13chalcogel is derived throughoperandoRaman spectroscopy, synchrotron X‐ray pair distribution function (PDF), X‐ray absorption near edge structure (XANES), and extended X‐ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three‐dimensional (3D) network is the connection of Mo3S13units through S−S bonds. Li/Mo3S13half‐cells deliver initial capacity of 1013 mAh g−1during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g−1at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high‐capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo−S coordination in Mo3S13chalcogel. These findings showcase the potential of Mo3S13chalcogels as metal‐sulfide electrode materials for LiSBs.  more » « less
Award ID(s):
2100797
PAR ID:
10506021
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Chemistry Europe
Date Published:
Journal Name:
ChemSusChem
ISSN:
1864-5631
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al (, Advanced Materials)
    Abstract This is the first report of molybdenum carbide‐based electrocatalyst for sulfur‐based sodium‐metal batteries. MoC/Mo2C is in situ grown on nitrogen‐doped carbon nanotubes in parallel with formation of extensive nanoporosity. Sulfur impregnation (50 wt% S) results in unique triphasic architecture termed molybdenum carbide–porous carbon nanotubes host (MoC/Mo2C@PCNT–S). Quasi‐solid‐state phase transformation to Na2S is promoted in carbonate electrolyte, with in situ time‐resolved Raman, X‐ray photoelectron spectroscopy, and optical analyses demonstrating minimal soluble polysulfides. MoC/Mo2C@PCNT–S cathodes deliver among the most promising rate performance characteristics in the literature, achieving 987 mAh g−1at 1 A g−1, 818 mAh g−1at 3 A g−1, and 621 mAh g−1at 5 A g−1. The cells deliver superior cycling stability, retaining 650 mAh g−1after 1000 cycles at 1.5 A g−1, corresponding to 0.028% capacity decay per cycle. High mass loading cathodes (64 wt% S, 12.7 mg cm−2) also show cycling stability. Density functional theory demonstrates that formation energy of Na2Sx(1 ≤x ≤ 4) on surface of MoC/Mo2C is significantly lowered compared to analogous redox in liquid. Strong binding of Na2Sx(1 ≤x ≤ 4) on MoC/Mo2C surfaces results from charge transfer between the sulfur and Mo sites on carbides’ surface. 
    more » « less
  2. ; ; ; ; ; (, Advanced Materials)
    Abstract This study presents a new material, “HxCrS2” (denotes approximate composition) formed by proton‐exchange of NaCrS2which has a measured capacity of 728 mAh g−1with significant improvements to capacity retention, sustaining over 700 mAh g−1during cycling experiments. This is the highest reported capacity for a transition metal sulfide electrode and outperforms the most promising proposed sodium anodes to date. HxCrS2exhibits a biphasic structure featuring alternating crystalline and amorphous lamella on the scale of a few nanometers. This unique structural motif enables reversible access to Cr redox in the material resulting in higher capacities than seen in the parent structure which features only S redox. Pretreatment by proton‐exchange offers a route to materials such as HxCrS2which provide fast diffusion and high capacities for sodium‐ion batteries. 
    more » « less
  3. ; ; ; ; ; ; ; ; (, Advanced Energy Materials)
    Abstract Sulfide solid‐state electrolytes have remarkable ionic conductivity and low mechanical stiffness but suffer from relatively narrow electrochemical and chemical stability with electrodes. Therefore, pairing sulfide electrolytes with the proper cathode is crucial in developing stable all‐solid‐state Li batteries (ASLBs). Herein, one type of thioantimonate ion conductor, Li6+xGexSb1−xS5I, with different compositions is systematically synthesized and studied, among these compositions, an outstanding ionic conductivity of 1.6 mS cm−1is achieved with Li6.6Ge0.6Sb0.4S5I. To improve the energy density and advance the interface compatibility, a metal sulfide FeS2cathode with a high theoretical capacity (894 mAh g−1) and excellent compatibility with sulfide electrolytes is coupled with Li6.6Ge0.6Sb0.4S5I in ASLBs without additional interface engineering. The structural stabilities of Li6.6Ge0.6Sb0.4S5I and FeS2during cycling are characterized by operando energy dispersive X‐ray diffraction, which allows rapid collection of structural data without redesigning or disassembling the sealed cells and risking contamination by air. The electrochemical stability is assessed, and a safe operating voltage window ranging from 0.7≈2.4 V (vs. In–Li) is confirmed. Due to the solid confinement in the ASLBs, the Fe0aggregation and polysulfides shuttle effects are well addressed. The ASLBs exhibit an outstanding initial capacity of 715 mAh g−1at C/10 and are stable for 220 cycles with a high capacity retention of 84.5% at room temperature. 
    more » « less
  4. ; ; ; ; ; ; ; ; (, Advanced Functional Materials)
    Abstract Si‐based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li‐ion and electronic conductivity. Here, a novel ternary compound ZnSi2P3with a cation‐disordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li‐ion and electron transport and greater tolerance to volume change during cycling than the existing Si‐based anodes. A composite electrode consisting of ZnSi2P3and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g−1at 10 A g−1) while maintaining superior cycling stability (1955 mAh g−1after 500 cycles at 300 mA g−1), surpassing the performance of most Si‐ and P‐based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li‐storage mechanism involving intercalation and conversion reactions. Moreover, the cation‐disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si2+xP3solid solution anodes (x= 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next‐generation, high‐performance, and low‐cost Li‐ion batteries. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; ; et al (, Small Methods)
    Abstract A stable lean‐electrolyte operating lithium–sulfur (Li–S) battery based on a cathode of Li2S in situ electrocatalytically deposited from L2S8catholyte onto a support of metallic molybdenum disulfide (1T‐MoS2) on carbon cloth (CC) is created. The 1T‐MoS2significantly accelerates the conversion Li2S8catholyte to Li2S, chemically adsorbs lithium polysulfide (LiPSs) from solution, and suppresses crossover of the LiPSs to the anode. These experimental findings are explained by density functional theory calculations that show that 1T‐MoS2gives rise to strong adsorption of polysulfides on its surface and is electrocatalytic for the targeted reversible Li–S conversion reactions. The CC/1T‐MoS2electrode in a Li–S battery delivers an initial capacity of 1238 mAh g−1, with a low capacity fade of only 0.051% per cycle over 500 cycles at 0.5C. Even at a high sulfur loading (4.4 mg cm−2) and low electrolyte/S (E/S) ratio of 3.7 µL mg−1, the battery achieves an initial reversible capacity of 1176 mA h g−1at 0.5C, with 87% capacity retention after 160 cycles. The post 500 cycles Li metal opposing 1T‐MoS2is substantially smoother than the Li opposing CC, with XPS supporting the role of 1T‐MoS2in inhibiting LiPSs crossover. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email