skip to main content


Title: Li 2 Mg 2 Si 2 S 6 and Li 2 Mg 2 Ge 2 S 6 : Two nonlinear optical sulfides featuring a unique, polar trigonal structure incorporating ethane‐like anions
Abstract

The new compounds Li2Mg2Si2S6and Li2Mg2Ge2S6have been prepared via traditional high‐temperature, solid‐state synthesis. The title compounds crystallize in the polar, noncentrosymmetric, trigonal space groupP31m(No. 157) and adopt a new structure type featuring staggered, ethane‐like (T2S6)6−units, where T=Si or Ge. These (T2S6)6−units are nestled within the holes of magnesium‐sulfide “layers” that are created through the edge‐sharing of MgS6octahedra. The holes found in the lithium‐sulfide “layers”, created by LiS6edge‐sharing octahedra, remain vacant, containing no (T2S6)6−anionic group. Through the face sharing of the respective MgS6and LiS6octahedra, the magnesium‐sulfide and lithium‐sulfide “layers” are stitched together resulting in an overall three‐dimensional structure. The optical bandgaps of Li2Mg2Si2S6and Li2Mg2Ge2S6are 3.24 and 3.18 eV, respectively, as estimated from optical diffuse reflectance UV‐Vis‐NIR spectroscopy. The compounds exhibit second harmonic generation responses of ∼0.24×KDP and ∼2.92×α‐quartz for Li2Mg2Si2S6and ∼0.17×KDP and ∼2.08×α‐quartz for Li2Mg2Ge2S6, using a Nd:YAG laser at 1.064 μm. Electronic structure calculations were performed using density functional theory and the linearized augmented plane‐wave approach within the WIEN2k software package. Examination of the electronic band structures shows that these compounds are indirect bandgap semiconductors.

 
more » « less
NSF-PAR ID:
10369663
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Zeitschrift für anorganische und allgemeine Chemie
Volume:
648
Issue:
15
ISSN:
0044-2313
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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
  2. Abstract

    Several Ba−Li−Ge ternary phases are known and structurally characterized, including the title compound Ba2LiGe3. Its structure is reported to contain [Ge6]10−anions that exhibit delocalized bonding with a Hückel‐like aromatic character. The Ge atoms are in the same plane with the Li atoms, and if both types of atoms are considered as covalently bonded, [LiGe3]4−honeycomb‐like layers will result. The latter are separated by slabs of Ba2+cations. However, based on the systematic work detailed herein, it is necessary to re‐evaluate the phase as Ba2Li1−xGe3+x(x<0.05). Although small, the homogeneity range is clearly demonstrated in the gradual change of the unit cell for four independent samples. Subsequent characterization by single‐crystal X‐ray diffraction methods shows that the Ba2Li1−xGe3+xstructure, responds to the varied number of valence electrons and the changes are most pronounced for the refined lengths of the Li−Ge and Ge−Ge bonds. Indirectly, the changes in the Ge−Li/Ge distances within layers affect the stacking too, and these changes can be correlated to the variation of thec‐cell parameter. Chemical bonding analysis based on TB‐LMTO‐ASA level calculations affirms the notion for covalent character of the Ge−Ge bonds; the Ba−Ge and Li−Ge interactions also show some degree of covalency.

     
    more » « less
  3. 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
  4. 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
  5. Abstract

    The making of BaZrS3thin films by molecular beam epitaxy (MBE) is demonstrated. BaZrS3forms in the orthorhombic distorted‐perovskite structure with corner‐sharing ZrS6octahedra. The single‐step MBE process results in films smooth on the atomic scale, with near‐perfect BaZrS3stoichiometry and an atomically sharp interface with the LaAlO3substrate. The films grow epitaxially via two competing growth modes: buffered epitaxy, with a self‐assembled interface layer that relieves the epitaxial strain, and direct epitaxy, with rotated‐cube‐on‐cube growth that accommodates the large lattice constant mismatch between the oxide and the sulfide perovskites. This work sets the stage for developing chalcogenide perovskites as a family of semiconductor alloys with properties that can be tuned with strain and composition in high‐quality epitaxial thin films, as has been long‐established for other systems including Si‐Ge, III‐Vs, and II‐VIs. The methods demonstrated here also represent a revival of gas‐source chalcogenide MBE.

     
    more » « less