Abstract
A Series of Non-Van Der Waals 2D Quaternary Thiophosphates with Nominal Composition, Li2MP2S6 (M = V, Mn, Fe, Co, Ni, and Zn), Has Been Successfully Synthesized through Solid-State Metathesis Reactions by a Building Block Approach as Well as Starting with a Stoichiometric Combination of Elements. Li4-NxMxn+P2S6 (M = V, Fe, Ni, Co, and Zn; X = 0.5-1, N = 2 or 3) Crystallize in the P3̅1m Space Group, While Li2MnP2S6 Crystallizes in R3̅. All the Compounds Form a 2D Layered Structure through Edge Sharing MS6 Octahedra and P2S6 Units with Li Atoms Occupying the Interlayer Spaces. X-Ray Diffraction and Thermogravimetric Analyses Reveal Spontaneous Water Intercalation Tendencies of These Materials, Leading to Two Distinct Hydrated Phases (HY-I and HY-II) When They Are Exposed to Air for Shorter and Extended Times, respectively. Thermodiffractograms Demonstrate the Reversibility of Phase Transformation Upon Deintercalation of Water Molecules from the Interlayer Regions. the Crystal Structure of Hydrated Phase I from Single-Crystal and Synchrotron Powder X-Ray Diffraction Indicates Formation of a Monolayer of Water with Interlayer Expansion. Additionally, Li4-NxMxn+P2S6 (M = V, Mn, Fe, and Ni) Also Display Huge Affinity toward NH3 Intercalation in the Interlayer Space When Subjected to a Liquid or Gaseous Ammonia Environment. the Magnetic Measurements on Li2MP2S6 (M = Mn and Ni) Show the Paramagnetic Nature of the Compounds Down to 2 K. AC Impedance Spectroscopy on Li2.56Zn0.72P2S6 Shows a Room-Temperature Ionic Conductivity of 2.69 X 10-3 MS/cm, which is Four Order Higher in Magnitude Than Li4P2S6, While Hydrated Li2.56Zn0.72P2S6 Display 7-Fold Higher Ionic Conductivity (1.85 X 10-2 MS/cm) Than its Anhydrous Counterpart. the Study Also Reports Electrochemical Li (De)intercalation in Li2FeP2S6 in a Li-Ion Battery with a Liquid Electrolyte for the First Time.
Recommended Citation
S. Sundaramoorthy et al., "Li2MP2S6: Building-Block Approach to a Family of 2D Non-van Der Waals-Layered Materials and their Water, Ammonia, and Ion Intercalation Properties," Chemistry of Materials, vol. 36, no. 8, pp. 3574 - 3587, American Chemical Society, Apr 2024.
The definitive version is available at https://doi.org/10.1021/acs.chemmater.3c02829
Department(s)
Chemistry
International Standard Serial Number (ISSN)
1520-5002; 0897-4756
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 American Chemical Society, All rights reserved.
Publication Date
23 Apr 2024
Comments
Office of Science, Grant DMR-1809128