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1. Importance of multimodal characterization and influence of residual Li ₂ S impurity in amorphous Li ₃ PS ₄ inorganic electrolytes

   https://doi.org/10.1039/d1ta02754a  

   Mirmira, Priyadarshini; Zheng, Jin; Ma, Peiyuan; Amanchukwu, Chibueze V. (September 2021, Journal of Materials Chemistry A)

   Amorphous Li 3 PS 4 (LPS) solid-state electrolytes are promising for energy-dense lithium metal batteries. LPS glass, synthesized from a 3 : 1 mol ratio of Li 2 S and P 2 S 5 , has high ionic conductivity and can be synthesized by ball milling or solution processing. Ball milling has been attractive because it provides the easiest route to access amorphous LPS with a conductivity of 3.5 × 10 −4 S cm −1 (20 °C). However, achieving the complete reaction of precursors via ball milling can be difficult, and most literature reports use X-ray diffraction (XRD) or Raman spectroscopy to confirm sample purity, both of which have limitations. Furthermore, the effect of residual precursors on ionic conductivity and lithium metal cycling is unknown. In this work, we illustrate the importance of multimodal characterization to determine LPS phase and chemical purity. To determine the residual Li 2 S content in LPS, we show that (1) XRD and 31 P solid state nuclear magnetic resonance (ssNMR) are insufficient and (2) Raman loses sensitivity at concentrations below 12 mol% Li 2 S. Most importantly, we show that 7 Li ssNMR is highly sensitive. Using 7 Li ssNMR, we investigate the effect of ball milling parameters and develop a robust and highly reproducible procedure for pure LPS synthesis. We find that as the residual Li 2 S precursor content increases, LPS conductivity decreases and lithium metal batteries exhibit higher overpotentials and poor cycle life. Our work reveals the importance of multimodal characterization techniques for amorphous solid-state electrolyte characterization and will enable better synthetic strategies for highly conductive electrolytes for efficient energy-dense solid-state lithium metal batteries. 

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2. The Nature of Lithium Bonding in C ₂ H ₂ Li ₂ , C ₆ Li ₆ , and Lithium Halide Dimers

   https://doi.org/10.1021/acs.organomet.9b00683  

   Liu, Yameng; Peng, Bin; Wang, Xiao; Xie, Yaoming; Schaefer, Henry F. (November 2019, Organometallics)
3. Oxygen‐Induced Structural Disruption for Improved Li ⁺ Transport and Electrochemical Stability of Li ₃ PS ₄

   https://doi.org/10.1002/aenm.202302785  

   Deck, Michael J.; Chien, Po‐Hsiu; Poudel, Tej P.; Jin, Yongkang; Liu, Haoyu; Hu, Yan‐Yan (December 2023, 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 Li₃PS_4−xO_x(x = 0.31). Optimal O substitution transforms Li⁺transport from 2D to 3D pathways with increased ion mobility. Li₃PS_3.69O_0.31exhibits improvements in the critical current density and stability against Li metal and retains its electrochemical stability window compared with Li₃PS₄. The practical implementation of Li₃PS_3.69O_0.31in 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. 

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4. Emergence of ferrimagnetism in Li-intercalated NiPS ₃

   https://doi.org/10.1088/1361-648X/ac8a81  

   Basnet, Rabindra; Ford, Dawn; TenBarge, Kaylee; Lochala, Joshua; Hu, Jin (September 2022, Journal of Physics: Condensed Matter)

   Abstract Intercalation has become a powerful approach to tune the intrinsic properties and introduce novel phenomena in layered materials. Intercalating van der Waals (vdW) magnetic materials is a promising route to engineer the low-dimensional magnetism. Recently, metal thiophosphates,MPX₃, has been widely studied because their magnetic orders are highly tunable and persist down to the two-dimensional limit. In this work, we used electrochemical technique to intercalate Li into NiPS₃single crystals and found the emergence of ferrimagnetism at low temperature in Li-intercalated NiPS₃. Such tuning of magnetic properties highlights the effectiveness of intercalation, providing a novel strategy to manipulate the magnetism in vdW magnets. 

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5. Li _2.9 Fe _0.9 Zr _0.1 Cl ₆ as Redox-Active Catholyte for Solid-State Li-Ion Batteries

   https://doi.org/10.1021/acs.chemmater.4c01385  

   Zhang, Guangxing; Liu, Zhantao; Ma, Yifan; Pepas, Jakub; Bai, Jianming; Zhong, Hui; Tang, Yuanzhi; Chen, Hailong (October 2024, Chemistry of Materials)