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1. Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li ₁₅ Ge ₄ vs Li ₁₄ ZnGe ₄

   https://doi.org/10.1002/ejic.202100901  

   Osman, Hussien_H; Bobev, Svilen (December 2021, European Journal of Inorganic Chemistry)

   Abstract A new ternary lithium zinc germanide, Li_13.83Zn_1.17(2)Ge₄, was synthesized by a high‐temperature solid state reaction of the respective elements. The crystal structure was determined by single‐crystal X‐ray diffraction methods. The new phase crystallizes in the body‐centered cubic space groupI3d(no. 220) with unit cell parameter of 10.695(1) Å. The crystal structure refinements show that the parent Li₁₅Ge₄structure is stabilized as Li_15−xZn_xGe₄(x≈1) via random substitution of Li atoms by the one‐electron‐richer atoms of the element Zn, by virtue of which the number of valence electrons increases, leading to a more electronically stable system. The substitution effects in the parent Li₁₅Ge₄structure were investigated through both theory and experiment, which confirm that the Zn atoms in this structure prefer to occupy only one of the two available crystallographic sites for Li. The preferred substitution pattern established from experimental results is supported by DFT electronic structure calculations, which also explore the subtleties of the chemical bonding and the electronic properties of the title compounds. 

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2. 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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3. Assessing the 4f Orbital Participation in the Ln–C Bonds of [Li(THF) ₄ ][Ln(C ₆ Cl ₅ ) ₄ ] (Ln = La, Ce)

   https://doi.org/10.1021/acs.inorgchem.2c02304  

   Ordoñez, Osvaldo; Yu, Xiaojuan; Wu, Guang; Autschbach, Jochen; Hayton, Trevor W. (September 2022, Inorganic Chemistry)
4. Elucidation of Active Oxygen Sites upon Delithiation of Li ₃ IrO ₄

   https://doi.org/10.1021/acsenergylett.0c02040  

   Li, Haifeng; Perez, Arnaud J.; Taudul, Beata; Boyko, Teak D.; Freeland, John W.; Doublet, Marie-Liesse; Tarascon, Jean-Marie; Cabana, Jordi (January 2021, ACS Energy Letters)

   null (Ed.)
5. 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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