Toward Achieving a High Ionic Conducting Halide Solid Electrolyte through Low-Cost Metal (Zr and Fe) and F Substitution and Their Admirable Performance in All-Solid-State Batteries.

Recently, the halide solid electrolyte (SE) system has been widely used in lithium solid-state batteries due to their specific properties, such as the high electrochemical stability window that prevents any side reaction with the electrode/electrolyte interface. Conspicuously, the halide SE possesses very low ionic conductivity values in the range (0.2-0.5) mS cm-1. In this work, we enhance the ionic conductivity of Li3YCl6 SE by the substitution of low-cost Fe and Zr elements on the Y-site and F on the Cl site, in which the electrolyte is prepared through high-energy ball milling without a heat treatment process. The structural analysis reveals that the prepared halide SEs showed the pure phase of the Li3YCl6 tetragonal crystal structure and were free from impurity phases. In the prepared composition, the Li2.4Y0.4Zr0.6Cl6 and Li2.4Y0.4Zr0.6Cl5.85F0.15 electrolyte exhibited a higher ionic conductivity of 2.05 and 1.45 mS cm-1, respectively, than Li3YCl6 (0.26 mS cm-1). Interestingly, the Li2.4Y0.4Zr0.6Cl5.85F0.15 electrolyte possesses a better electrochemical stability window of 1.29-3.9 V than Li2.4Y0.4Zr0.6Cl6 (2.1-3.79 V). Moreover, the electrochemical results revealed that the assembled solid-state battery using Li2.4Y0.4Zr0.6Cl6 and Li2.4Y0.4Zr0.6Cl5.85F0.15 electrolyte demonstrated the higher initial Coulombic efficiency of 84.7 and 87%, respectively, than Li3YCl6 of 82.6%. We consider Li2.4Y0.4Zr0.6Cl5.85F0.15 to be an important electrolyte candidate in all-solid-state batteries.

Preparation of Metal-Oxide-Doped Li7P2S8Br0.25I0.75 Solid Electrolytes for All-Solid-State Lithium Batteries.

The all-solid-state lithium battery (ASSB) has received great attention due to its greater safety than the conventional lithium-ion battery (LIB). Sulfide-based inorganic solid electrolytes are an important component to fabricate the ASSB. But to attain a better performance, the ionic conductivity and electrochemical stability of the sulfide-based solid electrolytes need to be improved. In this work, we prepared the metal-oxide-doped/mixed Li7P2S8I0.75Br0.25 lithium superionic conductors by a dry ball-milling process. The high ionic conductivity was achieved by a low-temperature (200 °C) heat-treatment process. The metal-oxide-doped Li7P2S8I0.75Br0.25 solid electrolyte exhibited a higher ionic conductivity value of 7.3 mS cm-1 at room temperature than the bare Li7P2S8I0.75Br0.25 solid electrolyte. The structural characteristics of the prepared solid electrolytes were studied by solid NMR and laser Raman analysis. The electrochemical stability of the prepared solid electrolyte was studied by cyclic voltammetry and DC charge-discharge analysis. The addition of metal oxide increased the electrochemical stability and dry-air stability of the Li7P2S8I0.75Br0.25 solid electrolyte. The Ta2O5-doped Li7P2S8I0.75Br0.25 solid electrolyte was stable even after 300 charge-discharge DC cycles and also 100 h of dry-air exposure. Further, the Ta2O5-doped Li7P2S8I0.75Br0.25 solid electrolyte-based ASSB exhibited a high discharge capacity value of 184 mA h g-1 at 0.1 C rate with 66% initial cycle Coulombic efficiency.

Improving the electrochemical performance of cathode composites using different sized solid electrolytes for all solid-state lithium batteries.

We studied the efficiency of different particle-sized sulfide solid electrolyte-based cathode composites. First, we prepared the Li7P2S8I solid electrolytes with different particle sizes through a high energy ball milling process and solution method. The structural details of the prepared solid electrolytes were studied by powder X-ray diffraction. The surface morphologies and particle size of the electrolytes were studied by field emission electron microscopy. The ionic conductivity of the prepared solid electrolytes was studied by the electrochemical impedance spectroscopy technique. Finally, we have prepared a LiNi0.8Co0.1Mn0.1O2 (NCM 811) based cathode composite and studied the electrochemical performance of the fabricated all-solid-state lithium batteries. The mixed particle-sized solid electrolyte-based cathode composite exhibited higher specific capacitance (127.2 mA h g-1) than the uniform-sized solid electrolyte-based cathode composite (117.1 mA h g-1). The electrochemical analysis confirmed that the sulfide solid electrolytes with mixed particle size exhibited better electrochemical performance.

Facile hydrothermal synthesis and characterization of Co2GeO4/r-GO@C ternary nanocomposite as negative electrode for Li-ion batteries.

Ternary nanocomposite of Co2GeO4/r-GO@C is synthesized by single step hydrothermal method followed by calcination. The XRD analysis reveals the formation of cubic structured Co2GeO4 and their corresponding functional groups identified through Raman analysis. The TEM analysis assures that uniform distribution of Co2GeO4 nanoparticles on the r-GO layers. The Galvanostatic charge-discharge (GCD) curve demonstrates that the initial discharge capacity of pristine Co2GeO4, Co2GeO4/r-GO and Co2GeO4/r-GO@C composite is 1400, 1284 and 1594mAhg-1 at 50mAg-1, respectively. The cycling stability curve shows the specific capacity of 609, 970 and 1180mAhg-1 for pristine, Co2GeO4/r-GO and Co2GeO4/r-GO@C composite, respectively over 15 cycles. The ternary composite of Co2GeO4/r-GO@C delivers the discharge capacity of 323mAhg-1 at high current density of 1Ag-1 over 500 cycles with capacity retention of 71%. The rate capability curve indicates that Co2GeO4/r-GO@C composite shows the better rate capability.