Synergized Tricomponent All‐Inorganics Solid Electrolyte for Highly Stable Solid‐State Li‐Ion Batteries

Abstract

AbstractGarnet‐type oxide Li6.4La3Zr1.4Ta0.6O12 (LLZTO) features superior ionic conductivity and good stability toward lithium (Li) metal, but requires high‐temperature sintering (≈1200 °C) that induces high fabrication cost, poor mechanical processability, and high interface resistance. Here, a novel high‐performance tricomponent composite solid electrolyte (CSE) comprising LLZTO−4LiBH4/xLi3BN2H8 is reported, which is prepared by ball milling the LLZTO−4LiBH4 mixture followed by hand milling with Li3BN2H8. Green pellets fabricated by heating the cold‐pressed CSE powders at 120 °C offer ultrafast room‐temperature ionic conductivity (≈1.73 × 10−3 S cm−1 at 30 °C) and ultrahigh Li‐ion transference number (≈0.9999), which enable the Li|Li symmetrical cells to cycle over 1600 h at 30 °C with only 30 mV of overpotential. Moreover, the Li|CSE|TiS2 full cells deliver 201 mAh g−1 of capacity with long cyclability. These outstanding performances are due to the low open porosity in the electrolyte pellets as well as the high intrinsic ionic conductivity and easy deformability of Li3BN2H8.