A LaCl3-based lithium superionic conductor compatible with lithium metal.

Inorganic superionic conductors possess high ionic conductivity and excellent thermal stability but their poor interfacial compatibility with lithium metal electrodes precludes application in all-solid-state lithium metal batteries1,2. Here we report a LaCl3-based lithium superionic conductor possessing excellent interfacial compatibility with lithium metal electrodes. In contrast to a Li3MCl6 (M = Y, In, Sc and Ho) electrolyte lattice3-6, the UCl3-type LaCl3 lattice has large, one-dimensional channels for rapid Li+ conduction, interconnected by La vacancies via Ta doping and resulting in a three-dimensional Li+ migration network. The optimized Li0.388Ta0.238La0.475Cl3 electrolyte exhibits Li+ conductivity of 3.02 mS cm-1 at 30 °C and a low activation energy of 0.197 eV. It also generates a gradient interfacial passivation layer to stabilize the Li metal electrode for long-term cycling of a Li-Li symmetric cell (1 mAh cm-2) for more than 5,000 h. When directly coupled with an uncoated LiNi0.5Co0.2Mn0.3O2 cathode and bare Li metal anode, the Li0.388Ta0.238La0.475Cl3 electrolyte enables a solid battery to run for more than 100 cycles with a cutoff voltage of 4.35 V and areal capacity of more than 1 mAh cm-2. We also demonstrate rapid Li+ conduction in lanthanide metal chlorides (LnCl3; Ln = La, Ce, Nd, Sm and Gd), suggesting that the LnCl3 solid electrolyte system could provide further developments in conductivity and utility.

Lithium Fluoride in Electrolyte for Stable and Safe Lithium-Metal Batteries.

Electrolyte engineering via fluorinated additives is promising to improve cycling stability and safety of high-energy Li-metal batteries. Here, an electrolyte is reported in a porous lithium fluoride (LiF) strategy to enable efficient carbonate electrolyte engineering for stable and safe Li-metal batteries. Unlike traditionally engineered electrolytes, the prepared electrolyte in the porous LiF nanobox exhibits nonflammability and high electrochemical performance owing to strong interactions between the electrolyte solvent molecules and numerous exposed active LiF (111) crystal planes. Via cryogenic transmission electron microscopy and X-ray photoelectron spectroscopy depth analysis, it is revealed that the electrolyte in active porous LiF nanobox involves the formation of a high-fluorine-content (>30%) solid electrolyte interphase layer, which enables very stable Li-metal anode cycling over one thousand cycles under high current density (4 mA cm-2 ). More importantly, employing the porous LiF nanobox engineered electrolyte, a Li || LiNi0.8 Co0.1 Mn0.1 O2 pouch cell is achieved with a specific energy of 380 Wh kg-1 for stable cycling over 80 cycles, representing the excellent performance of the Li-metal pouch cell using practical carbonate electrolyte. This study provides a new electrolyte engineering strategy for stable and safe Li-metal batteries.