Synthesis of Deliquescent Lithium Sulfide in Air

In the field of lithium-sulfur batteries (LSBs) and all-solid-state batteries, lithium sulfide (Li2S) is a critical raw material. However, its practical application is greatly hindered by its high price due to its deliquescent property and production at high temperatures (above 700 °C) with carbon emission. Hereby, we report a new method of preparing Li2S, in air and at low temperatures (∼200 °C), which presents enriched and surprising chemistry. The synthesis relies on the solid-state reaction between inexpensive and air-stable raw materials of lithium hydroxide (LiOH) and sulfur (S), where lithium sulfite (Li2SO3), lithium thiosulfate (Li2S2O3), and water are three major byproducts. About 57% of lithium from LiOH is converted into Li2S, corresponding to a material cost of ∼$64.9/kg_Li2S, less than 10% of the commercial price. The success of conducting this water-producing reaction in air lies in three-fold: (1) Li2S is stable with oxygen below 220 °C; (2) the use of excess S can prevent Li2S from water attack, by forming lithium polysulfides (Li2Sn); and (3) the byproduct water can be expelled out of the reaction system by the carrier gas and also absorbed by LiOH to form LiOH·H2O. Two interesting and beneficial phenomena, i.e., the anti-hydrolysis of Li2Sn and the decomposition of Li2S2O3 to recover Li2S, are explained with density functional theory computations. Furthermore, our homemade Li2S (h-Li2S) is at least comparable with the commercial Li2S (c-Li2S), when being tested as cathode materials for LSBs.