Enhanced Cycling Performance of Ni-Rich Positive Electrodes (NMC) in Li-Ion Batteries by Reducing Electrolyte Free-Solvent Activity

The interfacial (electro)chemical reactions between electrode and electrolyte dictate the cycling stability of Li-ion batteries. Previous experimental and computational results have shown that replacing Mn and Co with Ni in layered LiNi_xMn_yCo_1-x-yO₂ (NMC) positive electrodes promotes the dehydrogenation of carbonate-based electrolytes on the oxide surface, which generates protic species to decompose LiPF₆ in the electrolyte. In this study, we utilized this understanding to stabilize LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) by decreasing free-solvent activity in the electrolyte through controlling salt concentration and salt dissociativity. Infrared spectroscopy revealed that highly concentrated electrolytes with low free-solvent activity had no dehydrogenation of ethylene carbonate, which could be attributed to slow kinetics of dissociative adsorption of Li⁺-coordinated solvents on oxide surfaces. The increased stability of the concentrated electrolyte against solvent dehydrogenation gave rise to high capacity retention of NMC811 with capacities greater than 150 mA h g^-1 (77% retention) after 500 cycles without oxide-coating and Ni-concentration gradients or electrolyte additives.