Lithium plating in lithium-ion batteries at sub-ambient temperatures investigated by in situ neutron diffraction

Abstract Lithium plating in commercial LiNi1/3Mn1/3Co1/3O2/graphite cells at sub-ambient temperatures is studied by neutron diffraction at Stress-Spec, MLZ. Li plating uses part of the active lithium in the cell and competes with the intercalation of lithium into graphite. As a result, the degree of graphite lithiation during and after charge is lower. Comparison of graphite lithiation after a C/5 charging cycle fast enough to expect a considerable amount of Li plating with a much slower C/30 reference cycle reveals a lower degree of graphite lithiation in the first case; neutron diffraction shows less LiC6 and more LiC12 is present. If the cell is subjected to a 20 h rest period after charge, a gradual transformation of remaining LiC12 to LiC6 can be observed, indicating Li diffusion into the graphite. During the rest period after the C/5 charging cycle, the degree of graphite lithiation can be estimated to increase by 17%, indicating at least 17% of the active lithium is plated. Data collected during discharge immediately after C/5 charging give further evidence of the presence and amount of metallic lithium: in this case 19% of discharge capacity originates from the oxidation of metallic lithium. Also, lithium oxidation can be directly related to the high voltage plateau observed during discharge in case of lithium plating.