Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively.

Matchmaker of Marriage between a Li Metal Anode and NASICON-Structured Solid-State Electrolyte: Plastic Crystal Electrolyte and Three-Dimensional Host Structure.

The marriage between a Li metal anode and the solid-state electrolyte is expected to limit the safety risk of secondary batteries. However, dendrites and interfacial stability hinder the combination of Li metal anode and solid-state electrolyte. Herein, a plastic crystal electrolyte (PCE) and three-dimensional (3D) host structure played the role of a matchmaker in combining the solid-state electrolyte and Li metal anode. Succinonitrile cooperated with Li salt and Li6.4La3Zr1.4Ta0.6O12 nanosize powder and built a PCE interphase, which enhanced the interfacial stability between Li1.5Al0.5Ge1.5(PO4)3 and Li metal anode. To protect the soft PCE from the dendrite penetration, commercially sold Super P, carbon nanotube, KS6, and Ketjen black were co-heated with the melted Li metal. However, only KS6 built a 3D host in Li metal successfully because of its high graphitization and layered structure. Benefitting from the matchmakers, the solid-state batteries exhibited enhanced cycling stability.