Quantifying Degradation Parameters of Single-Crystalline Ni-Rich Cathodes in Lithium-Ion Batteries.

Single-crystal LiNix Coy Mnz O2 (SC-NCM, x+y+z=1) cathodes are renowned for their high structural stability and reduced accumulation of adverse side products during long-term cycling. While advances have been made using SC-NCM cathode materials, careful studies of cathode degradation mechanisms are scarce. Herein, we employed quasi single-crystalline LiNi0.65 Co0.15 Mn0.20 O2 (SC-NCM65) to test the relationship between cycling performance and material degradation for different charge cutoff potentials. The Li/SC-NCM65 cells showed >77 % capacity retention below 4.6 V vs. Li+ /Li after 400 cycles and revealed a significant decay to 56 % for 4.7 V cutoff. We demonstrate that the SC-NCM65 degradation is due to accumulation of rock-salt (NiO) species at the particle surface rather than intragranular cracking or side reactions with the electrolyte. The NiO-type layer formation is also responsible for the strongly increased impedance and transition-metal dissolution. Notably, the capacity loss is found to have a linear relationship with the thickness of the rock-salt surface layer. Density functional theory and COMSOL Multiphysics modeling analysis further indicate that the charge-transfer kinetics is decisive, as the lower lithium diffusivity of the NiO phase hinders charge transport from the surface to the bulk.

Redox Targeting-Based Thermally Regenerative Electrochemical Cycle Flow Cell for Enhanced Low-Grade Heat Harnessing.

A large amount of low-grade heat (<100 °C) is produced in electrical devices and mostly wasted. This type of heat without effective dissipation also causes compromised device performance, reliability, and lifespan. To tackle these issues, a redox targeting (RT)-based flow cell with judiciously designed thermoelectrically active redox materials is demonstrated for the first time for efficient heat-to-electricity conversion through a thermally regenerative electrochemical cycle (TREC). Compared with the conventional TREC systems, the RT-based flow cell not only reveals considerably enhanced thermoelectric efficiency, but the flow of redox fluids also provides a cooling function to the system. In this work, solid material Ni0.2 Co0.8 (OH)2 and redox mediator [Fe(CN)6 ]4-/3- , both of which have negative temperature coefficient and share identical redox potential, are paired via RT-reactions to boost the capacity and meanwhile thermoelectric efficiency of a [Fe(CN)6 ]4-/3- /Zn0/2+ -based flow cell. Upon operating over the TREC cycle, the RT-based flow cell converts heat to electricity at an unprecedented absolute thermoelectric efficiency of 3.61% in the temperature range of 25-55 °C.