Novel Method for Monitoring the Electrochemical Capacitance by In Situ Impedance Spectroscopy as Indicator for Particle Cracking of Nickel-Rich NCMs: Part II. Effect of Oxygen Release Dependent on Particle Morphology

Nickel-rich NCMs (LiMO2, with M = Ni, Co, and Mn) are increasingly commercialized as cathode active materials for lithium-ion batteries due to their high specific capacity. However, the available capacity is limited due to their structural instability at high state of charge, causing the formation of a resistive surface layer upon release of lattice oxygen, observed at different upper cutoff potentials depending on the NCM composition. To understand the impact of this instability, the correlation of oxygen release, capacity fading, and particle cracking was investigated as a function of state of charge for three nickel-rich NCMs, differing either in composition (i.e., in transition metal ratio) or in morphology (i.e., in primary crystallite size). First, the onset of the release of lattice oxygen was identified by on-line electrochemical mass spectrometry (OEMS). In electrochemical cycling experiments, the NCM capacitance was tracked in situ by impedance spectroscopy (EIS) using a micro-reference electrode while the upper cutoff potential was increased every third cycle stepwise from 3.9 V to 5.0 V. Hereby, the effect of the degree of delithiation on the discharge capacity and on the particle integrity (tracked via its surface area) was examined, both for poly- and single-crystalline NCMs.

Stress-Affected Lithiation Reactions in Elasto-Viscoplastic Si Particles with Hyperelastic Polymer Coatings: A Nonlinear Chemo-Mechanical Finite-Element Study

Stress-affected two-phase lithiation reactions in spherical elasto-viscoplastic Si particles for Li-ion batteries are studied here to determine the effects of a hyperelastic polymer coating on particle stresses, reaction front velocity, and degree of lithiation. The problem is modelled using finite-strain chemo-mechanical equations that couple stress, with Li-ion diffusion and reaction front velocity, and are solved using the finite-element (FE) approach, taking advantage of spherical symmetry of the problem. FE simulations and the sensitivity analysis reveal: (1) coating thickness is the most influential design parameter that affects the velocity of the reaction front, and (2) increasing values of the coating shear and bulk moduli, and the coating thickness reduce tensile circumferential stresses at the edge of the particle. The latter minimises the risk of particle cracking in the opening mode, but it can also accelerate the arrest of the reaction front, and thus reduce the particle lithiation degree in Li-ion battery anodes.

Chemo-mechanical expansion of lithium electrode materials – on the route to mechanically optimized all-solid-state batteries

The volume effects of electrode materials can cause local stress development, contact loss and particle cracking in the rigid environment of a solid-state battery.