Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries.

Ni-rich layered cathode materials are among the most promising candidates for high-energy-density Li-ion batteries, yet their degradation mechanisms are still poorly understood. We report a structure-driven degradation mechanism for NMC811 (LiNi0.8Mn0.1Co0.1O2), in which a proportion of the material exhibits a lowered accessible state of charge at the end of charging after repetitive cycling and becomes fatigued. Operando synchrotron long-duration X-ray diffraction enabled by a laser-thinned coin cell shows the emergence and growth in the concentration of this fatigued phase with cycle number. This degradation is structure driven and is not solely due to kinetic limitations or intergranular cracking: no bulk phase transformations, no increase in Li/Ni antisite mixing and no notable changes in the local structure or Li-ion mobility of the bulk are seen in aged NMCs. Instead, we propose that this degradation stems from the high interfacial lattice strain between the reconstructed surface and the bulk layered structure that develops when the latter is at states of charge above a distinct threshold of approximately 75%. This mechanism is expected to be universal in Ni-rich layered cathodes. Our findings provide fundamental insights into strategies to help mitigate this degradation process.

Oxidation and flow-injection amperometric determination of 5-hydroxytryptophan at an electrode modified by electrochemically assisted deposition of a sol-gel film with templated nanoscale pores.

The oxidation of 5-hydroxytryptophan (5-HTPP) yielded a passivating polymeric film at an indium tin oxide (ITO) electrode. Coating ITO with a nanoscale sol-gel film with a mesoporous structure was shown to change the pathway of the chemical reaction coupled to the electron transfer. The sol-gel film was deposited by an electrochemically assisted process, and the mesoporosity was imparted by including generation-4 poly(amidoamine) dendrimer in the precursor solution. The dendrimer was removed subsequently with an atmospheric oxygen plasma. This electrode remained active during cyclic voltammetry and controlled potential electrolysis of 5-HTPP, which was attributed to dimer, rather than polymer, formation from the oxidation product. Mass spectrometry confirmed this hypothesis. The anodic current was limited by the electron-transfer kinetics. Modification of the sol-gel film by inclusion of cobalt hexacyanoferrate, which catalyzes the oxidation, resulted in a diffusion-limited current. Determination of 5-HTPP by flow-injection amperometry had a detection limit of 17nM.