Electrolyte reactivity at the charged Ni-rich cathode interface and degradation in Li-ion batteries

The chemical and electrochemical reactions at the positive electrode-electrolyte interface in Li-ion batteries are hugely influential on cycle life and safety. Ni-rich layered transition metal oxides exhibit higher interfacial reactivity than their lower Ni-content analogues, reacting via poorly understood mechanisms. Here, we study the role of the electrolyte solvent, specifically cyclic ethylene carbonate (EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial reactivity at LiNi0.33Mn0.33Co0.33O2 (NMC111) and LiNi0.8Mn0.1Co0.1O2 (NMC811). Parasitic currents are measured during high voltage holds in NMC/Li4Ti5O12 (LTO) cells, LTO avoiding parasitic currents related to anode-cathode reduction species cross-over, and are found to be higher for EC-containing vs. EC-free electrolytes with NMC811. No difference between electrolytes are observed with NMC111. On-line gas analysis reveals this to be related to lattice oxygen release, and accompanying electrolyte decomposition, which increases substantially with greater Ni content, and for EC-containing electrolytes with NMC811. This is corroborated by electrochemical impedance spectroscopy (EIS) and transmission electron microscopy (TEM) of NMC811 after the voltage hold, which show a higher interfacial impedance and a thicker oxygen-deficient rock-salt surface reconstruction layer, respectively. Combined findings from solution NMR, ICP (of electrolytes) and XPS analysis (of electrodes) reveal that higher lattice oxygen release from NMC811 in EC-containing electrolytes is coupled with more electrolyte breakdown and higher amounts of transition metal dissolution compared to EC-free electrolyte. Finally, new mechanistic insights for the chemical oxidation pathways of electrolyte solvents and, critically, the knock-on chemical and electrochemical reactions that further degrade the electrolyte and electrodes curtailing battery lifetime are provided.

Tungsten Infused Grain Boundaries Enabling Universal Performance Enhancement of Co-Free Ni-Rich Cathode Materials

Ni-rich cathode materials suffer from poor capacity retention due to micro-cracking and interfacial reactivity with electrolyte. Addition of tungsten (W) to some Ni-rich materials can improve capacity retention. Here, a WO3 surface coating is applied on Ni-rich hydroxide precursors before heating with lithium hydroxide. After heating in oxygen, Ni-rich materials with any of the commonly used dopants (magnesium, aluminum, manganese, etc.) show a “universal” improvement in capacity retention. Experimental characterization and theoretical modelling showed W was concentrated in the grain boundaries between the primary particles of secondary particles of the layered oxides, and W is incorporated in amorphous LixWyOz phases rather than as a substituent in the LiNiO2 lattice. This self-infusion of W in the grain boundaries during synthesis also significantly restricts primary crystallite grain growth. Along with smaller primary grain size, the LixWyOz phases in the grain boundaries lead to improved resistance to microcracking and reduced surface or interfacial reactivity. Improving the intrinsic properties of primary grains through doping of Mg, Al or Mn and reinforcing the secondary particle structure mechanically and chemically using W or a similar element, M, that forms LixMOy phases and does not substitute into LiNiO2 is a universal strategy to improve polycrystalline Ni-rich materials.

A Solid Electrolyte Interphase to Protect the Sulfurized Polyacrylonitrile (SPAN) Composite for Li-S Batteries: Computational Approach Addressing the Electrolyte/SPAN Interfacial Reactivity

This study addresses the reactivity of multiple solvents and lithium bis(fluorosulfonyl)imide (LiFSI) against sulfurized polyacrylonitrile (SPAN) in multiple stages of lithiation via ab initio molecular dynamics simulations. Both ether 1,3-dioxolane...

Interfacial Reactivity of the Filled Skutterudite Smy(FexNi1−x)4Sb12 in Contact with Liquid In-Based Alloys and Sn

The study of the wettability of thermoelectric materials, as well as the search for the most proper brazing alloys, is of the maximum importance to get one step closer to the realization of a thermoelectric device. In this work, a wettability study of the filled skutterudite Smy(FexNi1−x)4Sb12 by Sn and In-based alloys is presented. Samples, having both p- and n- characters were prepared by the conventional melting-quenching-annealing technique and subsequently densified by spark plasma sintering (SPS). Afterward, wettability tests were performed by the sessile drop method at 773 K for 20 min. Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analyses performed on the cross-section of the solidified drops suggest quite a complicated scenario due to the coexistence and the interaction of a large number of different elements in each analyzed system. Indeed, the indication of a strong reaction of In-based alloys with skutterudite, accompanied by the formation of the InSb intermetallic compound, is clear; on the contrary, Sn exhibits a milder reactivity, and thus, a more promising behavior, being its appreciable wettability, whilst coupled to a limited reactivity.