Dynamic Response of Ion Transport in Nanoconfined Electrolytes.

Ion transport in nanoconfined electrolytes exhibits nonlinear effects caused by large driving forces and pronounced boundary effects. An improved understanding of these impacts is urgently needed to guide the design of key components of the electrochemical energy systems. Herein, we employ a nonlinear Poisson-Nernst-Planck theory to describe ion transport in nanoconfined electrolytes coupled with two sets of boundary conditions to mimic different cell configurations in experiments. A peculiar nonmonotonic charging behavior is discovered when the electrolyte is placed between a blocking electrode and an electrolyte reservoir, while normal monotonic behaviors are seen when the electrolyte is placed between two blocking electrodes. We reveal that impedance shapes depend on the definition of surface charge and the electrode potential. Particularly, an additional arc can emerge in the intermediate-frequency range at potentials away from the potential of zero charge. The obtained insights are instrumental to experimental characterization of ion transport in nanoconfined electrolytes.

Li2CO3 Nanocomposites as Cathode Lithium Replenishment Material for High-Energy-Density Li-Ion Batteries.

The irreversible capacity loss of lithium-ion batteries during initial cycling directly leads to a decrease in energy density, and promising lithium cathode replenishment can significantly alleviate this problem. In response to the problems of complex preparation, instability in air, and unfavorable residue of the conventional cathode lithium replenishment materials, a Li2CO3/carbon nanocomposite is prepared and utilized as the lithium replenishment material. With high-speed ball-milling, a nanocomposite with a tight embedment structured Li2CO3/Ketjen Black (KB) composite composed of nanosized Li2CO3 and KB is synthesized. The decomposition potential of Li2CO3 is effectively decreased to 3.8 V, and the amount of the active lithium ion being released is significantly increased, corresponding to a specific capacity of 645.2 mAh·g-1 during the initial charging cycle. It has been introduced into the full-cells composed of the NCM523 cathode and graphite anode, resulting in a capacity increase of 44 mAh·g-1 in the initial cycle and a 26.4% improvement in capacity retention over 100 cycles. The working mechanism of the Li2CO3/KB nanocomposite as the lithium replenishment agent has been discussed. The outcome of the work provides a practically feasible route to realize lithium-ion battery technology with improved energy density and cycling life.

Impedance response of electrochemical interfaces: part II-chemisorption.

Physical modeling helps to acquire fundamental insights from experimental data when electrochemical impedance spectroscopy is employed for mechanistic understandings of electrocatalytic reactions. Herein, we report an analytical model for chemisorption impedance with a consistent treatment of ion transport in the solution and electron transfer on the electrode surface. Our formulation avoids botha prioridecoupling of double-layer charging and electron transfer reaction, and a strict separation of double-layer charging and ion transport. Ion transport in the entire solution region is described by the Poisson-Nernst-Planck theory and electron transfer kinetics on the electrode surface by the Frumkin-Butler-Volmer theory. Surface dipoles caused by partially charged chemisorbates are considered. The classical Frumkin-Melik-Gaikazyan model for chemisorption is retrieved as a limiting case. The obtained formula is validated using experimental data of hydrogen adsorption at Pt(111). Characteristic frequencies and asymptotic behaviors of chemisorption impedance are analyzed.