The Fundamentals and Advances of Solid‐State Electrochemistry: Intercalation (Insertion) and Deintercalation (Extraction) in Solid‐State Electrodes

Abstract

Over several decades, solid-state electrodes in which reversible intercalation (insertion) and deintercalation (extraction) of cationic guest atoms occur along with accompanying electron flow without any change of their crystal structure, have attracted great interest in fundamental and practical perspectives for improving the performance of rechargeable batteries. This chapter provides comprehensive reviews of principle and recent advances especially in thermodynamic and kinetic approaches to lithium intercalation into, and deintercalation from, transition metals oxides and carbonaceous materials. Thermodynamic properties such as chemical potential, entropy and enthalpy of lithium intercalation/deintercalation are first discussed, based on a lattice gas model with various approximations. Lithium intercalation/deintercalation involving an order-disorder transition or a two-phase coexistence caused by strong interaction of lithium ions in solid-state electrodes is explained, based on the lattice gas model and with the help of computational methods. Second, the kinetics of lithium intercalation/ deintercalation is treated in detail on the basis of a cell-impedance-controlled model. Anomalous features of potentiostatic current transients obtained experimentally from transitional metal oxide and carbonaceous electrodes, which are hardly explained under a diffusion control model, are readily analyzed by the cell-impedancecontrolled lithium transport concept, with the aid of computational methods. IntroductionWhen cationic guest atoms such as lithium, hydrogen, and sodium reversibly enter or leave the host oxide crystal, along with an accompanying electron flow but without any change in crystal structure, the reaction is referred to as intercalation/ deintercalation as follows [1,2]::1Þ Solid State Electrochemistry I: Fundamentals, Materials and their Applications. Edited by Vladislav V. Kharton

A comprehensive overview of MXene‐based anode materials for univalent metal ions (Li+, Na+, and K+) and bivalent zinc ion capacitor application

“…Generally speaking, the intercalation-deintercalation implies a reversible shuttling of metal ions into/from the layered materials without any phase transformation. [37] The insertion-extraction of metal ions in the battery-type materials is conducive to diffusion-controlled electrochemical process accompanied by the phase transformation in crystallographic structure, while the intercalation pseudocapacitive materials offer intercalation-deintercalation via much fast ion diffusion process without any phase transformation. [20] It is also possible to reduce the kinetics limitations of diffusion using an appropriate intercalation pseudocapacitive material such as MXene.…”

“…“Insertion‐extraction” is more generic term for all kinds of battery‐type materials; however, for layered materials, researchers frequently use the term “intercalation‐deintercalation” to represent the insertion‐extraction process of metal ions. Generally speaking, the intercalation‐deintercalation implies a reversible shuttling of metal ions into/from the layered materials without any phase transformation [37] . The insertion‐extraction of metal ions in the battery‐type materials is conducive to diffusion‐controlled electrochemical process accompanied by the phase transformation in crystallographic structure, while the intercalation pseudocapacitive materials offer intercalation‐deintercalation via much fast ion diffusion process without any phase transformation [20] .…”