Rational Design of Anode Materials Based on Group IVA Elements (Si, Ge, and Sn) for Lithium‐Ion Batteries

Abstract

Lithium-ion batteries (LIBs) represent the state-of-the-art technology in rechargeable energy-storage devices and they currently occupy the prime position in the marketplace for powering an increasingly diverse range of applications. However, the fast development of these applications has led to increasing demands being placed on advanced LIBs in terms of higher energy/power densities and longer life cycles. For LIBs to meet these requirements, researchers have focused on active electrode materials, owing to their crucial roles in the electrochemical performance of batteries. For anode materials, compounds based on Group IVA (Si, Ge, and Sn) elements represent one of the directions in the development of high-capacity anodes. Although these compounds have many significant advantages when used as anode materials for LIBs, there are still some critical problems to be solved before they can meet the high requirements for practical applications. In this Focus Review, we summarize a series of rational designs for Group IVA-based anode materials, in terms of their chemical compositions and structures, that could address these problems, that is, huge volume variations during cycling, unstable surfaces/interfaces, and invalidation of transport pathways for electrons upon cycling. These designs should at least include one of the following structural benefits: 1) Contain a sufficient number of voids to accommodate the volume variations during cycling; 2) adopt a "plum-pudding"-like structure to limit the volume variations during cycling; 3) facilitate an efficient and permanent transport pathway for electrons and lithium ions; or 4) show stable surfaces/interfaces to stabilize the in situ formed SEI layers.

Metallic Sn‐Based Anode Materials: Application in High‐Performance Lithium‐Ion and Sodium‐Ion Batteries

“…Besides carbon, other IVA group elements (especially Si, Ge, and Sn) have attracted great research interest owing to their ultrahigh theoretical capacities 9, 10, 11 1 shows the capacity and volume change comparison of IVA group elements.…”

Atomistic Study of Lithium Ion Dynamics in Li12Si7

“…They concluded that electron-rich effect plays an important role in the electrochemical solid-state amorphization. Although the thermo-dynamically stable crystalline lithium silicides, i.e., Li 12 Si 7 , Li 13 Si 4 and Li 7 Si 3 are difficult to observe upon lithiation, they have received considerable interest because they can serve as the reference compounds for the amorphous Li x Si materials formed upon lithiation. Solid state nuclear magnetic resonance (NMR) studies showed that the amorphous materials have local lithium environments comparable to those present in crystalline silicides, and their quantitative distribution is dependent on the extent of the electrochemical charge transfer, demonstrating their reference capability 24,25 .…”

“…Group IV elements, such as silicon, germanium, and tin as promising anode materials for the LIBs were extensively investigated by experiments and computational simulation methods 3,[5][6][7][8] . Among them, Si was paid considerable attention because of its higher theoretical specific capacity (~3579 mA h g -1 for Li 15 Si 4 at room temperature), low cost and abundant resources.…”

High Energy Density Germanium Anodes for Next Generation Lithium Ion Batteries

“…This has led to a remarkable interest, of late, on high energy density anodes based on Group IVA elements (Si, Ge, and Sn), although not without major challenges [10]. In this focus review, we summarize the brief history and working principles of LIBs, in order to provide the proper context.…”

“…nanosize effects, one-dimensional nanostructures) and material of choice (e.g. metal oxides and oxysalts, Si-based, Sn-based) and are too broad in scope [10][11][12][13][14][15][16][17][18]22]. This article will be the first to provide an in-depth review and discussion on Ge-based LIB anodes, with particular emphasis on Ge and Ge oxides and the electrochemical lithiation behaviour of Ge nanostructures.…”