Review on Improving the Performance of SiO_x Anodes for a Lithium-Ion Battery through Insertion of Heteroatoms: State of the Art and Outlook

Abstract

Anode materials for Li-ion batteries have attracted significant research interest owing to the growing demand for efficient and cost-effective energy storage systems. Among the various anode materials being studied, silicon-based anodes have garnered considerable attention as a result of their potential to overcome many of the limitations associated with graphite anodes. However, silicon-based anodes undergo high volumetric expansion during cycling, which results in anode failure. In contrast, silicon-oxide-based (SiO x ) materials exhibit limited volumetric expansion, making them viable candidates as anode materials in lithium-ion batteries. Despite this, there remain several challenges associated with SiO x anodes, including volumetric expansion (160−200%), poor capacity retention, and low initial coulombic efficiency. To address these issues, the incorporation of heteroatoms into SiO x anodes has been proposed as a promising strategy. In this review, we aim to provide an overview of the current state of research on SiO x anodes, including experiments and theoretical calculations, with a focus on the insertion of heteroatoms to improve the anode performance. In particular, we examine the effects of heteroatom incorporation on the anode conductivity, lithium diffusion, durability, and initial coulombic efficiency. In addition, we present a design strategy for the insertion of heteroatoms into the SiO x anodes. This review aims to provide a comprehensive understanding of the role of heteroatoms in SiO x anodes and highlight the potential for further research in this area.

Insights into the reactivity and lithium plating mechanisms of ultra-thin metal oxide coatings for anode-free solid-state lithium metal batteries

“…Oxides with early transition metals like zirconium may also be able to form stable reduced structures; Zr 4+ in lithium garnets has been shown to form stable Zr 2+ species at the lithium metal-oxide interface (Zhu et al, 2019). SiO x , a promising anode material itself, is known to undergo a mixture of Mechanisms 1 and 2, where residual pockets of Si 0 alloy with Li while the remaining SiO x species reversibly reduce and form lithium silicates, Li y SiO x (Kim et al, 2023b). There is wide room to explore a range of single-metal and multiple-metal or layered oxide coatings to achieve efficient lithium metal plating.…”

Facile synthesis of multi-phase (Si+SiO2)@C anode materials for lithium-ion batteries

“…The silicon monoxide (SiO) expansion rate relative to Si reduced a lot, and its cycling performance has been greatly improved, but the widely used method for synthesizing SiO on an industrial scale is thermal evaporation, whereby SiO 2 and Si are sublimated and condensed at high temperatures to produce SiO lumps, which are crushed and pulverized in a process to obtain the corresponding powders. [32][33][34] In addition, SiO x (0 < x < 2) materials with different Si/O ratios can be prepared by adjusting the ratio of raw materials and process conditions at Shinmatsu Chemical Co. Ltd in Japan, Osaka Titanium Technology Co. Ltd in Japan, and Samsung SDI Co. Ltd in Korea. 32 Nonetheless, their use for commercial-scale lithium-ion battery synthesis still has several problems, including high investment in process equipment, high energy consumption, and low productivity, leading to costly SiO products and an ICE generally below 60%, as well as stacking of subsequent pre-lithiation and pre-magnification modification processes.…”

“…[32][33][34] In addition, SiO x (0 < x < 2) materials with different Si/O ratios can be prepared by adjusting the ratio of raw materials and process conditions at Shinmatsu Chemical Co. Ltd in Japan, Osaka Titanium Technology Co. Ltd in Japan, and Samsung SDI Co. Ltd in Korea. 32 Nonetheless, their use for commercial-scale lithium-ion battery synthesis still has several problems, including high investment in process equipment, high energy consumption, and low productivity, leading to costly SiO products and an ICE generally below 60%, as well as stacking of subsequent pre-lithiation and pre-magnification modification processes. In addition, Mg-thermal/Al-thermal reduction of low-cost and highly stable SiO 2 is also commonly used to prepare silicon-based (Si or SiO x ) anode materials, but usually, the process involves an etching process, which has some limitations for homogenized mass production.…”

Unveiling Electrochemical Properties of Silicon for Stable Cycling Performance of Silicon Anode Materials

“…To address this issue, many strategies have been taken to mitigate the volume-induced cracking and pulverization of Si materials, and consequently improve the cycling performance of Si electrodes. The most studied approaches can be divided into the following four strategies: (1) nanostructured Si materials such as one-dimensional (1D) Si nanowires or nanorods and 3D porous or hollow Si materials, [4][5][6][7][8] (2) Si-carbon [9][10][11] or Si-graphite 12,13 composites, (3) silicon suboxides (SiO x , x < 2) and their composites with conductive carbon or graphite, [14][15][16] and (4) functional binders. [17][18][19] A common principle of these strategies is to mitigate the cracking or pulverization of Si materials by either reducing Si particle size or providing a volumetric buffer to relieve mechanical stress during lithiation and delithiation.…”

“…The pros and cons of each strategy have been individually summarized and critically reviewed in many recent articles. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] However, little attention has been given to the electrochemical properties of Si materials, which indeed affect the cycling performance of Si electrodes.…”