In-Situ Convertible Amorphous Silicon Nitride (SiNx) Anode: Resolving the Long-Term Cyclic Instability of Silicon

Abstract

Silicon (Si) has shown its promises as anode material for next-generation high-energy lithium-ion batteries (LIBs) due to its high theoretical capacity1. However, its practical application has been impeded by the severe cyclic instability caused by a large volume change during (de) lithiation. Recently, a new family of silicon-based anode materials called “in-situ convertible-type anode materials” has emerged to resolve the cyclic instability of silicon.2,3 This family includes sub-stoichiometric oxides, nitrides, and carbides of silicon (SiAx, where A = N, C, O). The working principle of these materials follow two mechanisms: (1) irreversible conversion and (2) reversible alloying/dealloying. During initial lithiation, the conversion reaction occurs, forming Si-Li nanodomains inside a stable Li-conductive matrix denoted as LiySixA (A=N, C, O). In the subsequent cycles, the Si-Li nanodomains reversibly alloying/dealloying with Li, while the Li-conductive matrix ensures stable cycling and good rate capability. Such composition mitigates the challenges associated with Si’s large volume change ensuring long-term cyclic stability.In this study, we demonstrate our approach on the development of silicon-rich, sub-stochiometric, amorphous silicon nitride (SiNx) nanoparticles, as an in-situ convertible-type anode material and its long-term cyclic performance for LIBs. In this approach, the SiNx nanoparticles are produced via the decomposition of silane gas in the presence of ammonia using an industrially scalable, free space reactor (FSR), which is developed and customized in our research institute (IFE) (Fig. 1a). Proper proportions of silane and ammonia gases are introduced into the reactor, leading to the nucleation and growth of SiNx nanoparticles. The synthesized SiNx nanoparticles exhibited Si-rich domain and amorphous structure with particle size between 100 nm - 200 nm (Fig. 1b), as confirmed by SEM, TEM and XRD characterizations. The presence of nitrogen in silicon dominated composition is revealed by energy dispersive electron spectroscopy (EDS) and Fourier-transform infrared spectroscopy (FTIR). The scalability and reproducibility of the FSR synthesis method makes it a promising approach for the industrial production of SiNx for advance anode materials for LIBs.The electrochemical performance of the synthesized SiNx anode is evaluated by galvanostatic cycling and electrochemical impedance spectroscopy. The electrochemical performance of the SiNx performed on the electrodes with the active mass loading of 0.987 mg/cm2 and cycled at C/5 rate has preserved its capacity about 852 mAh/g after around 600 cycles. As seen from Fig. 1c, the improved cyclic stability of the SiNx compared with pure silicon indicates that the Li-conductive matrix plays crucial role in stabilizing the anode. The authors emphasize the need for further investigation and collaboration, particularly in advance characterization, to better understand the composition and mechanisms of the Li-conductive matrix in the SiNx anode. Such detailed understanding can significantly benefit the conversion-type anode materials for their widespread use in future LIB technologies.References Zuo, X., Zhu, J., Müller-Buschbaum, P. & Cheng, Y.-J. Silicon based lithium-ion battery anodes: A chronicle perspective review. Nano Energy 31, 113–143 (2017).Ulvestad, A. et al. Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction. ACS Nano 15, 16777–16787 (2021).Kilian, S. O. et al. Active Buffer Matrix in Nanoparticle-Based Silicon-Rich Silicon Nitride Anodes Enables High Stability and Fast Charging of Lithium-Ion Batteries. Advanced Materials Interfaces 9, 2201389 (2022). Figure 1