Robust Micron-Sized Silicon Secondary Particles Anchored by Polyimide as High-Capacity, High-Stability Li-Ion Battery Anode

Abstract

Silicon is an attractive high-capacity anode material for lithium-ion battery. With the help of nanostructures, cycling performance of silicon anode has improved significantly in the past couple of years. However, three major shortcomings associated with nanostructures still need to be addressed, namely, their high surface area, low tap density, and poor scalability. Herein, we present a facile and practical method to produce micron-sized Si secondary particle cluster (SiSPC) with a high tap density and a low surface area from bulk Si by high-energy ball-milling. By coupling SiSPC with a mechanically robust polyimide binder, more than 95% of the initial capacity is retained after 500 cycles at 3500 mA g (1C rate). Reversibility of electrode thickness change is confirmed by in situ dilatometry. In addition, the polyimide binder suppresses the surface reaction of the particles with electrolyte, resulting in a high Coulombic efficiency of 99.7%. Excellent cycling performance is obtained even for thick electrodes with an areal capacity of 3.57 mAh cm, similar to those in commercial lithium-ion batteries. The presented Si electrode system has a high volumetric capacity of 598 mAh cm, which is higher than that of the commercial graphite anode materials.

Recent Advances in Silicon‐Based Electrodes: From Fundamental Research toward Practical Applications

“…A multitude of strategies have been employed to address these challenges, which are briefly summarized below. [23][24][25] Nanostructured Si materials (nanoparticles, nanowires, nanotubes, etc.) have been utilized in LIBs to overcome pulverization and shorten the Li-ion diffusion path.…”

A Stable Core–Shell Si@SiOx/C Anode Produced via the Spray and Pyrolysis Method for Lithium-Ion Batteries

“…Nevertheless, graphite fails to satisfy the increasing energy density requirements as a result of the limited discharging capacity (the theoretical value of LiC 6 = 372 mAh g −1 ). In recent years, Si is regarded as one of the most potential anode materials for the next-generation lithium-ion batteries in virtue of the eminent specific capacity (∼4,200 mAh g −1 ) and low delithiation potential (∼0.4 V vs. Li + /Li) ( Lee et al, 2018 ; Nava et al, 2019 ; Zhou et al, 2020 ). Nevertheless, the extremely huge volume expansion/contraction (∼300%) in the lithiation/delithiation process has impeded the application of Si anode, which leads to the pulverization of bulk particles and deteriorates the long-term cycle life ( Chan et al, 2008 ; Liu et al, 2014 ; Li et al, 2016 ; Cook et al, 2017 ).…”

Progress of Binder Structures in Silicon-Based Anodes for Advanced Lithium-Ion Batteries: A Mini Review

“…Numerous single-component binders with linear structures have been reported, such as polyvinylidene fluoride (PVDF) ( Li et al, 2008 ; Huang et al, 2021 ), polyacrylic acid (PAA) ( Magasinski et al, 2010 ; Parikh et al, 2019 ; Hu et al, 2021 ), carboxymethyl cellulose (CMC) ( Drofenik et al, 2003 ; Wu and Li, 2020 ), sodium alginate (SA) ( Kovalenko et al, 2011 ; Cai et al, 2019 ), polymerized styrene butadiene rubber (SBR) ( Li et al, 2007 ), polyvinyl alcohol (PVA) ( Park et al, 2011 ; Mandal et al, 2021 ), chitosan (CS) ( Yue et al, 2014 ; Rajeev et al, 2020 ), polyacrylonitrile (PAN) ( Luo et al, 2016 ), polyimide (PI) ( Kim et al, 2013 ; Lee et al, 2018 ), gum arabic (GA) ( Ling et al, 2015 ; He et al, 2021 ; Zhong et al, 2021 ), and guar gum (GG) ( Liu et al, 2015 ; Zhao et al, 2021 ). Properly designed binders with hybrid structures, such as branched binders and cross-linked binders, show broader feasibility for improving the electrochemical performance of Si-based LIBs( Preman et al, 2020 ).…”