Porous Silicon Nano-Quill Anodes for Lithium-Ion Batteries
Authors: Chen Nancy , Sabet Morteza , Sapkota Nawraj , Clemons Craig M. , Rao Apparao M. , Pilla Srikanth 
Published: November 2022

The growing population and increasing demands for energy are overwhelming our supply of fossil fuels and limiting the availability for future generations. Technologies for energy storage devices are emerging to replace conventional fuel-based technologies to meet emissions goals set by world governments and the rapid electrification of the transportation sector. Lithium-ion batteries (LIBs) are widely used for energy storage in devices across many commercial applications. LIB electrodes are continuously evolving due to demands for higher energy density and long cycling life. Among the recent developments in anode electrode materials, silicon (Si) is regarded as the most promising replacement for graphite due to its high theoretical specific capacity (~4200 mAh g-1), which is over 10 times greater than that of conventional graphite anodes (~372 mAh g-1). Despite the advancements, persisting challenges hinder the commercialization of Si for LIB anodes. Si-based electrodes are susceptible to rapid degradation due to the large volume change (approx. 400%) of Si particles during lithium insertion and extraction. The repeated volume change leads to the pulverization of the Si material, ultimately leading to decreased cycling stability from the loss of contact with the current collector. To overcome this obstacle, 3-dimensional porous and hollow nanostructures have been employed to provide sufficient void space to accommodate the volume change during electrochemical cycling. However, with the demands for material cost-reduction from industry, Si structures' strategic engineering must be cost-effective for commercial viability.
Our team has developed a patent-pending cost-effective, scalable, and green methodology to use bio-renewable templates to synthesize a 3-dimensional Si architecture, called Si nano-quills (SiNQs). We innovated a two-step, cost-effective process that yields SiNQs with a porous morphology and hollow interior structure. First, in a scalable sol-gel process, silica gel particles were prepared using commonly available low-cost chemicals. The unique mesoporous SiNQ morphology was engineered using surfactant-modified cellulose nanocrystals as a bio-renewable sacrificial template. The templates were removed via thermal treatment to form silica nanoparticles. These particles, called silica nano-quills (SilicaNQs), possess a 3-dimensional bulk structure comprised of hollow quill-like arms and a high degree of porosity. In the second step, we employed a low-temperature magnesiothermic reduction method to convert SilicaNQs into SiNQs with a relatively large surface area. Anode electrodes were fabricated using SiNQs as the active material for electrochemical testing. The slurry was prepared using the active material, carbon black, and PVDF with a mass ratio of 60:20:20 coated onto an ion-permeable Bucky Paper (BP, a flexible and conductive paper made of carbon nanotubes). The 2032-type coin cells were assembled for battery testing using SiNQ electrodes (with an active mass loading of 1 mg cm-2) and a lithium metal chip as the counter electrode. The coin cells were cycled at a current rate of 0.1C (420 mA g-1) over the potential range of 0.01 – 1.0 V at room temperature. The SiNQ anode offered superior battery capacity retention of 73% of the initial reversible capacity of 963 mAh g-1 after 220 cycles. In comparison, batteries fabricated from the Mg reduction of commercially available mesoporous silica, SBA-15, offer capacity retention of only 52.6% after 100 cycles. The SiNQ precursor is engineered to possess porous walls with a superior BET surface area (1265 m2 g-1) compared to SBA-15 (550 m2 g-1). After Mg reduction, the SiNQs retain a BET surface area of 232 m2 g-1, whereas the surface area of reduced SBA-15 is 74 m2 g-1. The superior performance of SiNQs is due to their unique morphology that offers high surface area and porosity for effective diffusion of lithium ions and more sites for interactions with lithium ions, leading to a higher reversible capacity. Moreover, the porous architecture of SiNQs can effectively mitigate the volume change issue during lithiation and delithiation processes, thus providing a good cycling performance.