Carbon Encapsulated Silicon for High-Capacity Durable Anodes
Authors: Karki Peshal , Sabet Morteza , Rao Apparao M. , Pilla Srikanth 
Published: November 2022

One of the biggest challenges of the near future is how to meet the increasing energy demand without any adverse environmental impact. Lithium-Ion batteries (LIBs) are one of the promising alternative energy storage systems to replace conventional non-rechargeable batteries. LIBs are becoming one of the most widely used energy storage devices because of their relatively high specific energy density (~300 Wh/kg), excellent stability over a wide temperature range, and lower cost than other battery systems. Intense research is in progress to increase the capacity of anode electrodes for realizing high-energy LIBs. In this context, silicon (Si) has a great potential to replace commercial graphitic anode active materials mainly due to its high theoretical specific capacity (4200 mAh/g) and low working potential (0.37 to 0.45 V vs. Li/Li+). To harness and maintain a high capacity from Si-based anodes, we must deal with two main challenges: (i) volume changes of Si (>300%) during charging and discharging, which cause pulverization of the material and loss of electrical contact, and (ii) unstable growth of solid-electrolyte interphase (SEI) layer, which can cause early degradation of performance in Si-anode batteries. To overcome these challenges, different approaches have been taken. This includes developing graphite/Si anodes with limited amounts of Si (<30 wt.%), conformal coating of Si active materials (e.g., CVD carbon coating), etc. However, these challenges still could not be fully overcome.
To advance the use of Si materials in LIB anodes, we developed a viable technology to create a hybrid silicon-carbon material, called Si@C, in which a soybean-derived carbon cloud protects Si nanoparticles during the battery operation. We employed soybean oil in a scalable oil-in-water emulsion polymerization technique to produce Si-containing polymeric particles. In this method, we emulsified two immiscible solutions. One contains a homogeneous Si mixture in epoxidized soybean oil (ESO), and another contains a uniform dispersion of ball-milled lignin or soyhull powders in water. Citric acid, a crosslinking agent, was used to help polymerize the ESO and integrate carbon-rich lignin/soyhull with polymerized particles. The final Si@C product was achieved by carbonizing the polymerized solid product at 500 °C (under argon) and ball milling to get a fine powder. Several Si@C hybrid materials containing 20 wt.% to 50 wt.% Si were successfully prepared and utilized for anode preparation. Electrodes were made by coating a slurry of Si@C active material, carbon black, and binder with a mass ratio of 60:20:20 onto an ion-permeable Bucky Paper (BP, a flexible and conductive paper made of carbon nanotubes). Anodes with different binding systems were prepared to determine an appropriate binder for Si@C based batteries. The 2032-type coin cells were assembled for battery testing using 1M LiPF6 in EC:DMC in a volume ratio of 1:1 as the electrolyte, Li chips as the counter electrode, and Celgard 2325 as the separator. The coin cells were cycled at a current rate of 0.1C (420 mA/gSi) over the potential range of 0.01 – 1.0 V at room temperature.
Battery results showed that Si@C hybrid materials increased the capacity of Si anodes by a factor of >2. At Si mass loading of 1.0 mg/cm2, implementing our carbon cloud approach led to an increase in the discharge capacity of anodes from 0.5 mAh (corresponding to anode with bare Si) to >1.0 mAh (corresponding to anode with Si@C hybrids). Results from battery cycling at 0.1C demonstrated excellent capacity retention of >95% after 130 cycles for anodes prepared using our Si@C active materials. The Si content of Si@C hybrid particles was also found to be an influential factor in the cycling performance of anodes. Finally, we observed that the use of water-based polyacrylic acid (PAA) and carboxymethyl cellulose (CMC) binders improve the electrochemical performance of Si@C based anodes. These water-based binders are ideal for preparing Si-based slurries, and the need for using toxic solvents (e.g., NMP) to prepare slurries can be averted. In conclusion, we innovated a viable technology that uses biomass (soybean oil and soyhulls) to enhance Si-based batteries' performance. We demonstrated that our Si@C materials with a carbon cloud protecting the Si nanoparticles are promising active materials to improve the capacity and cycling stability of LIB anodes.