Effects of Pyrolysis on High-Capacity Si-Based Anode of Lithium Ion Battery with High Coulombic Efficiency and Long Cycling Life.

Yonhua Tzeng,Cheng-Ying Jhan,Yi-Hsuan Wu

doi:10.3390/nano12030469

Yonhua Tzeng, Cheng-Ying Jhan + Show 1 more

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https://doi.org/10.3390/nano12030469

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Abstract

We report a facile pyrolysis process for the fabrication of a porous silicon-based anode for lithium-ion battery. Silicon flakes of 100 nm × 800 nm × 800 nm were mixed with equal weight of sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) as the binder and the conductivity enhancement additive, Ketjen Black (KB), at the weight ratio of silicon–binder–KB being 70%:20%:10%, respectively. Pyrolysis was carried out at 700 °C in an inert argon environment for one hour. The process converts the binder to graphitic carbon coatings on silicon and a porous carbon structure. The process led to initial coulombic efficiency (ICE) being improved from 67% before pyrolysis to 75% after pyrolysis with the retention of 2.1 mAh/cm2 areal capacity after 100 discharge–charge cycles at 1 A/g rate. The improved ICE and cycling performance are attributed to graphitic coatings, which protect silicon from irreversible reactions with the electrolyte to form compounds such as lithium–silicon–fluoride (Li2SiF6) and the physical integrity and buffer space provided by the porous carbon structure. By eliminating the adverse effects of KB, the anode made with silicon-to-binder weight ratio of 70%:30% exhibited further improvement of the ICE to approximately 90%. This demonstrated that pyrolysis is a facile and promising one-step process for the fabrication of silicon-based anode with high ICE and long cycling life. This is especially true when the amount and choice of conductivity enhancement additive are optimized.

Highlights

Silicon is abundant and used in large quantity in the global semiconductor industry.It exhibits a very high theoretical capacity of 4200 mAhg−1 as an anode for lithium-ion battery with a very low oxidation-reduction potential of less than 0.5 V vs. Li/Li+, and low reactivity with electrolytes [1]
The anode made of silicon flake, binder, and conductivity enhancement additives but without pyrolysis process lacks graphitic carbon coatings on silicon flakes and a porous structure of pyrolyzed binder
Silicon flakes of about 100 nm × 800 nm × 800 nm in size were recycled from wastes of silicon wafer manufacturing processes for the fabrication of silicon-based anode for lithium-ion battery

Summary

Introduction

Silicon is abundant and used in large quantity in the global semiconductor industry.It exhibits a very high theoretical capacity of 4200 mAhg−1 as an anode for lithium-ion battery with a very low oxidation-reduction potential of less than 0.5 V vs. Li/Li+ , and low reactivity with electrolytes [1]. Silicon is abundant and used in large quantity in the global semiconductor industry. It exhibits a very high theoretical capacity of 4200 mAhg−1 as an anode for lithium-ion battery with a very low oxidation-reduction potential of less than 0.5 V vs Li/Li+ , and low reactivity with electrolytes [1]. Silicon exhibits high electrical resistivity and suffers from a very large change (about 300%) in volume due to the formation of silicon-lithium compounds during lithiation. The formation of SEI before silicon is primed to store charges by lithiation results in a significant irreversible loss of lithium [2]. An initial coulombic efficiency (ICE) of 80% causes the loss of 20% of the lithium that reacts to form SEI during the first-time lithiation of silicon.

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