Silicon Oxycarbide-Coated Bismuth for Enhanced Anode Stability in Lithium-Ion Batteries

Abstract

The current state-of-the-art lithium-ion batteries (LIBs) with graphite as an anode foresees shortcomings to demands in energy storage and supplies with high energy and power densities for large-scale applications such as electric vehicles. Metallic Bi alloy is among the promising alternative alloy candidates to replace the graphitic anode owing to its high volumetric capacity (3765 mAh cm−3), relatively small volume expansion (~215%), and unique layered crystalline structure with large interlayer spacing along the c-axis (d 003 = 3.95 Å). Nevertheless, inevitable volume expansion during repetitive Li+-ion insertion/extraction build-ups localized mechanical strain, causing particle pulverization, cracking, and isolations, eventually leading to cell failure. Herein, to achieve decent reversibility of alloys, we introduce a polymer-derived ceramic silicon oxycarbide (SiOC) coating onto Bi nanoparticles (NPs) via facile dispersion of bismuth hydroxide in silicone oil and consecutive heat treatment. The SiOC coating layer alone is an active conversion material with a higher specific capacity but lower volumetric capacity than Bi. To promote the fabrication of high volumetric capacity Bi-based composites using higher tap density materials with a well-balanced specific capacity, the content of the metal precursor and silicone oil were varied. The sturdy SiOC matrix embedded with the Bi NPs cushions the stress cultivated upon (de)lithiation reactions, achieving stable capacity (507 mAh g−1 at 0.05 A g−1 after 150 cycles), high volumetric capacity (872 mAh cm−3), superb cyclic stability (380 mAh g−1 at 0.5 A g−1 after 500 cycles), and adequate cell integrity when tested as an anode in a half cell. In a full cell configuration coupled with a LiNi0.5Co0.2Mn0.3O2 cathode, high gravimetric and volumetric energy densities of 343 Wh kg−1 and 607 Wh L−1 can be estimated, respectively. The conducted kinetic and postmortem analyses provide additional insights into the effectiveness of amorphous SiOC as a protective layer in preventing excess solid electrolyte interface passivation and preserving the electrically conductive network for continuous transport of ions and electrons. Figure 1