Delineating the Effects of Transition‐Metal‐Ion Dissolution on Silicon Anodes in Lithium‐Ion Batteries

Abstract

AbstractSilicon anode is an appealing alternative to enhance the energy density of lithium‐ion batteries due to its high capacity, but it suffers from severe capacity fade caused by its fast degradation. The crossover of dissolved transition‐metal (TM) ions from the cathode to the anode is known to catalyze the decomposition of electrolyte on the graphite anode surface, but the relative impact of dissolved Mn2+ versus Ni2+ versus Co2+ on silicon anode remains to be delineated. Since all three TM ions can dissolve from LiNi1−x−yMnxCoyO2 (NMC) cathodes and migrate to the anode, here a LiFePO4 cathode is paired with SiOx anode and assess the impact by introducing a specific amount of Mn2+ or Ni2+ or Co2+ ions into the electrolyte. It is found that Mn2+ ions cause a much larger increase in SiOx electrode thickness during cycling due to increased electrolyte decomposition and solid–electrolyte interphase (SEI) formation compared to Ni2+ and Co2+ ions, similar to previous findings with graphite anode. However, with a lower impedance, the SEI formed with Mn2+ protects the Si anode from excessive degradation compared to that with Co2+ or Ni2+ ions. Thus, Mn2+ ions have a less detrimental effect on Si anodes than Co2+ or Ni2+ ions, which is the opposite of that seen with graphite anodes.