Phosphorus‐Enhanced Anodes: A Scalable Solution to Transition‐Metal Ion Crosstalk in High‐Energy Lithium‐Ion Batteries

Lithium-ion batteries (LIBs) with high-voltage transition-metal (TM) oxide cathodes and graphite and/or silicon anodes are widely recognized for their high energy density. However, such high-energy systems are often hindered by their poor cycling stability, especially due to anode failure caused by dissolved TM ions like Ni²⁺, Co²⁺, and Mn²⁺. Herein, we discovered phosphorus's unique phagotrophic effect, which absorbs TM ions into its bulk phase rather than allowing them to accumulate on the anode surface that typically happens for graphite and silicon. This effect allows a hybrid anode design by incorporating down to 2 wt.% phosphorus into graphite or silicon anodes, which is simple yet effectively prevents the TM-ion-induced decomposition of the electrolyte and solid-electrolyte interphase (SEI), even at high TM-ion concentrations (up to 100 mM). Consequently, full cells with phosphorus-enhanced graphite or silicon anodes demonstrate remarkable extended cycling life. Importantly, this phosphorus-based TM-ion phagotrophic effect can be incorporated with standard electrode processing techniques for both graphite and silicon, ensuring seamless integration into existing LIB manufacturing. By improving the stability of graphite and silicon anodes across a variety of TM-oxide cathodes, this approach provides a practical and scalable solution for advancing next-generation high-energy LIBs, offering both simplicity and transformative impact for battery technology.