All-solid-state batteries stabilized with electro-mechano-mediated phosphorus anodes

Aggressive anodes like Li metal and silicon promise high-energy, all-solid-state lithium batteries (ASSLBs) but are restricted by dendritic lithium growth. Ideally, anodes should inherently resist dendritic growth while offering high specific energy. Herein, we describe a class of resource-abundant and dendrite-resistant phosphorus anodes for high-areal-capacity, all-solid-state lithium batteries (ASSLBs). This is achieved by leveraging phosphorus's well-balanced redox potential which thermodynamically mitigates lithium plating while offering high energy. Importantly, we present an electro-mechano-mediation strategy based on compositing engineering to simultaneously promote the charge transport and chemo-mechanical behavior of the phosphorus electrode. As a proof-of-concept, we demonstrated a P/Sb anode wherein the Sb/Li_xSb filler – mixed conducting, stiff, and low-volume-breathing – not only promotes percolated electron/ion transport (electro-mediation effect), but also constrains the volume changes of P/Li₃P and suppresses crack formation in the electrode (mechano-mediation effect). Impressively, the anode delivers 340 mA h g⁻¹ at an extreme rate of 30C (90 mA cm⁻², 60 °C), and shows remarkable stability retaining 64.0% capacity after 10 000 cycles at 10C. Furthermore, full cells loaded with 53.5 mg cm_LiCoO2⁻² deliver a high areal capacity of 6.4 mA h cm⁻² at C/5 and retain 90.0% capacity over 800 cycles at C/2 (25 °C). Our work represents a unique perspective for exploiting high-capacity, dendrite-resistant anode materials which are resourcefully sustainable but have been historically deemed unsuitable for high-energy all-solid-state batteries.