Co‐Optimized Potassium Deposition and Interfacial Stability Enabled by 3D‐Printed GO/ATP Hosts for Durable Dendrite‐Free Potassium Metal Anodes

Potassium metal batteries (PMBs) are promising candidates for next‐generation large‐scale energy storage owing to their high energy density and cost‐effectiveness. However, their rate capability and cycling stability are severely hindered by sluggish K + transport kinetics, uncontrolled dendrite growth, and fragile solid electrolyte interphase (SEI) at the K anode. Herein, a hierarchically porous three‐dimensional (3D) host integrating graphene oxide (GO) and attapulgite (ATP) is fabricated by direct ink writing (denoted 3DP‐GO/ATP), combining strong potassiophilicity with anion affinity. Its interconnected porous architecture provides continuous ion‐transport pathways, facilitating rapid K + transport. The potassiophilic sites lower the K nucleation barrier and promote dendrite‐free K deposition, whereas the strong anion affinity drives interfacial FSI– enrichment and favors the formation of an inorganic‐rich SEI. The resulting K||3DP‐GO/ATP asymmetric batteries deliver stable cycling for 2750 cycles (5500 h), while the 3DP‐GO/ATP@K||3DP‐GO/ATP@K symmetric batteries sustain stable operation for over 3750 h at 0.5 mA cm −2 /0.5 mAh cm −2 . When paired with a perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTCDA) cathode, the full batteries retain a reversible capacity of 93.56 mAh g −1 after 1000 cycles at 20C and remain reversibly operational at 100C. This strategy enables synergistic regulation of K deposition and interfacial chemistry, promoting high‐rate and long‐life PMBs.