Dual interlayer engineering via organic-ion pillaring and electrostatic shielding in V2O5 cathode toward accelerated Al3+ transport and zero-strain aluminum batteries

Developing advanced cathode modification strategies to address the inherent high charge density of Al3+ is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries (RABs). Herein, we engineer tetraethylammonium (TEA) cation intercalation as a dual-function strategy that concurrently enables interlayer distance enlargement and electrostatic shielding effects, resolving Al3+ polarization-induced sluggish kinetics and cathode degradation in RABs. TEA intercalation triggers exceptional V2O5 interlayer expansion from 4.37 to 13.10 Å, while the modulated charge distribution generates an electrostatic shielding effect that significantly weakens the Coulombic interactions between Al3+ and V2O5 frameworks. This dual mechanism collectively enhances ion diffusion kinetics and suppresses lattice stress accumulation. Ex situ X-ray diffraction and transmission electron microscopy analyses confirm that the “molecular pillar effect” of TEA enables minimal and highly reversible structural deformation of the cathode (<2.0% volume change after 200 cycles), demonstrating zero-strain aluminum-storage behavior. The optimized cathode delivers a high reversible capacity of 258 mAh g−1 at 0.5 A g−1, maintains 99% capacity retention at 5.0 A g−1, and exhibits an ultralow capacity decay rate of 0.01% per cycle over 6000 cycles. This work opens new pathways for designing stable high-performance RAB cathodes through synergistic modulation of electronic and lattice structures.