Optimizing Li ⁺ Transport in Lithium–Sulfur Batteries via Directional Pore Channels

Carbon hosts are indispensable for enabling sulfur redox reactions in lithium–sulfur (Li–S) batteries. However, their intrinsically tortuous and spatially heterogeneous pore networks constitute a fundamental barrier to lithiumion (Li + ) transport in sulfur cathodes, giving rise to long diffusion paths, nonuniform ionic flux and pronounced reaction polarization. In this study, we report a directionally aligned graphene framework (DG) with an orientation degree of 0.88 and an aspect ratio of 2.25 engineered via upward‐assisted solvent evaporation, which enables continuous and low tortuosity pore channels. Such structural ordering markedly improves the diffusion coefficient increasing during the rate‐determining lithium polysulfide‐to‐Li 2 S conversion, from 1.56 × 10 −16 to 3.32 × 10 −13 cm 2 s −1 , together with a pronounced reduction in the corresponding Tafel slope from 187 to 108 mV dec −1 , indicative of the accelerated reaction kinetics. Consequently, the DG/S cathode delivers low polarization and stable reversible capacities exceeding 500 mAh g −1 over 250 cycles at 0.1°C. Moreover, the self‐supporting DG/S electrode maintains a high capacity of 564 mAh g −1 at 1°C, far outperforming its isotropic counterpart. These results demonstrate that directional architectural regulation of porous electrodes offers a powerful and scalable strategy to overcome intrinsic ion‐transport limitations in Li–S batteries.