NASICON‐structured NaTi₂(PO₄)₃ (NTP) is an attractive anode material for aqueous rechargeable sodium-ion batteries (ARSIBs) thanks to its three-dimensional open framework and appropriate negative voltage window. Nevertheless, the lack of flexible and high-performance binder-free NTP-based anodes remains stumbling blocks to the development of wearable ARSIBs. Herein, hollow-structure NTP evenly encapsulated in cross-linked porous N-doped carbon nanofiber (HNTP@PNC) is prepared through electrospinning technology and subsequent carbonization treatment, directly acting as binder-free anode for flexible ARSIBs. Benefiting from its unique hollow structure, continuous conductive network and favorable synergistic effect, the HNTP@PNC electrode displays as high as of 108.3 mAh g⁻¹ rate capacity at 5.50 A g⁻¹ and an impressive cycling stability of 97.2% capacity retention after 3000 cycles. Further, theoretical calculations reveal that NTP with NC coating significantly enhances electronic conductivity and accelerates Na⁺ diffusion kinetics. Pairing with potassium zinc hexacyanoferrate free-standing cathode, a prototype quasi-solid-state ARSIB with a high-voltage discharge plateau of 1.6 V is successfully constructed, achieving a high volumetric capacity of 24.5 mAh cm⁻³ and an admirable energy density of 39.2 mWh cm⁻³, outperforming most reported flexible aqueous rechargeable energy-storage devices. These exciting results provide valuable intuition into the design of novel binder-free NTP-based anodes for next-generation wearable ARSIBs.

NASICON结构的NaTi ₂（PO ₄）₃NTP（NTP）由于具有三维开放框架和适当的负电压窗口，是用于水性可充电钠离子电池（ARSIB）的有吸引力的阳极材料。尽管如此，缺乏基于柔性和高性能无粘结剂NTP的阳极仍然是可穿戴ARSIBs开发的绊脚石。在此，通过静电纺丝技术和随后的碳化处理，将均匀封装在交联的多孔N掺杂碳纳米纤维（HNTP @ PNC）中的中空结构NTP直接用作柔性ARSIB的无粘合剂阳极。从它的独特的中空结构，连续的导电网络和有利的协同效应中受益，所述HNTP @ PNC电极显示高达108.3毫安克^-1率容量在5.50 A G ^-13000次循环后，令人印象深刻的循环稳定性（容量保持率为97.2％）。此外，理论计算表明，带有NC涂层的NTP可以显着增强电子导电性并加速Na ⁺扩散动力学。与六氰合铁酸钾锌自立阴极配对，成功构建了具有1.6 V高压放电平稳期的准固态ARSIB原型，实现了24.5 mAh cm ^-3的高体积容量和39.2的可观能量密度mWh cm ^-3，胜过大多数报道的柔性水可充电储能装置。这些令人振奋的结果为下一代可穿戴ARSIBs的新型无粘结剂NTP阳极设计提供了宝贵的直觉。