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Vol. 18 (2026)

Nano-Space Confinement Drives Rational Closed Pore Design in Hard Carbons for High-Capacity and High-Rate Sodium Storage

https://doi.org/10.1007/s40820-026-02223-7
Run Ren
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Ling Zhang
Zhongyuan Critical Metals Laboratory, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Jianhua Zhu
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Yunfeng Chao
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Junlin Guo
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Yijun Cao
Zhongyuan Critical Metals Laboratory, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Xiaobo Ji
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People’s Republic of China
Xinwei Cui
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China

Corresponding Author: Xinwei Cui

xinweic@zzu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 382

Abstract

Hard carbons are emerging as the most viable anodes for the commercialization of Na-ion batteries. However, their performance limits are far from being disclosed because of ambiguous Na-storage mechanism. Here, we report that nano-space confinement regulates heterogeneous nucleation of quasi-metallic Na clusters in closed pores, uncovering a coupled “intercalation-pore filling” and stage-wise storage mechanism for high capacities. Theoretical studies reveal that the energy barrier for Na-cluster growth decreases as the nanocavity size decreases; however, it remains energetically unfavorable at potentials (V vs. Na/Na+) > 0. Interestingly, in the coupled storage, Na-ion intercalation in nanoconfined orifices triggers stepwise pre-nucleation, reducing energy barriers for spontaneous Na-cluster growth in progressively larger cavities at positive potentials, thus enabling Na-cluster deposition into previously unused closed pores. This understanding guides the rational design of stage-wise closed pores, resulting in superior performance of 500 mAh g−1 at 50 mA g−1 and 344 mAh g−1 at 2000 mA g−1. Mechanistic studies further identify a new stage, where confined nano-spaces at 0.4–0.6 nm facilitate pre-desolvation and enhance Na-ion transport kinetics for high-rate capabilities. This work identifies the origin governing Na-storage behavior in the closed pores of hard carbons, boosting their overall performance beyond prior expectations.


Highlights:
1 Nano-space confinement regulates heterogeneous nucleation of quasi-metallic Na clusters in closed graphitic pores of hard carbons, suggesting a coupled “intercalation-pore filling” and stage-wise storage mechanism for high Na-storage capacities.
2 A new stage near the end of slope region was identified, where confined nano-spaces at 0.4–0.6 nm facilitate pre-desolvation and enhance Na-ion transport kinetics for high-rate capabilities.
3 Rational design of stage-wise closed pores was achieved in hard carbons, resulting in superior performance of 500 mAh g−1 at 50 mA g−1 and 344 mAh g−1 at 2000 mA g−1.

Keywords

Sodium-ion batteries Hard carbon Nanoconfinement Closed pore Sodium storage mechanism
Ren, Run, Ling Zhang, Jianhua Zhu, Yunfeng Chao, Junlin Guo, Yijun Cao, Xiaobo Ji, and Xinwei Cui. 2026. “Nano-Space Confinement Drives Rational Closed Pore Design in Hard Carbons for High-Capacity and High-Rate Sodium Storage”. Nano-Micro Letters 18 (May):382. https://doi.org/10.1007/s40820-026-02223-7.
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