Template method is an effective strategy for the construction of microporous structure in hard carbons. However, the introduction of templates will inevitably affect the original structure of hard carbon, making it necessary to develop an adjustable template for the high sodium storage property of Sodium-ion battery anodes. Herein, we propose an effective strategy of developing size-controlled ZnO microcrystal in precursor carbon by zinc salts templates and promoting the formation of numerous closed pores during subsequent pyrolysis. All of the obtained hard carbons exhibit high specific capacities of over 340 mAh/g, and initial Coulomb efficiencies of over 90%. Besides, the information of closed pore structure in hard carbon, accompanying with the diffusive behavior of Na+ and the in-situ Raman spectroscopy reveal a strong link between the increased plateau and the closed pore volume, providing a compelling insight for the mechanism of Na+ storage in hard carbon. The optimal sample exhibits the highest closed pore volume, which performs a remarkable specific capacity of 374 mAh/g and a high initial Coulombic efficiency of 92.4%. Furthermore, all zinc salt-derived hard carbon exhibit analogous microstructures and electrochemical behaviors, demonstrating the universality of utilizing both inorganic and organic zinc salts as templates for adjusting the microporous structure of hard carbon. These findings provide a systematic approach to enhance the reversible capacity and maintain high initial Coulombic efficiency for sodium-ion battery anodes.
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