As the demand for energy storage escalates, sodium⁃ion batteries （SIBs） are increasingly in the spotlight due to their low cost and the plentiful availability of sodium resources. Particularly, hard carbon anode materials have emerged as a focal point of research, attributed to their superior cyclic stability and elevated energy density. This review delves into the advancements in hard carbon anode materials for SIBs, encompassing the screening and design of HCs precursors, surface modifications, pore structure adjustments, carbonization induction, heteroatom doping strategies, and additional tactics to augment the performance of HCs. By thoroughly examining the influence of HCs's pore structure, surface functional groups, and microstructure on the sodium storage mechanism, the review explores the potential for optimizing HCs performance through various fabrication processes. Furthermore, the article addresses the interfacial reaction mechanisms between HCs and electrolytes, along with possible avenues for enhancing HCs's cycling and rate capabilities through interface engineering. Ultimately, the review anticipates the future trajectory of HCs technology, including the design of nanostructures, surface modifications, and green manufacturing processes, underscoring the pressing need for the development of high⁃performance, cost⁃effective, and environmentally benign SIBs.
Keywords：Sodium⁃ion batteries
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Hard carbon anode
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Electrochemical performance
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Material preparation
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Interface engineering
Chang LIU, Yanqi WANG, Baixun ZHOU, Wenqi ZHUO, Zhenbo WANG. Research Progress on Hard Carbon Anode Materials for Sodium⁃Ion Batteries: From Material Design to Electrochemical Performance Optimization. Journal of Petrochemical Universities[J], 2025, 38(3): 1-9 DOI:10.12422/j.issn.1006-396X.2025.03.001
Fig.2
Schematic diagram of electrochemical performance, cycling stability, and Al2O3 layer improvement of hard carbon electrode ICE by surface modification of hard carbon[33]
随着碳化温度的升高，硬碳的石墨化程度增加，更多的开孔转化为闭孔，比表面积减小。同时，在此过程中缺陷和氧元素含量降低，由活性位点吸附引起的不可逆容量降低，有利于ICE的提升。但是，碳化温度的升高也会使碳层间距减小，不利于Na+的嵌入和脱嵌，导致电极比容量下降。针对这一矛盾，研究者在前驱体中引入金属离子催化剂催化碳化。T.LI等[42]等的研究结果表明，通过与前驱体的螯合作用引入Ni+，可促进多孔结构和石墨纳米晶体的形成，在提高比容量的同时可保证较高的ICE（见图5（a）—（b））。J.H.ZHAO等[43]开发了离子辅助催化策略，并研究了离子类型和浓度对性能的影响。结果表明，该策略将纸张衍生的前驱体浸渍适当浓度的Mn2+溶液，使Mn2+与天然纤维素上的含氧官能团交联，实现了对硬碳石墨化程度的精准调控，消除了缺陷，保持了Na+的有效路径；在20 mA /g的电流密度下，可逆比容量由247.0 mA·h/g增加到336.8 mA·h/g，ICE由86.5%提升到92.1%。
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Hard carbon prepared by different precursors and their electrochemical properties<sup>[<xref ref-type="bibr" rid="R21">21</xref>-<xref ref-type="bibr" rid="R24">24</xref>,<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig.12 硬碳表面修饰
Hard carbon prepared by different precursors and their electrochemical properties<sup>[<xref ref-type="bibr" rid="R21">21</xref>-<xref ref-type="bibr" rid="R24">24</xref>,<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig.12 硬碳表面修饰
Hard carbon prepared by different precursors and their electrochemical properties<sup>[<xref ref-type="bibr" rid="R21">21</xref>-<xref ref-type="bibr" rid="R24">24</xref>,<xref ref-type="bibr" rid="R26">26</xref>]</sup>Fig.12 硬碳表面修饰
... [33]Schematic diagram of electrochemical performance, cycling stability, and Al<sub>2</sub>O<sub>3</sub> layer improvement of hard carbon electrode ICE by surface modification of hard carbon<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>Fig.2
Schematic diagram of preparation of mixed hard carbon precursor and its XRD spectrum, initial charge discharge curve of SIBs<sup>[<xref ref-type="bibr" rid="R41">41</xref>]</sup>Fig.4
Schematic diagram of preparation of mixed hard carbon precursor and its XRD spectrum, initial charge discharge curve of SIBs<sup>[<xref ref-type="bibr" rid="R41">41</xref>]</sup>Fig.4
... [41]Schematic diagram of preparation of mixed hard carbon precursor and its XRD spectrum, initial charge discharge curve of SIBs<sup>[<xref ref-type="bibr" rid="R41">41</xref>]</sup>Fig.4
Carbonization-induced mechanisms and heteroatom doping in hard carbon<sup>[<xref ref-type="bibr" rid="R42">42</xref>,<xref ref-type="bibr" rid="R44">44</xref>]</sup>Fig.55 结 论
... ，44]Carbonization-induced mechanisms and heteroatom doping in hard carbon<sup>[<xref ref-type="bibr" rid="R42">42</xref>,<xref ref-type="bibr" rid="R44">44</xref>]</sup>Fig.55 结 论
