分子填充策略调控木质素基硬碳封闭孔结构提升钠离子存储性能

黄智玮; 钟磊; 马国丽; 杨东杰; 张文礼; 邱学青

doi:10.11949/0438-1157.20260711

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分子填充策略调控木质素基硬碳封闭孔结构提升钠离子存储性能

能源和环境工程 | 更新时间：2026-07-09

- 分子填充策略调控木质素基硬碳封闭孔结构提升钠离子存储性能
- Molecular Filling Engineering-Tailored Closed Pore Formation in Lignin-Derived Hard Carbon for Enhanced Sodium-Ion Storage Performance
- 化工学报 2026年
- 作者机构：
  
  1.广东工业大学轻工化工学院，广东广州 510006
  2.华南理工大学，化学与化工学院，广东广州，510641
  3.广东工业大学先进制造学院，广东揭阳 522000
  4.广东省化学与精细化工实验室揭阳中心，广东揭阳 522000
  5.广东工业大学广东省生态安全与绿色发展卓越基础研究中心，广东广州 510006
- 作者简介：
  
  黄智玮（2002—），男，硕士研究生，zhiweihuang2002@163.com
  张文礼（1988—），博士，教授，wlzhang@gdut.edu.cn
  邱学青（1965—），博士，教授，cexqqiu@scut.edu.cn
- 基金信息：
  
  国家自然科学基金(U23A6005;22478083);广东省重点领域研发计划项目(2020B1111380002);上海交通大学绍兴新能源与分子工程研究院开放基金(JDSX2023002)
- DOI：10.11949/0438-1157.20260711
  中图分类号： TK6;TM911.3
- 收稿：2026-05-25，
  
  修回：2026-07-08，
  
  录用：2026-07-09，
- 稿件说明：
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黄智玮, 钟磊, 马国丽, 等. 分子填充策略调控木质素基硬碳封闭孔结构提升钠离子存储性能[J/OL]. 化工学报, 2026.

HUANG Zhiwei, ZHONG Lei, MA Guoli, et al. Molecular Filling Engineering-Tailored Closed Pore Formation in Lignin-Derived Hard Carbon for Enhanced Sodium-Ion Storage Performance[J/OL]. CIESC Journal, 2026.
黄智玮, 钟磊, 马国丽, 等. 分子填充策略调控木质素基硬碳封闭孔结构提升钠离子存储性能[J/OL]. 化工学报, 2026. DOI： 10.11949/0438-1157.20260711.

HUANG Zhiwei, ZHONG Lei, MA Guoli, et al. Molecular Filling Engineering-Tailored Closed Pore Formation in Lignin-Derived Hard Carbon for Enhanced Sodium-Ion Storage Performance[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260711.

摘要

制备封闭孔结构丰富的硬碳负极利于开发高能量密度钠离子电池。然而，封闭孔结构的提升通常需要较高的碳化温度。本研究提出一种分子填充策略在低碳化温度下制备封闭孔结构丰富的硬碳材料，选用木质素热解碳为基底，苝四甲酸二酐（PTCDA）为客体分子，通过PTCDA熔融扩散过程填充热解碳的孔隙结构，PTCDA热解产物在微孔壁形成堆叠伪石墨域结构，促使开放微孔转变为封闭孔，在1000 ℃下形成具有封闭孔结构丰富的填充硬碳。通过调控PTCDA的用量，填充硬碳的封闭孔体积从0.16 cm

/g提升至0.25 cm

/g，平均孔径从1.79 nm缩小至1.45 nm。经过优化的填充硬碳负极较木质素基硬碳负极表现了更高的储钠容量和倍率性能，在0.05 A/g电流密度下容量可达300 mAh/g，5 A/g的电流密度下仍保留186 mAh/g。该工作为木质素基硬碳封闭孔结构的调控和高性能钠离子电池负极开发提供了简便、高效的途径。

Abstract

The fabrication of hard carbon anodes with abundant closed pore structures is beneficial for the development of high-energy-density sodium-ion batteries. However

the design of such closed pore structures typically necessitates higher carbonization temperatures. In this study

we propose a molecular filling strategy to synthesize hard carbon materials with rich closed pore structures at low carbonization temperatures. Lignin pyrolytic carbon serves as the substrate

while perylene tetracarboxylic dianhydride (PTCDA) acts as the guest molecule to fill the pores of the pyrolytic carbon through the melting and diffusion process of PTCDA. The pyrolysis product of PTCDA forms a stacked pseudo-graphitic domain structure on the micropore walls

facilitating the conversion of open micropores into closed pores

and resulting in the formation of filled hard carbon with abundant closed pore structures at 1000 ℃. By adjusting the amount of PTCDA

the closed pore volume of the filled hard carbon increases from 0.16 cm

‒1

to 0.25 cm

‒1

while the pore size decreases from 1.79 nm to 1.45 nm. The optimized filled hard carbon anode exhibits superior sodium storage capacity and rate performance compared to the lignin-based hard carbon anode

achieving a capacity of 300 mAh g

‒1

at 0.05 A g

‒1

and retaining 186 mAh g

‒1

at 5 A g

‒1

. This work provides a straightforward and efficient approach for constructing lignin-based hard carbon closed-pore structures and developing high-performance sodium-ion battery anodes.

关键词

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references

Li T Y , Zhang C K , Li X F . Machine learning for flow batteries: opportunities and challenges [J ] . Chemical Science , 2022 , 13 ( 17 ): 4740 - 4752 .

Li L Y , Yan S M , Ding Y , et al . Recent advances in sodium iron sulfate cathodes for sodium-ion batteries: crystal structure, synthesis, and performance [J ] . ChemSusChem , 2025 , 18 ( 19 ): e202500694 .

Mai G R , Tian X , Mei Z N , et al . Construction of a free-standing bismuth carbon nanofiber-based composite anode integrated with molybdenum disulfide for high-performance sodium-ion batteries [J ] . Nanomaterials , 2026 , 16 ( 5 ): 327 .

Hou H S , Shao L D , Zhang Y , et al . Large-area carbon nanosheets doped with phosphorus: a high-performance anode material for sodium-ion batteries [J ] . Advanced Science , 2016 , 4 ( 1 ): 1600243 .

Zhong L , Yao J J , Hao S H , et al . From natural lignocellulosic resources to commercially reliable hard carbon materials: Insights and prospects [J ] . Resources Chemicals and Materials , 2025 , 4 ( 4 ): 100146 .

Canbaz E , Aydin M , Çakan R D . Investigation of hazelnut shells driven hard carbons as anode for sodium-ion batteries produced by hydrothermal carbonization method [J ] . Turkish Journal of Chemistry , 2022 , 46 ( 2 ): 356 - 366 .

Song N J , Guo N N , Ma C L , et al . Modulating the graphitic domains and pore structure of corncob-derived hard carbons by pyrolysis to improve sodium storage [J ] . Molecules , 2023 , 28 ( 8 ): 3595 .

Chen Z H , Shen J L , Deng W J , et al . Achieving over 200 Wh kg –1 sodium-ion pouch cell by quantitative engineering of hard carbon pores [J ] . National Science Review , 2026 , 13 ( 3 ): nwaf566 .

Qiu C , Li A , Qiu D P , et al . One-step construction of closed pores enabling high plateau capacity hard carbon anodes for sodium-ion batteries: closed-pore formation and energy storage mechanisms [J ] . ACS Nano , 2024 , 18 ( 18 ): 11941 - 11954 .

Yuan M , Cao B , Liu H , et al . Sodium storage mechanism of nongraphitic carbons: a general model and the function of accessible closed pores [J ] . Chemistry of Materials , 2022 , 34 ( 7 ): 3489 - 3500 .

Lan N , Li J Y , Zeng L , et al . Hyper-crosslinking to customize ultrathin-wall closed pores in pitch-derived carbon for sodium-ion batteries [J ] . Advanced Materials , 2025 , 37 ( 46 ): 2419528 .

Guo Y J , Ji S , Liu F , et al . A review of the preparation and characterization techniques for closed pores in hard carbon and their functions in sodium-ion batteries [J ] . Energy Materials , 2025 , 5 : 500030 .

Huang J H , Jian W B , Zhong L , et al . Fabrication of lignin-derived high-rate hard carbon anodes for sodium-ion batteries [J ] . Chemical Engineering Science , 2026 , 319 : 122343 .

Ma H Q , Yin B , Ye T , et al . Regulating open pores to engineer closed pores in ZIF-8-derived hard carbon for high-plateau-capacity sodium-ion batteries [J ] . Journal of Colloid and Interface Science , 2026 , 702 : 139042 .

Xiao S M , Li H C , Huang Z Q , et al . Engineering of closed pores and transport channels in polymer-derived hard carbon via chemical vapor deposition for sodium-ion batteries [J ] . ACS Nano , 2026 , 20 ( 14 ): 11096 - 11107 .

Zheng J Q , Liu W G , Li S M , et al . Spatial confinement strategy modulated by kinetic diameters of gaseous molecules for sodium storage [J ] . Energy Storage Materials , 2024 , 73 : 103835 .

Chen X X , Chen L H , Chen J H , et al . Achieving both large plateau capacity and high ICE of hard carbon via multi-steps of micropores tuning for high performance sodium ion batteries [J ] . Chemical Engineering Journal , 2026 , 529 : 172763 .

Wong H , Li Y Y , Wang J , et al . Two-dimensional materials for high density, safe and robust metal anodes batteries [J ] . Nano Convergence , 2023 , 10 : 37 .

Lou R , Tian J , Zhang Y N , et al . Fabrication of hierarchical lignin-based carbon through direct high-temperature pyrolysis and its electrochemical application [J ] . ACS Omega , 2021 , 6 ( 49 ): 34129 - 34136 .

Gao J D , Wang H , Liu X Y , et al . Regulating CO 2 adsorption performance of lychee seed-based porous carbon materials: Insights into oxygen groups and pore structure [J ] . Environmental Research , 2025 , 284 : 122245 .

Jing F , Huang T , Tao G Z , et al . An acid-pasting strategy towards PTCDA based high performance lithium/sodium ion battery cathodes [J ] . Electrochimica Acta , 2018 , 276 : 207 - 213 .

Zhang X F , Li L L , Wang L Y , et al . Physical properties of ovalbumin/sodium carboxymethyl cellulose composite gels Induced by glucono-δ-lactone and heat treatment [J ] . Gels , 2025 , 11 ( 10 ): 779 .

Zhong L , Qiu X Q , Hao S H , et al . Molecular pillaring driven microcrystalline structure engineering of hard carbon for high-rate sodium storage [J ] . Chemical Engineering Journal , 2025 , 516 : 164007 .

Li H , Zhou Y , Yang Y T , et al . Manipulating interphase chemistry by endogenous doping toward high-performance hard carbon anodes for sodium-ion batteries [J ] . Nano-Micro Letters , 2026 , 18 : 276 .

Chen H , Sun N , Wang Y X , et al . One stone two birds: Pitch assisted microcrystalline regulation and defect engineering in coal-based carbon anodes for sodium-ion batteries [J ] . Energy Storage Materials , 2023 , 56 : 532 - 541 .

Yang Y R , Wu C , He X X , et al . Boosting the Development of Hard Carbon for Sodium-Ion Batteries: Strategies to Optimize the Initial Coulombic Efficiency [J ] . Advanced Functional Materials , 2024 , 34 ( 5 ): 2302277 .

Xiao Z H , Chen Z , Sun Y K , et al . Spherical nano-graphite anode derived from electrochemical stripping for high performance Li-ion capacitors [J ] . Chemical Engineering Journal , 2023 , 474 : 145623 .

Ma G L , Yang D J , Jian W B , et al . Regulating lignin aggregation structure to construct high-performance hard carbon anodes for Sodium-Ion batteries [J ] . Chemical Engineering Science . 2026 , 321 : 122817 .

Stratford J M , Allan P K , Pecher O , et al . Mechanistic insights into sodium storage in hard carbon anodes using local structure probes [J ] . Chemical Communications , 2016 , 52 ( 84 ): 12430 - 12433 .

Morikawa Y , Nishimura S I , Hashimoto R I , et al . Mechanism of sodium storage in hard carbon: an X-ray scattering analysis [J ] . Advanced Energy Materials , 2020 , 10 ( 3 ): 1903176 .

Hu Q , Xu L Q , Liu G G , et al . Understanding the sodium storage behavior of closed pores/carbonyl groups in hard carbon [J ] . ACS Nano , 2024 , 18 ( 32 ): 21491 - 21503 .

Qiu S , Xiao L F , Sushko M L , et al . Manipulating adsorption–insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage [J ] . Advanced Energy Materials , 2017 , 7 ( 17 ): 1700403 .

Duan Y K , Li Z W , Zhang S C , et al . Stannate-based materials as anodes in lithium-ion and sodium-ion batteries: a review [J ] . Molecules , 2023 , 28 ( 13 ): 5037 .

Zou H L , Liang X , Feng X Y , et al . Chromium-modified Li 4 Ti 5 O 12 with a synergistic effect of bulk doping, surface coating, and size reducing [J ] . ACS Applied Materials & Interfaces , 2016 , 8 ( 33 ): 21407 - 21416 .

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