Partial Oxidation Strategy Toward Carbonyl-Dominated Surfaces for Enhanced Sodium Storage in Biomass-Derived Hard Carbon

Abstract

The practical application of biomass-derived hard carbon (HC) in sodium-ion batteries (SIBs) remains hindered by low initial Coulombic efficiency (ICE) and limited rate capability, primarily caused by unstable surface functionalities and inefficient interfacial chemistry. In this study, we propose a facile precisely controlled partial oxidation strategy to selectively regulate the surface chemical environment of glucose-derived hard carbon, enabling the transformation of unstable hydroxyl and carboxyl groups into more stable carbonyl functionalities without significantly altering the carbon framework. This mild, low-temperature partial oxidation process partially unifies surface functional groups, promotes the formation of a thin and uniform solid electrolyte interphase (SEI), and enhances Na⁺ adsorption and diffusion kinetics. The optimized sample (CS-HO) exhibits a reversible capacity of 310.5 at 50 mA g^–1, a high ICE exceeding 70%, and excellent rate performance and cycling stability, with 73% capacity retention after 1000 cycles at 1 A g^–1. Mechanistic investigations, including in situ Raman spectroscopy and galvanostatic intermittent titration technique (GITT), reveal a dominant “adsorption–intercalation–pore filling” storage mechanism, attributed to the homogenized carbonyl-rich surface and optimized porous environment. This study offers mechanistic insights into bond-specific surface engineering and establishes a scalable, energy-efficient, and chemically rational pathway toward the design of high-performance SIB anode materials.

Keywords

biomass-derived hard carbon / initial Coulombic efficiency / partial oxidation strategy / sodium-ion batteries / surface functional groups

References

[1] M. Li, J. Lu, Z. Chen, and K. Amine, “30 Years of Lithium-Ion Batteries,” Advanced Materials 30 (2018): 1800561.

[2] Y. Gao, H. Zhang, J. Peng, et al., “A 30-year Overview of Sodium-Ion Batteries,” Carbon Energy 6 (2024): e464.

[3] H. Jiang, Y. Zhang, M. Waqar, et al., “Anomalous Zn²⁺ Storage Behavior in Dual-Ion-in-Sequence Reconstructed Vanadium Oxides,” Adv Funct Materials 33 (2023): 2213127.

[4] Y. Zhang, Z. Zhou, X. Tan, et al., “Tailoring Electronic Structure to Enhance the Ammonium-Ion Storage Properties of VO₂ by Molybdenum Doping Toward Highly Efficient Aqueous Ammonium-Ion Batteries,” Inorganic Chemistry Frontiers 12 (2025): 355–368.

[5] C. Yang, S. Xin, L. Mai, and Y. You, “Materials Design for High-Safety Sodium-Ion Battery,” Advanced Energy Materials 11 (2021): 2000974.

[6] W.-J. Shi, H.-X. Li, D. Zhang, et al., “Insights Into Unrevealing the Effects of the Monovalent Cation Substituted Tunnel-Type Cathode for High-Performance Sodium-Ion Batteries,” Chemical Engineering Journal 477 (2023): 146976.

[7] W. Shi, X. Duan, Z. Xiao, et al., “Enhancing the Structural Stability and Diffusion Kinetics of a Tunnel-Phase Cathode by the Synergistic Effect of Cation-Anion Co-Doping for Advanced Sodium-Ion Batteries,” Molecules 30 (2025): 2299.

[8] W. Shi, H. Li, Z. Wang, et al., “Constructing Layered/Tunnel Biphasic Structure via Trace W-Substitution in Tunnel-Type Cathode for Elevating Sodium Ion Storage,” Molecules 30 (2025): 2175.

[9] X. Zhang, F. Zhang, H. Li, et al., “Dual Graphitization to Fabricate Graphitic Carbon Aerogel for Superior Sodium-Ion Storage,” Journal of Alloys and Compounds 1010 (2025): 177282.

[10] H. Hou, X. Qiu, W. Wei, Y. Zhang, and X. Ji, “Carbon Anode Materials for Advanced Sodium-Ion Batteries,” Advanced Energy Materials 7 (2017): 1602898.

[11] K. Sada, J. Darga, and A. Manthiram, “Challenges and Prospects of Sodium-Ion and Potassium-Ion Batteries for Mass Production,” Advanced Energy Materials 13 (2023): 2302321.

[12] D. Chen, W. Zhang, K. Luo, et al., “Hard Carbon for Sodium Storage: Mechanism and Optimization Strategies Toward Commercialization,” Energy & Environmental Science 14 (2021): 2244–2262.

[13] R. R. Gaddam, D. Yang, R. Narayan, K. Raju, N. A. Kumar, and X. S. Zhao, “Biomass Derived Carbon Nanoparticle as Anodes for High Performance Sodium and Lithium Ion Batteries,” Nano Energy 26 (2016): 346–352.

[14] B. Zhong, C. Liu, D. Xiong, et al., “Biomass-Derived Hard Carbon for Sodium-Ion Batteries: Basic Research and Industrial Application,” ACS Nano 18 (2024): 16468–16488.

[15] T. Yang, T. Qian, M. Wang, et al., “A Sustainable Route From Biomass Byproduct Okara to High Content Nitrogen-Doped Carbon Sheets for Efficient Sodium Ion Batteries,” Advanced Materials 28 (2016): 539–545.

[16] J. Chen, J. Zhou, W. Zheng, et al., “A Complete Review on the Oxygen-Containing Functional Groups of Biochar: Formation Mechanisms, Detection Methods, Engineering, and Applications,” Science of the Total Environment 946 (2024): 174081.

[17] R. Väli, A. Jänes, T. Thomberg, and E. Lust, “Synthesis and Characterization of D-Glucose Derived Nanospheric Hard Carbon Negative Electrodes for Lithium- and Sodium-Ion Batteries,” Electrochimica Acta 253 (2017): 536–544.

[18] M. Li, W. Li, and S. Liu, “Hydrothermal Synthesis, Characterization, and KOH Activation of Carbon Spheres From Glucose,” Carbohydrate Research 346 (2011): 999–1004.

[19] L. Liu, F. Xu, A. Zou, et al., “Biomass-Derived Hard Carbon Anodes: An Overview on Strategies of Improving Initial Coulombic Efficiency for Sodium-Ion Batteries,” Materials Today Communications 41 (2024): 110271.

[20] H. He, D. Sun, Y. Tang, H. Wang, and M. Shao, “Understanding and Improving the Initial Coulombic Efficiency of High-Capacity Anode Materials for Practical Sodium Ion Batteries,” Energy Storage Materials 23 (2019): 233–251.

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

[22] M. Zhang, Y. Li, F. Wu, Y. Bai, and C. Wu, “Boost Sodium-Ion Batteries to Commercialization: Strategies to Enhance Initial Coulombic Efficiency of Hard Carbon Anode,” Nano Energy 82 (2021): 105738.

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

[24] W. Xing and J. R. Dahn, “Study of Irreversible Capacities for Li Insertion in Hard and Graphitic Carbons,” Journal of the Electrochemical Society 144 (1997): 1195–1201.

[25] X. Chen, C. Liu, Y. Fang, et al., “Understanding of the Sodium Storage Mechanism in Hard Carbon Anodes,” Carbon Energy 4 (2022): 1133–1150.

[26] H. Wang, F. Sun, Z. Qu, et al., “Oxygen Functional Group Modification of Cellulose-Derived Hard Carbon for Enhanced Sodium Ion Storage,” ACS Sustainable Chemistry & Engineering 7 (2019): 18554–18565.

[27] C. Yang, J. Zhao, B. Dong, et al., “Advances in the Structural Engineering and Commercialization Processes of Hard Carbon for Sodium-Ion Batteries,” Journal of Materials Chemistry A 12 (2024): 1340–1358.

[28] Y. Zhao, J. Ye, P. Zhang, Z. Li, and H. Zhao, “Abnormal Preferential Oxygen Functionalization on the Surface of Soft/Hard Carbon for Sodium Storage,” Applied Surface Science 602 (2022): 154336.

[29] Q. Lin, J. Zhang, W. Lv, et al., “A Functionalized Carbon Surface for High-Performance Sodium-Ion Storage,” Small 16 (2020): 1902603.

[30] S. Dong, Y. Lyu, and Z. S. Guo, “Effect of Carbon Nanotubes Conductors on Electrolyte Wettability and Electrochemical Performance of Lithium-Ion Battery Electrodes,” Chemsuschem 18 (2025): e202402517.

[31] M. Song, Z. Yi, R. Xu, et al., “Towards Enhanced Sodium Storage of Hard Carbon Anodes: Regulating the Oxygen Content In Precursor by Low-Temperature Hydrogen Reduction,” Energy Storage Materials 51 (2022): 620–629.

[32] H. Xie, Z. Wu, Z. Wang, et al., “Solid Electrolyte Interface Stabilization via Surface Oxygen Species Functionalization in Hard Carbon for Superior Performance Sodium-Ion Batteries,” Journal of Materials Chemistry A 8 (2020): 3606–3612.

[33] T. Xu, X. Qiu, X. Zhang, and Y. Xia, “Regulation of Surface Oxygen Functional Groups and Pore Structure of Bamboo-Derived Hard Carbon for Enhanced Sodium Storage Performance,” Chemical Engineering Journal 452 (2023): 139514.

[34] Z. Song, M. Di, S. Chen, and Y. Bai, “Three-Dimensional N/O Co-Doped Hard Carbon Anode Enabled Superior Stabilities for Sodium-Ion Batteries,” Chemical Engineering Journal 470 (2023): 144237.

[35] N. Sun, J. Qiu, and B. Xu, “Understanding of Sodium Storage Mechanism in Hard Carbons: Ongoing Development under Debate,” Advanced Energy Materials 12 (2022): 2200715.

[36] S. Qiu, L. Xiao, M. L. Sushko, et al., “Manipulating Adsorption–Insertion Mechanisms in Nanostructured Carbon Materials for High-Efficiency Sodium Ion Storage,” Advanced Energy Materials 7 (2017): 1700403.

[37] X. Feng, Y. Li, Y. Li, et al., “Unlocking the Local Structure of Hard Carbon to Grasp Sodium-Ion Diffusion Behavior for Advanced Sodium-Ion Batteries,” Energy & Environmental Science 17 (2024): 1387–1396.

[38] W. Meng, Y. Gao, K. Zhu, and D. Cao, “Preparation of Mesoporous Hard Carbon Anode Materials by Nitrogen Doping of Biomass to Enhance the Specific Capacity of Sodium Ion Adsorption,” Journal of Electroanalytical Chemistry 991 (2025): 119190.

[39] Y. Chu, J. Zhang, Y. Zhang, et al., “Reconfiguring Hard Carbons With Emerging Sodium-Ion Batteries: A Perspective,” Advanced Materials 35 (2023): 2212186.

[40] B. Wang, J. R. Fitzpatrick, A. Brookfield, et al., “Electron Paramagnetic Resonance as a Tool to Determine the Sodium Charge Storage Mechanism of Hard Carbon,” Nature Communications 15 (2024): 3013.

[41] M. Ding, Z. Zhang, W. Wei, et al., “Ultrapure Graphite From Solid Refining,” Advanced Materials 37 (2025): 2500461.

[42] B. Wang, S. Zhang, X. Jia, et al., “Tailoring Closed Pore Structure in Phenolic Resin Derived Hard Carbon Enables Excellent Sodium Ion Storage,” Chemical Engineering Journal 499 (2024): 156126.

[43] J. Zhao, X. He, W. Lai, et al., “Catalytic Defect-Repairing Using Manganese Ions for Hard Carbon Anode With High-Capacity and High-Initial-Coulombic-Efficiency in Sodium-Ion Batteries,” Advanced Energy Materials 13 (2023): 2300444.

[44] H. Wang, F. Sun, Y. Wang, et al., “Thermal Shock Reducing Amorphous Carbon Ratio in Hard Carbon for Improved Rate Capability of Sodium Ion Storage,” Carbon 229 (2024): 119528.

[45] J. Zhou, P. Yang, P. A. Kots, et al., “Tuning the Reactivity of Carbon Surfaces With Oxygen-Containing Functional Groups,” Nature Communications 14 (2023): 2293.

[46] T. Wu, M. Jing, Y. Tian, et al., “Surface-Driven Energy Storage Behavior of Dual-Heteroatoms Functionalized Carbon Material,” Advanced Functional Materials 29 (2019): 1900941.

[47] E. Lee and D. H. Kim, “Simple Fabrication of Asphalt-Based Superhydrophobic Surface With Controllable Wetting Transition From Cassie-Baxter to Wenzel Wetting State,” Colloids and Surfaces, A: Physicochemical and Engineering Aspects 625 (2021): 126927.

[48] C. Bommier, W. Luo, W.-Y. Gao, A. Greaney, S. Ma, and X. Ji, “Predicting Capacity of Hard Carbon Anodes in Sodium-Ion Batteries Using Porosity Measurements,” Carbon 76 (2014): 165–174.

[49] R. Zhou, S. Peng, Z. Wang, et al., “Dynamic Sodiation-Driven Pore Reconstruction for Superior Initial-Coulombic-Efficiency and High-Rate in Xylose-Based Hard Carbon Anode,” Advanced Functional Materials 35 (2025): 2423530.

[50] Y. Liu, J. Yin, R. Wu, et al., “Molecular Engineering of Pore Structure/Interfacial Functional Groups Toward Hard Carbon Anode in Sodium-Ion Batteries,” Energy Storage Materials 75 (2025): 104008.

[51] Y. Huang, X. Zhong, X. Hu, et al., “Rationally Designing Closed Pore Structure by Carbon Dots to Evoke Sodium Storage Sites of Hard Carbon in Low-Potential Region,” Advanced Functional Materials 34 (2024): 2308392.

[52] H. Alptekin, H. Au, E. Olsson, et al., “Elucidation of the Solid Electrolyte Interphase Formation Mechanism in Micro-Mesoporous Hard-Carbon Anodes,” Advanced Materials Interfaces 9 (2022): 2101267.

[53] J. Li, J. Hao, Q. Yuan, et al., “The Effect of Salt Anion in Ether-Based Electrolyte for Electrochemical Performance of Sodium-Ion Batteries: A Case Study of Hard Carbon,” Carbon Energy 6 (2024): e518.

[54] M. Liu, F. Wu, Y. Gong, et al., “Interfacial-Catalysis-Enabled Layered and Inorganic-Rich SEI on Hard Carbon Anodes in Ester Electrolytes for Sodium-Ion Batteries,” Advanced Materials 35 (2023): 2300002.

[55] S. Alvin, D. Yoon, C. Chandra, et al., “Revealing Sodium Ion Storage Mechanism in Hard Carbon,” Carbon 145 (2019): 67–81.

[56] S. Qiu, L. Xiao, M. L. Sushko, et al., “Manipulating Adsorption–Insertion Mechanisms in Nanostructured Carbon Materials for High-Efficiency Sodium Ion Storage,” Advanced Energy Materials 7 (2017): 1700403.

[57] Y. Guo, W. Liu, R. Wu, et al., “Marine-Biomass-Derived Porous Carbon Sheets With a Tunable N-Doping Content for Superior Sodium-Ion Storage,” ACS Applied Materials & Interfaces 10 (2018): 38376–38386.

[58] H. Liu, X. Liu, H. Wang, et al., “High-Performance Sodium-Ion Capacitor Constructed by Well-Matched Dual-Carbon Electrodes From a Single Biomass,” ACS Sustainable Chemistry & Engineering 7 (2019): 12188–12199.

[59] X. Ren, S.-D. Xu, S. Liu, L. Chen, D. Zhang, and L. Qiu, “Lath-Shaped Biomass Derived Hard Carbon as Anode Materials With Super Rate Capability for Sodium-Ion Batteries,” Journal of Electroanalytical Chemistry 841 (2019): 63–72.

[60] W. Nie, H. Cheng, X. Liu, et al., “Surface Organic Nitrogen-Doping Disordered Biomass Carbon Materials With Superior Cycle Stability in the Sodium-Ion Batteries,” Journal of Power Sources 522 (2022): 230994.

[61] X. Hu, X. Sun, S. J. Yoo, et al., “Nitrogen-Rich Hierarchically Porous Carbon as a High-Rate Anode Material With Ultra-Stable Cyclability and High Capacity for Capacitive Sodium-Ion Batteries,” Nano Energy 56 (2019): 828–839.

[62] Y. Li, Y. S. Hu, M. M. Titirici, L. Chen, and X. Huang, “Hard Carbon Microtubes Made From Renewable Cotton as High-Performance Anode Material for Sodium-Ion Batteries,” Advanced Energy Materials 6 (2016): 1600659.

[63] S. Alvin, H. S. Cahyadi, J. Hwang, W. Chang, S. K. Kwak, and J. Kim, “Revealing the Intercalation Mechanisms of Lithium, Sodium, and Potassium in Hard Carbon,” Advanced Energy Materials 10 (2020): 2000283.

[64] D. Chen, K. Luo, Z. Yang, et al., “Direct Conversion of Ester Bond-Rich Waste Plastics Into Hard Carbon for High-Performance Sodium Storage,” Carbon 173 (2021): 253–261.

[65] Q. He, H. Chen, X. Chen, et al., “Tea-Derived Sustainable Materials,” Advanced Functional Materials 34 (2024): 2310226.

[66] X. Li, S. Zhang, J. Tang, et al., “Structural Design of Biomass-Derived Hard Carbon Anode Materials for Superior Sodium Storage via Increasing Crystalline Cellulose and Closing the Open Pores,” Journal of Materials Chemistry A 12 (2024): 21176–21189.

[67] H. Chen, N. Sun, Q. Zhu, R. A. Soomro, and B. Xu, “Microcrystalline Hybridization Enhanced Coal-Based Carbon Anode for Advanced Sodium-Ion Batteries,” Advanced Science (Weinheim, Baden-Wurttemberg, Germany) 9 (2022): 2200023.

[68] M. Anji Reddy, M. Helen, A. Groß, M. Fichtner, and H. Euchner, “Insight Into Sodium Insertion and the Storage Mechanism in Hard Carbon,” ACS Energy Letters 3 (2018): 2851–2857.

[69] V. Živanović, Surface-Enhanced Raman Scattering as an Approach to Monitor Lysosomal Function (2020).

[70] Z. Guo, Z. Xu, F. Xie, et al., “Investigating the Superior Performance of Hard Carbon Anodes in Sodium-Ion Compared With Lithium- and Potassium-Ion Batteries,” Advanced Materials 35 (2023): 2304091.

[71] X. Lin, Y. Liu, H. Tan, and B. Zhang, “Advanced Lignin-Derived Hard Carbon for Na-Ion Batteries and a Comparison With Li and K Ion Storage,” Carbon 157 (2020): 316–323.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.