Sulfur-Enriched Pitch-Based Carbon Nanofibers With Lotus Root-Like Axial Pores for Boosting Sodium Storage Performance

Abstract

Pitch is a promising precursor for preparing carbon materials for anode of sodium-ion batteries. Heteroatom doping is an effective way to increase the sodium storage capacity while constructing reasonable pores and nanosizing the carbon skeleton help to achieve a high-rate performance of anodes. In this work, sulfur-doped carbon nanofibers with lotus root-like axial pores were prepared using coal liquefaction pitch as the main precursor by electrospinning, pre-oxidation, sulfurization, and carbonization. A considerable content of 7.41 wt.% of sulfur was doped into the carbon skeleton after low-temperature gas-phase sulfurization and subsequent carbonization. The as-prepared sulfur-doped porous carbon nanofiber films, used as self-supporting electrodes of sodium-ion batteries, display high specific capacity (528.5 mAh g^-1 at 25 mA g^-1), high-rate performance (209.3 mAh g^-1 at 500 mA g^-1) and exceptional cycling stability (96.97% of retention at 500 mA g^-1 over 1000 cycles). With desirable flexibility and excellent sodium storage performance, the achieved sulfur-doped porous carbon nanofibers hold great promise for potential applications as self-supporting anodes of sodium-ion batteries.

Keywords

carbon nanofibers / lotus root-like pores / pitch / sodium-ion battery / sulfur dopping

References

[1] L. F. Zhao, Z. Hu, W. H. Lai, et al., “Hard Carbon Anodes: Fundamental Understanding and Commercial Perspectives for Na-Ion Batteries Beyond Li-Ion and K-Ion Counterparts,” Advanced Energy Materials 11, no. 1 (2021): 2002704.

[2] T. Li, X. Li, Z. Wang, and H. Guo, “A Short Process for the Efficient Utilization of Transition-Metal Chlorides in Lithium-Ion Batteries: A Case of Ni_0.8Co_0.1Mn_0.1O_1.1 and LiNi_0.8Co_0.1Mn_0.1O₂,” Journal of Power Sources 342 (2017): 495-503.

[3] W. Hua, Z. Yang, H. Nie, et al., “Polysulfide-Scission Reagents for the Suppression of the Shuttle Effect in Lithium-Sulfur Batteries,” ACS Nano 11, no. 2 (2017): 2209-2218.

[4] W. Wang, W. Li, S. Wang, Z. Miao, H. K. Liu, and S. Chou, “Structural Design of Anode Materials for Sodium-Ion Batteries,” Journal of Materials Chemistry A 6, no. 15 (2018): 6183-6205.

[5] X. Chen, J. Tian, P. Li, et al., “An Overall Understanding of Sodium Storage Behaviors in Hard Carbons by an ‘Adsorption-Intercalation/Filling’ Hybrid Mechanism,” Advanced Energy Materials 12, no. 24 (2022): 2200886.

[6] X. Song, R. Jiang, and L. Zhang, “In-Situ Growth of CNTs-Porous Carbon From Asphalt With Superior Double-Layer Capacitive Performance,” Applied Surface Science 583 (2022): 152549.

[7] M. Jiang, N. Sun, R. Ali Soomro, and B. Xu, “The Recent Progress of Pitch-Based Carbon Anodes in Sodium-Ion Batteries,” Journal of Energy Chemistry 55 (2021): 34-47.

[8] B. Lu, C. Zhang, D. R. Deng, et al., “Synthesis of Low-Cost and High-Performance Dual-Atom Doped Carbon-Based Materials With a Simple Green Route as Anodes for Sodium-Ion Batteries,” Molecules 28, no. 21 (2023): 7314.

[9] Z. Liu, L. Zhang, L. Sheng, et al., “Edge-Nitrogen-Rich Carbon Dots Pillared Graphene Blocks With Ultrahigh Volumetric/Gravimetric Capacities and Ultralong Life for Sodium-Ion Storage,” Advanced Energy Materials 8, no. 30 (2018): 1802042.

[10] Y. Qiao, R. Han, Y. Pang, et al., “3D Well-Ordered Porous Phosphorus Doped Carbon as an Anode for Sodium Storage: Structure Design, Experimental and Computational Insights,” Journal of Materials Chemistry A 7, no. 18 (2019): 11400-11407.

[11] Z. Hong, Y. Zhen, Y. Ruan, et al., “Rational Design and General Synthesis of S-Doped Hard Carbon With Tunable Doping Sites Toward Excellent Na-Ion Storage Performance,” Advanced Materials 30, no. 29 (2018): 1802035.

[12] X. Xu, H. Zeng, D. Han, et al., “Nitrogen and Sulfur Co-Doped Graphene Nanosheets to Improve Anode Materials for Sodium-Ion Batteries,” ACS Applied Materials & Interfaces 10, no. 43 (2018): 37172-37180.

[13] L. Qie, W. Chen, X. Xiong, et al., “Sulfur-Doped Carbon With Enlarged Interlayer Distance as a High-Performance Anode Material for Sodium-Ion Batteries,” Advanced Science 2, no. 12 (2015): 1500195.

[14] Y. Li, M. Chen, B. Liu, Y. Zhang, X. Liang, and X. Xia, “Heteroatom Doping: An Effective Way to Boost Sodium Ion Storage,” Advanced Energy Materials 10, no. 27 (2020): 2000927.

[15] H. Kim, H. Yang, J. Kang, and N. Takeuchi, “Multifunctional Disordered Sulfur-Doped Carbon for Efficient Sodium-Ion-Exchange and 2-Electron-Transfer-Dominant Oxygen Reduction,” Carbon 182 (2021): 242-253.

[16] X. Chen, N. Sawut, K. Chen, et al., “Filling Carbon: A Microstructure-Engineered Hard Carbon for Efficient Alkali Metal Ion Storage,” Energy & Environmental Science 16 (2023): 4041-4053.

[17] F. Xie, Y. Niu, Q. Zhang, et al., “Screening Heteroatom Configurations for Reversible Sloping Capacity Promises High-Power Na-Ion Batteries,” Angewandte Chemie International Edition 61, no. 11 (2022): e202116394.

[18] Z. Wang, Y. Zhang, H. Jiang, et al., “Free-Standing Na₂C₆O₆ MXene Composite Paper for High-Performance Organic Sodium-Ion Batteries,” Nano Research 16, no. 1 (2023): 458-465.

[19] P. R. Lu, J. L. Xia, and X. L. Dong, “Rapid Sodium-Ion Storage in Hard Carbon Anode Material Derived From Ganoderma Lucidum Residue With Inherent Open Channels,” ACS Sustainable Chemistry & Engineering 7, no. 17 (2019): 14841-14847.

[20] T. Li, Z. Liu, Y. Gu, Y. Tang, and F. Huang, “Hierarchically Porous Hard Carbon With Graphite Nanocrystals for High-Rate Sodium Ion Batteries With Improved Initial Coulombic Efficiency,” Journal of Alloys and Compounds 817 (2020): 152703.

[21] T. Liu, Z. Zhou, Y. Guo, D. Guo, and G. Liu, “Block Copolymer Derived Uniform Mesopores Enable Ultrafast Electron and Ion Transport at High Mass Loadings,” Nature Communications 10 (2019): 675.

[22] Y. Fang, Y. Zeng, Q. Jin, et al., “Nitrogen-Doped Amorphous Zn-Carbon Multichannel Fibers for Stable Lithium Metal Anodes,” Angewandte Chemie International Edition 60 (2021): 8515-8520.

[23] C. Kim, Y. I. Jeong, B. T. N. Ngoc, et al., “Synthesis and Characterization of Porous Carbon Nanofibers With Hollow Cores Through the Thermal Treatment of Electrospun Copolymeric Nanofiber Webs,” Small 3, no. 1 (2007): 91-95.

[24] N. Sun, Z. Guan, Q. Zhu, B. Anasori, Y. Gogotsi, and B. Xu, “Enhanced Ionic Accessibility of Flexible Mxene Electrodes Produced by Natural Sedimentation,” Nano-Micro Letters 12, no. 1 (2020): 89.

[25] Y. Bai, Y. Liu, Y. Li, L. Ling, F. Wu, and C. Wu, “Mille-Feuille Shaped Hard Carbons Derived From Polyvinylpyrrolidone via Environmentally Friendly Electrostatic Spinning for Sodium Ion Battery Anodes,” RSC Advances 7, no. 9 (2017): 5519-5527.

[26] J. Xie, R. Zhuang, Y. Du, Y. Pei, D. Tan, and F. Xu, “Advances in Sulfur-Doped Carbon Materials for Use as Anodes in Sodium-Ion Batteries,” New Carbon Materials 38 (2023): 305-316.

[27] Y. Zhang, C. Zhu, Y. Xiong, et al., “Multi-Channel Hollow Carbon Nanofibers With Graphene-Like Shell-Structure and Ultrahigh Surface Area for High-Performance Zn-Ion Hybrid Capacitors,” Small Methods 7, no. 11 (2023): 2300714.

[28] 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, no. 12 (2018): 2851-2857.

[29] J. Qian, F. Wu, Y. Ye, et al., “Boosting Fast Sodium Storage of a Large-Scalable Carbon Anode With an Ultralong Cycle Life,” Advanced Energy Materials 8, no. 16 (2018): 1703159.

[30] J. Yang, X. Zhou, D. Wu, X. Zhao, and Z. Zhou, “S-Doped N-Rich Carbon Nanosheets With Expanded Interlayer Distance as Anode Materials for Sodium-Ion Batteries,” Advanced Materials 29, no. 6 (2017): 1703159.

[31] Y. Xiao, J. Y. Hwang, and Y. K. Sun, “Transition Metal Carbide-Based Materials: Synthesis and Applications in Electrochemical Energy Storage,” Journal of Materials Chemistry A 4, no. 27 (2016): 10379-10393.

[32] D. Wang, Y. Shen, Y. Chen, L. Liu, and Y. Zhao, “Microwave-Assistant Preparation of N/S Co-Doped Hierarchical Porous Carbons for Hydrogen Adsorption,” Chemical Engineering Journal 367 (2019): 260-268.

[33] Y. Shen, C. Huang, Y. Li, et al., “Enhanced Sodium and Potassium Ions Storage of Soft Carbon by a S/O Co-Doped Strategy,” Electrochimica Acta 367 (2021): 137526.

[34] W. Chen, J. Shi, T. Zhu, Q. Wang, J. Qiao, and J. Zhang, “Preparation of Nitrogen and Sulfur Dual-Doped Mesoporous Carbon for Supercapacitor Electrodes With Long Cycle Stability,” Electrochimica Acta 177 (2015): 327-334.

[35] W. Li, M. Zhou, H. Li, K. Wang, S. Cheng, and K. Jiang, “A High Performance Sulfur-Doped Disordered Carbon Anode for Sodium Ion Batteries,” Energy & Environmental Science 8, no. 10 (2015): 2916-2921.

[36] Z. Wang, L. Qie, L. Yuan, W. Zhang, X. Hu, and Y. Huang, “Functionalized N-Doped Interconnected Carbon Nanofibers as an Anode Material for Sodium-Ion Storage With Excellent Performance,” Carbon 55 (2013): 328-334.

[37] S. Chae, T. Lee, W. Kwon, et al., “Longitudinally Grown Pyrolyzed Quinacridones for Sodium-Ion Battery Anode,” Chemical Engineering Journal 453 (2023): 139805.

[38] G. Zhao, G. Zou, H. Hou, P. Ge, X. Cao, and X. Ji, “Sulfur-Doped Carbon Employing Biomass-Activated Carbon as a Carrier With Enhanced Sodium Storage Behavior,” Journal of Materials Chemistry A 5, no. 46 (2017): 24353-24360.

[39] W. Zhong, X. Lv, Q. Chen, et al., “Metal-Organic Framework/Polythiophene Derivative: Neuronlike S-Doped Carbon 3D Structure With Outstanding Sodium Storage Performance,” ACS Applied Materials & Interfaces 11, no. 41 (2019): 37850-37858.

[40] J. He, J. Du, C. Feng, et al., “S/O Co-Doped Honeycomb-Like Porous Carbon Nanosheets With Ultra-High Edge Defects for High-Performance Sodium Storage,” Carbon 219 (2024): 118825.

[41] G. Ning, X. Ma, X. Zhu, et al., “Enhancing the Li Storage Capacity and Initial Coulombic Efficiency for Porous Carbons by Sulfur Doping,” ACS Applied Materials & Interfaces 6, no. 18 (2014): 15950-15958.

[42] L. J. Song, S. S. Liu, B. J. Yu, C. Y. Wang, and M. W. Li, “Anode Performance of Mesocarbon Microbeads for Sodium-Ion Batteries,” Carbon 95 (2015): 972-977.

[43] C. Yuan, Y. Zhu, P. Zhao, B. Yu, Q. Li, and C. Wang, “Enhanced Electrochemical Performance of Mesocarbon-Microbeads-Based Anodes Through Air Oxidation for Sodium-Ion Batteries,” ChemElectroChem 4, no. 10 (2017): 2583-2592.

[44] Y. Zhao, Y. Cong, H. Ning, et al., “N, P Co-Doped Pitch Derived Soft Carbon Nanoboxes as High-Performance Anodes for Sodium-Ion Batteries,” Journal of Alloys and Compounds 918 (2022): 165691.

[45] Y. Qi, Y. Lu, L. Liu, et al., “Retarding Graphitization of Soft Carbon Precursor: From Fusion-State to Solid-State Carbonization,” Energy Storage Materials 26 (2020): 577-584.

[46] J. Wang, L. Yan, B. Liu, et al., “A Solvothermal Pre-Oxidation Strategy Converting Pitch From Soft Carbon to Hard Carbon for Enhanced Sodium Storage,” Chinese Chemical Letters 34, no. 4 (2023): 107526.

[47] Q. Li, Y. Zhu, P. Zhao, C. Yuan, M. Chen, and C. Wang, “Commercial Activated Carbon as a Novel Precursor of the Amorphous Carbon for High-Performance Sodium-Ion Batteries Anode,” Carbon 129 (2018): 85-94.

[48] Y. Sun, P. Lu, X. Liang, C. Chen, and H. Xiang, “High-Yield Microstructure-Controlled Amorphous Carbon Anode Materials through a Pre-Oxidation Strategy for Sodium Ion Batteries,” Journal of Alloys and Compounds 786 (2019): 468-474.

[49] Y. Y. Wang, B. H. Hou, H. Y. Lü, C. L. Lü, and X. L. Wu, “Hierarchically Porous N-Doped Carbon Nanosheets Derived From Grapefruit Peels for High-Performance Supercapacitors,” ChemistrySelect 1, no. 7 (2016): 1441-1447.

[50] S. Li, Z. Han, W. Hu, et al., “Manipulating Kinetics of Sulfurized Polyacrylonitrile With Tellurium as Eutectic Accelerator to Prevent Polysulfide Dissolution in Lithium-Sulfur Battery Under Dissolution-Deposition Mechanism,” Nano Energy 60 (2019): 153-161.

[51] X. Li, W. Chen, Q. Qian, et al., “Electrospinning-Based Strategies for Battery Materials,” Advanced Energy Materials 11, no. 2 (2021): 2000845.

[52] J. Ye, H. Zhao, W. Song, N. Wang, M. Kang, and Z. Li, “Enhanced Electronic Conductivity and Sodium-Ion Adsorption in N/S Co-Doped Ordered Mesoporous Carbon for High-Performance Sodium-Ion Battery Anode,” Journal of Power Sources 412 (2019): 606-614.

[53] Y. Jiang, G. Zou, W. Hong, et al., “N-Rich Carbon-Coated Co₃S₄ Ultrafine Nanocrystals Derived From ZIF-67 as an Advanced Anode for Sodium-Ion Batteries,” Nanoscale 10, no. 39 (2018): 18786-18794.

[54] H. Kim, M. K. Sadan, C. Kim, et al., “Enhanced Reversible Capacity of Sulfurized Polyacrylonitrile Cathode for Room-Temperature Na/S Batteries by Electrochemical Activation,” Chemical Engineering Journal 426 (2021): 130787.

[55] Q. Li, H. Li, Q. Xia, et al., “Extra Storage Capacity in Transition Metal Oxide Lithium-Ion Batteries Revealed by In Situ Magnetometry,” Nature Materials 20, no. 1 (2021): 76-83.

[56] Q. Wang, X. Ge, J. Xu, et al., “Fabrication of Microporous Sulfur-Doped Carbon Microtubes for High-Performance Sodium-Ion Batteries,” ACS Applied Energy Materials 1, no. 11 (2018): 6638-6645.

[57] H. Feng, Z. Liu, F. Wang, et al., “The C―S/C═S Bonds Synergistically Modify Porous Hollow-Carbon-Nanocages Anode for Durable and Fast Sodium-Ion Storage,” Advanced Functional Materials 34, no. 33 (2024): 202400020.

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