Polymer-derived SiOC materials are widely regarded as a new generation of anodes owing to their high specific capacity, low discharge platform, tunable chemical/structural composition, and good structural stability. However, tailoring the structure of SiOC to improve its electrochemical performance while simultaneously achieving elemental doping remains a challenge. Besides, the lithium storage mechanism and the structural evolution process of SiOC are still not fully understood due to its complex structure. In this study, a hollow porous SiOCN (Hp-SiOCN) featuring abundant oxygen defects is successfully prepared, achieving both the creation of a hollow porous structure and nitrogen element doping in one step, finally enhancing the structural stability and improving the lithium storage kinetics of Hp-SiOCN. In addition, the formation of a fully reversible structural unit, SiO3C—N, through the chemical interaction between N and Si/C, showcases a strong lithium adsorption capacity. Taking advantage of these combined benefits, the as-prepared Hp-SiOCN electrode delivers a reversible specific capacity of 412 mAh g–1 (93% capacity retention) after 500 cycles at 1.0 A g–1 and exhibited only 4% electrode expansion. This work offers valuable mechanistic insights into the synergistic optimization of elemental doping and structural design in SiOC, paving the way for advanced developments in battery technology.
| [1] |
X. F. Liu, Y. J. Yu, K. Z. Li, et al., “Ingenious Co-Control of Hollow Multishelled Structure and High Entropy Engineering for Enhanced Mechano-Electrochemical Properties in Lithium Battery,” Advanced Materials 36, no. 19 (2024): 2312583.
|
| [2] |
F. Degen, M. Winter, D. Bendig, et al., “Energy Consumption of Current and Future Production of Lithium-Ion and Post Lithium-Ion Battery Cells,” Nature Energy 8, no. 11 (2023): 1284–1295.
|
| [3] |
D. Lu, R. Li, M. M. Rahman, et al., “Ligand-Channel-Enabled Ultrafast Li-Ion Conduction,” Nature 627, no. 8002 (2024): 101–107.
|
| [4] |
Y. Y. Liu, H. D. Shi, and Z. S. Wu, “Recent Status, Key Strategies and Challenging Perspectives of Fast-Charging Graphite Anodes for Lithium-Ion Batteries,” Energy & Environmental Science 16, no. 11 (2023): 4834–4871.
|
| [5] |
J. Shen, Z. Zeng, and W. Tang, “Emerging High-Entropy Material Electrodes for Metal-Ion Batteries,” SusMat 4, no. 4 (2024): e215.
|
| [6] |
J. X. Li, G. M. Liang, W. Zheng, et al., “Addressing Cation Mixing in Layered Structured Cathodes for Lithium-Ion Batteries: A Critical Review,” Nano Materials Science 5, no. 4 (2023): 404–420.
|
| [7] |
J. Guo, Y. L. Xu, M. Exner, et al., “Unravelling the Mechanism of Pulse Current Charging for Enhancing the Stability of Commercial LiNi0.5Mn0.3Co0.2O2/Graphite Lithium-Ion Batteries,” Advanced Energy Materials 14, no. 22 (2024): 2400190.
|
| [8] |
J. Huang, W. Li, W. Zhang, et al., “Lithium Sulfide: A Promising Prelithiation Agent for High-Performance Lithium-Ion Batteries,” SusMat 4, no. 1 (2024): 34–47.
|
| [9] |
K. Cheng, S. B. Tu, B. Zhang, et al., “Material-Electrolyte Interfacial Interaction Enabling the Formation of an Inorganic-Rich Solid Electrolyte Interphase for Fast-Charging Si-Based Lithium-Ion Batteries,” Energy & Environmental Science 17, no. 7 (2024): 2631–2641.
|
| [10] |
K. Z. Li, G. Q. Yuan, X. F. Liu, et al., “Deciphering Fast Lithium Storage Kinetics via R-Based Self-Derivation Effects in Siloxanes,” Energy Storage Materials 65 (2024): 103194.
|
| [11] |
G. Mera, A. Navrotsky, S. Sen, et al., “Polymer-Derived SiCN and SiOC Ceramics-Structure and Energetics at the Nanoscale,” Journal of Materials Chemistry A 1, no. 12 (2013): 3826.
|
| [12] |
A. D. M Sarofil, W. Devina, I. Albertina, et al., “Toad Egg-Like Bismuth Nanoparticles Encapsulated in an N-Doped Carbon Microrod via Supercritical Acetone as Anodes in Lithium-Ion Batteries,” Journal of Industrial and Engineering Chemistry 106 (2022): 128–141.
|
| [13] |
K. Z. Li, G. Q. Yuan, and X. F. Liu, “On the Practical Applicability of Rambutan-Like SiOC Anode With Enhanced Reaction Kinetics for Lithium-Ion Storage,” Advanced Functional Materials 33, no. 43 (2023): 2302348.
|
| [14] |
S. H. Lee, C. Y. Park, K. Do, et al., “Maximizing the Utilization of Active Sites Through the Formation of Native Nanovoids of Silicon Oxycarbide as Anode Materials in Lithium-Ion Batteries,” Energy Storage Materials 35 (2021): 130–141.
|
| [15] |
M. B. Ma, H. J. Wang, L. L. Xiong, et al., “Self-Assembled Homogeneous SiOC@C/Graphene With Three-Dimensional Lamellar Structure Enabling Improved Capacity and Rate Performances for Lithium Ion Storage,” Carbon 186 (2022): 273–281.
|
| [16] |
J. H. Kim, A. Song, J. M. Park, et al., “Analogous Design of a Microlayered Silicon Oxide-Based Electrode to the General Electrode Structure for Thin-Film Lithium-Ion Batteries,” Advanced Materials 36, no. 14 (2024): 2309183.
|
| [17] |
D. X. Zhang, G. L. Liu, S. F. Tan, et al., “Application of N-Doped Carbon-Silicon Oxycarbide Based on POSS Synthesis in Lithium-Ion Batteries,” Energy & Fuels 37, no. 2 (2022): 1387–1395.
|
| [18] |
L. M. Reinold, M. Graczyk-Zajac, Y. Gao, et al., “Carbon-Rich SiCN Ceramics as High Capacity/High Stability Anode Material for Lithium-Ion Batteries,” Journal of Power Sources 236 (2013): 224–229.
|
| [19] |
T. H. Wang, F. Wang, W. L. Yang, et al., “Facile Fabrication of Hierarchical Porous Silicon N-Doped Carbon Composites via Biomass Fermentation Treatment for High-Performance Lithium-Ion Batteries,” Journal of Alloys and Compounds 898 (2022): 162781.
|
| [20] |
H. D. Xie, C. P. Hou, Z. Y. Yue, et al., “Facile Synthesis of C, N, P Co-Dope. SiO as Anode Material for Lithium-Ion Batteries With Excellent Rate Performance,” Journal of Energy Storage 64 (2023): 107147.
|
| [21] |
X. L. Yuan, Z. T. Ma, S. F. Jian, et al., “Mesoporous Nitrogen-Doped Carbon MnO2 Multichannel Nanotubes With High Performance for Li-Ion Batteries,” Nano Energy 97 (2022): 107235.
|
| [22] |
E. Ricohermoso, E. Heripre, S. Solano-Arana, et al., “Hierarchical Microstructure Growth in a Precursor-Derived SiOC Thin Film Prepared on Silicon Substrate,” International Journal of Applied Ceramic Technology 20, no. 2 (2022): 735–746.
|
| [23] |
H. Nara, T. Yokoshima, M. Otaki, et al., “Structural Analysis of Highly-Durable SiOC Composite Anode Prepared by Electrodeposition for Lithium Secondary Batteries,” Electrochimica Acta 110 (2013): 403–410.
|
| [24] |
I. Abdallah, C. Dupressoire, L. Laffont, et al., “STEM-EELS Identification of TiOXNY, TiN, Ti2N and O, N Dissolution in the Ti2642S Alloy Oxidized in Synthetic Air at 650°C,” Corrosion Science 153 (2019): 191–199.
|
| [25] |
F. Zheng, Y. Yang, and Q. Chen, “High Lithium Anodic Performance of Highly Nitrogen-Doped Porous Carbon Prepared From a Metal-Organic Framework,” Nature Communications 5, no. 1 (2014): 5261.
|
| [26] |
P. Naveenkumar, M. Maniyazagan, H. W. Yang, et al., “Nitrogen-Doped Graphene/Silicon-Oxycarbide Nanosphere as Composite Anode for High-Performance Lithium-Ion Batteries,” Journal of Energy Storage 59 (2023): 106572.
|
| [27] |
H. S. Medeiros, R. S. Pessoa, J. C. Sagás, et al., “Effect of Nitrogen Content in Amorphous SiCxNyOz Thin Films Deposited by Low Temperature Reactive Magnetron Co-Sputtering Technique,” Surface and Coatings Technology 206, no. 7 (2011): 1787–1795.
|
| [28] |
M. A. Schiavon, K. J. Ciuffi, and I. V. P. Yoshida, “Glasses in the Si–O–C–N System Produced by Pyrolysis of Polycyclic Silazane Siloxane Networks,” Journal of Non-Crystalline Solids 353, no. 22–23 (2007): 2280–2288.
|
| [29] |
D. Su, Y. L. Li, and Y. Feng, “Electrochemical Properties of Polymer-Derived SiCN Materials as the Anode in Lithium Ion Batteries,” Journal of the American Ceramic Society 92, no. 12 (2009): 2962–2968.
|
| [30] |
R. X. Wu, X. F. Du, T. Liu, et al., “Robust and Fast-Ion Conducting Interphase Empowering SiOx Anode Toward High Energy Lithium-Ion Batteries,” Advanced Energy Materials 14, no. 2 (2024): 2302899.
|
| [31] |
H. Y. Huo, M. Jiang, Y. Bai, et al., “Chemo-Mechanical Failure Mechanisms of the Silicon Anode in Solid-State Batteries,” Nature Materials 23, no. 4 (2024): 543–551.
|
| [32] |
M. Ko, S. Chae, J. M. Ma, et al., “Scalable Synthesis of Silicon-Nanolayer-Embedded Graphite for High-Energy Lithium-Ion Batteries,” Nature Energy 1, no. 9 (2016): 1–8.
|
| [33] |
S. Bai, W. Bao, K. Qian, et al., “Elucidating the Role of Prelithiation in Si-Based Anodes for Interface Stabilization,” Advanced Energy Mater 13, no. 28 (2023): 2301041.
|
| [34] |
J. Chen, X. L. Fan, Q. Li, et al., “Electrolyte Design for LiF-Rich Solid-Electrolyte Interfaces to Enable High-Performance Microsized Alloy Anodes for Batteries,” Nature Energy 5, no. 5 (2020): 386–397.
|
| [35] |
C. H. Gao, H. R. Zhang, P. Z. Mu, et al., “Hard-Soft Segment Synergism Binder Facilitates the Implementation of Practical SiC600 Electrodes,” Advanced Energy Materials 13, no. 46 (2023): 2302411.
|
| [36] |
G. F. Shao, D. A. H. Hanaor, J. Wang, et al., “Polymer-Derived SiOC Integrated With a Graphene Aerogel as a Highly Stable Li-Ion Battery Anode,” ACS Applied Materials & Interfaces 12, no. 41 (2020): 46045–46056.
|
| [37] |
M. Y. Yan, G. Li, J. Zhang, et al., “Enabling SiOx/C Anode With High Initial Coulombic Efficiency Through a Chemical Pre-Lithiation Strategy for High-Energy-Density Lithium-Ion Batteries,” ACS Applied Materials & Interfaces 12, no. 24 (2020): 27202–27209.
|
| [38] |
A. D. Mohd Sarofil, W. Devina, H. S. Park, et al., “Silicon Oxycarbide-Encapsuled Bismuth for Superior Lithium Storage,” Chemical Engineering Journal 466 (2023): 142965.
|
| [39] |
D. Knozowski, M. Graczyk-Zajac, D. Vrankovic, et al., “New Insights on Lithium Storage in Silicon Oxycarbide/Carbon Composites: Impact of Microstructure on Electrochemical Properties,” Composites Part B: Engineering 225 (2021): 109302.
|
| [40] |
M. B. Ma, H. J. Wang, X. Li, et al., “Free-Standing SiOC/Nitrogen-Doped Carbon Fibers With Highly Capacitive Li Storage,” Journal of the European Ceramic Society 40, no. 15 (2020): 5238–5246.
|
| [41] |
J. Wang, D. Kober, G. F. Shao, et al., “Stable Anodes for Lithium-Ion Batteries Based on Tin-Containing Silicon Oxycarbonitride Ceramic Nanocomposites,” Materials Today Energy 26 (2022): 100989.
|
| [42] |
Z. Wu, X. Q. Cheng, D. Tian, et al., “SiOC Nanolayers Directly-Embedded in Graphite as Stable Anode for High-Rate Lithium Ion Batteries,” Chemical Engineering Journal 375 (2019): 121997.
|
| [43] |
J. K. Meng, Y. Cao, Y. Suo, et al., “Facile Fabrication of 3D SiO2@Graphene Aerogel Composites as Anode Material for Lithium Ion Batteries,” Electrochimica Acta 176 (2015): 1001–1009.
|
| [44] |
J. L. Deng, C. D. Gu, H. R. Xu, et al., “Oxygen Vacancy-Rich Defects Porous Cu2MgO3/Mg0.78Cu0.22O Composite With Sinter-Resistant and Highly Reactive for Long-Duration High-Temperature Thermochemical Energy Storage,” Advanced Functional Materials 34, no. 26 (2024): 2470146.
|
| [45] |
V. K. Saroja, Z. P. Wang, H. R. Tinker, et al., “Enabling Intercalation-Type TiNb24O62 Anode for Sodium and Potassium-Ion Batteries via a Synergetic Strategy of Oxygen Vacancy and Carbon Incorporation,” SusMat 3, no. 2 (2023): 222–234.
|
| [46] |
C. Yan, Q. Shao, Y. Yang, et al., “Oxygen Release Suppression and Electronic Conductivity Enhancement for High Performance Li-and Mn-Rich Layered Oxides Cathodes by Chalcogenide Redox Couple and Oxygen Vacancy Generations,” Advanced Functional Materials 34, no. 19 (2024): 2310873.
|
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2024 The Author(s). SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.
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