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Scalable synthesis of N-doped Si/G@voids@C with porous structures for high-performance anode of lithium-ion batteries

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Abstract

The co-utilization of silicon (Si) and graphite (G) has been considered as the preferred strategy to achieve high energy density anode materials, but the effective synergistic integration of Si and graphite is still a challenge and it is necessary to find a scheme to accommodate the large-scale production of Si/graphite anodes. In this work, silicon cutting waste from the photovoltaic industry was used as raw material, mixed with graphite, pitch, and polyvinylpyrrolidone, and subjected to high-energy ball milling. The mixture was then heated in an Ar atmosphere for the carbon coating, and the resulting Si/graphite/carbon (Si/G/C) composite was etched to remove the thicker SiOx layer formed on the Si surface to allow the pores between the Si and the carbon matrix to obtain Si@voids/G@C. Benefiting from the integrated structural design and the significantly enhanced electronic conductivity, the Si/G@voids@C composite exhibited the first discharge-specific capacity of 2530 mAh·g−1 with an initial coulombic efficiency (ICE) of 86.7%, and the remaining capacity exceeded 1000 mAh·g−1 after 550 cycles at 1.5 A·g−1. Notably, full lithium-ion batteries with a Si/G@voids@C anode and LiFePO4 cathode delivered a stable capacity of 140 mAh·g−1. The synthesis method is facile and cost-effective, providing an integration strategy for Si and G with a potential scheme for large-scale commercial applications.

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摘要

硅和石墨的共同利用被认为是实现高能量密度阳极材料的首选策略, 但硅和石墨的有效协同整合仍是一个挑战, 同时也有必要找到一个适应硅/石墨阳极大规模生产的方案。在这项工作中, 以光伏行业中产生的硅切割废料为原料, 与石墨、沥青和聚乙烯吡咯烷酮混合后进行高能球磨, 然后将得到的混合物在氩气气氛中加热进行碳涂层, 并对得到的硅/石墨/碳复合材料进行蚀刻, 以去除在硅表面形成的较厚的SiOx层, 使硅和碳基体之间出现孔隙得到Si@voids/G@C复合材料。受益于集成的结构设计和明显增强的电子传导性, Si/G@voids@C复合材料表现出2530 mAh·g−1的首次放电比容量, 初始库仑效率为86.7%, 在1.5 A·g−1的电流密度下充放电循环550次后, 剩余容量超过1000 mAh·g−1, 值得注意的是, 采用Si/G@voids@C阳极和LiFePO4阴极组装成的锂离子全电池提供了140 mAh·g−1的稳定容量。该合成方法简单易行, 具有成本效益, 为硅和石墨提供了一种集成策略, 并且具有大规模商业应用的潜力。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 51974143, 52274408, 5220041313, 52164050 and 51904134); Major Science and Technology Projects in Yunnan Province (Nos. 202102AB080016, 202103AA080004 and 202202AB080010); Yunnan Fundamental Research Projects (No. 202201AW070014); Yunnan Ten Thousand Talents Project (No. YNWR-QNBJ-2018-111), Yunnan High-level Talent Project (No. YNQR-GCC-2019-010) and the Program for Innovative Research Team in University of Ministry of Education of China (No. IRT_17R48).

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  1. Faculty of Metallurgical and Energy Engineering, State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, 650093, China

    Lei Wang, Yan Jiang, Shao-Yuan Li, Feng-Shuo Xi & Xiao-Han Wan

  2. School of Materials Science and Engineering, Yunnan University, Kunming, 650091, China

    Xiu-Hua Chen

  3. School of Science and Technology, Pu’er University, Pu’er 665000, China

    Wen-Hui Ma

  4. School of Photovoltaic and Renewable Energy Engineering (SPREE), University of New South Wales, Sydney, 2052, Australia

    Rong Deng

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Wang, L., Jiang, Y., Li, SY. et al. Scalable synthesis of N-doped Si/G@voids@C with porous structures for high-performance anode of lithium-ion batteries. Rare Met. 42, 4091–4102 (2023). https://doi.org/10.1007/s12598-023-02472-0

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