镶嵌于NH2-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO2作为高活性和稳定性的锂离子电池负极材料

doi:10.3866/PKU.WHXB202106002

物理化学学报 >> 2022, Vol. 38 >> Issue (6): 2106002.doi: 10.3866/PKU.WHXB202106002

所属专题：面向电化学储能与转化的表界面工程

镶嵌于NH₂-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO₂作为高活性和稳定性的锂离子电池负极材料

杨越¹^,², 朱加伟¹, 王鹏彦¹, 刘海咪¹, 曾炜豪¹, 陈磊¹, 陈志祥¹, 木士春¹^,²^,*()

¹ 武汉理工大学，材料复合新技术国家重点实验室，武汉 430070
² 佛山仙湖实验室，先进能源科学与技术广东省实验室佛山分中心，广东佛山 528200

收稿日期:2021-06-02 录用日期:2021-08-09 发布日期:2021-08-19
通讯作者: 木士春 E-mail:msc@whut.edu.cn
基金资助:
国家重点研发计划(2016YFA0202603);国家自然科学基金(22075223)

NH₂-MIL-125 (Ti) Derived Flower-Like Fine TiO₂ Nanoparticles Implanted in N-doped Porous Carbon as an Anode with High Activity and Long Cycle Life for Lithium-Ion Batteries

Yue Yang¹^,², Jiawei Zhu¹, Pengyan Wang¹, Haimi Liu¹, Weihao Zeng¹, Lei Chen¹, Zhixiang Chen¹, Shichun Mu¹^,²^,*()

¹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
² Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Xianhu Hydrogen Valley, Foshan 528200, Guangdong Province, China

Received:2021-06-02 Accepted:2021-08-09 Published:2021-08-19
Contact: Shichun Mu E-mail:msc@whut.edu.cn
About author:Shichun Mu, Email: msc@whut.edu.cn
Supported by:
the National Key Research and Development Program of China(2016YFA0202603);the National Natural Science Foundation of China(22075223)

摘要/Abstract

摘要：

由于具有高安全性和优异的循环稳定性，二氧化钛(TiO₂)作为负极材料被广泛地应用于锂离子电池领域。但是较差的导电性和离子传输速率限制了TiO₂的进一步应用和发展。鉴于此，我们以花状NH₂-MIL-125 (Ti)为前驱体和硬模板，成功合成出了具有花状结构的超细纳米TiO₂/多孔氮掺杂碳片(N-doped porous carbon)复合物(记为FL-TiO₂/NPC)。过程中所制备的纳米TiO₂-金属有机构架(Ti-MOF)展现出由二维褶皱多孔纳米片堆积、组装而成的花状结构。一方面，二维褶皱纳米片包含TiO₂纳米颗粒可以增大活性物质与电解液的接触面积；另一方面，氮掺杂多孔碳基体可以提高整体复合物的导电性和结构完整性。将所获得的FL-TiO₂/NPC作为负极组装成的锂半电池, 在0.5 A·g^-1、300圈后仍有384.2 mAh·g^-1以及在1 A·g^-1、500圈仍有279.1 mAh·g^-1的比容量。进一步性能测试表明，在2 A·g^-1、2000圈长循环测试后，其仍能保持256.5 mAh·g^-1的比容量和接近100%的库伦效率。该优异的电化学活性和稳定性主要起源于材料独特的花状结构。我们的合成策略为今后制备高储锂性能的金属氧化物/多孔氮掺杂碳负极提供了一种新的思路。

关键词: 纳米TiO₂, 氮掺杂多孔碳纳米片, 花状结构, NH₂-MIL-125(Ti), 负极, 锂离子电池

Abstract:

Owing to their advantages such as safe operation, high power density, long cycle life, and low self-discharge rate, lithium-ion batteries (LIBs) have attracted attention for applications ranging from portable electronics to electric vehicles (EVs)/hybrid EVs (HEVs). However, the striking exothermic reaction and growth of lithium dendrites during lithiation-delithiation cycles for commercial graphite anodes are hidden safety risks associated with LIBs. Titanium dioxide (TiO₂) is considered as an important material for LIBs because of its high safety and excellent cycling stability. In addition, TiO₂ anode used in lithium-ion storage system has a relatively high voltage (~1.5 V vs. Li/Li⁺), and thus, it meets the strict safety standards of commercial LIBs. However, the unsatisfactory conductivity and ion diffusion rate prevent the further application of TiO₂ in LIBs. To date, the combination of graphene, carbon nanotubes (CNTs), carbon quantum dots (QDs) and porous carbon with TiO₂ has attracted significant research attention. Nevertheless, it is still challenging to introduce a unique nanostructure design by organically compounding TiO₂ with N-doped porous carbon matrix. Herein, N-doped porous carbon incorporating fine TiO₂ nanoparticles (NPs) with a flower-like structure (denoted as FL-TiO₂/NPC) is successfully prepared using flower-like NH₂-MIL-125(Ti) as the hard template. The as-prepared Ti-based framework shows a flower-like structure, which is assembled with two-dimensional (2D) corrugated porous nanosheets. On the one hand, the corrugated carbon nanosheets incorporating fine TiO₂ particles can offer a magnifying contact area between electrode matrix and electrolyte. On the other hand, the N-doped porous carbon plays a crucial role in improving the conductivity and structural integrity of the whole matrix. Therefore, the as-prepared FL-TiO₂/NPC can deliver an excellent reversible lithium storage capacity of 384.2 mAh·g^-1 at the current density of 0.5 A·g^-1 after 300 cycles and 279.1 mAh·g^-1 at 1 A·g^-1 after 500 cycles. Furthermore, even when tested at 2 A·g^-1, FL-TiO₂/NPC can deliver a reversible capacity of 256.5 mAh·g^-1 with a coulombic efficiency of 100% after 2000 cycles. The superior electrochemical performance and the structural toughness of LIBs originate from the unique flower-like structure. We believe that the proposed synthesis strategy will provide a new idea for the preparation of metal oxides/N-doped porous carbon composites with high lithium storage performance.

Key words: TiO₂ nanoparticles, N-doped porous carbon nanosheet, Flower-like structure, NH₂-MIL-125 (Ti), Anode, Lithium-ion battery

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杨越, 朱加伟, 王鹏彦, 刘海咪, 曾炜豪, 陈磊, 陈志祥, 木士春. 镶嵌于NH₂-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO₂作为高活性和稳定性的锂离子电池负极材料[J]. 物理化学学报, 2022, 38(6), 2106002. doi: 10.3866/PKU.WHXB202106002

Yue Yang, Jiawei Zhu, Pengyan Wang, Haimi Liu, Weihao Zeng, Lei Chen, Zhixiang Chen, Shichun Mu. NH₂-MIL-125 (Ti) Derived Flower-Like Fine TiO₂ Nanoparticles Implanted in N-doped Porous Carbon as an Anode with High Activity and Long Cycle Life for Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin. 2022, 38(6), 2106002. doi: 10.3866/PKU.WHXB202106002

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202106002

https://www.whxb.pku.edu.cn/CN/Y2022/V38/I6/2106002

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镶嵌于NH₂-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO₂作为高活性和稳定性的锂离子电池负极材料

NH₂-MIL-125 (Ti) Derived Flower-Like Fine TiO₂ Nanoparticles Implanted in N-doped Porous Carbon as an Anode with High Activity and Long Cycle Life for Lithium-Ion Batteries

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