还原氧化石墨烯原位包覆纳米MnTiO3颗粒的简易合成及储锂性能研究

doi:10.15541/jim20180143

无机材料学报 ›› 2018, Vol. 33 ›› Issue (9): 1022-1028.DOI: 10.15541/jim20180143 CSTR: 32189.14.10.15541/jim20180143

还原氧化石墨烯原位包覆纳米MnTiO₃颗粒的简易合成及储锂性能研究

刘焕龙^{1, 2}, 赵伟², 李睿哲², 黄谢意², 唐宇峰², 李冬梅¹, 黄富强^{2, 3}

1. 上海大学材料科学与工程学院, 上海 200444;
2.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050;
3. 北京大学化学与分子工程学院, 北京分子科学国家实验室, 稀土材料化学及应用国家重点实验室, 北京 100871

收稿日期:2018-04-03 修回日期:2018-05-01 出版日期:2018-09-20 网络出版日期:2018-08-14
作者简介:刘焕龙. E-mail: huanlongliu@outlook.com

Facile Synthesis of Reduced Graphene Oxide In-situ Wrapped MnTiO₃ Nanoparticles for Excellent Lithium Storage

LIU Huan-Long^{1, 2}, ZHAO Wei², LI Rui-Zhe², HUANG Xie-Yi², TANG Yu-Feng², LI Dong-Mei¹, HUANG Fu-Qiang^{2, 3}

1. School of Material Science and Engineering, Shanghai University, Shanghai 200444, China;
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
3. Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2018-04-03 Revised:2018-05-01 Published:2018-09-20 Online:2018-08-14
About author:LIU Huan-Long (1990-), male, candidate of Master degree. E-mail: huanlongliu@outlook.com
Supported by:
National Key Research and Development Program (2016YFB0901600);Science and Technology Commission of Shanghai (16ZR1440500, 16JC1401700);National Science Foundation of China (51672301);Key Research Program of Chinese Academy of Sciences (QYZDJ-SSW-JSC013, KGZD-EW-T06);Youth Innovation Promotion Association CAS

摘要/Abstract

摘要：

对于高能量密度的锂离子电池而言, 研究稳定、高容量负极材料的需求十分迫切。基于此, 本工作设计了一种简单有效的溶胶-凝胶法, 来合成高性能的被还原石墨烯氧化物原位包覆的MnTiO₃纳米颗粒(MnTiO₃@rGO)。合成的MnTiO₃纳米粒子分散均匀, 被少层的石墨烯包裹。由于还原氧化石墨烯的高电导率, MnTiO₃@rGO作为锂离子电池负极表现出优异的倍率性能, 在5.0 A·g^-1的高电流密度时, MnTiO₃@rGO展现出了286 mAh·g^-1的比容量。此外, 得益于MnTiO₃@rGO的多孔结构和柔性的还原氧化石墨烯外层, MnTiO₃@rGO负极具有显著的长期循环稳定性。在500个循环后, 比容量仍保持在441 mAh·g^-1, 仅损失了8.4%。结果表明, 该方法对提高金属氧化物负极的导电性和循环稳定性具有较高的应用价值。

关键词: 原位包覆, 还原氧化石墨烯, MnTiO₃纳米颗粒, 锂离子电池负极

Abstract:

The stable high-capacity anode has been an urgent demand for high energy density lithium-ion batteries (LIBs). Herein, a simple and effective strategy to synthesize high-performance reduced graphene oxide (rGO) in-situ wrapped MnTiO₃ nanoparticles (MnTiO₃@rGO) by Sol-Gel method is designed. The MnTiO₃ nanoparticles are uniformly dispersed and wrapped by few-layer graphene. Due to high conductivity of rGO, MnTiO₃@rGO nanoparticles show excellent rate performance, with a specific capacity of 286 mAh·g^-1 being displayed at the higher rate of 5.0 A·g^-1. Moreover, benefited from porous structure and flexible rGO shell, the MnTiO₃@rGO anode delivers a remarkable long-term cycling stability. The specific capacity maintains 441 mAh·g^-1 after 500 cycles at 0.5 A·g^-1, only losing 8.4%. Therefore, the results demonstrate that the facile synthetic strategy is highly desirable for improving the conductivity and stability of metal oxide anodes.

Key words: in-situ wrapped, reduced oxide graphene, MnTiO₃ nanoparticles, lithium-ion batteries anode

中图分类号:

TQ174

刘焕龙, 赵伟, 李睿哲, 黄谢意, 唐宇峰, 李冬梅, 黄富强. 还原氧化石墨烯原位包覆纳米MnTiO₃颗粒的简易合成及储锂性能研究[J]. 无机材料学报, 2018, 33(9): 1022-1028.

LIU Huan-Long, ZHAO Wei, LI Rui-Zhe, HUANG Xie-Yi, TANG Yu-Feng, LI Dong-Mei, HUANG Fu-Qiang. Facile Synthesis of Reduced Graphene Oxide In-situ Wrapped MnTiO₃ Nanoparticles for Excellent Lithium Storage[J]. Journal of Inorganic Materials, 2018, 33(9): 1022-1028.

图/表 5

Fig. 1 (a) SEM image with inset showing the optical photograph of MnTiO3@rGO powder, (b) TEM image, (c) HRTEM image, and (d) SAED pattern, (e) high-angle annular dark field (HAADF) of MnTiO3@rGO, and EDS mapping of C, Mn, Ti, and O elements which indicates uniformly elemental distribution in the MnTiO3@rGO

Table 1 EDS data of MnTiO3@rGO

Materials	C/wt%	O/wt%	Ti/wt%	Mn/wt%
MnTiO₃@rGO	9.01	18.87	32.11	40.01

Fig. 2 (a) XRD patterns, (b) Raman spectra in the range of 100-2000 cm-1, (c) nitrogen sorption isotherms and corresponding pore size distribution curves (inset), and (d) electrical conductivity of as-obtained materials

Fig. 3 Electrochemical measurements of samples(a) CV curves of MnTiO3@rGO electrode; (b) Comparison of the specific capacity at different rates; (c) Cycling performance at 0.5 A·g-1 between MnTiO3@rGO, rGO and MnTiO3 electrodes; (d) Nyquist plots of electrodes of MnTiO3@rGO and MnTiO3 after 3 cyclingAll of the measurements were conducted using a voltage window of 0.01 V-3.0 V

Fig. 4 (a) Capacity retention curves versus various current densities, and (b) capacity retention curves versus various cycles of MnTiO3@rGO anodes

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还原氧化石墨烯原位包覆纳米MnTiO₃颗粒的简易合成及储锂性能研究

Facile Synthesis of Reduced Graphene Oxide In-situ Wrapped MnTiO₃ Nanoparticles for Excellent Lithium Storage

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