Ni/Mn3O4/NiMn2O4@RGO空心微球负极的制备及其储钠性能

颜冲; 寇华日; 颜波; 刘晓静; 李德军; 李喜飞

doi:10.13208/j.electrochem.180546

电化学 >

2019 , Vol. 25 >Issue 1: 112 - 121

DOI: https://doi.org/10.13208/j.electrochem.180546

研究论文

Ni/Mn₃O₄/NiMn₂O₄@RGO空心微球负极的制备及其储钠性能

颜冲 ,
寇华日 ,
颜波 ,
刘晓静 ,
李德军 ,
李喜飞

展开

1. 天津师范大学物理与材料科学学院，天津市储能材料表面技术国际联合研究中心，天津 300387；2. 西安理工大学先进电化学能源研究院&材料科学与工程学院，陕西西安 710048

收稿日期: 2018-07-02

修回日期: 2018-08-03

网络出版日期: 2019-02-28

基金资助

获国家自然科学基金（No.51572194）、国家重点研究计划项目（No. 2018YFB0105900 ）和天津新材料科学与技术重大专项项目（No. 16ZXCLGX00070）资助

收起

Ni/Mn₃O₄/NiMn₂O₄ Double-Shelled Hollow Spheres Embedded into Reduced Graphene Oxide as Advanced Anodes for Sodium-Ion Batteries

YAN Chong ,
KOU Hua-ri ,
YAN Bo ,
LIU Xiao-jing ,
LI De-jun ,
LI Xi-fei

Expand

1. Tianjin International Joint Research Centre of Surface Technology for Energy Storage Materials, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387, China; 2. Institute of Advanced Electrochemical Energy & School of Materials Science and Engineering, Xi’an University of
Technology, Xi’an, Shanxi 710048, China, Xi’an University of Technology, Xi’an 710048, China

Received date: 2018-07-02

Revised date: 2018-08-03

Online published: 2019-02-28

Supported by

This research was supported by the National Natural Science Foundation of China (No. 51572194), the national Key Research and Development Program of China (No. 2018YFB0105900), and the Tianjin Major Program of New Materials Science and Technology (No. 16ZXCLGX00070).

Fold

摘要

采用溶剂热法制备前驱体，后经350 °C热处理，首次合成了空心结构的NiMn₂O₄微球以及不同含量氧化石墨烯包覆的Ni/Mn₃O₄/NiMn₂O₄@RGO复合材料. 电化学性能测试表明，复合负极材料中，含25wt%还原氧化石墨烯的材料储钠性能最佳，其在50 mA·g^-1电流密度下，100次循环后放电比容量保持在187.8 mAh·g^-1，且800 mA·g^-1电流密度下的可逆容量高达149.9 mAh·g^-1，明显优于NiMn₂O₄及其他石墨烯基复合材料. 研究指出，复合材料性能的提升得益于空心微球和还原的氧化石墨烯构成的特殊结构，一方面缩短了电子/离子传输距离，缓解了体积效应，另一方面高导电网络有效增强了活性物质利用率.

关键词： Ni/Mn₃O₄/NiMn₂O₄; 还原氧化石墨烯; 负极材料; 钠离子电池

本文引用格式

颜冲 , 寇华日 , 颜波 , 刘晓静 , 李德军 , 李喜飞 . Ni/Mn₃O₄/NiMn₂O₄@RGO空心微球负极的制备及其储钠性能[J]. 电化学, 2019 , 25(1) : 112 -121 . DOI: 10.13208/j.electrochem.180546

Abstract

Delicately building the unique nanocomposite with the combination of hollow structure and reduced graphene oxide (rGO) is highly desirable and still remains a great challenge in the field of energy conversion and storage. In this work, Ni/Mn₃O₄/NiMn₂O₄ double-shelled hollow spheres coated by rGO (denoted as R-NMN) have been successfully synthetized via one-step rapid solvothermal treatment followed by subsequent annealing for the first time. Served as anodes for sodium ion batteries (SIBs), the R-NMN composite containing 25wt% rGO exhibits a high discharge capacity of 187.8 mAh·g^-1 after 100 cycles at 50 mA·g^-1 in the potential range between 0.01 V and 3.0 V (vs. Na⁺/Na). When cycled at different current densities of 100, 200, 400, and 800 mA·g^-1, the nanocomposites deliver the reversible capacities of 213.45, 192.9, 171.7, and 149.9 mAh·g^-1, respectively, indicating a satisfactory rate capability. Our conclusions reveal that the significant improvement in electrochemical performance is mainly attributed to the enhanced conductivity, reduced ion diffusion distance and suppressed volume fluctuation. The modification strategy proposed in this study can be extended to the design of other electrode materials for sodium storage and beyond.

Key words： Ni/Mn₃O₄/NiMn₂O₄; reduced graphene oxide; anode materials; sodium-ion batteries

参考文献

[1] Bruce P G, Scrosati B, Tarascon J M. Nanomaterials for rechargeable lithium batteries[J]. Angewandte Chemie International Edition, 2008, 47(16): 2930-2946.
[2] Wu H B, Chen J S, Hng H H, et al. Nanostructured metal oxide-based materials as advanced anodes for lithium-ion batteries[J]. Nanoscale, 2012, 4(8): 2526-2542.
[3] Armand M, Tarascon J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657.
[4] Larcher D, Tarascon J M. Towards greener and more sustainable batteries for electrical energy storage[J]. Nature Chemistry, 2015, 7(1): 19-29.
[5] Scrosati B, Hassoun J, Sun Y K. Lithium-ion batteries. A look into the future[J]. Energy & Environmental Science, 2011, 4(9): 3287-3295.
[6] Stevens D A, Dahn J R. The mechanisms of lithium and sodium insertion in carbon materials[J]. Journal of The Electrochemical Society, 2001, 148(8): A803-A811.
[7] Hong S Y, Kim Y, Park Y, et al. Charge carriers in rechar-
geable batteries: Na ions vs. Li ions[J]. Energy & Environmental Science, 2013, 6(7): 2067-2081.
[8] Kundu D, Talaie E, Duffort V, et al. The emerging chemistry of sodium ion batteries for electrochemical energy storage[J]. Angewandte Chemie International Edition, 2015, 54(11): 3431-3448.
[9] Wang J Y, Yang N L, Tang H J, et al. Accurate control of multishelled Co₃O₄ hollow microspheres as high-performance anode materials in lithium-ion batteries[J]. Angewandte Chemie-International Edition, 2013, 52(25): 6417-6420.
[10] Ren S H, Zhao X G, Chen R Y, et al. A facile synthesis of encapsulated CoFe₂O₄ into carbon nanofibres and its application as conversion anodes for lithium ion batteries[J]. Journal of Power Sources, 2014, 260: 205-210.
[11] Sekhar B C, Packiyalakshmi P, Kalaiselvi N. Custom designed ZnMn₂O₄/nitrogen doped graphene composite anode validated for sodium ion battery application[J]. RSC Advances, 2017, 7(32): 20057-20061.
[12] Yuan C Z, Wu H B, Xie Y, et al. Mixed transition-metal oxides: design, synthesis, and energy-related applications[J]. Angewandte Chemie International Edition, 2014, 53(6): 1488-1504.
[13] Zhang W M, Cao P, Li L, et al. Carbon-encapsulated 1D SnO₂/NiO heterojunction hollow nanotubes as high-performance anodes for sodium-ion batteries[J]. Chemical Engineering Journal, 2018, 348: 599-607.
[14] Shen L, Yu L, Yu X Y, et al. Self-templated formation of uniform NiCo₂O₄ hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors[J]. Angewandte Chemie International Edition, 2015, 54(6): 1868-1872.
[15] Yuan S(袁双), Zhu Y H(朱云海), Wang S(王赛), et al. Micro/nano-structured electrode materials for sodium-ion batteries[J]. Journal of Electrochemistry(电化学), 2016, 22(5): 464-476.
[16] Zhou W(周文), Lu X F(卢雪峰), Wu M M(吴明娒), et al. Template-assisted hydrothermal synthesis of NiO@Co₃O₄ hollow spheres with hierarchical porous surfaces for supercapacitor applications[J]. Journal of Electrochemistry(电化学), 2016, 22(5): 513-520.
[17] Duan S Y(段舒怡), Zhang W(张伟), Piao J Y(朴俊宇), et al. Uniform nanoshells for functional materials: Constructions and applications[J]. Journal of Electrochemistry(电化学), 2016, 22(3): 260-270.
[18] Chen J F, Ru Q, Mo Y D, et al. Design and synthesis of hollow NiCo₂O₄ nanoboxes as anode for lithium-ion and sodium-ion batteries[J]. Physical Chemistry Chemical Physics, 2016, 18(28): 18949-18957.
[19] Choi J S, Lee H J, Ha J K, et al. Synthesis and electrochemical properties of amorphous carbon coated Sn anode material for lithium ion batteries and sodium ion batteries[J]. Journal of Nanoscience and Nanotechnology, 2018, 18(9): 6459-6462.
[20] Che Q, Zhang F, Zhang X G, et al. Preparation of ordered mesoporous carbon/NiCo₂O₄ electrode and its electrochemical capacitive behavior[J]. Acta Physico-Chimica Sinica, 2012, 28(4): 837-842.
[21] Zhou D, Li X, Fan L Z, et al. Three-dimensional porous graphene-encapsulated CNT@ SnO₂ composite for high-performance lithium and sodium storage[J]. Electrochimica Acta, 2017, 230: 212-221.
[22] Zhang R F, Wang Y K, Zhou H, et al. Mesoporous TiO₂ nanosheets anchored on graphene for ultra long life Na-ion batteries[J]. Nanotechnology, 2018, 29(22): 225401.
[23] Jiang H(江恒), Fan J M(范镜敏), Zheng M S(郑明森), et al. Co₃(HCOO)₆@rGO as a promising anode for lithium ion batteries[J]. Journal of Electrochemistry(电化学), 2018, 24(3): 207-215.
[24] Cai D P, Qu B H, Li Q H, et al. Reduced graphene oxide uniformly anchored with ultrafine CoMn₂O₄ nanoparticles as advance anode materials for lithium and sodium storage[J]. Journal of Alloys and Compounds, 2017, 716: 30-36.
[25] Zou F, Chen Y M, Liu K W, et al. Metal organic frameworks derived hierarchical hollow NiO/Ni/graphene composites for lithium and sodium storage[J]. ACS Nano, 2016, 10(1): 377-386.
[26] Zeng L Z, Zhang W G, Xia P, et al. Porous Ni_0.1Mn_0.9O_1.45 microellipsoids as high-performance anode electrocatalyst for microbial fuel cells[J]. Biosensors and Bioelectronics, 2018, 102: 351-356.
[27] Ren M M, Li F Y, Xu H, et al. CoO/CoFe₂O₄ bi-component nanorod core with S-doped carbon shell as excellent anode for lithium ion battery[J]. Journal of Alloys and Compounds, 2018, 737: 442-447.
[28] Huang G, Zhang F F, Zhang L L, et al. Hierarchical NiFe₂O₄/Fe₂O₃ nanotubes derived from metal organic frameworks for superior lithium ion battery anodes[J]. Journal of Materials Chemistry A, 2014, 2(21): 8048-8053.
[29] Ma Y, Ma Y J, Geiger D, et al. ZnO/ZnFe₂O₄/N-doped C micro-polyhedrons with hierarchical hollow structure as high-performance anodes for lithium-ion batteries[J]. Nano Energy, 2017, 42: 341-352.
[30] Xu J M, He L, Wang Y J, et al. Preparation of bi-component ZnO/ZnCo₂O₄ nanocomposites with improved electrochemical performance as anode materials for lithium-ion batteries[J]. Electrochimica Acta, 2016, 191: 417-425.
[31] Hummers Jr W S, Offeman R E. Preparation of graphitic oxide[J]. Journal of the American Chemical Society, 1958, 80(6): 1339-1339.
[32] Shan H, Xiong D B, Li X F, et al. Tailored lithium storage performance of graphene aerogel anodes with controlled surface defects for lithium-ion batteries[J]. Applied Surface Science, 2016, 364: 651-659.
[33] Li J F, Xiong S L, Li X W, et al. A facile route to synthesize multiporous MnCo₂O₄ and CoMn₂O₄ spinel quasihollow spheres with improved lithium storage properties[J]. Nanoscale, 2013, 5(5): 2045-2054.
[34] Huang J R, Wang W, Lin X R, et al. Three-dimensional sandwich-structured NiMn₂O₄@reduced graphene oxide nanocomposites for highly reversible Li-ion battery anodes[J]. Journal of Power Sources, 2018, 378: 677-684.
[35] Yu Z X, Li X F, Yan B, et al. Rational design of flower-like tin sulfide@ reduced graphene oxide for high performance sodium ion batteries[J]. Materials Research Bulletin, 2017, 96: 516-523.
[36] Maiti S, Pramanik A, Dhawa T, et al. Bi-metal organic framework derived nickel manganese oxide spinel for lithium-ion battery anode[J]. Materials Science and Engineering B - Advanced Functional Solid-State Materials, 2018, 229: 27-36.
[37] Li F, Ma J Y, Ren H J, et al. Fabrication of MnO nanowires implanted in graphene as an advanced anode material for sodium-ion batteries[J]. Materials Letters, 2017, 206: 132-
135.
[38] Chang L, Wang K, Huang L G, et al. Hierarchically porous CoNiO₂ nanosheet array films with superior sodium storage performance[J]. New Journal of Chemistry, 2017, 41(23): 14072-14075.
[39] Sekhar B C, Packiyalakshmi P, Kalaiselvi N. Custom designed ZnMn₂O₄/nitrogen doped graphene composite anode validated for sodium ion battery application[J]. RSC Advances, 2017, 7(32): 20057-20061.
[40] Kou H R, Li X F, Shan H, et al. An optimized Al₂O₃ layer for enhancing the anode performance of NiCo₂O₄ nanosheets for sodium-ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(34): 17881-17888.
[41] Wu X H, Wu W W, Wang K T, et al. Synthesis and electrochemical performance of flower-like MnCo₂O₄ as an anode material for sodium ion batteries[J]. Materials Letters, 2015, 147: 85-87.
[42] Wu Z Y, Li X F, Tai L M, et al. Novel synthesis of tin oxide/graphene aerogel nanocomposites as anode materials for lithium ion batteries[J]. Journal of Alloys and Compounds, 2015, 646: 1009-1014.
[43] Yang M, Li X F, Yan B, et al. Reduced graphene oxide decorated porous SnO₂ nanotubes with enhanced sodium storage[J]. Journal of Alloys and Compounds, 2017, 710: 323-330.

Options

文章导航

模态框（Modal）标题

摘要

本文引用格式

Abstract

参考文献