中空核壳结构α-MoO3-SnO2复合电极可控制备及储锂性能研究

doi:10.15541/jim20140612

摘要/Abstract

摘要：

采用醇热技术可控制备了中空核壳结构α-MoO₃-SnO₂二次锂离子电池复合负极材料。通过XRD、SEM、TEM、CV和恒流充放电等测试手段对材料结构、形貌和电化学性能进行了表征。结果表明: 构建的多元金属氧化物既具有电化学活性成分, 又含有骨架支撑部分, 独特的中空结构有效地缩短了电子和锂离子传输路径。电化学测试表明: 该材料在电流密度50 mA/g时循环100次后放电比容量仍高达865 mAh/g。在电流密度为1000 mA/g时循环100次后放电比容量仍达到545 mAh/g, 表现出优异的循环性能和倍率性能。该合成方法简单、成本低, 产量高, 可为制备其它中空核壳结构先进功能材料提供借鉴。

关键词: 二氧化锡, 三氧化钼, 中空核壳材料, 纳米结构, 电化学

Abstract:

An effective approach of alcoholysis was employed to prepare hollow core-shell MoO₃-SnO₂ hybrid nanoparticle aggregates as anode materials for Li-ion batteries. The as-prepared samples were characterized by XRD, SEM, TEM, CV, and galvanostatical method. The results show that the unique hollow structures can shorten the distance Li-ion diffusion, and the hollow structure offers a sufficient void space, which sufficiently alleviates the mechanical stress caused by volume change. The as-obtained hollow core-shell MoO₃-SnO₂ hybrid electrodes can retain a discharge capacity of 865 mAh/g at current density of 50 mA/g after 100 charge-discharge cycles. Even at the current density of 1000 mA/g, the MoO₃-SnO₂ hybrid electrodes can still deliver a high reversible discharge capacity of 545 mAh/g. Therefore, the hollow MoO₃-SnO₂ hybrid electrode exhibits stable cyclability and good rate capability. This method is simple, low cost and mass-productive, and may also be used to prepare other advanced functional materials.

Key words: SnO2, MoO3, hollow core-shell materials, nanostructures, electrochemistry

中图分类号:

TQ174

王亚朋, 刘佳佳, 刘春晓, 陈伟伟, 李婷婷, 郭洪. 中空核壳结构α-MoO₃-SnO₂复合电极可控制备及储锂性能研究[J]. 无机材料学报, 2015, 30(9): 919-924.

WANG Ya-Peng, LIU Jia-Jia, LIU Chun-Xiao, CHEN Wei-Wei, LI Ting-Ting, GUO Hong. Morphology-controlled Synthesis of Hollow Core-shell Structural α-MoO₃-SnO₂ with Superior Lithium Storage[J]. Journal of Inorganic Materials, 2015, 30(9): 919-924.

图/表 7

图1 不同醇热反应时间(6~36 h)合成Mo-Sn-O产品及前驱体的XRD图谱(A)和醇热反应的前驱体及400℃煅烧后样品的红外光谱图(B)(其中, 曲线a为醇热反应24 h的样品, 曲线b为其前驱体)

Fig. 1 (A) XRD pattern of Mo-Sn-O samples prepared by alcoholysis synthesis process and subsequent calcination at 400 ℃, (B) FTIR spectra of the sample and its precursor, and the curve a and b corresponding to the Mo-Sn-O sample alcoholysis synthesis for 24 h and calcined at 400℃ and the precursor, respectively

图2 醇热反应24 h, 并经400℃煅烧样品的SEM(a~c), TEM (d~e)和HRTEM(f)照片

Fig. 2 SEM (a-c), TEM (d-e) and HRTEM (f) images of Mo- Sn-O sample prepared by alcoholysis syntheses for 24 h and subsequent calcination at 400 ℃

图3 醇热反应24 h, 并经400℃煅烧样品的氮气吸附/脱附等温线和Barrett-Joyner-Halenda(BJH)孔径分布图

Fig. 3 Nitrogen adsorption/desorption isotherm and Barrett- Joyner-Halenda (BJH) pore size distribution plot (inset) of the Mo-Sn-O samples prepared by alcoholysis syntheses for 24 h and subsequent calcination at 400 ℃

图4 醇热(180 ℃)反应6 h(a)、12 h(b)、18 h(c)、30 h(d)、36 h(e)和48 h(f)所得Mo-Sn-O样品的SEM照片

Fig. 4 SEM images of Mo-Sn-O samples after solvothermal alcoholysis at 180 ℃ for 6 h (a), 12 h (b), 18 h (c), 30 h (d), 36 h (e) and 48 h (f)

图1 中空核壳结构Mo-Sn-O混合纳米材料形成过程">

示意图1 中空核壳结构Mo-Sn-O混合纳米材料形成过程

Scheme 1 Illustration of core-shell Mo-Sn-O@C hybrid nanoparticle aggregates synthesized by solvothermal alcoholysis

图5 Mo-Sn-O材料电极的电化学性能

Fig. 5 Electrochemical performance of the prepared Mo-Sn-O materials electrode (a) Cycling performance of Mo-Sn-O materials prepared with different solvothermal alcoholysis time from 6 h to 48 h at constant current density of 200 mA/g; (b) charge/discharge curves of Mo-Sn-O (24 h) electrode for the 1st, 2nd, and 100th cycle at current density of 200 mA/g. The inset in (b) is the first cycle CV curve of f Mo-Sn-O (24 h) electrode with a scan rate of 0.05 mV/s; (c) Cycling performance of Mo-Sn-O (24 h) electrode at different current densities o. Electrode potential range of 0.01-3.0 V (vs Li/Li+)

图6 恒定电流密度为500 mA/g, 充放电循环100次后中空核壳结构Mo-Sn-O电极的TEM照片

Fig. 6 TEM image of hybrid hollow Mo-Sn-O hybrid electrodes after 100 charge-discharge cycles at current density of 500 mA/g

参考文献 28

[1]	BRUCE P G, SCROSATI B, TARASCON J M, et al.Nanomaterials for rechargeable lithium batteries.Angewandte Chemie International Edition, 2008, 47(16): 2930-2946.
[2]	WANG B, CHEN J S, WU H B, et al.Quasiemulsion-templated formation of α-Fe2O3 hollow spheres with enhanced lithium storage properties.Journal of the American Chemical Society, 2011, 133(43): 17146-17148.
[3]	YUAN C, ZHANG L, HOU L, et al.Green template-free synthesis of mesoporous ternary CoNi-Mn oxide nanowires towards high-performance electrochemical capacitors.Particle & Particle Systems Characterization, 2014, 31(7): 778-787.
[4]	LOU X W, LI C M, ARCHER L A.Designed synthesis of coaxial SnO2@carbon hollow nanospheres for highly reversible lithium storage.Advanced Materials, 2009, 21(24): 2536-2539.
[5]	NITTA N, YUSHIN G.High-capacity anode materials for lithium- ion batteries: choice of elements and structures for active particles.Particle & Particle Systems Characterization, 2014, 31(3): 317-336.
[6]	YIN Y, RIOUX R M, ERDONMEZ C K, et al.Formation of hollow nanocrystals through the nanoscale Kirkendall effect.Science, 2004, 304(5671): 711-714.
[7]	ANUMOL E, NETHRAVATHI C, RAVISHANKAR N.Mechanistic insights into a non-classical diffusion pathway for the formation of hollow intermetallics: a route to multicomponent hollow structures.Particle & Particle Systems Characterization, 2013, 30(7): 590-598.
[8]	LIU L, GUO Y, WANG Y, et al.Hollow NiO nanotubes synthesized by bio-templates as the high performance anode materials of lithium-ion batteries.Electrochimica Acta, 2013, 114: 42-47.
[9]	YUAN C, LI J, HOU L, et al.Template-free fabrication of mesoporous hollow ZnMn2O4 sub-microspheres with enhanced lithium storage capability towards high-performance Li-ion batteries.Particle & Particle Systems Characterization, 2014, 31(6): 613.
[10]	AZIZI A, KHOSLA T, MITCHELL B S, et al.Tuning carbon content and morphology of FeCo/graphitic carbon core-shell nanoparticles using a sal-matrix-assisted CVD process.Particle & Particle Systems Characterization, 2014, 31(4): 474-480.
[11]	GAO J, MU X, LI J J, et al.Preparation and characterization of porous spherical Li4Ti5O12/C anode material for lithium batteries.Journal of Inorganic Materials, 2012, 27(3): 253-257.
[12]	GUO H, WANG Y, WANG W, et al.Template-free fabrication of hollow NiO-carbon hybrid nanoparticle aggregates with improved lithium storage.Particle & Particle Systems Characterization, 2014, 31(3): 374-381.
[13]	LIU L, YUAN Z Z, QIU C X, et al.Synthesis and electrochemical characteristics of the novel FeS2/VGCF material for lithium-ion batteries.Journal of Inorganic Materials, 2013, 28(12): 1291-1295.
[14]	LIU S, ZHANG N, XU Y.Core-shell structured nanocomposites for photocatalytic selective organic transformations.Particle & Particle Systems Characterization, 2014, 31(5): 540-556.
[15]	BAO Y, YANG Y Q, MA J Z.Research progress of hollow structural materials prepared via templating method.Journal of Inorganic Materials, 2013, 28(5): 459-468.
[16]	GUO H, HE Y, WANG Y, et al.Morphology-controlled synthesis of cage-bell Pd@CeO2 structured nanoparticle aggregates as catalysts for the low-temperature oxidation of CO.Journal of Materials Chemistry A, 2013, 1(25): 7494-7499.
[17]	GUO H, WANG W, LIU L, et al.Shape-controlled synthesis of Ag@TiO2 cage-bell hybrid structure with enhanced photocatalytic activity and superior lithium storage.Green Chemistry, 2013, 15(10): 2810-2816.
[18]	DENG J, YAN C, YANG L, et al.Sandwich-stacked SnO2/Cu hybrid nanosheets as multichannel anodes for lithium ion batteries.ACS Nano, 2013, 7(8): 6948-6954.
[19]	SCHILLING C, THEISSMANN R, NOTTHOFF C, et al.Synthesis of small hollow ZnO nanospheres from the gas phase.Particle & Particle Systems Characterization, 2013, 30(5): 434-437.
[20]	XIN S, YIN Y, WAN L, et al.Batteries: encapsulation of sulfur in a hollow porous carbon substrate for superior Li-S batteries with long lifespan.Particle & Particle Systems Characterization, 2013, 30(4): 392.
[21]	GUO H, LIU L, LI T, et al.Accurate hierarchical control of hollow crossed NiCo2O4 nanocubes for superior lithium storage.Nanoscale, 2014, 6: 5491-5497.
[22]	GUO H, MAO R, YANG X, et al.Hollow nanotubular SnO2 with improved lithium storage.Journal of Power Sources, 2012, 219: 280-284.
[23]	LOU X W, ARCHER L A.A general route to nonspherical anatase TiO2 hollow colloids and magnetic multifunctional particles.Advanced Materials, 2008, 20(10): 1853-1858.
[24]	SUN Y, HU X, YU J, et al.Morphosynthesis of hierarchical MoO2 nanoarchitectures as a binder-free anode for lithium-ion batteries.Energy & Environmental Science, 2011, 4: 2870-2877.
[25]	WANG X, CHEN Z, LIU D, et al.Solar cells: triple-yolked ZnO/CdS hollow spheres for semiconductor-sensitized solar cells.Particle & Particle Systems Characterization, 2014, 31(7): 757-762.
[26]	MAO R, GUO H, TIAN D X, et al.Hollow nanotubular SnO2 templated by cellulose fibers for lithium ion batteries.Journal of Inorganic Materials, 2013, 28(11): 1213-1216.
[27]	CAI L, RAO P M, ZHENG X.Morphology-controlled flame synthesis of single, branched, and flower-like α-MoO3 nanobelt arrays.Nano Letters, 2011, 11(2): 872-877.
[28]	RILEY L A, LEE S H, GEDVILIAS L, et al.Optimization of MoO3 nanoparticles as negative-electrode material in high-energy lithium ion batteries.Journal of Power Sources, 2010, 195(2): 588-592.

中空核壳结构α-MoO₃-SnO₂复合电极可控制备及储锂性能研究

Morphology-controlled Synthesis of Hollow Core-shell Structural α-MoO₃-SnO₂ with Superior Lithium Storage

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