Component and Structure modification of Sn-base anode materials for Lithium ion batteries
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摘要: 针对锡负极材料充放电过程中的体积效应，本文综合采用组分改性与结构改性的研究方法，合成Sn-Cu合金负极材料，研究Cu的掺入对Sn电化学稳定性的影响，同时基于优化改性的Sn-Cu合金开展核壳结构设计，研究最佳核壳结构构造工艺。结果表明，掺入Cu能在一定程度上改善Sn的循环稳定性，Sn-Cu样品的容量在60周循环后趋于稳定，库伦效率较高；核壳结构处理能大幅提升Sn-Cu合金负极材料的循环稳定性，采用球形改性天然石墨(d50=15μm)作为内核的样品首次放电比容量接近800mAh/g，充电比容量最大值超过了500mAh/g，100周容量保持率大于85%，最佳的核壳结构构造工艺是使用片状石墨作为内核，内核粒径为d50=15μm，外壳厚度为柠檬酸裂解碳占复合材料质量比的20%。核壳结构能将Sn-Cu合金的体积效应控制在“囚笼”式结构内，利于材料容量的发挥及循环稳定性的提升。核壳结构的可控制备对实现锡基合金负极材料的产业化具有重要的作用。
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关键词:
- 核壳结构
Abstract: In this paper, with the method of component and structure modifications, Sn-Cu alloy anode material was synthesized, and the preparation technology of the core-shell structure was studied, to solve the volume expansion during the charge and discharge process of Sn-based anode materials. The results showed that, the addition of Cu could improve the cyclic stability. The specific capacity of the Sn-Cu sample became stable after the 60th cycles, with high coulomb efficiency. And the core-shell structure could dramatically improve the cyclic stability of the Sn-Cu alloy. For the sample whose core was modificated natural spherical graphite(d50=15μm), the initial specific discharge capacity was nearly 800mAh/g, the max charge specific capacity was higher than 500mAh/g, and the capacity retention of 100 cycles was higher than 85%.The best preparation technology of the core-shell structure was that, flake graphite whose particle size was d50=15μm as core, the thickness of the shell was 20%(wt). The volume expansion can be contorlled within the “cage structure” by the core-shell structure, which benefits for the capacity performance and the improvement of the cyclic stability. The controllable preparation of the core-shell structure is important for the commercialization of Sn-based anode materials.-
Keywords:
- Core-shell structure
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[1] FOTOUHI A, AUGER D J, PROPP K, et al.A review on electric vehicle battery modelling: From Lithium-ion toward Lithium–Sulphur[J]. Renewable and Sustainable Energy Reviews, 2016, 56:1008-1021.[J].Renewable and Sustainable Energy Reviews, 2016, 56:1008-1021
[2] WARNER J.Chapter 7 ? Lithium-Ion Battery Packs for Evs[M]. Lithium-Ion Batteries: Advances and Applications, 2014, 127-150.
[3] HORIE H.EVs and HEVs: The Need and Potential Functions of Batteries for Future Systems[M]. Lithium-Ion Batteries: Advances and Applications, 2014, 83-95.
[4] BAI X J, YU Y Y, KUNG H H, et al.Si@SiOx/graphene hydrogel composite anode for lithium-ion battery[J]. Journal of Power Sources, 2016, 306:42-48.[J].Journal of Power Sources, 2016, 306:42-48
[5] HUANG Y G, PAN Q C, WANG H Q, et al.Sn/SnOx embedded in carbon nanosheets as high-performance anode material for lithium ion battery[J]. Ceramics International, 2016, 42:4586–4593.[J].Ceramics International, 2016, 42:4586-4593
[6] YAN Y, BEN L B, ZHAN Y J, et al.Nano-Sn embedded in expanded graphite as anode for lithium ion batteries with improved low temperature electrochemical performance[J]. Electrochimica Acta, 2016, 187:186–192.[J].Electrochimica Acta, 2016, 187:186-192
[7] AGUBRA V A, ZUNIGA L, GARZA D D L, et al.Forcespinning: A new method for the mass production of Sn/C composite nanofiber anodes for lithium ion batteries[J]. Solid State Ionics, 2016, 286: 72–82.[J].Solid State Ionics, 2016, 286:72-82
[8] WEI L, ZHANG K, TAO Z L, et al.Sn–Al core–shell nanocomposite as thin film anode for lithium-ion Batteries[J]. Journal of Alloys and Compounds, 2015, 644: 742–749.[J].Journal of Alloys and Compounds, 2015, 644:742-749
[9] UYSAL M, CETINKAYA T, ALP A, et al.Active and inactive buffering effect on the electrochemical behavior of Sn–Ni/MWCNT composite anodes prepared by pulse electrodeposition for lithium-ion batteries[J]. Journal of Alloys and Compounds, 2015, 645: 235–242.[J].Journal of Alloys and Compounds, 2015, 645:235-242
[10] WU X M, ZHANG S C, QI T, et al.Novel insight toward engineering of arrayed Cu@Sn nanoelectrodes: Rational microstructure refinement and its remarkable “harvesting effect” on lithium storage capability[J]. Journal of Power Sources, 2016, 307:753-761.[J].Journal of Power Sources, 2016, 307:753-761
[11] YUI Y, HYAYASHI M, HAYASHI K, et al.Electrochemical properties of Sn-Co electrode with various kinds of binder materials for sodium ion batteries[J]. Solid State Ionics, 2016, in-press.[J].Solid State Ionics, 2016, in-press:in-press-in-press
[12] SCHMUELLING G, OEHL N, FROMM O, et al.Synthesis and electrochemical characterization of nano-sized Ag4Sn particles as anode material for lithium-ion batteries[J]. Electrochimica Acta, 2016, 196:597–602.[J].Electrochimica Acta, 2016, 196:597-602
[13] LIU C J, XUE F H, HUANG H, et al.Preparation and Electrochemical properties of Fe-Sn (C) Nanocomposites as Anode for Lithium-ion Batteries[J]. Electrochimica Acta, 2014, 129:93–99.[J].Electrochimica Acta, 2014, 129:93-99
[14] GUO W, LI F, DUAN X C, et al.Synthesis of Cd–Sn–SnO2@C heterocomposite anode with superior electrochemical performance[J]. Materials Letters, 2016, 166:210–214.[J].Materials Letters, 2016, 166:210-214
[15] CUI C Y, LIU X G, WU N D.Facile synthesis of core/shell-structured Sn/onion-like carbon nanocapsules as high-performance anode material for lithium-ion batteries[J]. Materials Letters, 2015, 143:35–37.[J].Materials Letters, 2015, 143:35-37
[16] ZHANG J, MA Z S, JIANG W J, et al.Sandwich-like CNTs@SnO2/SnO/Sn anodes on three-dimensional Ni foam substrate for lithium ion batteries[J]. Journal of Electroanalytical Chemistry, 2016, 767:49–55.[J].Electroanalytical Chemistry, 2015, 767:49-55
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