Research progress and preparation of nanometer zinc ferrite used in anode materials of lithium ion batteries
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摘要: 铁酸锌(ZnFe2O4)因其优良的性能被用作锂离子电池新型负极材料,但ZnFe2O4导电性差,充放电过程中的体积效应严重,导致其循环稳定性低、容量衰减快、倍率性能差,限制了其的应用。本文介绍了几种制备纳米铁酸锌及铁酸锌复合材料的方法,通过扫描电子显微镜对纳米级铁酸锌的形貌结构进行了研究,总结了水热法、溶剂热法、静电纺丝技术、共沉淀法、固相反应法等工艺制备铁酸锌,并对制备产物的电化学性能进行了分析,得出了限制其发展的真正原因。Abstract: Zinc ferrite (ZnFe2O4) is used as a new anode material for the lithium ion batteries due to its excellent performance. However, ZnFe2O4 has the poor electrical conductivity and the serious volume effects during the charging and discharging, which results in the low cycle stability, fast capacity decay, and poor rate performance, limiting its application. Several methods for preparing the nano-ZnFe2O4 and ZnFe2O4 composites were introduced in this paper. The morphology and microstructure of the nano-scale ZnFe2O4 were studied by scanning electron microscope (SEM). The electrochemical performance of the products produced by the hydrothermal method, solvothermal method, electrospinning technology, co-precipitation method, and solid-phase reaction method were analyzed, and the real reasons that limited the ZnFe2O4 development were summarized.
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图 10 ZnFe2O4/C复合材料恒定电流循环的脱锂能力和库伦效率(a)及可逆容量曲线(截止电压:0.01 V和3.00 V)(b)[27]
Figure 10. De-lithiation capacity and coulombic efficiency at the constant current cycling (a) and the reversible capacity curves of the ZnFe2O4/C composite materials at the different specific currents (cut-off voltages: 0.01 V and 3.00 V) (b)[27]
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[1] Yao J H, Zhang Y F, Qiu X P, et al. Research progress in improving electrochemical performance of zinc ferrite as anode material for lithium ion batteries. Mod Chem Ind, 2016, 36(12): 33姚金环, 张玉芳, 丘雪萍, 等. 改进锂离子电池负极材料ZnFe2O4电化学性能的研究进展. 现代化工, 2016, 36(12): 33 [2] Landi B J, Ganter M J, Cress C D, et al. Carbon nanotubes for lithium ion batteries. Energy Environ Sci, 2009, 2(6): 638 doi: 10.1039/b904116h [3] Yan J, Xia B J, Su Y C, et al. Phenomenologically modeling the formation and evolution of the solid electrolyte interface on the graphite electrode for lithium-ion batteries. Electrochim Acta, 2008, 53(24): 7069 doi: 10.1016/j.electacta.2008.05.032 [4] Liao L X, Wang M, Fang T, et al. Synthesis and characterization of ZnFe2O4 anode for lithium ion battery. J Inorg Mater, 2016, 31(1): 34 doi: 10.15541/jim20150272廖丽霞, 王明, 方涛, 等. ZnFe2O4锂离子电池负极材料的制备及电化学性能研究. 无机材料学报, 2016, 31(1): 34 doi: 10.15541/jim20150272 [5] Yang T B. Synthesis and Modification of ZnM2O4 (M=Mn, Fe) as Anode Materials for Lithium-Ion Batteries [Dissertation]. Changchun: Jilin University, 2017杨天博. 锂离子电池负极材料ZnM2O4(M= Mn, Fe)的合成、改性与电化学性能研究[学位论文]. 长春: 吉林大学, 2017 [6] Poizot P, Baudrin E, Laruelle S, et al. Low temperature synthesis and electrochemical performance of crystallized FeVO4·1.1H2O. Solid State Ionics, 2000, 138(1-2): 31 doi: 10.1016/S0167-2738(00)00784-0 [7] Cao H. Synthesis, Characterization and Li-Storage Performance of Carbon-Coated ZnFe2O4-Based Anode Materials for Li-Ion Batteries [Dissertation]. Ma’ anshan: Anhui University of Technology, 2017曹慧. 碳包覆ZnFe2O4 基锂离子电池负极材料的制备、表征及其储锂性能[学位论文]. 马鞍山: 安徽工业大学, 2017 [8] Cabana J, Monconduit L, Larcher D, et al. Beyond intercalation-based Li-ion batteries: the state of the art and challenges of electrode materials reacting through conversion reactions. Adv Mater, 2010, 22(35): E170 doi: 10.1002/adma.201000717 [9] Wang J C, Chen Y H, Chen Q Y. Latest development of nanometer particles in chemical fibers. China Dyeing Finish, 2004, 30(7): 45 doi: 10.3321/j.issn:1000-4017.2004.07.015王锦成, 陈月辉, 陈琼云. 纳米材料在化学纤维中的应用现状. 印染, 2004, 30(7): 45 doi: 10.3321/j.issn:1000-4017.2004.07.015 [10] Han L J. Synthesis of Nano-Zinc Ferrite via Hydrothermal Synthesis Route and Study on their Photocatalytic Properties [Dissertation]. Guangzhou: South China University of Technology, 2012韩黎君. 水热法合成纳米铁酸锌及其光催化性能研究[学位论文]. 广州: 华南理工大学, 2012 [11] Yan X, Hu X L, Yue H, et al. Hydrothermal synthesis of nano zinc ferrite. Chemistry, 2002, 65(9): 623 doi: 10.3969/j.issn.0441-3776.2002.09.013阎鑫, 胡小玲, 岳红, 等. 纳米铁酸锌的水热合成. 化学通报, 2002, 65(9): 623 doi: 10.3969/j.issn.0441-3776.2002.09.013 [12] Xing Z, Ju Z C, Yang J, et al. One-step hydrothermal synthesis of ZnFe2O4 nano-octahedrons as a high capacity anode materialfor Li-ion batteries. Nano Res, 2012, 5(7): 477 doi: 10.1007/s12274-012-0233-2 [13] Xie J, Song W T, Cao G S, et al. One-pot synthesis of ultrafine ZnFe2O4 nanocrystals anchored on graphene for high-performance Li and Li-ion batteries. RSC Adv, 2014, 4(15): 7703 doi: 10.1039/c3ra46904b [14] Xu J, Gu S, Fan L, et al. Electrospun lotus root-like CoMoO4@graphene nanofibers as high-performance anode for lithium ion batteries. Electrochim Acta, 2016, 196: 125 doi: 10.1016/j.electacta.2016.01.228 [15] Guo X, Lu X, Fang X, et al. Lithium storage in hollow spherical ZnFe2O4 as anode materials for lithium ion batteries. Electrochem Commun, 2010, 12(6): 847 doi: 10.1016/j.elecom.2010.04.003 [16] Sun X. Preparation of Three-Dimensional TiO2 Microspheres by Solvothermal Method and the Photocatalytic Activities [Dissertation]. Jinan: Shandong University, 2018孙翔. 溶剂热法制备三维分级TiO2纳米棒微球及其光催化性能研究[学位论文]. 济南: 山东大学, 2018 [17] Gao J, Mu X, Li J J, et al. Preparation and characterization of porous spherical Li4Ti5O12/C anode material for lithium ion batteries. J Inorg Mater, 2012, 27(3): 253 [18] Han Z Z, Jia H M, Yang S H, et al. Synthesis and supercapacitor properties of ZnFe2O4 nanoparticles-graphene composites. China Powder Sci Technol, 2018, 24(1): 86韩臻臻, 贾慧敏, 杨树华, 等. ZnFe2O4纳米粒子-石墨烯复合材料制备和超级电容器性能. 中国粉体技术, 2018, 24(1): 86 [19] Xia H, Qian Y, Fu Y, et al. Graphene anchored with ZnFe2O4 nanoparticles as a high-capacity anode material for lithium-ion batteries. Solid State Sci, 2013, 17: 67 doi: 10.1016/j.solidstatesciences.2012.12.001 [20] Wang Y Z. A brief history of electrospinning technology development and application. China Synth Fiber Ind, 2018, 41(4): 52 doi: 10.3969/j.issn.1001-0041.2018.04.013王艳芝. 静电纺丝技术发展简史及应用. 合成纤维工业, 2018, 41(4): 52 doi: 10.3969/j.issn.1001-0041.2018.04.013 [21] Fei Y Q. Preparation and Electrochemical Properties of ZnFe2O4 Composite Nanofibers [Dissertation]. Wuxi: Jiangnan University, 2017费雅倩. 铁酸锌复合纳米纤维材料的制备和电化学性能研究[学位论文]. 无锡: 江南大学, 2017 [22] Zhang M, Sun Z H, Zhang T F, et al. Excellent cycling stability with high SnO2 loading on a three-dimensional graphene network for lithium ion batteries. Carbon, 2016, 102: 32 doi: 10.1016/j.carbon.2016.02.032 [23] Xiao Y L, Zai J T, Tao L Q, et al. MnFe2O4–graphene nanocomposites with enhanced performances as anode materials for Li-ion batteries. Phy Chem Chem Phy, 2013, 15(11): 3939 doi: 10.1039/c3cp50220a [24] Teh P F, Sharma Y, Pramana S S, et al. Nanoweb anodes composed of one-dimensional, high aspect ratio, size tunable electrospun ZnFe2O4 nanofibers for lithium ion batteries. J Mater Chem, 2011, 21(38): 14999 doi: 10.1039/c1jm12088c [25] Zhong X B, Yang Z Z, Wang H Y, et al. A novel approach to facilely synthesize mesoporous ZnFe2O4 nanorods for lithium ion batteries. J Power Sources, 2016, 306: 718 doi: 10.1016/j.jpowsour.2015.12.102 [26] Ye L, Duan Y Q, Yuan Z H. Preparation of nanosized zinc ferrite by co-precipitation and crystallization behavior. J Tianjin Univ Technol, 2007, 23(6): 36 doi: 10.3969/j.issn.1673-095X.2007.06.012叶琳, 段月琴, 袁志好. 共沉淀法制备的铁酸锌纳米材料的晶化与晶粒生长行为. 天津理工大学学报, 2007, 23(6): 36 doi: 10.3969/j.issn.1673-095X.2007.06.012 [27] Jia H, Kloepsch R, He X, et al. Nanostructured ZnFe2O4 as anode material for lithium ion batteries: Ionic liquid-assisted synthesis and performance evaluation with special emphasis on comparative metal dissolution. Acta Chim Slov, 2016, 63(3): 470 [28] Ding Y, Yang Y, Shao H. High capacity ZnFe2O4 anode material for lithium ion batteries. Electrochim Acta, 2011, 56(25): 9433 doi: 10.1016/j.electacta.2011.08.031 [29] Bai Y, Ding L H, Zhang W F. Investigation of electrochemical performances of ZnFe2O4 prepared by solid state and hydrothermal method. Acta Phys Sin, 2011, 60(5): 778白莹, 丁玲红, 张伟风. ZnFe2O4的固相法和水热法制备及其电化学性能研究. 物理学报, 2011, 60(5): 778