CoFe2O4@C composite nanofiber films as self-standing anodes for lithium-ion batteries
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摘要: 为了提高CoFe2O4作为锂离子电池负极材料的综合电化学性能,将其与高导电性的碳纤维进行复合。通过静电纺丝及低温碳化制备了均匀镶嵌CoFe2O4纳米颗粒的碳纳米纤维(CoFe2O4@CNFs)柔性复合膜,使用XRD、TG、Raman、SEM、TEM、CV、GCD和EIS等对复合物进行表征,着重研究了CoFe2O4含量对其储锂性能的影响。该复合膜直接用作自支撑锂离子电池负极时表现出较好的电化学性能。CoFe2O4的引入显著提高了碳纳米纤维膜的电化学性能,随着CoFe2O4含量的增加,CoFe2O4@CNFs电极的比容量先增加后减小,CoFe2O4含量约为33.3%(w/w)的CoFe2O4@CNFs-3电极具有最高的比容量和更好的循环及倍率性能。在0.1 A·g−1的电流密度下,充放电循环100圈后比容量为611.4 mA·h·g−1,相对第二圈的容量保持率为94%; 当电流密度增大到2 A·g−1时,其比容量仍有353.6 mA·h·g−1。CoFe2O4@CNFs-3更好的电化学性能主要归因于高电化学活性CoFe2O4和高导电纳米碳纤维的恰当结合及更好的协同效应。Abstract: In order to improve the comprehensive electrochemical performance of the CoFe2O4 electrode material for lithium-ion batteries (LIBs), the CoFe2O4 is integrated with highly conductive carbon materials. Flexible carbon nanofibers uniformly embedded with CoFe2O4 nanoparticles (CoFe2O4@CNFs) composite films were synthesized by an electrospinning and subsequent low-temperature carbonization process, and were characterized by XRD, TG, Raman, SEM, TEM, CV, GCD and EIS. The influence of CoFe2O4 content on the lithium storage performances of CoFe2O4@CNFs composites was investigated in detail. It is found that the as-prepared composite films directly used as self-standing anodes in lithium ion batteries exhibit good electrochemical properties. The incorporation of CoFe2O4 nanoparticles into CNFs can significantly improve their electrochemical performances, and the specific capacities first increase and then decrease with increasing CoFe2O4 content in CoFe2O4@CNFs, in which the CoFe2O4@CNFs-3 electrode with about 33.3% (w/w) CoFe2O4 presents an optimal specific capacity as well as better cycle stability and rate capability. The CoFe2O4@CNFs-3 electrode delivers a high reversible specific capacity of 611.4 mA·h·g−1 after 100 charge/discharge cycles at the current density of 0.1 A·g−1, corresponding to a capacity retention of 94% relative to the capacity of the second cycle. Moreover, even at a high current density of 2 A·g−1, the specific capacity still remains at 353.6 mA·h·g−1. The superior performance for CoFe2O4@CNFs-3 is mainly attributed to the proper combination and highly synergistic effect of electrochemically active CoFe2O4 and high conductive CNFs matrix.
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Key words:
- CoFe2O4 /
- carbon nanofibers /
- composite /
- lithium-ion batteries /
- self-standing anode
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图 10 CoFe2O4@CNFs和CNFs原始电池的EIS图谱及相应等效电路 (a) 和低频区域Z'与ω−1/2的关系图 (b)
Figure 10. EIS spectra and corresponding equivalent circuit (inset) of the pristine batteries with CoFe2O4@CNFs and CNFs anode (a); Plots of Z' versus ω−1/2 in the low-frequency region (b)
Rct—Charge transfer resistance; Rs—Resistance of solution between working electrode and opposite electrode; Zw—Weber impedance; CPE—Phase angle element
表 1 CoFe2O4@碳纳米纤维(CoFe2O4@CNFs)复合膜的命名
Table 1. Naming of CoFe2O4@carbon nanofibers (CoFe2O4@CNFs) composite films
PAN/wt% CoFe2O4/wt% CoFe2O4@CNFs-1 9.5 1 CoFe2O4@CNFs-3 9.5 3 CoFe2O4@CNFs-5 9.5 5 Note: PAN—Polyacrylonitrile. 表 2 CoFe2O4@CNFs-3与其他一些双金属氧化物基负极材料的性能比较
Table 2. Performance comparison of CoFe2O4@CNFs-3 and some bimetallic oxides based anode materials
Samples Current density/(mA·g−1) Capacity/(mA·h·g−1) Cycle number Ref. NiFe2O4@C fibers 100 497 100 [31] CoMn2O4/N doped carbon 100 585 10 [32] ZnCo2O4 50 572 30 [33] Porous CoFe2O4 nanocubes 50 360 50 [34] ZnMn2O4 100 433 50 [35] FeCo2O4 50 422 100 [36] ZnCo2O4/C 50 463 100 [37] CoFe2O4@CNFs-3 100 611 100 This work -
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