聚吡咯包覆FeCl<sub>3</sub>-石墨层间化合物的制备与电化学储钠性能

柳小玄; 韩飞; 刘洪波; 刘金水

doi:10.13801/j.cnki.fhclxb.20210119.002

聚吡咯包覆FeCl₃-石墨层间化合物的制备与电化学储钠性能

doi: 10.13801/j.cnki.fhclxb.20210119.002

湖南大学　材料科学与工程学院，长沙 410082

基金项目: 湖南省科技创新人才计划项目(2020RC3023)；湖南省科技重大专项项目(2018GK1030)；湖南大学汽车车身先进设计制造国家重点实验室人才培育项目(51965010)

详细信息

通讯作者:
韩飞，博士，副教授，博士生导师，研究方向为石墨层间化合物的结构设计与储能应用　 E-mail：feihan@hnu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2020-11-24
- 录用日期: 2021-01-13
- 网络出版日期: 2021-01-19
- 刊出日期: 2021-11-01

Preparation and electrochemical sodium storage performance of polypyrrole coated FeCl₃-intercalated graphite intercalation compound

College of Materials Science and Engineering, Hunan University, Changsha 410082, China

摘要

摘要: 以FeCl₃和天然鳞片石墨为原料，通过融盐法制得1阶FeCl₃插层的石墨层间化合物(FeCl₃-GIC)。用原位聚合法对FeCl₃-GIC进行聚吡咯(PPy)包覆改性，形成具有核壳结构的(FeCl₃-GIC)@PPy复合材料。通过多种表征方法研究聚吡咯包覆前后FeCl₃-GIC的表面形貌和微观结构变化。结果表明：聚吡咯均匀致密地包覆在十微米级的FeCl₃-GIC颗粒外部，包覆层厚度为35 nm，经过聚吡咯包覆后(FeCl₃-GIC)@PPy的导电性能显著提高((FeCl₃-GIC)@PPy粉末电阻率2.3×10⁻³ Ω·cm，FeCl₃-GIC粉末电阻率3.1×10⁻³ Ω·cm)。采用多种电化学测试探究产物的钠离子存储特性，聚吡咯外壳能够显著提高FeCl₃-GIC作为钠离子电池负极材料的充放电容量、倍率性能和循环性能。在0.1 A·g⁻¹电流密度下循环100次后，FeCl₃-GIC的比容量逐渐衰减到157 mA·h·g⁻¹，而(FeCl₃-GIC)@PPy材料的比容量达到281 mA·h·g⁻¹左右且容量基本保持不变；在电流密度1 A·g⁻¹的条件下循环500次后，(FeCl₃-GIC)@PPy的比容量仍有181 mA·h·g⁻¹，容量保持率约为89%。
- 聚吡咯 /
- 石墨层间化合物 /
- 氯化铁 /
- 钠离子存储 /
- 二次电池
Abstract: The 1-stage FeCl₃-intercalated graphite intercalation compound (FeCl₃-GIC) were prepared by a molten salt method using FeCl₃ and natural flake graphite as raw materials. Subsequently, a conductive layer of polypyrrole (PPy) were uniformly coated on the surface of the FeCl₃-GIC particles by in-situ polymerization to form a core-shell structured (FeCl₃-GIC)@PPy composite material. Various characterization methods were employed to study the surface morphology and microstructure evolution of FeCl₃-GIC before and after polypyrrole coating. The results show that a uniform and dense polypyrrole layer with a thickness of 35 nm is tightly coated on the surface of the micro-sized FeCl₃-GIC particles. After coating, the conductivity of the (FeCl₃-GIC)@PPy composite is significantly improved for the powder resistivity is reduced from 3.1×10⁻³ Ω·cm of FeCl₃-GIC to 2.3×10⁻³ Ω·cm of (FeCl₃-GIC)@PPy. As an anode material for sodium ion storage, it is found that the (FeCl₃-GIC)@PPy anode exhibits the improved reversible capacitiy, rate capability and cycling stability compared with the naked FeCl₃-GIC anode. Specially, the specific capacity of (FeCl₃-GIC)@PPy remains steady with a high sodium storage value of 281 mA·h·g⁻¹ after 100 cycles at the current density of 0.1 A·g⁻¹, while the FeCl₃-GIC anode shows a continuous capacity decay with a low value of 157 mA·h·g⁻¹ after 100 cycles. Additionally, even at a high current density of 1.0 A·g⁻¹, the (FeCl₃-GIC)@PPy anode delivers a remained sodium storage capacity of 181 mA·h·g⁻¹ after 500 cycles, accompanying with a fascinating capacity retention ratio of 89%.
- polypyrrole /
- graphite intercalation compound /
- ferric chloride /
- sodium ion storage /
- secondary battery

HTML全文

图 1 30℃-6 h-(FeCl₃-GIC)@PPy、0℃-10 h-(FeCl₃-GIC)@PPy和FeCl₃-GIC的XRD图谱 (a) 和FTIR图谱 (b)

Figure 1. XRD patterns (a) and FTIR spectra (b) of 30℃-6 h-(FeCl₃-GIC)@PPy, 0℃-10 h-(FeCl₃-GIC)@PPy and FeCl₃-GIC

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图 2 FeCl₃-GIC、0℃-10 h-(FeCl₃-GIC)@PPy、30℃-6 h-(FeCl₃-GIC)@PPy的SEM图像 ((a)~(c)) ；30℃-6 h-(FeCl₃-GIC)@PPy的TEM图像 (d)

Figure 2. SEM images of FeCl₃-GIC, 0℃-10 h-(FeCl₃-GIC)@PPy and 30℃-6 h-(FeCl₃-GIC)@PPy ((a)-(c))； TEM image of 30℃-6 h-(FeCl₃-GIC)@PPy (d)

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图 3 FeCl₃-GIC、0℃-10 h-(FeCl₃-GIC)@PPy和30℃-6 h-(FeCl₃-GIC)@PPy的微观结构示意图 ((a)~(c))、拉曼光谱 (d)、粉末电阻率 (e)、热重曲线 (f)

Figure 3. Schematic diagram of the microstructure ((a)-(c)), Raman spectra (d), powder electronic resistivity (e) and thermogravimetry curves (f) of FeCl₃-GIC, 30℃-6 h-(FeCl₃-GIC)@PPy and 0℃-10 h-(FeCl₃-GIC)@PPy

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图 4 (a) 30℃-6 h-(FeCl₃−GIC)@PPy电极的循环伏安曲线；(b)恒流充放电曲线；(c) FeCl₃−GIC、30℃-6 h-(FeCl₃−GIC)@PPy、0℃-10 h-(FeCl₃−GIC)@PPy和PPy电极在100 mA·g⁻¹电流密度下的循环性能图；(d) FeCl₃−GIC电极循环后FeCl₃溶解逃逸示意图；(e) 30℃-6 h-(FeCl₃−GIC)@PPy电极循环100次之后的SEM和(f) TEM图片

Figure 4. Cyclic voltagmmograms (a) and galvanostatic discharge/charge profiles (b) of the 30℃-6 h-(FeCl₃−GIC)@PPy anode; (c) Comparison of cycle performance of FeCl₃−GIC, 0℃-10 h-(FeCl₃−GIC)@PPy, 30℃-6 h-(FeCl₃−GIC)@PPy and PPy at 100 mA·g⁻¹ for SIBs; (d) FeCl₃ dissolution and escape diagram of the FeCl₃−GIC anode after cycling several times; SEM (e) and TEM (f) of 30℃-6 h-(FeCl₃−GIC)@PPy anode after cycling 100 times

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图 5 (a) FeCl₃-GIC、0℃-10 h-(FeCl₃-GIC)@PPy和30℃-6 h-(FeCl₃-GIC)@PPy电极的倍率性能；(b) FeCl₃-GIC、30℃-6 h-(FeCl₃-GIC)@PPy和0℃-10 h-(FeCl₃-GIC)@PPy电极的奈奎斯特曲线；(c) 30℃-6 h-(FeCl₃-GIC)@PPy外层PPy阻碍溶剂化Na⁺插层示意图；(d) 30℃-6 h-(FeCl₃-GIC)@PPy电极的长循环性能

Figure 5. (a) Rate permance of FeCl₃-GIC, 0℃-10 h-(FeCl₃-GIC)@PPy and 30℃-6 h-(FeCl₃-GIC)@PPy anode; (b) Nyquist plots of FeCl₃-GIC, 30℃-6 h-(FeCl₃-GIC)@PPy and 0℃-10 h-(FeCl₃-GIC)@PPy anode; (c) Schematic diagram of out layer PPy for 30℃-6 h-(FeCl₃-GIC)@PPy blocking solvated Na⁺ intercalating; (d) Long-cycle performance of the 30℃-6 h-(FeCl₃-GIC)@PPy anode

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