水系钠离子电池普鲁士蓝正极材料的制备与电化学性能研究

doi:10.15541/jim20180272

摘要/Abstract

摘要：

普鲁士蓝(PB)是一种金属有机骨架配合物, 作为正极材料在水系钠离子电池中有广泛的应用前景。本文采用单一源法制备PB, 系统研究了反应温度、反应时间以及盐酸浓度对PB形貌结构和电化学性能的影响。研究结果表明, 升高反应温度能提高PB结晶性和循环稳定性, 以80 ℃合成的PB为正极材料组装的电池在100圈充放电循环后容量保持率为93.9%。延长反应时间可以使PB粒径增大, 但是反应时间超过6 h后PB粒径基本保持不变。延长反应时间有利于提高循环性能, 10 h所合成PB组装的电池在100圈充放电循环后容量保持率可以达到90%。提高盐酸浓度会改变PB的表面形貌, 同时改善电化学性能。盐酸浓度为0.20 mol/L时, 所得PB组装的电池经过100个循环后, 比容量仍有67.5 mAh/g。本研究可以为制备高性能PB基水系钠离子电池提供理论和实验指导。

关键词: 水系钠离子电池, 单一源法, 普鲁士蓝, 循环稳定性

Abstract:

Prussian blue (PB) is a kind of metal-organic framework complex that displays wide application prospect as cathode material for aqueous sodium-ion batteries. In this study, PB composites were prepared by a single source method. Furthermore, effects of reaction temperature, time and concentration of hydrochloric acid on PB morphology and electrochemical performance were systematically investigated. The results showed that crystallinity and electrochemical stability of PB were improved by increasing reaction temperature. The aqueous sodium-ion battery with PB synthesized at 80 ℃ as cathode material displayed a capacity retention of 93.9% after 100 cycles. The particle size of PB grew with the extension of reaction time until 6 h. It’s exhibited that the extended reaction time was beneficial to the cycle performance of device fabricated with PB prepared for 10 h, delivering 90% capacity retention after 100 cycles. Increment of the hydrochloric concentration acid changed the surface morphology, and thus improved electrochemical performance of PB. When the concentration of hydrochloric acid reached 0.20 mol/L, a capacity of 67.5 mAh/g could be maintainted after 100 discharge-charge. This work may provide theoretical and experimental gaidence for preparing high performance PB-based aqueous sodium-ion batteries.

Key words: aqueous sodium-ion battery, single source method, Prussian blue, cycle performance

中图分类号:

TM912

李勇, 何玮鑫, 郑芯月, 于胜兰, 李海同, 黎弘毅, 张蓉, 王雨. 水系钠离子电池普鲁士蓝正极材料的制备与电化学性能研究[J]. 无机材料学报, 2019, 34(4): 365-372.

Yong LI, Wei-Xin HE, Xin-Yue ZHENG, Sheng-Lan YU, Hai-Tong LI, Hong-Yi LI, Rong ZHANG, Yu WANG. Prussian Blue Cathode Materials for Aqueous Sodium-ion Batteries:Preparation and Electrochemical Performance[J]. Journal of Inorganic Materials, 2019, 34(4): 365-372.

图/表 19

图1 PB沉淀形成机理图

Fig. 1 Diagram of PB precipitation mechanism

图2 不同反应温度下所合成PB的XRD图谱

Fig. 2 XRD patterns of PB synthesized at different reaction temperatures

图3 不同反应温度下所合成PB的(a)~(e) SEM和(f) TEM照片

Fig. 3 (a-e) SEM and (f) TEM images of PB synthesized at different reaction temperatures

图4 不同反应温度下所合成PB的产率曲线

Fig. 4 Yield curve of PB synthesized at different reaction temperatures

图5 以不同反应温度下所得PB作为电极材料的电池的充放电曲线

Fig. 5 Charge/discharge curves of batteries based on PB synthesized at different reaction temperatures

图6 以不同反应温度下所得PB作为电极材料的电池的循环性能

Fig. 6 Cycle performances of batteries based on PB synthesized at different reaction temperatures

图7 以不同反应温度下所得PB作为电极材料的电池的倍率性能

Fig. 7 Rate performances of batteries based on PB synthesized at different reaction temperatures

图8 不同反应时间下所合成PB的XRD图谱

Fig. 8 XRD patterns of PB synthesized with different reaction time

图9 不同反应时间下所合成PB的SEM照片

Fig. 9 SEM images of PB synthesized with different reaction time

图10 不同反应时间下所合成PB的(a)粒径曲线和(b)产率曲线

Fig. 10 (a) Particle size and (b) yield curves of PB synthesized with different reaction time

图11 以不同反应时间下所得PB作为电极材料的电池的充放电曲线

Fig. 11 Charge/discharge curves of batteries based on PB synthesized with different reaction time

图12 以不同反应时间下所得PB作为电极材料的电池的循环性能

Fig. 12 Cycle performances of batteries based on PB synthesized with different reaction time

图13 以不同反应时间下所得PB作为电极材料的电池的倍率性能

Fig. 13 Rate performances of batteries based on PB synthesized with different reaction times

图14 不同盐酸浓度下所合成PB 的XRD图谱

Fig. 14 XRD patterns of PB synthesized at different concentrations of hydrochloric acid

图15 不同盐酸浓度下所合成PB的SEM照片

Fig. 15 SEM images of PB synthesized at different concentrations of hydrochloric acid

图16 不同盐酸浓度下所合成PB的产率曲线

Fig. 16 Yield curve of PB synthesized at different concentrations of hydrochloric acid

图17 以不同盐酸浓度下所得PB作为电极材料的电池的充放电曲线

Fig. 17 Charge/discharge curves of batteries based on PB synthesized at different concentrations of hydrochloric acid

图18 以不同盐酸浓度下所得PB作为电极材料的电池的循环性能

Fig. 18 Cycle performances of batteries based on PB synthesized at different concentrations of hydrochloric acid

图19 以不同盐酸浓度下所得PB作为电极材料的电池的倍率性能

Fig. 19 Rate performances of batteries based on PB synthesized at different concentrations of hydrochloric acid

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