NaOH浓度对Na0.44MnO2储钠性能的影响

doi:10.3866/PKU.WHXB201907049

物理化学学报 >> 2021, Vol. 37 >> Issue (3): 1907049.doi: 10.3866/PKU.WHXB201907049

NaOH浓度对Na_0.44MnO₂储钠性能的影响

李慧¹, 刘双宇¹, 袁天赐², 王博¹, 盛鹏¹, 徐丽¹, 赵广耀¹, 白会涛¹, 陈新¹, 陈重学³^,*(), 曹余良²^,*()

¹ 全球能源互联网研究院有限公司，先进输电技术国家重点实验室，北京 102211
² 武汉大学化学与分子科学学院，湖北省电源材料与技术重点实验室，武汉 430072
³ 武汉大学动力与机械学院，水力机械过渡过程教育部重点实验室，武汉 430072

收稿日期:2019-07-16 录用日期:2019-08-30 发布日期:2019-09-04
通讯作者: 陈重学,曹余良 E-mail:zxchen_pmc@whu.edu.cn;ylcao@whu.edu.cn
基金资助:
国家电网公司(SGRIDGKJ[2017]841);国家重点基础研究发展计划(2016YFB0901500);国家自然科学基金(21875171);国家自然科学基金(21673165)

Influence of NaOH Concentration on Sodium Storage Performance of Na_0.44MnO₂

Hui Li¹, Shuangyu Liu¹, Tianci Yuan², Bo Wang¹, Peng Sheng¹, Li Xu¹, Guangyao Zhao¹, Huitao Bai¹, Xin Chen¹, Zhongxue Chen³^,*(), Yuliang Cao²^,*()

¹ State Key Laboratory of Advanced Power Transmission Technology, Global Energy Interconnection Research Institute Co. Ltd., Beijing 102211, China
² Hubei Key Laboratory of Electrochemical Power Sources, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China
³ Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, China

Received:2019-07-16 Accepted:2019-08-30 Published:2019-09-04
Contact: Zhongxue Chen,Yuliang Cao E-mail:zxchen_pmc@whu.edu.cn;ylcao@whu.edu.cn
About author:Email: ylcao@whu.edu.cn (Y.C.)
Email: zxchen_pmc@whu.edu.cn (Z.C.). Tel.: +86-27-68754526
Supported by:
the Science and Technology Project of State Grid, China(SGRIDGKJ[2017]841);the National Key Basic Research Program of China(2016YFB0901500);the National Natural Science Foundation of China(21875171);the National Natural Science Foundation of China(21673165)

摘要/Abstract

摘要：

我们通过球磨法及后续的高温焙烧合成出了短棒状的Na_0.44MnO₂，并研究了其作为碱性水溶液钠离子电池正极时，电解液NaOH浓度对其电化学性能的影响。结果表明，提高NaOH浓度有利于抑制嵌氢反应的发生并改善电极的循环性能和倍率性能，但同时也会造成析氧反应的提前触发，浓度过高时则又会降低其倍率性能。Na_0.44MnO₂在8 mol·L^-1 NaOH中表现出了最佳的电化学性能，0.5C (1C = 121 mA·g^-1)的电流密度下，比容量达到79.2 mAh·g^-1，50C时，仍能释放出35.3 mAh·g^-1的比容量，在0.2–1.2 V (vs. NHE)的电压窗口内，500周后容量保持率64.3%。此外，我们也发现缩小电压窗口可以减少副反应、改善循环性能。Na_0.44MnO₂在浓碱电解液中也表现出了优异的耐过充能力。上述结果不仅表明通过优化电解液体系和测试条件可大大改善Na_0.44MnO₂的储钠性能，同时也证实了Na_0.44MnO₂作为一种水溶液钠离子电池正极材料，在大规模储能领域具有良好的应用前景。

关键词: 离子电池, Na_0.44MnO₂, 电化学性能, 浓度, 过充

Abstract:

Aqueous sodium ion batteries (ASIBs) have attracted considerable attention for large-scale energy storage because of their prominent advantages of low cost, high safety, and environment-friendliness. Among the reported cathode materials for ASIBs, Na_0.44MnO₂ exhibits outstanding structural and hydrochemical stability, and hence is of much interest to research scholars. However, the reversible capacity of Na_0.44MnO₂ in most of the reported ASIBs was only 40 mAh·g^-1 due to the restriction of stable working windows, although the in spite of theoretical capacity is121 mAh·g^-1. Recently, we reported a Zn/Na_0.44MnO₂ dual-ion battery (AZMDIB) based on a Na_0.44MnO₂ positive electrode, Zn negative electrode, and 6 molL^-1 NaOH electrolyte. The alkaline solution lowered the proton insertion potential and expanded the stable working window of the Na_0.44MnO₂ electrode, thus enhancing the reversible capacity to 80 mAh·g^-1. Previous studies have demonstrated that the composition, concentration, and pH of the electrolytes have significant effects on the stable electrochemical window, rate performance, cycling performance, and other electrochemical properties of aqueous batteries. In addition, it has been reported that the co-intercalation of hydrogen ions can be inhibited by increasing the pH of the electrolyte in order to improve the cyclic stability of the electrode. Therefore, exploring the effect of electrolyte concentration and pH on the electrochemical performance of Na_0.44MnO₂ can provide insight into the design and optimization of high-performance Zn/Na_0.44MnO₂ aqueous batteries. Hence, in this work, rod-like Na_0.44MnO₂ was synthesized by ball milling and subsequent high-temperature calcination, and the influence of NaOH concentration on the electrochemical performance of the Na_0.44MnO₂ electrode was investigated by adopting five different concentrated electrolytes, 1, 3, 6, 8, and 10 mol·L^-1 NaOH. The results showed that an increase in NaOH concentration is beneficial for preventing the insertion of protons and improving the cycling performance and the rate performance of the electrode; however, it also leads to premature triggering of the oxygen evolution reaction. Moreover, the rate performance would decrease at high NaOH concentration. The Na_0.44MnO₂ electrode showed optimal electrochemical performance in 8 mol·L^-1 NaOH. At a current density of 0.5C (1C = 121 mA·g^-1), a reversible specific capacity of 79.2 mAh·g^-1 was obtained, and a capacity of 35.3 mAh·g^-1 was maintained even at a high current density of 50C. In the potential window of 0.2–1.2 V (vs. NHE), the capacity retention after 500 weeks was 64.3%, which increased to 78.2% when the potential window was reduced to 0.25–1.15 V, because of the fewer side reactions. In addition, Na_0.44MnO₂ showed an exceptional ability to sustain overcharging up to 30% in a concentrated alkaline electrolyte (based on the reversible capacity of 79.2 mAh·g^-1), and the discharge capacity within 80 cycles was almost steady. The above mentioned results form the basis for possible technical directions toward the development of low-cost cathode materials to be used in ASIBs.

Key words: Sodium ion battery, Na_0.44MnO₂, Electrochemical performance, Concentration, Overcharging

李慧, 刘双宇, 袁天赐, 王博, 盛鹏, 徐丽, 赵广耀, 白会涛, 陈新, 陈重学, 曹余良. NaOH浓度对Na_0.44MnO₂储钠性能的影响[J]. 物理化学学报, 2021, 37(3), 1907049. doi: 10.3866/PKU.WHXB201907049

Hui Li, Shuangyu Liu, Tianci Yuan, Bo Wang, Peng Sheng, Li Xu, Guangyao Zhao, Huitao Bai, Xin Chen, Zhongxue Chen, Yuliang Cao. Influence of NaOH Concentration on Sodium Storage Performance of Na_0.44MnO₂[J]. Acta Phys. -Chim. Sin. 2021, 37(3), 1907049. doi: 10.3866/PKU.WHXB201907049

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201907049

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I3/1907049

图/表 6

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Electrolytes concentration/ (mol·L^-1)	Working voltage window	Reversible capacity at 0.5C/(mAh·g^-1)	Rate performance, capacity at 50C/(mAh·g^-1)	Cyclic stability (capacity retention after 500 cycles)
1	0.25-1.2 V	69.3	13.4	27.4%
3	0.2-1.2 V	80.6	21.8	33.2%
6	0.2-1.2 V	82.5	29.3	54.2%,
8	0.2-1.2 V	79.2	30.3	64.3%,
10	0.2-1.2 V	67.9	13.4	65.8%

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NaOH浓度对Na_0.44MnO₂储钠性能的影响

Influence of NaOH Concentration on Sodium Storage Performance of Na_0.44MnO₂

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