基于活性炭||Na0.44MnO2的低成本、高倍率和长寿命碱性钠离子电池电容器

doi:10.3866/PKU.WHXB202303041

物理化学学报

基于活性炭||Na_0.44MnO₂的低成本、高倍率和长寿命碱性钠离子电池电容器

薛晴¹, 李圣驿¹, 赵亚楠², 盛鹏¹, 徐丽¹, 李正曦³, 张波⁴, 李慧¹, 王博¹, 杨立滨³, 曹余良², 陈重学⁵

1 北京智慧能源研究院, 北京 102200;
2 武汉大学化学与分子科学学院, 化学电源材料与技术湖北省重点实验室, 武汉 430072;
3 国网青海省电力公司经济技术研究院, 西宁 810008;
4 国网金华供电公司, 浙江金华 321017;
5 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:2023-03-20 修回日期:2023-04-14 录用日期:2023-04-17 发布日期:2023-04-21
通讯作者: 曹余良, 陈重学 E-mail:ylcao@whu.edu.cn;zxchen_pmc@whu.edu.cn
基金资助:
国家电网公司科技计划(5500-202158251A-0-0-00)资助项目

Novel Alkaline Sodium-Ion Battery Capacitor Based on Active Carbon||Na_0.44MnO₂ towards Low Cost, High-Rate Capability and Long-Term Lifespan

Qing Xue¹, Shengyi Li¹, Yanan Zhao², Peng Sheng¹, Li Xu¹, Zhengxi Li³, Bo Zhang⁴, Hui Li¹, Bo Wang¹, Libin Yang³, Yuliang Cao², Zhongxue Chen⁵

1 Beijing Institute of Smart Energy, Beijing 102200, China;
2 Hubei Key Laboratory of Chemical Power Source Materials and Technology, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China;
3 State Grid Qinghai Electric Power Company, Economic and Technological Research Institute, Xining 810008, China;
4 State Grid Jinhua Power Supply Company, Jinhua 321017, Zhejiang Province, China;
5 Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, China

Received:2023-03-20 Revised:2023-04-14 Accepted:2023-04-17 Published:2023-04-21
Contact: Yuliang Cao, Zhongxue Chen E-mail:ylcao@whu.edu.cn;zxchen_pmc@whu.edu.cn
Supported by:
The project was supported by the Science and Technology Project of State Grid Corporation of China (5500-202158251A-0-0-00).

1. WHXB202303041-SI-2p.pdf(244KB)

摘要/Abstract

摘要： 水系钠离子电池电容器具有成本低、功率大、安全性好等优点，是下一代大规模储能系统的理想选择之一。本文采用Na_0.44MnO₂正极、活性炭(AC)负极、6 mol∙L^-1 NaOH电解液和廉价的不锈钢集流体构建了可充电碱性钠离子电池电容器。由于Na_0.44MnO₂正极在碱性电解液中具有较高的过充耐受性，通过首次充电时的原位过充预活化过程可以解决半钠化Na_0.44MnO₂正极和AC负极初始库伦效率低的缺点。因此，AC||Na_0.44MnO₂可充电碱性钠离子电池电容器具有优异的电化学性能，在功率密度为85 W∙kg^-1时，能量密度达26.6 Wh∙kg^-1，循环10000次后容量保持率为89%。同时，在50 °C的高温和-20 °C的低温也具有良好的电化学性能。这些结果表明AC||Na_0.44MnO₂可充电碱性钠离子电池电容器具备应用于大规模储能的潜力。

关键词: 钠离子电池电容, 碱性电解液, 过充自保护, 低成本, 宽工作温程

Abstract: As the most advanced battery technology to date, lithium-ion battery has occupied the main battery markets for electric vehicles and grid scale energy storage systems. However, the limited lithium reserves as well as the high price raise concerns about the sustainability of lithium-ion battery. Although sodium-ion battery is proposed as a good supplement to lithium-ion battery, expensive and flammable electrolyte components, harsh assembly environments and potential safety hazards have limited the rapid development to a certain extent. The organic electrolyte was replaced with an aqueous solution to construct a new type of aqueous sodium ion battery capacitor (ASIBC). It is of great significance for next-generation energy storage system owing to its low cost, high power, and inherent safety. However, applicable ASIBC system is rarely reported so far. Here, a rechargeable alkaline sodium ion battery capacitors constructed by using Na_0.44MnO₂ cathode, activated carbon (AC) anode, 6 mol∙L^-1 NaOH electrolyte, and cheap stainless-steel current collector. Because of high overcharge tolerance of Na_0.44MnO₂ cathode in alkaline electrolyte, the shortcomings of the half-sodium Na_0.44MnO₂ cathode and low initial Coulombic efficiency of AC anode can be resolved by in situ overcharging pre-activation process during first charging. The available capacity of Na_0.44MnO₂ in half cell largely increased from ~40 mAh∙g^-1 (neutral electrolyte) to 77.3 mAh∙g^-1 (alkaline electrolyte) due to broadened Na⁺ intercalation potential region. Thus, the AC||Na_0.44MnO₂ ASIBC delivers outstanding electrochemical properties with a high energy density of 26.6 Wh∙kg^-1 at a power density of 85 W∙kg^-1 and long cycling stability with a capacity retention of 89% after 10,000 cycles. The advantages of the alkaline electrolyte for the AC||Na_0.44MnO₂ ASIBC can be concluded as follows: (1) through the in situ electrochemical pre-activation process, the overcharging oxygen evolution reaction during first charging process can balance the adverse effects of the half-sodium Na_0.44MnO₂ cathode and low initial Coulombic efficiency of AC anode on the energy density of full cell; (2) the overcharging self-protection function can promote the generated oxygen to be eliminated at anode during overcharging, which improves the system safety; (3) the low-cost materials in alkaline environment can be scaled up to construct AC||Na_0.44MnO₂ ASIBC. In addition, the AC||Na_0.44MnO₂ ASIBC also possesses wide operating temperature range, achieving satisfied electrochemical performance at a high temperature of 50 °C and a low temperature of -20 °C. Considering the merits of low-cost, high safety, no toxicity and environment-friendly, we believe the AC||Na_0.44MnO₂ rechargeable alkaline sodium-ion battery capacitors have the potential to be applied to large-scale energy storage.

Key words: Sodium-ion battery capacitor, Alkaline electrolyte, Overcharging self-protection, Low cost, Wide operating temperature range

薛晴, 李圣驿, 赵亚楠, 盛鹏, 徐丽, 李正曦, 张波, 李慧, 王博, 杨立滨, 曹余良, 陈重学. 基于活性炭||Na_0.44MnO₂的低成本、高倍率和长寿命碱性钠离子电池电容器[J]. 物理化学学报 2303041. doi: 10.3866/PKU.WHXB202303041

Qing Xue, Shengyi Li, Yanan Zhao, Peng Sheng, Li Xu, Zhengxi Li, Bo Zhang, Hui Li, Bo Wang, Libin Yang, Yuliang Cao, Zhongxue Chen. Novel Alkaline Sodium-Ion Battery Capacitor Based on Active Carbon||Na_0.44MnO₂ towards Low Cost, High-Rate Capability and Long-Term Lifespan[J]. Acta Phys. -Chim. Sin. 2303041. doi: 10.3866/PKU.WHXB202303041

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202303041

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基于活性炭||Na_0.44MnO₂的低成本、高倍率和长寿命碱性钠离子电池电容器

Novel Alkaline Sodium-Ion Battery Capacitor Based on Active Carbon||Na_0.44MnO₂ towards Low Cost, High-Rate Capability and Long-Term Lifespan

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