锌离子电池低温性能研究进展

doi:10.19799/j.cnki.2095-4239.2022.0436

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (1): 278-298.doi: 10.19799/j.cnki.2095-4239.2022.0436

锌离子电池低温性能研究进展

袁紫微¹(), 林楚园¹, 袁紫嫣¹, 孙晓丽¹, 钱庆荣¹^,², 陈庆华¹^,², 曾令兴¹^,²()

^1.聚合物资源绿色循环利用教育部工程研究中心，福建师范大学环境与资源学院，福建福州 350007
^2.先进能源材料化学教育部重点实验室，南开大学化学学院，天津 300071

收稿日期:2022-08-02 修回日期:2022-08-26 出版日期:2023-01-05 发布日期:2023-02-08
通讯作者: 曾令兴 E-mail:ziweiyuan2001@163.com;lingxing@fjnu.edu.cn
作者简介:袁紫微（2001—），女，本科，研究方向为宽温域水系电池，E-mail：ziweiyuan2001@163.com；
基金资助:
国家重点研发计划项目(2019YFC1904500);国家自然科学基金(NSFC 21801251);福建省杰出青年科学基金(2019J06015)

The research process on low temperature performance of zinc ion batteries

Ziwei YUAN¹(), Chuyuan LIN¹, Ziyan YUAN¹, Xiaoli SUN¹, Qingrong QIAN¹^,², Qinghua CHEN¹^,², Lingxing ZENG¹^,²()

^1.Engineering Research Center of Polymer Green Recycling of Ministry of Education, College of Environment and Resources, Fujian Normal University, Fuzhou 350007, Fujian, China
^2.Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

Received:2022-08-02 Revised:2022-08-26 Online:2023-01-05 Published:2023-02-08
Contact: Lingxing ZENG E-mail:ziweiyuan2001@163.com;lingxing@fjnu.edu.cn

摘要/Abstract

摘要：

新兴的可充电锌离子电池具有高安全性、环境友好、低成本、操作简单等优势，因此成为极具应用前景的下一代储能设备之一。然而，其在低温条件下展现出较低的放电容量以及功率密度，有时甚至无法正常运行，严重制约可充电锌离子电池的实用性。因此，本文对近期相关文献进行探讨，从电极材料的设计、优化电解质以及改进其他组件三个方面综述了提高锌离子电池低温性能的策略，着重介绍了晶体工程和组分设计在提高电极材料低温离子传导率方面的作用机制。对于电解质优化策略，重点分析了水系高浓度电解质、有机电解质、准固态/固态电解质、电解质添加剂、共晶电解质五种方法对降低电解质凝固点和提升锌离子电池低温电化学性能的机理。此外，简要阐述了高亲水性黏结剂以及高电导率隔膜等改进方法。综合分析表明，通过晶体工程、准固态/固态电解质和电解质添加剂等多种策略的协同耦合，有望实现研制具有高比容量、长循环稳定性和大倍率性能的低温锌离子电池。

关键词: 锌离子电池, 低温性能, 电极材料的设计, 电解质的优化, 电解质添加剂

Abstract:

New rechargeable zinc-based energy storage technologies have the advantages of high safety, environmental friendliness, cheap cost, and ease of use; as a result, they are thought to be among the most promising next-generation energy storage technologies. However, it displays poor discharge capacity and power density at low temperatures or even malfunctions, significantly limiting applicability. Therefore, through the discussion of recent related research, this review contemplates on the strategies to improve the low-temperature performance of zinc-ion batteries from three perspectives: the design of electrode materials, the optimization of electrolytes, and the improvement of other components. The mechanisms of crystal engineering and component design in improving the ion conductivity of electrode materials at low temperatures are emphasized. Regarding the electrolyte optimization strategy, the mechanism of five approaches, including aqueous high concentration electrolyte, organic electrolyte, quasi-solid/solid electrolyte, electrolyte additive, and eutectic electrolyte, to lower the freezing point of the electrolyte and enhance the electrochemical performance of zinc ion battery at low temperature was examined. Additionally, the enhancement techniques of high hydrophilic binder and high conductivity diaphragm are briefly mentioned. The thorough research reveals that the creation of low-temperature zinc-ion batteries with a high-specific capacity, long-cycle stability, and high-rate capability is anticipated to be realized through the cooperative coupling of crystal engineering, quasi-solid/solid electrolyte, and electrolyte additives.

Key words: zinc-ion batteries, low-temperature performance, electrode material design, electrolyte optimization, electrolyte additive

中图分类号:

TM 911

袁紫微, 林楚园, 袁紫嫣, 孙晓丽, 钱庆荣, 陈庆华, 曾令兴. 锌离子电池低温性能研究进展[J]. 储能科学与技术, 2023, 12(1): 278-298.

Ziwei YUAN, Chuyuan LIN, Ziyan YUAN, Xiaoli SUN, Qingrong QIAN, Qinghua CHEN, Lingxing ZENG. The research process on low temperature performance of zinc ion batteries[J]. Energy Storage Science and Technology, 2023, 12(1): 278-298.

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表1

低温锌离子电池物理化学性能以及电化学性能对比表"

电解质	分类	正极材料	负极材料	离子电导率/[(mS/cm)/℃]	运行温度范围/℃	凝固点/℃	容量/[(mAh/g)/(A/g)]	年份
7.5 mol/L ZnCl₂	高浓度电解质	聚苯胺(PANI)	Zn	1.79/-60	-90～60	-114	-90 ℃：50.6/0.01	2020^[11]
4 mol/L Zn(BF₄)₂	高浓度电解质	四氯苯醌(TCBQ)	Zn	1.47/-70	-95～25	-122	-95 ℃：63.5/0.022	2021^[49]
2 mol/L Zn(CF₃SO₃)₂	高浓度电解质	V₂O₅	Zn	4.47/-30	-30～25	-34.1	-30 ℃：194.1/1	2021^[51]
4 mol/L Zn(TFSI)₂	高浓度电解质	聚(邻苯二酚)氧化还原共聚物	Zn	90/25	-35～ 25	-38	-35 ℃：178/2C	2021^[54]
ZnOTf₂-DMF	有机电解质	菲醌大环三聚体(PQ-MCT)	Zn	18.9/25	-70～150	-70.8	-70 ℃：31.3/0.2	2020^[59]
PVA/G	凝胶电解质	δ-MgVO	Zn	10.7/-30	-30～60	-30	-30 ℃:136.7/5	2020^[68]
PVA-B-G	凝胶电解质	MnO₂	Zn	10.1/-30	-35～25	-60	-35 ℃：133.8/0.5	2020^[69]
21 mol/L LiTFSI+3 mol/L ZnOTf₂+PVA	高浓度凝胶电解质	V₂O₅/GO	Zn	2.1/20	0～40	—	0 ℃：325/0.02	2020^[43]
2 mol/L ZnSO₄+4 mol/L LiCl+PAM	高浓度凝胶电解质	LiFePO₄	Zn	—	-20～25	-45	-20 ℃：104/0.1	2019^[70]
海藻酸锌/PAM	水凝胶电解质	MnO₂	Zn	14.1/-20	-20～80	-30～-20	-20 ℃：165/0.2	2019^[44]
1 mol/L Zn(TFSI)₂+ 21 mol/L LiTFSI +PAM	高浓度凝胶电解质	[EMIM]PF₆-PEDOT:PSS/Bi₂S₃	Zn	—	—	—	0 ℃：73/1	2019^[45]
6 mol/L OH^-/ PANa	高浓度凝胶电解质	NiCo	Zn	5.7/-20	-20～50	—	-20 ℃：172/1.9C	2018^[75]
PAMPS-K/ MC	双网络水凝胶电解质	空气	Zn	18.1/-20	-20～25	-30	-20 ℃：754.2/824.6 mWh/g	2020^[79]
EG-waPUA+PAM	双交联水凝胶电解质	α-MnO₂/CNT	Zn	14.6/-20	-20～20	-24	-20 ℃：196/0.3	2019^[34]
EG+PVA	电解质添加剂	PANI	Zn	2.89/-30	-30～20	—	-20 ℃：101.2/0.1	2021^[87]
Et₂O+EG+2 mol/L ZnSO₄+0.2 mol/L MnSO₄	电解质添加剂	MnO₂	Zn	0.42/-10	-10～25	—	-10 ℃：65.1/3	2020^[88]
2 mol/L ZnSO₄+0.1 mol/L MnSO₄+GG/SA/EG	电解质添加剂	MnO₂	Zn	6.19/-20	-20～25	—	-20 ℃：181.5/0.1	2020^[90]
2 mol/L ZnSO₄/0.2 mol/L MnSO₄/甘油 /纤维素/ TEOS (CT3G30)	电解质添加剂	rGO/MnO₂	Zn	19.4/-40	-40～60	-64.6	-20 ℃：181.5/0.1	2021^[91]
ZnSO₄：CH₃COONH₄	电解质添加剂	Zn	Zn	—	-10～25	—	—	2022^[92]
0.05 mol/L SnCl₂-7.5 mol/L ZnCl₂	共晶电解质	VOPO₄	Zn	0.8/-70	-70～ 20	—	-70 ℃：48.7/—	2021^[102]

表1

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锌离子电池低温性能研究进展

The research process on low temperature performance of zinc ion batteries

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