有机电极材料在水系电池中的应用研究进展

doi:10.16085/j.issn.1000-6613.2023-0993

摘要/Abstract

摘要：

与商业化电池相比，水系有机电池（AOBs）具有低成本、高安全性、环保等特点，使其更适用于便携电子设备和电网储能应用。电极材料作为水系有机电池重要组成部分，在实现电池的高容量和长循环寿命方面起到至关重要的作用。基于绿色发展的需求，有机电极材料应具备理论比容量高、资源丰富、设计灵活性强等优点。本文综述了不同储能机理的有机电极材料的最新研究进展，包括羰基化合物、亚胺化合物、导电聚合物、COFs材料、MOFs材料以及复合材料等。同时总结了有机电极材料在水系电池中的导电性和溶解性问题，并提出了不同的解决策略。最后，讨论了水系有机电池的关键挑战以及未来努力方向，未来仍需要更多具有更好电子导电性和快速动力学的电极材料应用于水系有机电池。

关键词: 水系有机电池, 电极材料, 水系电解液, 有机化合物, 高安全性

Abstract:

Compared with present commercial batteries, aqueous organic batteries (AOBs), with improved safety, environmental benignity, and affordability, are very appealing for portable electronics and grid-scale applications. The electrode material is an important component of AOBs, which plays a critical role in achieving high energy and long cycle life of aqueous batteries. In the context of green development, organic electrode materials show advantages of environment friendliness, resource renewability and design flexibility. This paper reviewed the latest research progress of organic electrode materials with different storage mechanisms, including conducting polymers, carbonyl compounds, imine compounds, COFs/MOFs materials and compound materials, and summarizd their conductivity and dissolution issues. At the same time, their conductivity and dissolution issues, and strategies to enhance the electrochemical performance of organic electrode materials were also introduced. Finally, the critical challenges and future efforts of aqueous organic batteries were discussed. More organic electrode materials with better electronic conductivity and fast reaction kinetics were still needed to build AOBs.

Key words: aqueous organic batteries, electrode materials, aqueous electrolyte, organic compounds, improved safety

中图分类号:

TQ15

邵威, 马壮, 郑宏玮, 刘光举, 高翔, 谢健, 和庆钢. 有机电极材料在水系电池中的应用研究进展[J]. 化工进展, 2024, 43(7): 3872-3890.

SHAO Wei, MA Zhuang, ZHENG Hongwei, LIU Guangju, GAO Xiang, XIE Jian, HE Qinggang. Recent advances of organic materials for aqueous rechargeable batteries[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3872-3890.

图/表 18

参考文献 67

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材料结构	电解液	对电极	电极组成	放电容量 /mAh·g^-1，电流密度 /A·g^-1	倍率性能 /mAh·g^-1，电流密度 /A·g^-1	循环稳定性/%，循环次数	电池体系	参考文献
PT	1mol/L CaCl₂	—	PT∶AC 6∶3	150，5	86.1，100	66.6，3000	水系钙离子电池	[15]
PTO	4.4mol/L H₂SO₄	PbO₂	PTO∶羧基碳管 1∶1	395，0.04	331.8，8	96，1500	铅酸电池	[28]
PPTO	2.5mol/L Li₂SO₄	LiMn₂O₄	PPTO∶SP∶ PTFE	229	137.4，20C	80，3000	水系锂离子电池	[28]
PAQS	10mol/L KOH	AC	PAQS∶SP∶PTFE 7∶2∶1	200	—	176，1350	碱性水系电池	[28]
PQ	3mol/L Zn(CF₃SO₃)₂	Zn	PQ∶Super P∶PTFE 6∶3.5∶0.5	—	—	—	水系锌离子电池	[31]
C4Q	3mol/L Zn(CF₃SO₃)₂	锌箔	C4Q∶SP∶PVDF 6∶3.5∶0.5	335，0.02	—	87，1000	水系锌离子电池	[31]
PQ	2mol/L Zn(SO₄)₂	Zn	PQ：AC 6∶4	150，0.1	—	96.3，36000	水系锌离子电池	[32]
PT	17mol/L NaClO₄	NiHCF	PT∶KB∶PTFE 6∶3∶1	126，0.2	87.9，50	—	水系钠离子电池	[33]
锂化查尔酮	饱和Li₂SO₄	LiFePO₄	—	111.23，0.125C	58.9，1C	91，1000	水系锂离子电池	[34]
PTCDA	2mol/L ZnSO₄	Zn	PTCDA∶SP∶PVDF 6∶3∶1	136，0.01	77，1	80，2000	水系锌离子电池	[35]
PTCDA	0.8mol/L Mg(NO₃)₂	活性炭	PTCDA∶SP∶PVDF 7∶2∶1	125，0.02	70，0.5	—	水系镁离子电池	[36]
AQ	1mol/L Al₂(SO₄)₃	活性炭	AQ∶SP 7∶3	211，0.8	—	94.5，500	水系铝离子电池	[38]
PBQS	3mol/L Zn(CF₃SO₃)₂	Zn	PBQS∶KB∶PTFE 6∶3∶1	203，0.1C	126，5C	83，50	水系锌离子电池	[41]
NDA-△	—	锂箔	NDA-△：SP∶PVDF 5∶4∶1	146.4，0.1C	58.1，100C	—	锂离子电池	[42]
NTCDA	5mol/L LiNO₃	LiCoO₂	NTCDA∶ XE2 carbon∶PTFE 6∶3∶1	71，0.1	65，0.5	80，200	水系锂离子电池	[44]
PNFE	0.5mol/L Li₂SO₄	MnO₂	—	153.7，4C	86.2，128C	77.5，500	水系锂离子电池	[46]

材料结构	电解液	对电极	电极组成	放电容量 /mAh·g^-1，电流密度 /A·g^-1	倍率性能 /mAh·g^-1，电流密度 /A·g^-1	循环稳定性/%，循环次数	电池体系	参考文献
PT	1mol/L CaCl₂	—	PT∶AC 6∶3	150，5	86.1，100	66.6，3000	水系钙离子电池	[15]
PTO	4.4mol/L H₂SO₄	PbO₂	PTO∶羧基碳管 1∶1	395，0.04	331.8，8	96，1500	铅酸电池	[28]
PPTO	2.5mol/L Li₂SO₄	LiMn₂O₄	PPTO∶SP∶ PTFE	229	137.4，20C	80，3000	水系锂离子电池	[28]
PAQS	10mol/L KOH	AC	PAQS∶SP∶PTFE 7∶2∶1	200	—	176，1350	碱性水系电池	[28]
PQ	3mol/L Zn(CF₃SO₃)₂	Zn	PQ∶Super P∶PTFE 6∶3.5∶0.5	—	—	—	水系锌离子电池	[31]
C4Q	3mol/L Zn(CF₃SO₃)₂	锌箔	C4Q∶SP∶PVDF 6∶3.5∶0.5	335，0.02	—	87，1000	水系锌离子电池	[31]
PQ	2mol/L Zn(SO₄)₂	Zn	PQ：AC 6∶4	150，0.1	—	96.3，36000	水系锌离子电池	[32]
PT	17mol/L NaClO₄	NiHCF	PT∶KB∶PTFE 6∶3∶1	126，0.2	87.9，50	—	水系钠离子电池	[33]
锂化查尔酮	饱和Li₂SO₄	LiFePO₄	—	111.23，0.125C	58.9，1C	91，1000	水系锂离子电池	[34]
PTCDA	2mol/L ZnSO₄	Zn	PTCDA∶SP∶PVDF 6∶3∶1	136，0.01	77，1	80，2000	水系锌离子电池	[35]
PTCDA	0.8mol/L Mg(NO₃)₂	活性炭	PTCDA∶SP∶PVDF 7∶2∶1	125，0.02	70，0.5	—	水系镁离子电池	[36]
AQ	1mol/L Al₂(SO₄)₃	活性炭	AQ∶SP 7∶3	211，0.8	—	94.5，500	水系铝离子电池	[38]
PBQS	3mol/L Zn(CF₃SO₃)₂	Zn	PBQS∶KB∶PTFE 6∶3∶1	203，0.1C	126，5C	83，50	水系锌离子电池	[41]
NDA-△	—	锂箔	NDA-△：SP∶PVDF 5∶4∶1	146.4，0.1C	58.1，100C	—	锂离子电池	[42]
NTCDA	5mol/L LiNO₃	LiCoO₂	NTCDA∶ XE2 carbon∶PTFE 6∶3∶1	71，0.1	65，0.5	80，200	水系锂离子电池	[44]
PNFE	0.5mol/L Li₂SO₄	MnO₂	—	153.7，4C	86.2，128C	77.5，500	水系锂离子电池	[46]

种类	电解液	对电极	电极组成	放电容量/mAh·g^-1，电流密度/A·g^-1	倍率性能/mAh·g^-1，电流密度/A·g^-1	循环稳定性/%，循环次数	电池体系	参考文献
PANI	2mol/L ZnSO₄	Zn	—	160，1.5	—	79，700	水系锌离子电池	[52]
CLPy	30mol/L ZnCl₂	Zn	—	105，3	—	96.4，38000	水系锌离子电池	[53]
PPy	LiSO₄	LiCoO₂	PPy∶AB∶ PVDF 8∶1∶1	—	—	—	水系锂离子电池	[54]
Cu₃(HHTP)₂	3mol/L Zn(CF₃SO₃)₂	Zn	Cu₃(HHTP)₂∶AB∶PVDF 6∶2∶2	228，0.05	—	75，500	水系锌离子电池	[56]
PBA	0.5mol/L K₂SO₄	—	PBA∶AC∶PTFE 8∶1∶1	—	—	85，500	水系钾离子电池	[57]
PA-COF	1mol/L ZnSO₄	Zn	PA-COF∶AB∶PTFE 6∶3∶1	265，0.05	68，10	—	水系锌离子电池	[60]
HqTp	1mol/L CaCl₂	AC	PBA∶Super P∶PTFE 4∶4∶2	119.5，1	78.8，50	73.7，1600	水系钾离子电池	[61]

种类	电解液	对电极	电极组成	放电容量/mAh·g^-1，电流密度/A·g^-1	倍率性能/mAh·g^-1，电流密度/A·g^-1	循环稳定性/%，循环次数	电池体系	参考文献
PANI	2mol/L ZnSO₄	Zn	—	160，1.5	—	79，700	水系锌离子电池	[52]
CLPy	30mol/L ZnCl₂	Zn	—	105，3	—	96.4，38000	水系锌离子电池	[53]
PPy	LiSO₄	LiCoO₂	PPy∶AB∶ PVDF 8∶1∶1	—	—	—	水系锂离子电池	[54]
Cu₃(HHTP)₂	3mol/L Zn(CF₃SO₃)₂	Zn	Cu₃(HHTP)₂∶AB∶PVDF 6∶2∶2	228，0.05	—	75，500	水系锌离子电池	[56]
PBA	0.5mol/L K₂SO₄	—	PBA∶AC∶PTFE 8∶1∶1	—	—	85，500	水系钾离子电池	[57]
PA-COF	1mol/L ZnSO₄	Zn	PA-COF∶AB∶PTFE 6∶3∶1	265，0.05	68，10	—	水系锌离子电池	[60]
HqTp	1mol/L CaCl₂	AC	PBA∶Super P∶PTFE 4∶4∶2	119.5，1	78.8，50	73.7，1600	水系钾离子电池	[61]

材料分类	代表性材料	优点	缺点
羰基化合物	酮、醌、酰亚胺、酸酐	高容量、快速反应动力学	高溶解度、低电导率
导电聚合物	聚吡咯、聚苯胺	高电导率	低容量、倾斜放电平台
亚胺类化合物	吩嗪类、异咯嗪	高容量、快速反应动力学	高溶解度、低电导率
COFs	PA-COF	高容量	低电导率
MOFs	Cu₃(HHTP)₂	高电导率	—
复合材料	TTF-TCNQ	高电导率	—