水系锌离子电池二氧化锰正极改性研究进展

doi:10.19799/j.cnki.2095-4239.2022.0638

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (3): 754-767.doi: 10.19799/j.cnki.2095-4239.2022.0638

水系锌离子电池二氧化锰正极改性研究进展

婷婷¹^,²(), 林其杭¹^,², 刘长洋³, 卞刘振¹^,²^,⁴(), 孙超¹^,², 齐冀¹^,², 彭继华¹^,²^,⁴, 安胜利¹^,²^,³^,⁴()

^1.内蒙古科技大学材料与冶金学院
^2.内蒙古先进陶瓷材料与器件重点实验室，内蒙古包头 014010
^3.北京科技大学冶金与生态工程学院，北京 100083
^4.稀土资源绿色提取与高效利用教育部重点实验室，内蒙古包头 014010

收稿日期:2022-10-31 修回日期:2022-11-18 出版日期:2023-03-05 发布日期:2023-04-14
通讯作者: 卞刘振,安胜利 E-mail:borjiginting@163.com;liuzhenbian@126.com;shengli_an@ 126.com
作者简介:婷婷（1997—），女，硕士研究生，研究方向为锌离子电池， E-mail：borjiginting@163.com；
基金资助:
国家自然科学基金(52202257);内蒙古自治区自然科学基金博士基金(2020BS05032)

Research progress in modification of manganese dioxide as cathode materials for aqueous zinc-ion batteries

Ting TING¹^,²(), Qihang LIN¹^,², Changyang LIU³, Liuzhen BIAN¹^,²^,⁴(), Chao SUN¹^,², QI Ji¹^,², Jihua PENG¹^,²^,⁴, Shengli AN¹^,²^,³^,⁴()

^1.School of Materials and Metallurgy, Inner Mongolia University of Science and Technology
^2.Inner Mongolia Key Laboratory of Advanced Ceramic Materials and Devices, Baotou 014010, Inner Mongolia, China
^3.School of Metallurgical and Ecological Engineering, University of Science & Technology Beijing, Beijing 100083, China
^4.Key Laboratory of Green Extraction & Efficient Utilization of Rare-Earth Resources, Ministry of Education, Baotou 014010, Inner Mongolia, China

Received:2022-10-31 Revised:2022-11-18 Online:2023-03-05 Published:2023-04-14
Contact: Liuzhen BIAN, Shengli AN E-mail:borjiginting@163.com;liuzhenbian@126.com;shengli_an@ 126.com

摘要/Abstract

摘要：

水系锌离子电池(AZIBs)MnO₂正极材料由于具有较高的工作电压和低制造成本等特点而备受关注，MnO₂正极固有的导电性差和充放电过程中结构坍塌等问题，导致其比容量较低和循环稳定性较差，严重制约了AZIBs的发展。本文通过调研相关文献，综述了提高MnO₂正极材料电导率和循环稳定性的策略，重点介绍了MnO₂结构调控、纳米工程、掺杂改性和与高导材料复合等改性策略。通过分析不同晶体结构的MnO₂正极材料的电化学性能，建立了MnO₂晶体结构与电池比容量之间的构效关系。详细分析了不同的合成手段对MnO₂纳米形貌及电池比容量的影响，为不同形貌的MnO₂制备提供了指导。同时分析了元素体相掺杂以及高导电碳基材料的添加对MnO₂电导率和循环稳定性的影响规律。最后对高性能AZIBs用MnO₂正极材料的发展进行了展望，不同的改善策略可以混合使用，并起到协同作用。

关键词: 水系锌离子电池, MnO₂, 晶体结构, 纳米形貌, 优化策略

Abstract:

Due to its favorable operating voltage and affordable fabrication, MnO₂cathode for AZIBs has garnered considerable interest. However, the development of rechargeable Zn//MnO₂ batteries is severely restricted by the limited specific capacity and poor cycling stability arising from the inherently poor electrical conductivity and structural collapse of MnO₂ cathodes during the charge-discharge process. The common methods for increasing the conductivity and cycling stability of the MnO₂ cathode are discussed in this review through the use of related literature research and analysis. The relationship between the crystal structure of MnO₂ and the specific capacity of the battery was established by examining the electrochemical performance of various structures of MnO₂. Meanwhile, the effect of different synthesis methods on MnO₂ shapes was also summarized for MnO₂ synthesis in the future. Furthermore, a brief discussion of the improvement in conductivity and cycling stability of the MnO₂ cathode brought on by the addition of other elements to the MnO₂ lattice and carbon-based materials is provided. Finally, the future development of MnO₂ cathodes with high performance is investigated. The various enhancement strategies can be synergistically adopted to improve the electrochemical performance of the MnO₂ cathode.

Key words: aqueous zinc-ion battery, MnO₂, crystal structure, nanomorphology, optimization strategy

中图分类号:

TM 912

婷婷, 林其杭, 刘长洋, 卞刘振, 孙超, 齐冀, 彭继华, 安胜利. 水系锌离子电池二氧化锰正极改性研究进展[J]. 储能科学与技术, 2023, 12(3): 754-767.

Ting TING, Qihang LIN, Changyang LIU, Liuzhen BIAN, Chao SUN, QI Ji, Jihua PENG, Shengli AN. Research progress in modification of manganese dioxide as cathode materials for aqueous zinc-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(3): 754-767.

图/表 12

表1

图1

图2

图3

图4

图5

表2

AZIBs中掺杂改性后MnO2 材料的结构和电化学性能"

Cathode	Elactroyte	Voltage /V	Capacity	Capacity retention/ Capacity/n cls/y/(mA/g)	Ref.
Al-doped α-MnO₂ Nanospheres	0.5 mol/L Na₂SO₄	0～0.6	1127 mF/cm²(2 mA/cm²)	—	[46]
Cu-doped β-MnO₂ Nanorods	0.5 mol/L ZnSO₄	1～1.8	202.80 mAh/g	—	[47]
Cu-doped α-MnO₂Nanotubes	0.5 mol/L ZnSO₄	1～1.8	270.81 mAh/g	—	[47]
Cu-doped δ-MnO₂ Nanoflowers	0.5 mol/L ZnSO₄	1～1.8	205.54 mAh/g	—	[47]
Cu-doped γ-MnO₂ Nanostars	0.5 mol/L ZnSO₄	1～1.8	306.8 mAh/g	—	[47]
Cu-doped ε-MnO₂ Nanoflakes	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	0.8～1.8	235 mA/g(200 mA/g)	20/22%/60 cls	[48]
Cu-doped ε-MnO₂ Nanoflowers	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.8～1.9	493.3 mA/g(100 mA/g)	367.7/81%/150 cls /500	[34]
Cu-doped δ-MnO₂ Nanoflowers	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.8～1.9	363.7 mA/g(500 mA/g)	—	[34]
Bi-doped α-MnO₂ Nanoflowers	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.8～1.9	175.5 mA/g(100 mA/g)	114.5/99%/1100 cls /1000	[34]
Bi-doped α-MnO₂ Nanowires	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.8～1.9	325 mA/g(300 mA/g)	240/91%/2000 cls /1000	[27]
V-doped α-MnO₂ Nanoparticles	1 mol/L ZnSO₄	1～1.8	266 mA/g(66 mA/g)	131/50%/100 cls /100	[36]
Cr-doped α-MnO₂ Nanorods	1 mol/L KOH	-0.3～0.5	271 F/g(300 mA/g)	—	[37]
Cr-doped α-MnO₂ Nanorods	2 mol/L ZnSO₄	-1.5～1.5	257 mA/g(50 mA/g)	200/78%/10 cls /50	[49]
Fe-doped α-MnO₂ Nanorods	2 mol/L KOH	-0.3～0.4	620 F/g(1000 mA/g)	—	[38]
Fe-doped α-MnO₂@PPy	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.8～1.9	270 mA/g(100 mA/g)	100/75%/1000 cls /800	[50]
Ag-doped α-MnO₂ Nanorods	2 mol/L ZnSO₄	1～1.8	240 mA/g(50 mA/g)	—	[39]
Sn-doped α-MnO₂ Nanorods	1 mol/L ZnSO₄	-2～1.25	589 mA/g(50 mA/g)	557/95%/20 cls /50	[40]
Nb-doped α-MnO₂ Nanoparticles	2 mol/L ZnSO₄+0.5 mol/L MnSO₄	1～1.9	165 mA/g(1000 mA/g)	100/61%/50 cls /1000	[41]
Na-doped δ-MnO₂ Nanoparticles	1 mol/L ZnSO₄+0.1 mol/L MnSO₄	1～1.85	266 mA/g(100 mA/g)	130/80%/2000 cls /2000	[42]
Co-doped δ-MnO₂ Nanorflowers	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	1～1.85	250 mA/g(100 mA/g)	100/63%/5000 cls /2000	[43]
Co-doped δ-MnO₂ Nanorods@N-CC	2 mol/L ZnSO₄+0.07 mol/L MnSO₄	1～1.8	295 mA/g(93.5 mA/g)	280/100%/600 cls /1200	[51]
La-doped δ-MnO₂ Nanorflorets	1 mol/L ZnSO₄+0.4 mol/L MnSO₄	0.8～1.9	279 mA/g(100 mA/g)	175/71%/200 cls /800	[52]
La-doped δ-MnO₂ Nanoparticles	1 mol/L ZnSO₄+0.4 mol/L MnSO₄	0.8～1.9	227 mA/g(200 mA/g)	64/65%/200 cls /1600	[44]
Ca-doped δ-MnO₂ Nanoparticles	1 mol/L ZnSO₄+0.4 mol/L MnSO₄	0.8～1.9	216 mA/g(200 mA/g)	73/76%/200 cls /1600	[44]
La-Ca-doped ε-MnO₂ Nanoparticles	1 mol/L ZnSO₄+0.4 mol/L MnSO₄	0.8～1.9	297 mA/g(200 mA/g)	74/76%/200 cls /1600	[44]
Ce-doped β-MnO₂ Nanorods	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	1～1.8	260 mA/g(154 mA/g)	155/46%/400 cls /616	[45]

表2

图6

图7

表3

图8

图9

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Characteristic	Li	Na	K	Mg	Ca	Zn	Al
Standard Potential(verus SHE)/V	-3.040	-2.713	-2.924	-2.356	-2.840	-0.763	-1.676
Specific capacity/(mAh/g)	3860	1166	685	2206	1337	820	2980
Capacity density/(mAh/cm³)	2061	1129	610	3834	2072	5855	8046
Ionic radius/Å	0.76	1.02	1.38	0.72	1.00	0.75	0.53
Cost of metal anode/(USD/t)	16500	3527	19842	3307	—	2614	1744
Crustal abundance	17	23000	15000	29000	50000	79	82000

Cathode	Morphology	Elactroyte	Voltage /V	Capacity /(mA/g)	Capacity retention/ Capacity/n cls/y/(mA/g)	Ref.
δ -MnO₂/C	Nanoflower	2 mol/L ZnSO₄+0.5 mol/L MnSO₄	1.0～1.9	200(2000 mA/g)	279.7/92%/300 cls /300	[14]
β -MnO₂@CC	Nanolayer	3 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.98～1.8	326(100 mA/g)	80%/700 cls/2000	[53]
α -MnO₂/PCSs	Nanorods	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	1～1.9	350(100 mA/g)	—	[54]
α -MnO₂@ Porous-C	Nanorods	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	0.8～1.8	239(100 mA/g)	100%/1000 cls/1000	[65]
ε -MnO₂@CFP	Nanoparticles	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	1～1.8	290(1 C)	100%/1000 cls/6.5C	[55]
α -MnO₂/a-CNT	Nanorods	2 mol/L ZnSO₄+0.5 mol/L MnSO₄	1～1.9	400(1000 mA/g)	98%/500 cls/5000	[60]
γ -MnO₂/Graphene	Nanorods	2 mol/L ZnSO₄+0.4 mol/L MnSO₄	0.8～1.8	301(500 mA/g)	64%/300 cls/20 mA/cm²	[62]
α -MnO₂/Graphene Scroll	Nanowires	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	1～1.85	382(300 mA/g)	95%/100 cls/1000	[63]
α -MnO₂/Graphite	Nanospheres	2 mol/L ZnSO₄+0.5 mol/L MnSO₄	0.8～1.8	230(100 mA/g)	80%/1000 cls/1000	[64]
δ -MnO₂/Graphene Oxide	Nanosheets	1 mol/L ZnSO₄+0.1 mol/L MnSO₄	1～1.8	86(500 mA/g)	133/100 cls/100	[31]

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水系锌离子电池二氧化锰正极改性研究进展

Research progress in modification of manganese dioxide as cathode materials for aqueous zinc-ion batteries

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