钒氧化还原流电池技术综述

doi:10.13229/j.cnki.jdxbgxb20210047

摘要/Abstract

摘要：

钒氧化还原流电池（VRFB）具有响应速度快、储能量巨大、成本低、效率高、使用寿命长和低污染等特点，在大型储能系统领域有着广泛的应用潜力。虽然钒氧化还原流电池已被商用，但是其能量密度与效率仍然受电极活性、温度稳定性、膜内交叉污染和极化损失等因素的限制。针对当前钒氧化还原流电池领域的研究热点，从电池的电极、电解液、隔膜以及双极板流场4个方面分别展开综述，阐述VRFB技术的工作原理，介绍VRFB不同组件及其最新的研究现状，总结了限制VRFB进一步发展的技术因素，探讨这些限制的解决方法，并对VRFB技术今后的发展进行了展望与分析。

关键词: 钒氧化还原流电池, 储能设备, 可再生能源, 能量效率, 能量损失

Abstract:

Vanadium redox flow battery （VRFB） has a brilliant future in the field of large energy storage system （EES） due to its characteristics including fast response speed， large energy storage capacity， low cost， high efficiency， long service life and low pollution. Although vanadium redox flow batteries have been widely used in commercial applications， their energy density and efficiency are limited by electrode activity， temperature stability， cross contamination， and voltage loss. This review， which includes the four aspects of electrode， electrolyte， membrane， and bipolar plate on VRFB， mainly illustrates the working principle of VRFB technology， while introducing the different components of VRFB and their latest research status， summarizing the limitations of current VRFBs， and discussing the solutions to these limitations， so as to highlight the development direction of VRFB technology.

Key words: vanadium redox flow battery, energy storage system, renewable energy, energy efficiency, energy losses

中图分类号:

TK02

曲大为,杨帆,范鲁艳,冯啸宇,马家义. 钒氧化还原流电池技术综述[J]. 吉林大学学报(工学版), 2022, 52(1): 1-24.

Da-wei QU,Fan YANG,Lu-yan FAN,Xiao-yu FENG,Jia-yi MA. Review of vanadium redox flow battery technology[J]. Journal of Jilin University(Engineering and Technology Edition), 2022, 52(1): 1-24.

图/表 13

图1

表1

图2

表2

表3

图3

图4

图5

表4

表5

VRFB阴阳极电解液自放电副反应方程式"

电极	电解液中离子		反应方程式
阳极	阳极离子通过膜侵入阴极电解液	VO₂⁺	① $V O 2 + + 2 V 2 + + 4 H + → 3 V 3 + + 2 H 2 O$
		VO²⁺	② $V O 2 + + V 2 + + 2 H + → 2 V 3 + + H 2 O$
		VO₂⁺	③ $V O 2 + + V 3 + → V O 2 +$
阴极	阴极离子通过膜侵入阳电解液	V²⁺	④ $V 2 + + 2 V O 2 + + 2 H + → 2 V O 2 + + H 2 O$
		V³⁺	⑤ $V 3 + + V O 2 + → 2 V O 2 +$
		V²⁺	⑥ $V 2 + + V O 2 + + 2 H + → 2 V 3 + + H 2 O$

表5

图6

图7

图8

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优点	缺点
1.阴阳极电解液成分均为钒元素，电解液通过膜造成的交叉污染程度很小。	1.为了防止电解液发生沉淀，需要将电池温度环境控制在10~40 ℃范围内，稳定工作温度范围较窄。
2.即使存在小程度的交叉污染，可对阴阳极电解液充电，来平衡正负电解液，使得浓度达到原先的设定范围。	2.V⁵⁺具有很强的氧化性，将恶化离子交换膜，阳极材料发生腐蚀；而V²⁺极易被空气中氧气氧化，需要对阴极电解液通入保护气与氧隔绝，增加了成本。
3.电池的效率较高，可达到70%~90%，随着将来材料（用于电极、离子交换膜、双极板等）的发展，VRFB的效率将会更高。	3.由于析氢副反应的存在，钒氧化还原流电池的充电过程耗能增加；由于吸氧副反应的存在，电池的双极板和电极会受到腐蚀，缩短电池的寿命。
4.相比于其他氧化还原流电池，VRFB在快速的充电循环中，副反应产生的程度小，产生氢气和氧气较少。	4.VRFB在高电流密度的工作状态下会发生严重的极化，进一步降低系统的能量密度。
5.电解液在泵的推动下，在管路中循环利用，电解液具有可回收的特点。	5.电池系统中各组件之间（串联电堆、电解液管道）的密封性不足，会导致电解液的泄露，造成正负极电解液容量的不平衡。
6. 无论是运行还是待机的工况下，没有任何污染物以及CO₂等温室气体的排放。	5.电池系统中各组件之间（串联电堆、电解液管道）的密封性不足，会导致电解液的泄露，造成正负极电解液容量的不平衡。

电流密度 /（mA·cm^-2）	工作循环数	电池效率/%
电流密度 /（mA·cm^-2）	工作循环数	库仑效率	电压效率	能量效率
10	1	78.3	91.1	71.3
	50	83.2	91.5	76.1
	100	80.3	91.6	73.6
20	1	83.6	86.3	72.2
	50	83.9	86.4	72.5
	100	85.4	85.8	73.3
30	1	86.5	81.8	70.7
	50	86.3	81.9	70.7
	100	86.6	81.8	70.8
40	1	87.6	72.5	63.5
	50	90.7	72.1	65.4
	100	87.6	71.4	62.5

电极优化方法	类型	优点	不足
热处理	化学方法	操作容易、成本较低	反应较为剧烈，不利于控制
酸处理	化学方法	反应程度较为温和，易于控制	防腐要求较高
金属粒子修饰	化学方法	改性效果最好，电极效率提升明显	金属催化剂的成本较高，制备工艺较复杂
电极压缩	物理方法	操作容易、成本较低	不可过度压缩，优化能力有限

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