大规模蓄电储能全钒液流电池研究进展

全钒液流电池是一种新型蓄电储能设备,不仅可以用作太阳能、风能发电过程配套的储能装置,还可以用于电网调峰,提高电网稳定性,保障电网安全。本文综述全钒液流电池的国内外技术发展状况,包括研究开发历史、电池关键材料和典型工艺过程;展望大规模蓄电储能的电池技术未来发展趋势。     

全钒液流电池关键材料研究进展

全钒液流电池是一种新型高效电能转化与储存装置。由于其电池输出功率与储能容量彼此独立,适用于风能、太阳能等可再生能源发电过程和电网调峰过程作为规模化储能装置使用。本文在介绍全钒液流电池原理基础上,重点围绕电池过程的关键材料展开讨论,包括电极材料的种类、各自特点与电极改性方法;电池隔膜材料的筛选结果、材料改性方法等国内外研究进展。     

Membrane stability studies for vanadium redox cell applications

Accelerated degradation tests of selected membranes were carried out to determine their stability in the fully charged positive electrolyte solution of the vanadium redox battery. Each membrane was soaked in both 1.0 and 0.1 M V(V) solutions for extended periods of time and UV–visible spectroscopy was used to determine the rate of oxidation of the membrane by V(V) to produce V(IV) ions in solution. The membranes were then evaluated for any changes in their resistance, IEC, diffusivity and water transfer properties. FESEM was used to analyse the membranes for physical damage. Different trends were observed in the 1.0 and 0.1 M V(V) electrolytes. Of the membranes studied, Nafion 112E/H⁺ showed the worst stability in the 0.1 M V(V) solution but one of the best stabilities in 1.0 M V(V). The dilute V(V) electrolyte appears to enter the pores of the membrane more readily as the membranes swell significantly in this solution. The 0.1 M V(V) solution therefore causes accelerated deterioration of the membrane performance as a result of physical destruction, chemical modification or a combination of both. The effect is more pronounced in the membranes that have a higher degree of swelling in the vanadium electrolyte.     

Modification and evaluation of membranes for vanadium redox battery applications

Several commercial ion exchange membranes were evaluated for application in the vanadium redox battery. The polyether membrane, DF120 cationic exchange membrane, showed the highest permeability to vanadium ions and the worst chemical stability in V(V) solution, while the divinylbenzene membrane, JAM anionic exchange membrane, showed the lowest permeability to vanadium ions and the best chemical stability in V(V) solution. In order to impart some cationic exchange capacity to the JAM anionic exchange membrane, sodium 4-styrenesulfonate was used to modify the anionic membrane by in situ polymerization. Measurements by infrared spectroscopy (IR) and cationic ion exchange capacity (IEC) verified that the modification procedure imparts cationic exchange capability to the membrane. Incorporation of cationic exchange groups to the anionic exchange membrane further results in a reduction in permeability to vanadium ions. The current and energy efficiencies averaged over 8 charge/discharge cycles of the cell with the treated JAM membrane were higher than that with the untreated JAM membrane. The current and energy efficiencies of the cell with the treated JAM membrane did not change over several charge/discharge cycles, which indicates good chemical stability of the treated membrane in the vanadium redox cell. The average efficiencies of the cell with the treated JAM membrane are higher than that with Nafion 117 over 8 charge/discharge cycles.     

暂态边界电压法在线测试全钒液流电池阻抗

国内首次采用暂态边界电压法在线研究了全钒液流电池（VRB）的特性,建立了由电压源、电阻以及一个电阻与电容并联的3部分串联而成的等效电路模型;研究了电流密度和荷电状态（SOC）对等效电路元件的影响。实验结果表明,极化阻抗随电流密度的增加有轻微下降,在充电初期和放电末期达到最大值。与极化阻抗相比,充、放电过程中的欧姆阻抗最大,是导致电压损失的主要因素,分别为1.905Ω?cm2和 2.139 Ω?cm2,暂态边界电压法是一种简单且有效的表征全钒液流电池性能的新方法。     

全钒氧化还原液流电池的发展现状

简要介绍了全钒氧化还原液流电池的工作原理,并对钒电池的组成及其电解液的制备方法和钒电池的分类及市场前景进行了简明叙述。列举了钒电池在国外的商业化情况,并简要分析了国内外钒电池的发展过程和研究现状。中国风能、太阳能等可再生资源储量丰富,对环境友好的大容量存储电池需求迫切,因此认为近几年中国全钒氧化还原液流电池具有良好的发展前景,这将会极大促进中国钒资源的开发。     

全钒液流电池模拟与仿真研究进展

全钒液流电池(VRB)的模拟和仿真是电池系统设计、放大、控制和优化的基础。根据VRB模型的复杂程度,本文详细介绍了VRB经验和半经验模型的研究内容,重点分析了近年来发展迅速的机理模型研究,对比分析了每个模型的优缺点,指出了VRB模拟和仿真未来的研究方向主要是建立接近真实的模型以及与实际运行控制系统联合,同时模拟仿真的实体也应从单电池向电堆、模块和电池系统发展。     

全钒液流电池用质子传导膜研究进展

全钒液流电池(VRB)作为一种大规模蓄电储能装备,在可再生能源发电和节能技术领域将发挥重要作用。质子传导膜是VRB中的关键材料之一,其作用主要有两方面:传导质子连通电堆内电路;阻止正负极电解液间不同价态钒离子的相互渗透,避免能量损失。质子传导膜性能对电池效率和成本有重要影响。在分析VRB基本原理基础上,阐明质子传导膜需同时满足优良的导电性、阻钒性、稳定性和合理成本等要求。以高分子膜的化学组成与物理结构的演化过程为线索,分别论述三类膜材料,包括Nafion系列膜、非全氟型质子传导膜、纳米尺度孔径的多孔膜。在归纳现有膜材料化学结构、物理性质与电学性能的基础上,阐述高性能质子传导膜的重点研究方向与发展前景。     

钒液流电池变电流快速充电方法

  基于电池快速充电基本原理,采用了变电流间歇恒压充电方法,并结合正交试验方法,对自制单片钒液流电池进行了一系列的充放电测试,获得了最佳充电参数。结果表明：采用变电流间歇恒压充电方法,充电时间相比恒流恒压充电方法缩短近50%;且获得了大致相同的放电容量,放电比率为100%;多次充放电循环后,放电容量未见衰减,取得了良好充电效果。     

Corrosion behavior of a positive graphite electrode in vanadium redox flow battery

The graphite plate is easily suffered from corosion because of CO₂ evolution when it acts as the positive electrode for vanadium redox flow battery. The aim is to obtain the initial potential for gas evolution on a positive graphite electrode in 2 mol dm⁻³ H₂SO₄ + 2 mol dm⁻³ VOSO₄ solution. The effects of polarization potential, operating temperature and polarization time on extent of graphite corrosion are investigated by potentiodynamic and potentiostatic techniques. The surface characteristics of graphite electrode before and after corrosion are examined by scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The results show that the gas begins to evolve on the graphite electrode when the anodic polarization potential is higher than 1.60 V vs saturated calomel electrode at 20 °C. The CO₂ evolution on the graphite electrode can lead to intergranular corrosion of the graphite when the polarization potential reaches 1.75 V. In addition, the functional groups of COOH and CO introduced on the surface of graphite electrode during corrosion can catalyze the formation of CO₂, therefore, accelerates the corrosion rate of graphite electrode.     

羟基自由基对全钒液流电池石墨毡电极的性能影响

采用H2SO4和H2O2的分解产物羟基自由基,对石墨毡电极进行表面处理。循环伏安法和交流阻抗测试显示,处理后石墨毡的阴阳极峰电流分别提高160.96%和120.24%,极化反应电阻从74.95 Ω·cm2显著降低至18.92 Ω·cm2。红外光谱测试表明石墨毡处理后表面含有大量含氧亲水基团,拉曼光谱测试结果显示处理后石墨毡的石墨化度降低,进一步证明了石墨毡电极表面受到了不同程度的氧化。X射线光电子能谱测试显示石墨毡处理后的含氧量提高0.58%,定量地证明了红外光谱和拉曼光谱的测试结果。采用自制静态单电池对石墨毡电极进行测试,处理后石墨毡的充放电容量分别提高37.04%和22.22%,表明该方法处理石墨毡电极能够显著提高全钒液流电池性能。     

全钒液流电池电解液流场结构优化设计

全钒液流电池电解液流场结构合理可使电流密度、钒电解液分布均匀,降低极化,提高电池性能。设计3种不同的电解液流场,研究流场结构对电池极化、充放电电流电压、功率密度和能量效率的影响。结果表明蛇形流场结构简单且易于加工,可使钒电解液均匀分布,增强电解液对流传质能力,能较充分利用钒电解液储能容量,电池的输出功率密度最高可达31.6 mW/cm2,与传统平行流场相比,电池电流效率提高13.9%,电压效率提高6.3%,能量效率提高14.8%,放电容量提高了35.3%。     

Effect of organic additives on positive electrolyte for vanadium redox battery

Fructose, mannitol, glucose, d-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge–discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of d-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding d-sorbitol, which can be interpreted as the increase of available (–OH) groups providing active sites for electron transfer. The Raman spectra show that VO²⁺ ions take part in forming a complex with the d-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.     

离子液体BMIMBF4对全钒液流电池正极电解液的影响

为提高全钒液流电池的能量密度和正极电解液稳定性,采用循环伏安、交流阻抗等方法,研究了1-丁基-3-甲基咪唑四氟硼酸盐（BMIMBF₄）作为正极电解液添加剂对溶液稳定性和电化学反应活性的影响,并对其机理进行了初步探讨。实验结果表明,添加BMIMBF₄后,正极电解液中五价钒离子的稳定性显著提高,电解液的电化学反应活性也有所提升。当添加量为1%时,电池的单位体积电容量比有所增加,并且能量效率有所提升。     

Sulfonated polyimide/chitosan composite membrane for vanadium redox flow battery: Membrane preparation,characterization, and single cell performance

A novel sulfonated polyimide/chitosan (SPI/CS) composite membrane was prepared from self‐made SPI (50% of sulfonation degree) through an immersion and self‐assembly method, which was successfully applied in vanadium redox flow battery (VRB). The proton conductivity of SPI/CS composite membrane is effectively improved compared to the plain SPI membrane. The VO²⁺ permeability coefficient across SPI/CS composite membrane is 1.12 × 10^?7 cm² min^?1, which is only one tenth of that of Nafion® 117 membrane. Meanwhile, the proton selectivity of SPI/CS composite membrane is about eight times higher than that of Nafion® 117 membrane. In addition, the oxidative stability SPI/CS composite membrane is superior to that of pristine SPI membrane. The VRB single cell using SPI/CS composite membrane showed higher energy efficiency (88.6%) than that using Nafion® 117 membrane, indicating that SPI/CS composite membrane is a promising proton conductive membrane for VRB application. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

全钒液流电池开路电压模型

建立全钒液流电池六参数开路电压计算模型,揭示开路电压由电池总电势和VO₂⁺/VO²⁺电极电势决定,并与电解液中钒离子透膜扩散行为密切相关。模型计算得到开路电压存在两个电压平台和一个转折点,与实验结果较为一致。利用该模型计算了电池开路时电解液中4种钒离子浓度随时间的变化关系,指出电池电解液不均衡性是由不同价态钒离子在膜相的Donnan平衡和透膜扩散系数不同产生的。该模型可为优化电池操作提供理论指导,并可为电池长期运行时电解液管理提供工程指导。     

A simple model for the vanadium redox battery

A two-dimensional stationary model, based on the universal conservation laws and coupled with electrochemical reactions, is applied to describe a single all-vanadium redox flow cell. Emphasis is placed on studying the effects of applied current density, electrode porosity and local mass transfer coefficient on the cell performance. The model results indicate that bulk reaction rate depends on the applied current density. The transfer current density and over-potential increase almost twice as the applied current density doubled. A decrease in electrode porosity leads to a more rapid depletion of the reactant concentration, a higher integral average value of the transfer current density and a more uniform distribution of the over-potential. The local mass transfer coefficient only affects the value of the over-potential.     

木质素磺酸钠作为全钒液流电池添加剂的研究

摘要〖HTSS〗：采用电化学方法分析了不同含量木质素磺酸钠对钒电池正极电解液的影响。交流阻抗、紫外可见光谱和单电池充放电实验验证了木质素磺酸钠添加后的效果。分析结果表明：添加量为0.1% 时,电荷传递电阻由5.446Ω·cm2 减小到1.002Ω·cm2 ,双电层电容由4.16×10-4F·cm-2 减小到1.298×10-4F·cm-2 ,添加不同含量的木质素磺酸钠并没有显著影响激发态波长和吸光度,但是充放电性能显著提高,这表明木质素磺酸钠具有很强的化学及电化学稳定性,有利于提高钒离子的传导和电能的储存。     

Graphite–graphite oxide composite electrode for vanadium redox flow battery

A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer–Emmett–Teller method. The redox reactions of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.     

High-performance microfluidic vanadium redox fuel cell

We demonstrate a new microfluidic fuel cell design with high-surface area porous carbon electrodes and high aspect ratio channel, using soluble vanadium redox species as fuel and oxidant. The device exhibits a peak power density of 70 mW cm⁻² at room temperature. In addition, low flow rate operation is demonstrated and single pass fuel utilization levels up to 55% are achieved. The proposed design facilitates cost-effective and rapid fabrication, and would be applicable to most microfluidic fuel cell architectures.