A generalized reduced fluid dynamic model for flow fields and electrodes in redox flow batteries

High-dimensional models typically require a large computational overhead for multiphysics applications, which hamper their use for broad-sweeping domain interrogation. Herein, we develop a modeling framework to capture the through-plane fluid dynamic response of electrodes and flow fields in a redox flow cell, generating a computationally inexpensive two-dimensional (2D) model. We leverage a depth-averaging approach that also accounts for variations in out-of-plane fluid motion and departures from Darcy's law that arise from averaging across three-dimensions (3D). Our resulting depth-averaged 2D model successfully predicts the fluid dynamic response of arbitrary in-plane flow field geometries, with discrepancies of <5% for both maximum velocity and pressure drop. This corresponds to reduced computational expense, as compared to 3D representations (<1% of duration and 10% of RAM usage), providing a platform to screen and optimize a diverse set of cell geometries.     

Modeling flow distribution and pressure drop in redox flow batteries

The combination of interdigitated flow fields (IDFF) with porous electrodes offers lower pressure drop and better performance than conventional flow‐through porous electrodes in redox flow batteries. Comprehensive three‐dimensional and simplified one‐dimensional + two‐dimensional models describing flow uniformity and pressure losses within flow through, parallel, and interdigitated flow fields were developed and used to demonstrate the benefits of IDFF. Analytical solutions for IDFF that compare favorably with computational fluid dynamics quantify the trade between pressure loss and velocity maldistribution both along the channels and within the electrode. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3746–3755, 2018     

Comparing velocities and pressures in redox flow batteries with interdigitated and serpentine channels

Serpentine channels adjacent to a thin, porous medium are a potentially attractive alternative to a conventional thick flow-through electrode for redox flow batteries. The hydrodynamics of serpentine flow fields were investigated with computational fluid dynamics, a two-dimensional model of the porous electrode based on Darcy's law, and a resistance network model at the scale of the active area. Predictions from the three models were used to map the available design space. The optimal electrode thickness, in terms of minimizing nonuniformity, was identified and compared to the result for an interdigitated flow field. Serpentine favors thicker electrodes and higher flows than interdigitated, in qualitative agreement with experimental findings. Furthermore, interdigitated designs deliver more uniform intraelectrode velocities and lower overall pressure drops than serpentine flow fields.     

Pressure drop through platinized titanium porous electrodes for cerium‐based redox flow batteries

The pressure drop, , across a redox flow battery is linked to pumping costs and energy efficiency, making fluid properties of the electrolyte important in scale‐up operations. The at diverse platinized titanium electrodes in Ce‐based redox flow batteries is reported as a function of mean linear electrolyte velocity measured in a rectangular channel flow cell. Darcy's friction factor and permeability vs. Reynolds number are calculated. Average permeability values are: 7.10 × 10^?4 cm² for Pt/Ti mesh, 4.45 × 10^?4 cm² for Pt/Ti plate + turbulence promoters, 1.67 × 10^?5 cm² for Pt/Ti micromesh, and 1.31 × 10^?6 cm² for Pt/Ti felt. The electrochemical volumetric mass transport coefficient, , is provided as a function of . In the flow‐by configuration, Pt/Ti felt combines high values with a relatively high , followed by Pt/Ti micromesh. Pt/Ti mesh and Pt/Ti plate gave a lower but poorer electrochemical performance. Implications for cell design are discussed. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1135–1146, 2018     

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。     

Chromium redox couples for application to redox flow batteries

Both anodic and cathodic chromium-EDTA (ethylenediaminetetra-acetate) complex redox processes have been studied using cyclic voltammetry. Their potential use in a redox battery has been evaluated by comparing the charge and discharge performance of a simple redox battery employing several redox couples including the conventional Fe-Cr redox couples. The cyclic voltammetry experiments suggested that oxidation of Cr(III)-EDTA formed Cr(V)-EDTA rather than a hexavalent chromium species. It was found that the kinetics of the Cr(III)-EDTA/Cr(II)-EDTA redox reaction are fast at a graphite rod electrode, whereas the Cr(V)-EDTA/Cr(III)-EDTA redox reaction is relatively slow. In spite of the slow kinetics, the battery employing solely these chromium-EDTA based redox couples provided higher energy output and longer life than the conventional Fe-Cr redox system.     

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。     

锌溴液流电池通道的计算流体力学模拟

针对不同类型的锌溴液流电池通道,利用流体力学计算软件 FLUENT对流体的流动状态进行了模拟。结果表明,在相同流速条件下,直角通道和弯角通道流体的局部流速最大值都出现边壁突变处;在液流电池反应区,流体的局部流速和湍流程度的分布存在不均匀现象。通过改变进出反应区的分流通道数量和结构,可以使电解液在反应区流动均匀,改进整个流动体系的传质性能,进而使锌溴液流电池电堆的充放电性能得到提高。     

多硫化钠/溴液流电池研究进展

介绍了多硫化钠/溴液流电池(PSB)的原理与特点及其正负极电极材料的制备、离子交换膜改性及电池组等方面的国内外技术发展现状,指出PSB目前急待解决的问题是高性能低成本的离子交换膜、高稳定性的电极材料的研制及电池组结构优化设计。     

Nafion membranes with a sulfonated organic additive for the use in vanadium redox flow batteries

Sulfonated copper phthalocyanine (CuPCSA) was embedded into Nafion membranes in ratios of 0, 1.25, 2.5, 5, and 7.5 wt %. The absence of CuPCSA related peaks in WAXS patterns indicated that CuPCSA did not form crystalline phases during membrane formation. Tensile strength and Young's modulus were highest in the range of 2.5–5 wt % CuPCSA. As demonstrated for Nafion 212, the weight gain and swelling in water-based solutions decreases when the sulfuric acid concentration increases from 0 to 2 M. In 2 M sulfuric acid, addition of CuPCSA increases the weight gain. In contact with VO₂⁺, blue CuPCSA is oxidatively hydrolyzed to form colorless sulfonated phthalimide. XPS analysis showed that (1) this reaction is quantitative and (2) that the sulfonated phthalimide does not leach out from the membrane during operation in the flow battery. The coulomb efficiency increases with the amount of phthalimide. This affects the energy efficiency so strongly, that it follows the same trend as the coulomb efficiency. During cycling, the cell with Nafion/7.5 wt % filler showed the highest discharge capacity and the lowest difference between charge and discharge capacity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47547.     

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.     

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.     

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%。     

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。     

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。     

全钒液流电池电解液分布的数值模拟

为了提高全钒液流电池双极板流道电解液分布均匀性,考察流体流动行为,本文基于计算流体力学,在传统平直并联流道基础上通过增加倾斜挡板和入口流堰,改进流道结构;同时探究钒电池用电解液在分段式多通道蛇形流道内流体水力学特征。数值模拟结果表明：分段式多通道蛇形流道既可以保持传统蛇形流道流体均匀分配的性能,又能有效降低流阻,减少泵耗;合适的电解液流速及其均匀分布可以优化电解液活性物质浓度分布,提高电解液稳定性,增大钒电池能量效率。     

全钒液流电池用离子交换膜的研究进展

由于全钒氧化还原液流电池(VRB)具有大规模储能和稳定发电的特点,引起了国内外的广泛关注。离子交换膜(IEM)是VRB中的重要组件,它不仅要隔开阴阳极电解液,而且还要传输离子以构成闭合回路。对全钒液流电池用离子交换膜做了系统介绍。从离子交换膜的基本功能出发,详细阐述了近年来国内外全钒液流电池用离子交换膜的研究进展及目前面临的问题,并展望了全钒液流电池大规模商业化应用的前景。     

全钒液流电池用非氟咪唑型阴离子交换膜的制备

在全钒电池(VFB)用离子交换膜中,阴离子交换膜以其钒离子渗透率低这一主要优势受到了广泛的关注。以N-溴代丁二酰亚胺(NBS)为溴化试剂,2,2'-偶氮二异丁腈(AIBN)为引发剂,对聚苯醚(PPO)的苄甲基溴化;以N-正丁基咪唑为功能化试剂,制备了一种非氟咪唑型聚苯醚阴离子交换膜。研究了不同N-正丁基咪唑功能化程度的阴离子交换膜的离子传导率、离子交换容量(IEC)、含水率、钒离子传递系数等性能,并与N-甲基咪唑功能化的阴离子交换膜做了对比。结果显示,N-正丁基咪唑功能化聚苯醚阴离子交换膜的钒离子传递系数为4.8×10^-9 cm·min^-1,60℃时离子传导率为10.8 mS·cm^-1,且化学稳定性及力学性能优异,具有在钒电池中应用的潜力。     

全钒液流电池用磺化聚芴醚酮质子交换膜的制备及性能

质子交换膜(PEM)作为全钒液流电池(VRFB)的核心组件之一,应当解决成本高昂、合成过程复杂等问题,并具备高质子传导率、低钒离子渗透率、高机械强度和优异化学稳定性等关键性能。本文基于四甲基双酚芴单体通过缩聚反应合成了一系列聚芴醚酮化合物PFEKs,再利用溴代反应将苯甲基功能化为溴甲基,接着通过4-羟基苯磺酸钠的SN₂亲核取代制得了一系列不同离子交换容量的磺化聚芴醚酮聚合物(SPFEKs)。通过溶液浇铸法成膜并酸化,得到一系列新型低成本PEMs。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。所得膜都具有良好的机械性能和氧化稳定性,其中SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的VRFB在电流密度为80 mA/cm₂^{时的能量效率}(EE)为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量仅衰减至84.3%,远高于以Nafion 212膜组装的VRFB的66.1%。