Improving electrochemical properties of carbon paper as negative electrode for vanadium redox battery by anodic oxidation

Anodic oxidation with different electrolyte was employed to improve the electrochemical properties of carbon paper as negative electrode for vanadium redox battery(VRB).The treated carbon paper exhibits enhanced electrochemical activity for V^2+/V^3+redox reaction.The sample(CP-NH3)treated in NH3 solution demonstrates superior performance in comparison with the sample(CP-NaOH)treated in NaOH solution.X-ray photoelectron spectroscopy results show that oxygen-and nitrogen-containing functional groups have been introduced on CP-NH3 surface by the treatment,and Raman spectra confirm the increased surface defect of CP-NH3.Energy storage performance of cell was evaluated by charge/discharge measurement by using CP-NH3.Usage of CP-NH3 can greatly improve the cell performance with energy efficiency increase of 4.8%at 60 mA/cm^2.The excellent performance of CP-NH3 mainly results from introduction of functional groups as active sites and improved wetting properties.This work reveals that anodic oxidation is a clean,simple,and efficient method for boosting the performance of carbon paper as negative electrode for VRB.

KHCO_3 activated carbon microsphere as excellent electrocatalyst for VO^(2+)/VO_2^+ redox couple for vanadium redox flow battery

In this paper,carbon microsphere prepared by hydrothermal treatment was activated by KHCO_3 at high temperature,and employed as the catalyst for VO^(2+)/VO_2^+redox reaction for vanadium redox flow battery(VRFB).Carbon microsphere can be etched by KHCO_3 due to the reaction between the pyrolysis products of KHCO_3 and carbon atoms.Moreover,KHCO_3 activation can bring many oxygen functional groups on carbon microsphere,further improving the wettability of catalyst and increasing the active sites.The electrocatalytic properties of carbon microsphere from hydrothermal treatment are improved by high temperature carbonization,and can further be enhanced by KHCO_3 activation.Among carbon microsphere samples,the VO^(2+)/VO_2^+redox reaction exhibits the highest electrochemical kinetics on KHCO_3 activated sample.The cell using KHCO_3 activated carbon microsphere as the positive catalyst demonstrates higher energy efficiency and larger discharge capacity,especially at high current density.The results reveal that KHCO_3 activated carbon microsphere is an efficient,low-cost carbon-based catalyst for VO^(2+)/VO_2^+redox reaction for VRFB system.

Sucrose pyrolysis assembling carbon nanotubes on graphite felt using for vanadium redox flow battery positive electrode

In the present paper, multi-walled carbon nanotubes（MWCNTs） are successfully assembled on graphite felt（GF） using sucrose pyrolysis method for the first time. The in situ formed pyrolytic carbon is chosen as the binder because it is essentially carbon materials as well as CNTs and GF which has a natural tendency to achieve high bonding strength and low contact resistance. The MWCNTs/GF electrode is demonstrated to increase surface area, reduce polarization, lower charge transfer resistance and improve energy conversion efficiency comparing with GF. This excellent electrochemical performance is mainly ascribed to the high electro-catalytic activity of MWCNTs and increasing surface area.

Modified carbon cloth as positive electrode with high electrochemical performance for vanadium redox flow batteries

Carbon cloth modified by hydrothermal treatment in ammonia water is developed as the positive electrode with high electrochemical performance for vanadium redox flow batteries. The SEM shows that the treatment has no obvious influence on the morphology of carbon cloth. XPS measurements indicate that the nitrogenous functional groups can be introduced on the surface of carbon cloth successfully. The electrochemical performance of V(IV)/V(V) redox couple on the prepared electrode is evaluated with cyclic voltammetry and linear sweep voltammetry measurements. The N-doped carbon cloth exhibits outstanding electrochemical activity and reversibility toward V(IV)/V(V) redox couple. The rate constant of V(IV)/V(V) redox reaction on carbon cloth can increase to 2.27 x 10(-4) cm/s from 1.47 x 10(-4) cm/s after nitrogen doping. The cell using N-doped carbon cloth as positive electrode has larger discharge capacity and higher energy efficiency compared with the cell using pristine carbon cloth. The average energy efficiency of the cell using N-doped carbon cloth for 50 cycles at 30 mA/cm(2) is 87.8%, 4.3% larger than that of the cell using pristine carbon cloth. It indicates that the N-doped carbon cloth has a promise application prospect in vanadium redox flow batteries. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Glucose-derived hydrothermal carbons as energy storage booster for vanadium redox flow batteries

Fabricating of high performance electrodes by a sustainable and cost effective method is essential to the development of vanadium redox flow batteries(VRFBs).In this work,an effective strategy is proposed to deposit carbon nanoparticles on graphite felts by hydrothermal carbonization method.This in-situ method minimizes the drop off and aggregation of carbon nanoparticles during electrochemical testing.Such integration of felts and hydrothermal carbons(HTC)produces a new electrode that combines the outstanding electrical conductivity of felts with the effective redox active sites provided by the HTC coating layer.The presence of the amorphous carbon layers on the felts is found to be able to promote the mass/charge transfer,and create oxygenated/nitrogenated active sites and hence enhances wettability.Consequently,the most optimized electrode based on a rational approach delivers an impressive electrochemical performance toward VRFBs in wide range of current densities from 200 to 500 mAcm^-2.The voltage efficiency(VE)of GFs-HTC is much higher than the VEs of the pristine GFs,especially at high current densities.It exhibits a 4.18 times increase in discharge capacity over the pristine graphite felt respectively,at a high current density of 400 mAcm^-2.The enhanced performance is attributed to the abundant active sites from amorphous hydrothermal carbon,which facilitates the fast electrochemical kinetics of vanadium redox reactions.This work evidences that the glucose-derived hydrothermal carbons as energy storage booster hold great promise in practical VRFBs application.

Boosting catalytic activities of carbon felt electrode towards redox reactions of vanadium ions by defect engineering

Vanadium redox flow batteries(VRFBs)are one of the most promising energy storage systems owing to their safety,efficiency,flexibility and scalability.However,the commercial viability of VRFBs is still hindered by the low electrochemical performance of the available carbon-based electrodes.Defect engineering is a powerful strategy to enhance the redox catalytic activity of carbon-based electrodes for VRFBs.In this paper,uniform carbon defects are introduced on the surfaces of carbon felt(CF)electrode by Ar plasma etching.Together with a higher specific surface area,the Ar plasma treated CF offers additional catalytic sites,allowing faster and more reversible oxidation/reduction reactions of vanadium ions.As a result,the VRFB using plasma treated electrode shows a power density of 1018.3 mW/cm^(2),an energy efficiency(EE)of 84.5%,and the EE remains stable over 1000 cycles.

Properties of mesoporous carbon modified carbon felt for anode of all-vanadium redox flow battery

A novel anode material for all-vanadium redox flow battery was synthesized by dispersion coating of sol-gel processed(resorcinol-furaldehyde) mesoporous carbon(MPC) onto the surface of polyacrylonitrile carbon felt(CF).The coated samples were then annealed at 900℃ and1100℃ and the subsequent morphology,surface chemistry,and electrochemical properties of the MPC coated CF were characterized and compared with an uncoated CF.Addition of the MPC coating is shown to dramatically increase surface area while also increasing the number of active surface oxygen groups particularly for samples annealed at 1100℃.MPC coating shows a mixed effect on electrochemical properties.Characterization with cyclic voltammetry reveals the introduction of MPC coating provides roughly 30%increase in peak current density for the oxidation and reduction reactions of the V(IV)/V(V) redox couple,which is attributed to the significantly increased number of active reaction sites.However,MPC coating seems to be accompanied by a reduction in conductivity as demonstrated by increased redox peak separation and charge transfer resistance.This negative effect on conductivity can be mitigated by heat treatment(at or above 1100℃) which improves surface graphitization reducing redox peak separation and charge transfer resistance such that it is comparable with uncoated samples.

钒液流电池用碳纸电极改性的研究

采用红外光谱和扫描电镜等手段研究了浓硫酸处理前、后碳纸的表面结构和形貌的变化。并将这类碳纸用作全钒液流氧化还原电池电极材料,对其电化学性能进行了详细研究。结果表明通过酸处理,碳纸表面有-COOH官能团生成,其电化学活性增强。酸处理后的碳纸电极组装成的电池在电流密度20 mA.cm-2时有良好充放电性能,平均电流和电压效率达到95%和82%。

全钒氧化还原液流电池集流体的性能

用混炼法制备了以PP和SEBS共混物为基体材料、掺杂碳黑和碳纤维的高导电复合材料。用SEM、恒流充放电方法考察了复合材料的结构、形貌、力学性能及电化学性能。结果表明:导电介质在基体材料中高度分散,复合材料的体积电阻率小于0 1Ω·cm,组装的单体电池的充放电能量效率为84 5%。

钒液流电池用碳纸电极改性的研究

采用红外光谱、单点比表面积检测手段研究了碳纸435℃热处理前后的表面结构和比表面积的变化.并将这类碳纸用作全钒液流氧化还原电池电极材料,对其电化学性能进行了研究.结果表明:热处理10h的碳纸表面有-COOH官能团生成,比表面积显著增大,其电化学活性增强.热处理后的碳纸作为电极组装成的电池在电流密度50mA/cm2时有良好的充放电性能,平均电流和电压效率达到95%和89%.

钒(Ⅳ／Ⅴ)电对在碳纸电极上的反应机理研究

采用循环伏安、极化曲线和交流阻抗技术研究了在0.8mol·L-1VOSO4+3.0mol·L-1H2SO4中,V(Ⅳ/Ⅴ)电对在碳纸电极上的反应机理及可能的速度控制步骤。研究结果表明:V(Ⅳ/Ⅴ)电对在碳纸电极上的反应属准可逆过程,且氧化过程包含有后置化学转化步骤,计算得到VO2+的扩散系数为4.5×10-5cm2·s-1。理论计算得到了电化学步骤和后置化学转化过程分别为控制步骤时的Tafel斜率值为0.12和0.06,实验得到的Tafel斜率值为0.127,交换电流密度为6.7×10-4mA·cm-2。表明电极氧化过程受电化学过程控制,不同极化电位下的交流阻抗图谱拟合结果表明,电化学反应阻抗值远大于其他阻抗值,说明电化学反应可能是电极反应的控制步骤,与实验得到的极化曲线分析结果相一致。

电化学氧化改性石墨毡电极对VO^(2+)/VO_2^+电对的催化活性

采用循环伏安和恒流充放电试验研究了电化学氧化改性石墨毡对VO2+/VO+2电对的催化活性,并利用XPS、FT-IR、SEM、BET对改性前后石墨毡碳纤维表面O/C、官能团变化、形貌和比表面积进行比较。结果表明,电化学处理后,石墨毡表面的O/C比例由0.085增加至0.15,增加的主要是C OOH官能团。石墨毡碳纤维表面被刻蚀,比表面积有所增大。采用改性的石墨毡作为电极组装的全钒液流电池在50mA/cm2电流密度下,电压效率达75.99%,电流效率达96.79%,经多次循环性能稳定。电极活性的提高归因于碳纤维表面C OOH官能团数目的增加和比表面积的增大。

导电塑料作为钒电池集流板的研究

以聚乙烯为基体、炭黑为导电填料制备导电塑料板,研究了该导电塑料板导电性、力学性能以及在钒电池电解液中的电化学行为。导电塑料板与铜网复合后与石墨毡组成复合电极作为钒电池的正负极,考察了经过试验电池反复充放电后导电塑料集流板导电性与表面形貌的变化。研究结果表明导电塑料板可以代替石墨用作钒电池的集流板。当钒电池正极存在析氧过程时,会造成导电塑料集流板中的碳流失。

炭材料在全钒氧化还原液流电池中的电化学活性

炭材料在全钒氧化还原液流电池(钒电池)中主要用作电极。由于传统炭材料对钒电对氧化还原反应的电化学活性较差,因此,对以石墨毡为代表的炭材料电化学活性研究成为钒电池电极研究的重要组成部分。研究从石墨毡电极改性和炭材料作为催化剂应用两方面详述炭材料在钒电池中的电化学活性研究现状,先介绍含氧官能团和含氮官能团对钒电对氧化还原反应的电催化作用,回顾碳纳米管和石墨烯两类新型炭材料在钒电池中的应用。对炭材料电化学活性的今后研究工作进行展望,通过对炭材料性构关系的全面了解和对碳电极上的钒电对电化学反应过程动力学的深入研究,才能为炭材料在钒电池中的实际应用奠定扎实的理论和应用基础。

全钒液流电池用碳纳米管-石墨复合电极的研究

将石墨（GP）和多壁碳纳米管（MWNT）按不同比例压片制成电极,用于全钒氧化还原液流电池电极材料,通过循环伏安、交流阻抗、充放电测试、SEM手段对MWNT-GP复合电极进行表征和分析.研究结果表明,MWNT含量为15wt%的MWNT-GP复合电极性能最佳,对组装成的静态电池在电流密度20-80mA/cm^2进行充放电性能比较,电流效率均在93%以上,电压效率随着电流密度的增加而有所下降.

全钒液流电池用碳纸电极掺氮改性的研究（英文）

采用在氨气氛下加热(NCP-600:600℃下处理,NCP-900:900℃下处理)对全钒液流电池碳纸电极进行掺氮改性处理。通过此改性处理,含氮官能团成功地引入到碳纸表面。掺氮处理改善了碳纸表面的亲水性,NCP-900的接触角相比于空白碳纸由120.5°降到99.7°,且对表面形貌没有明显影响,不会影响其机械性能。同时,掺氮处理能明显地增强碳纸的电化学活性,循环伏安测试中,NCP-900的V(IV)/V(V)电对氧化峰为92.1 mA,远高于空白碳纸(68.9 mA)。由NCP-900和空白碳纸组装成电池考察了其充放电性能,在20 m A/cm2下进行充放电,由NCP-900组装的电池其能量效率为83.73%,较空白电池高2.59%。掺氮改性处理提高碳纸的电化学性能主要是由于钒电对活性位点的增加和亲水性能的增强。

全钒液流电池正极和负极材料的处理方法

为了获得大反应电流,全钒氧化还原液流电池使用聚丙烯腈基碳毡为电极活性材料.在空气中热处理碳毡可以增加其表面含氧官能团浓度,改善碳毡的亲水性,降低反应过电位.实验表明:电池的过电位主要由正极反应造成;热处理正极碳毡可以大大降低电池极化内阻,负极碳毡热处理后降低了析氢过电位,从而降低了电池的电流效率;正极使用热处理后的碳毡,负极使用未经处理的原毡,可以获得更好的电池能量效率.

氧化铅/碳纳米管复合材料的制备及其在钒电池中的应用

采用浸渍焙烧法制备了氧化铅/碳纳米管复合材料(PbO/CNTs).运用准稳态极化曲线、循环伏安以及电化学阻抗谱等方法研究了铅物种的引入对CNTs复合材料抑制析氢反应及电催化全钒氧化还原液流电池(VRFB)负极反应活性的影响,并采用恒电流充放电法对铅碳复合材料作为负极催化剂时VRFB的充放电稳定性进行了评价.实验结果发现:1A/cm^2时,引入PbO后CNTs析氢电位从-0.962 8V负移至-1.149V,PbO/CNTs复合材料具有良好的抑制析氢反应能力;同时,PbO/CNTs复合材料也显示出了更好的电催化VRFB负极反应的活性.同等条件下,以PbO/CNTs为负极催化剂的VRFB充放电容量比以CNTs为负极催化剂时高100~200mAh,并具有更好的容量稳定性.

水热氧化改性碳纸电极在全钒氧化还原电池中的应用(英文)

为了提高钒氧化还原电池电极的活性,在180°C下将碳纸电极与过氧化氢的硫酸溶液置于有聚四氟乙烯内衬的不锈钢反应釜中进行不同时间的水热酸氧化处理.水的接触角测试表明,随着处理时间从6h调整至18h,处理前后碳纸电极的接触角也从120.0°降低至100.8°,尤其是经过12h处理的样品的接触角最小,这说明在此条件下处理过的碳纸的亲水性得到了提高.而傅里叶变换红外测试表明,羰基和羧基等含氧基团被成功地引入到了碳纸电极中.使用扫描电镜,循环伏安,电化学阻抗以及充放电技术分别检测了处理前后样品的表面形貌及电化学性能.V(IV)/V(V)氧化还原电对在这些处理过的样品上表现出较大的活性.用处理12h的碳纸电极组装的单电池性能优异,在30mA·cm-2的电流密度下能量效率达到了80%,相应的电流效率和电压效率分别为96%和84%.

液相氧化法改性碳纳米管复合电极对钒电池性能的影响

为提升钒电池负极侧电极的电化学活性,采用液相氧化法对碳纳米管进行改性,并将其引入石墨毡表面制备复合电极。首先对碳纳米管与石墨毡的电化学性能进行对比,再通过液相氧化改性对碳纳米管的电化学活性进一步优化,最后制备了碳纳米管石墨毡复合电极,并采用充放电测试考察其性能表现。结果表明:在浓H_(2)SO_(4)与浓HNO_(3)体积比为1∶3,温度80℃,改性时间2 h条件下得到的碳纳米管电化学活性最佳。在120 mA cm 2的电流密度下,以复合电极为负极的电池电压效率和能量效率分别为87.96%、83.47%,分别比石墨毡(82.08%、77.31%)提高了5.88和6.16个百分点,具有良好的倍率性能。