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 ...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.展开更多
PAN-based graphite felt （PGF） treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery （VRB）. Structure and ...PAN-based graphite felt （PGF） treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery （VRB）. Structure and characteristic of treated PAN-based graphite felt （TPGF） were determined by means of Fourier Transform Infi-ared Spectroscopy, Scanning Electron Microscopy, Brunauer-Emmett-Teller surface area analysis and VRB test system. The results show that the acid and heat synergistic effect increase the number of --COOH functional groups on the PGF surface, and the PGF is eroded by sulphuric acid oxidation, resulting in the surface area increases from 0.31 m^2/g to 0.45 m^2/g. The V（ Ⅱ ）/V（Ⅲ） redox reaction is electrochemically reversible on the TPGF electrode, while the V（Ⅳ）/V（Ⅴ） couple is a quasi reversible process. The diffusion coefficients of the oxidation for V（Ⅳ）/V（Ⅴ） obtained from the scope of peak current Ip vs scan rate v^1/2 is 4.4×10^-5 cm^2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of ---COOH groups on the TPGF, which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.展开更多
首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化...首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,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膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为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次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。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。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。展开更多
荷电状态(state of charge,SOC)和峰值功率(state of peak power,SOP)的精确估计对保障电池安全稳定运行具有重要意义。为解决传统估计算法误差高、鲁棒性差等问题,本文提出了一种基于自适应无迹卡尔曼滤波(adaptive unscented Kalman f...荷电状态(state of charge,SOC)和峰值功率(state of peak power,SOP)的精确估计对保障电池安全稳定运行具有重要意义。为解决传统估计算法误差高、鲁棒性差等问题,本文提出了一种基于自适应无迹卡尔曼滤波(adaptive unscented Kalman filtering,AUKF)和经济模型预测控制(economic model predictive control,EMPC)的全钒液流电池(all-vanadium redox batteries,VRB)SOC/SOP联合估计方法。首先,为了提高传统模型的建模精度,本文综合考虑了VRB的电化学场和流体力学场的耦合特性,建立了一个能够全面刻画VRB运行过程的综合等效电路模型,并采用人工蜂群算法(artificial bee colony algorithm,ABC)对模型参数进行离线辨识。随后,考虑到传统的UKF算法无法适应系统噪声,收敛性差,且忽略电池参数变化等缺点,本文提出了基于AUKF的在线参数辨识和SOC估计算法,通过自适应调整UKF算法的参数来提高模型的精度。结合SOC的估计结果,采用EMPC算法估计VRB的SOP,并综合考虑了电压、电流、SOC和电解液流速等约束条件。最后,设计了多种实验工况验证了本文提出的SOC/SOP联合估计算法的精度。文章研究内容能够为液流电池不同运行状态下峰值功率预测和储能电站的精准调度提供依据。展开更多
基金Project(Xiang Zu [2016] 91) supported by the “100 Talented Teams” of Hunan Province,ChinaProject(2018RS3077) supported by the Huxiang High-level Talents Program,China+2 种基金Project(22002009) supported by the National Natural Science Foundation of ChinaProject(2021JJ40565) supported by the Natural Science Foundation of Hunan Province,ChinaProject(19C0054) supported by the Scientific Research Foundation of Hunan Provincial Education Department,China。
文摘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.
基金financially supported by grants from the National Natural Science Foundation of China (No. 51422301)Beijing Higher Education Young Elite Teacher Project (No. 29201493)the Fundamental Research Funds for the Central Universities(No.YWF-16-BJ-Y-68)
基金Project (03GKY3015) supported by the Foundation of Hunan Provincial Department of Science and Technology
文摘PAN-based graphite felt （PGF） treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery （VRB）. Structure and characteristic of treated PAN-based graphite felt （TPGF） were determined by means of Fourier Transform Infi-ared Spectroscopy, Scanning Electron Microscopy, Brunauer-Emmett-Teller surface area analysis and VRB test system. The results show that the acid and heat synergistic effect increase the number of --COOH functional groups on the PGF surface, and the PGF is eroded by sulphuric acid oxidation, resulting in the surface area increases from 0.31 m^2/g to 0.45 m^2/g. The V（ Ⅱ ）/V（Ⅲ） redox reaction is electrochemically reversible on the TPGF electrode, while the V（Ⅳ）/V（Ⅴ） couple is a quasi reversible process. The diffusion coefficients of the oxidation for V（Ⅳ）/V（Ⅴ） obtained from the scope of peak current Ip vs scan rate v^1/2 is 4.4×10^-5 cm^2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of ---COOH groups on the TPGF, which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.
文摘首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,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膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为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次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。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。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。
