Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(te...Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.展开更多
A method of ion-pair chromatography with direct conductivity detection was developed on a silicabased monolithic column for the fast and simultaneous determination of piperidinium and pyrrolidinium ionic liquid cation...A method of ion-pair chromatography with direct conductivity detection was developed on a silicabased monolithic column for the fast and simultaneous determination of piperidinium and pyrrolidinium ionic liquid cations. The effects of the mobile phase, column temperature and flow rate on the retention of the cations were investigated. The retention rules were discussed. As an ion-pair reagent, sodium heptanesulfonate is more suitable than sodium pentanesulfonate for the separation and determination of piperidinium and pyrrolidinium cations. The increase of ion-pair reagent concentration led to the increased retention time of the cations. When acetonitrile content and mobile phase flow were increased, the retention time of the cations became shorter. The retention of piperidinium and pyrrolidinium cations is an exothermic process, and the retention of the cations conforms to the carbon number rule. The chromatographic analysis was performed using the Chromolith Speed ROD RP-18 e column, 0.5 mmol/L sodium heptanesulfonate-5% acetonitrile as the mobile phase at a flow rate of3.0 m L/min and column temperature of 30℃. Separation of N-methyl-N-ethyl piperidinium, N-methylN-propyl piperidinium, N-methyl-N-butyl piperidinium and N-methyl-N-ethyl pyrrolidinium, Nmethyl-N-propyl pyrrolidinium, N-methyl-N-butyl pyrrolidinium cations were achieved within10 min. The detection limits（S/N = 3） were between 0.19 and 3.08 mg/L. Relative standard deviations（n = 5） for peak areas were less than 1.2%. The method has been applied to the determination of piperidinium and pyrrolidinium cations in ionic liquid samples. The spiked recoveries of ionic liquid cations were between 96% and 111%. The method is accurate, reliable, rapid, and has a better practicability.展开更多
A new series of poly(arylene piperidinium)-based anion exchange membranes(AEMs)are proposed for vanadium redox flow batteries(VRFBs).The AEMs are fabricated via the Menshutkin reaction between poly(arylene piperidine)...A new series of poly(arylene piperidinium)-based anion exchange membranes(AEMs)are proposed for vanadium redox flow batteries(VRFBs).The AEMs are fabricated via the Menshutkin reaction between poly(arylene piperidine)without ether bonds in the backbone and various quaternizing agents,including iodomethane,1-bromopentane,and(5-bromopentyl)-trimethylammonium bromide.The properties of the AEMs are investigated in terms of sulfuric acid doping content,swelling,vanadium permeability,ion selectivity,area-specific resistance,mechanical properties,VRFB performance,and cyclic testing.Particularly,a method of measuring the H^(+) permeability of the AEM is developed.It demonstrates that the poly(p-terphenyl-N-methylpiperidine)-quaternary ammonium(PTP-QA)membrane with a QA cation-tethered alkyl chain exhibits high H^(+) permeability,resulting in low area resistance.Combined with its low vanadium permeance,the PTP-QA membrane achieves nearly 370 times higher ion selectivity than Nafion 115.The VRFB based on PTP-QA-based AEM displays high Coulombic efficiencies above 99% at current densities of 80-160 mA cm^(-2).The higher energy efficiency of 89.8% is achieved at 100 mA cm^(-2)(vs.73.6% for Nafion 115).Meanwhile,the PTPQA-based AEM shows good cycling stability and capacity retention,proving great potential as the ion exchange membrane for VRFB applications.展开更多
【目的】在不同灌水量条件下研究增效缩节胺(1,1-dimethyl-piperidinium chloride,缓释型水乳剂,简称DPC+)对棉花化学封顶的效应,为完善新疆棉花化学封顶技术提供依据。【方法】以早熟陆地棉品种新陆早53号为材料,设置不同的灌水量(3000...【目的】在不同灌水量条件下研究增效缩节胺(1,1-dimethyl-piperidinium chloride,缓释型水乳剂,简称DPC+)对棉花化学封顶的效应,为完善新疆棉花化学封顶技术提供依据。【方法】以早熟陆地棉品种新陆早53号为材料,设置不同的灌水量(3000,4800,6600 m3·hm^(-2))和DPC+剂量(450,750,1050 m L·hm^(-2)),测定棉花农艺性状、生理特性及产量和品质等指标。【结果】棉花株高和单株果枝数随DPC+剂量的增加而下降,低(450m L·hm^(-2))、中(750 m L·hm^(-2))、高剂量(1050 m L·hm^(-2))DPC+处理的株高和单株果枝分别比人工打顶增加9.4cm和4.8个,6.2 cm和3.9个,2.2 cm和2.6个。中等灌水量(4800 m3·hm^(-2))下棉花产量最高,比低灌水量(3000m3·hm^(-2))处理增产20%左右,比高灌水量(6600 m3·hm^(-2))处理增产5%左右。低、中、高灌水量下,分别以低、中、高剂量DPC+的产量最高,一般较人工打顶提高5%~10%。低灌水量下低剂量DPC+处理主要依靠较大的群体生物量获得相对较高的产量,高灌水量下高剂量DPC+处理主要依靠较高的产量器官干物质分配率获得相对较高的产量,而中等灌水量下中等剂量DPC+处理的产量在所有处理中最高,得益于比较适宜的冠层生产能力和合理的干物质分配能力。【结论】灌水量需要与DPC+剂量互相配合,在增加群体物质生产能力的同时保障营养生长和生殖生长协调,这是提高棉花DPC+化学封顶技术成功率的关键途径之一。展开更多
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22379143)。
文摘Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.
基金supported by the Natural Science Foundation of Heilongjiang Province (No. B201307)
文摘A method of ion-pair chromatography with direct conductivity detection was developed on a silicabased monolithic column for the fast and simultaneous determination of piperidinium and pyrrolidinium ionic liquid cations. The effects of the mobile phase, column temperature and flow rate on the retention of the cations were investigated. The retention rules were discussed. As an ion-pair reagent, sodium heptanesulfonate is more suitable than sodium pentanesulfonate for the separation and determination of piperidinium and pyrrolidinium cations. The increase of ion-pair reagent concentration led to the increased retention time of the cations. When acetonitrile content and mobile phase flow were increased, the retention time of the cations became shorter. The retention of piperidinium and pyrrolidinium cations is an exothermic process, and the retention of the cations conforms to the carbon number rule. The chromatographic analysis was performed using the Chromolith Speed ROD RP-18 e column, 0.5 mmol/L sodium heptanesulfonate-5% acetonitrile as the mobile phase at a flow rate of3.0 m L/min and column temperature of 30℃. Separation of N-methyl-N-ethyl piperidinium, N-methylN-propyl piperidinium, N-methyl-N-butyl piperidinium and N-methyl-N-ethyl pyrrolidinium, Nmethyl-N-propyl pyrrolidinium, N-methyl-N-butyl pyrrolidinium cations were achieved within10 min. The detection limits（S/N = 3） were between 0.19 and 3.08 mg/L. Relative standard deviations（n = 5） for peak areas were less than 1.2%. The method has been applied to the determination of piperidinium and pyrrolidinium cations in ionic liquid samples. The spiked recoveries of ionic liquid cations were between 96% and 111%. The method is accurate, reliable, rapid, and has a better practicability.
基金supported by the National Natural Science Foundation of China(51603031)the Fundamental Research Funds for the Central Universities of China(N2005026)+1 种基金Liaoning Provincial Natural Science Foundation of China(20180550871 and 2020-MS-087)the Innovation Fund Denmark(DanFlow)。
文摘A new series of poly(arylene piperidinium)-based anion exchange membranes(AEMs)are proposed for vanadium redox flow batteries(VRFBs).The AEMs are fabricated via the Menshutkin reaction between poly(arylene piperidine)without ether bonds in the backbone and various quaternizing agents,including iodomethane,1-bromopentane,and(5-bromopentyl)-trimethylammonium bromide.The properties of the AEMs are investigated in terms of sulfuric acid doping content,swelling,vanadium permeability,ion selectivity,area-specific resistance,mechanical properties,VRFB performance,and cyclic testing.Particularly,a method of measuring the H^(+) permeability of the AEM is developed.It demonstrates that the poly(p-terphenyl-N-methylpiperidine)-quaternary ammonium(PTP-QA)membrane with a QA cation-tethered alkyl chain exhibits high H^(+) permeability,resulting in low area resistance.Combined with its low vanadium permeance,the PTP-QA membrane achieves nearly 370 times higher ion selectivity than Nafion 115.The VRFB based on PTP-QA-based AEM displays high Coulombic efficiencies above 99% at current densities of 80-160 mA cm^(-2).The higher energy efficiency of 89.8% is achieved at 100 mA cm^(-2)(vs.73.6% for Nafion 115).Meanwhile,the PTPQA-based AEM shows good cycling stability and capacity retention,proving great potential as the ion exchange membrane for VRFB applications.
文摘【目的】在不同灌水量条件下研究增效缩节胺(1,1-dimethyl-piperidinium chloride,缓释型水乳剂,简称DPC+)对棉花化学封顶的效应,为完善新疆棉花化学封顶技术提供依据。【方法】以早熟陆地棉品种新陆早53号为材料,设置不同的灌水量(3000,4800,6600 m3·hm^(-2))和DPC+剂量(450,750,1050 m L·hm^(-2)),测定棉花农艺性状、生理特性及产量和品质等指标。【结果】棉花株高和单株果枝数随DPC+剂量的增加而下降,低(450m L·hm^(-2))、中(750 m L·hm^(-2))、高剂量(1050 m L·hm^(-2))DPC+处理的株高和单株果枝分别比人工打顶增加9.4cm和4.8个,6.2 cm和3.9个,2.2 cm和2.6个。中等灌水量(4800 m3·hm^(-2))下棉花产量最高,比低灌水量(3000m3·hm^(-2))处理增产20%左右,比高灌水量(6600 m3·hm^(-2))处理增产5%左右。低、中、高灌水量下,分别以低、中、高剂量DPC+的产量最高,一般较人工打顶提高5%~10%。低灌水量下低剂量DPC+处理主要依靠较大的群体生物量获得相对较高的产量,高灌水量下高剂量DPC+处理主要依靠较高的产量器官干物质分配率获得相对较高的产量,而中等灌水量下中等剂量DPC+处理的产量在所有处理中最高,得益于比较适宜的冠层生产能力和合理的干物质分配能力。【结论】灌水量需要与DPC+剂量互相配合,在增加群体物质生产能力的同时保障营养生长和生殖生长协调,这是提高棉花DPC+化学封顶技术成功率的关键途径之一。
