Treating CsPbI_(3) Perovskite with Pyrrolidinium Iodide to Improve the Performance of Perovskite Solar Cells

All-inorganic CsPbI_(3) perovskite has attracted wide attention due to its desirable optical bandgap(Eg:∼1.7 eV)as well as high chemical stability.Nevertheless,the photovoltaic performance of CsPbI_(3) perovskite solar cells(PSCs)was limited by severe nonradiative charge recombination due to high defect density at the grain boundary and surface of perovskitefilms.To address this issue,a pyrrolidinium iodide(PyI)molecule was introduced to modify the surface and grain boundary of CsPbI_(3) perovskitefilms to passivate defects,which improves the quality of CsPbI_(3) perovskitefilms as well as induces the generation of a quasi-2D Py_(2)CsPb_(2)I_(7) capping layer between per-ovskite layer and hole transport layer.Such quasi-2D Py_(2)CsPb_(2)I_(7) capping layer optimizes interface contact between CsPbI_(3) perovskite layer and hole transport layer and blocks the electron transfer from CsPbI_(3) perovskite photoactive layer to the hole transport layer.As a result,the performance of CsPbI_(3) PSCs is well improved to 17.87%for power conversion efficiency(PCE)with an ultra-high fill factor(FF)of 0.84.In addition,the PyI mole-cule modified CsPbI_(3) perovskite devices exhibit excellent stability,which remains its initial PCE almost unchanged after aging for 35 days under the dry air atmosphere(temperature:20℃–30℃,control relative humid-ity(RH):<10%).

Synthesis and characterization on a novel series of protic pyrrolidinium surfactants

A novel series of protic tertiary pyrrolidinium surfactants were prepared and characterized by different techniques.These compounds show good conductivity and efficient ability to reduce surface tension.Thermogravimetric analysis proves their high thermal stability at decomposition temperatures over 250℃.Their lyotropic and thermotropic liquid crystalline properties are also discussed.

Separation and determination of pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection

A method for rapid and simultaneous determination of multiple pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection was developed.Chromatographic separations were performed on a cation exchange column using ethylenediamine-acetonitrile as the mobile phase.The effects of chromatographic column and the mobile phase,as well as the column temperature on the retention of the cations were investigated.The retention rules of the cations under different chromatographic conditions were formulated.The retention of the cations followed the carbon number rule.The method has been successfully applied to the determination of three ionic liquids synthesized by a chemical laboratory.

Rapid and simultaneous determination of piperidinium and pyrrolidinium ionic liquid cations by ion pair chromatography coupled with direct conductivity detection

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.

四氢吡咯烷离子液体液晶研究

合成了亲水性和疏水性的饱和杂环类离子液体N-十六烷基-N-甲基四氢吡咯烷溴化物与四氟合硼酸盐,采用偏光显微镜、变温X射线衍射仪和热化学等方法,研究两类离子液体液晶结构、自组装过程和相转变等特性,研究负离子对饱和杂环类离子液体自组装行为的影响.结果发现,该两种离子液体均可在熔点以上形成层状液晶,负离子结构与大小对离子液体液晶的结构与性质具有非常重要的影响,BF4-比Br-体积大,使吡咯烷环和环上的长碳链以较大的间隔排列,形成分子在近晶平面层内有序分布,结构非常接近固态的近晶型液晶.

新型吡咯烷键合反相高效液相色谱固定相的制备与研究（英文）

A new ionic liquid-based high-performance liquid chromatography stationary phase is reported.A derivative of N-methyl pyrrolidinium tetrafluoroborate was covalently immobilized on the surface of silica particles to prepare silica-based N-methyl pyrrolidinium tetrafluoroborate(SilprMP BF4)stationary phase.The obtained ionic liquid-modified silica was evaluated and confirmed by elemental analysis,infrared spectroscopy,and thermogravimetric analysis.A column was packed with the modified particles.The retention behavior of aromatic compounds,alkyl benzenes,and acidic and basic compounds on the SilprMP BF4 stationary phase was studied under reversed-phase liquid chromatography conditions.The effect of the eluent pH on the separation of the acidic and basic compounds was also studied.The new stationary phase involves multiple retention mechanisms,such as electrostatic,hydrophobic,ion-dipole,and anion-exchange interactions,which might lead to multipurpose separation media.

质子化吡咯烷表面活性剂的有序聚集行为

合成了一系列不同链长的质子化吡咯烷类表面活性剂,通过核磁共振和差示扫描量热法进行了结构和热分析,进一步结合变温偏光显微镜进行分析,结果表明,此类化合物通过升温可以形成排列有序的T相热致液晶,形成温度随链长的增加逐渐升高。此类化合物还可以在水中形成胶束,临界胶束浓度随着表面活性剂链长的增加逐渐降低,继续升高表面活性剂浓度,可以形成溶致液晶。

离子液体[MBPy]Tf2N的光谱特征及荧光法检测

为满足疏水性离子液体N-甲基-N-丁基吡咯烷双三氟甲烷磺酰亚胺盐（[MBPy]Tf2N）在甘草酸生物催化体系中分析检测的需要,研究了[MBPy]Tf2N的光谱特征,并考察了溶剂、醇-水混合溶剂和p H值对[MBPy]Tf2N荧光特性的影响,建立了生物催化体系中[MBPy]Tf2N的荧光光谱检测方法.研究结果表明,[MBPy]Tf2N在186 nm处有1个最大吸收峰,常规紫外检测法不适于对其进行检测;[MBPy]Tf2N荧光光谱最大激发波长为228 nm,发射波长为340 nm,且其耐光褪色性良好,在水溶液中荧光量子产率为0.067,在醇-水混合溶剂中其荧光强度有增大趋势,在碱性介质中其荧光强度受影响较大;荧光光谱法检测[MBPy]Tf2N的检出限（S/N=3）为1.00μg/m L,标准曲线在5.00-1.25×10^3μg/m L浓度范围内线性关系良好（R2=0.9999）,生物反应液中加标回收率为97.4%-107.4%（相对标准偏差RSD=4.6%）.

塑晶基离子液体合成及其电化学性能

通过简单、易于工业化的重结晶方法制备了高纯1-甲基-1-乙基吡咯烷鎓双(三氟甲基磺酰)亚胺盐(P12TFSI)塑晶化合物.在此化合物中加入30%(摩尔分数,x)双(氟磺酰)亚胺锂(Li FSI)后,得到P12TFSI/Li FSI塑晶基离子液体.采用循环伏安法、恒电压极化法及恒电流充放电法等电化学方法考察了该离子液体的电化学窗口、铝箔集流体的腐蚀性及电池性能.结果表明,该离子液体电解质具有5.00 V的电化学窗口,室温离子电导率达到0.92 m Scm-1,且不腐蚀Al集流体.以该塑晶离子液体作为电解液组装的实验电池Li Co O2/Li表现出良好的充放电特性及循环性能,在较低倍率下能够和使用碳酸酯类电解液组装的实验电池的性能相媲美.在4.50 V高电压下,循环20周后,容量仍能保持在175 m Ahg-1,容量保持率为95.1%.这些结果说明该离子液体在高性能锂二次电池中具有良好的应用前景.

新离子型添加剂对高镍锂离子电池性能影响研究

研究了一种新离子型负极成膜添加剂2D对NMC811/石墨电池性能的影响,并与当前最常用商业化负极成膜添加剂VC进行对比试验。微分容量dQ/dV显示2D先于EC和VC在2.1 V左右还原,在石墨负极形成较稳定的SEI膜,交流阻抗结果表明含2D成膜阻抗明显低于VC;含2D、VC、2D和VC复合电解液的NMC811/石墨电池的倍率循环、高温存储和高温循环等测试结果表明,含2D电解液电池的石墨负极钝化膜更加稳定,有效提升锂离子电池的循环、存储和倍率性能,60℃存储含2D电池的电压和电阻变化较小,高温循环200周后,不含2D添加剂电池容量损失达15%,含2D电池容量保持率在92%以上。