氧化镍/碳纳米管复合型超级电容器的研制

通过电化学阴极还原的方法制备了氧化镍电极材料。经250℃脱水处理后氧化镍材料表现出法拉第赝电容的电化学特性且材料单电极比容量达到210F·g^-1，优于普通活性炭材料。本文采用催化裂解法制备了碳纳米管电极材料，比容量达到了42F·g^-1。提出了采用电化学法沉积氧化镍和碳纳米管分别作为电容器正负极的新工艺，该工艺制备的复合型超级电容器的工作电位达到了1.6V，且具有良好的大电流放电特性。实验还表明该型氧化镍超级电容器具有极低的自放电率。     

电化学超级电容器电极材料的研究进展

回顾了电化学超级电容器电极材料的研究进展，并对不同电极材料的储能原理和性能特点进行了简要的阐述。参考文献29篇。     

单壁碳纳米管用做超级电容器的电极材料

摘要本文研究了采用电弧放电法大规模合成的单壁碳纳米管（SWNT）用作超级电容器电极材料的电化学性能。N₂吸脱附测试表明SWNT既有发达的微孔，又有发达的中孔，其比表面为435 m².g^-1。由于既有双电层电容，又有表面官能团产生的准电容，采用浓硝酸处理后的单壁碳纳米管在水相电解液中的比电容达到105 F/g。基于SWNT的超级电容器也有着良好的充放电可逆性和循环稳定性。     

MnO2超级电容器充放电过程研究

采用机械化学法,在高锰酸钾和乙酸锰摩尔配比为1/1的条件下制备了弱结晶性α-MnO2。采用循环伏安、交流阻抗等方法对MnO2电极进行测试;对MnO2超级电容器在6mol/L KOH溶液中以1.2V放电窗口、200mA/g电流密度下进行充放电过程研究。结果表明,超级电容器在低电位范围表现出双电层电容,在高电位范围表现为法拉第假电容;Mn3O4电化学惰性物质主要在初始40次充放电过程中生成,其使循环伏安图中氧化还原峰逐渐消失、高电位法拉第假电容逐渐减小、放电曲线逐渐接近直线,表现为双电层电容特征。电极最大比容量为416F/g,200次循环后为240F/g,等效串联电阻由17Ω逐渐增到41Ω。     

绿色电化学储能器件超级电容器的实验设计与实践*

以超级电容器实验为例,将绿色化学科学研究转化为实验教学的基本设计思路,学习双电层电容器和法拉第准电容器的工作原理、组装及性能测试方法(循环伏安法和恒流充放电法),分析循环伏安曲线、比电容、能量密度和功率密度,总结2者的不同。实践结果表明:电化学基础和科学研究的成功联通,让学生对电化学概念和原理有了更深刻的理解,并获得关于清洁能源储存器件的实践经验,同时也增强了学生的绿色化学素养。     

超级电容器炭电极材料孔结构对其性能的影响

采用无瓶颈的系列酚醛树脂活性炭为电极材料，用氮吸附和恒流充、放电，以及交流阻抗法，研究孔径和孔表面积等孔结构对其性能的影响.结果表明，活性炭电极材料双电层电容与微孔(孔宽度< 2.0 nm)表面和外孔(孔宽度 >2.0 nm)表面都有关系，但主要取决于微孔表面双电层电容.微孔表面比电容为21.4 μF•cm－2，外孔表面比电容< 10 μF•cm－2.外孔表面比电容较低可能是由于空间电荷层的影响.微孔孔径较大的炭材料具有高比电容和良好的高倍率放电的特性.     

胶体离子超级电容器

超级电容器具有功率密度大、循环寿命长等优点,但同时面临着能量密度低等缺点. 胶体离子超级电容器是最近开发的一种新型赝电容器,同时具有高功率密度和高能量密度的特点. 胶体离子超级电容器能够充分利用多价态金属阳离子的多电子氧化还原反应,完全释放储存的潜在电能,从而提高超级电容器的能量密度. 由于胶体离子的存在,缩短了电子、离子的扩散长度,加快了氧化还原反应动力学,从而保持高的功率密度. 本文主要介绍胶体离子超级电容器的发展过程、最新研究进展以及需要进一步开展的研究工作,作者希望从一个新的角度去研究发展下一代高性能电化学储能设备,实现新的突破.     

胶体离子超级电容器的比容量评价

胶体离子超级电容器作为一种新型的超级电容器,其同时具有能量密度和功率密度高的独特优势。 目前已经发展了包括多种过渡金属阳离子和稀土阳离子,例如Mn²⁺、Fe²⁺、Co²⁺、Ni²⁺、Cu²⁺、Sn²⁺、Sn⁴⁺、La³⁺、Ce³⁺、Er³⁺和Yb³⁺的胶体离子超级电容器体系。 在电化学反应中,识别出电活性物质的存在形式对研究电极反应机理和提高比容量具有重要价值。 本文主要通过对电活性物质比容量的探讨,理解这种新型胶体离子超级电容器的电化学储能机理。 评述了胶体离子超级电容器的比容量核算方式,提出了以阳离子为标准核算比容量的原因,并与传统超级电容器的核算方式进行了比较,表明胶体离子超级电容器在提高能量密度方面具有潜在优势,有望突破现有电化学储能设备的技术瓶颈,实现下一代高能量储能器件的开发。     

高比能超级电容器的研究进展

与传统蓄电池相比,超级电容器具有高功率密度、长循环寿命和使用温度范围宽等优势,但其能量密度较低.本文对超级电容器的结构、分类以及发展状况进行了简要介绍,重点阐述了本实验室近年来在研制高性能超级电容器方面的相关工作.主要从两个方面来提高超级电容器的能量密度:(1)通过采用中性水系电解液、有机电解液和离子液体提高对称型碳基超级电容器的电压窗口;(2)应用非对称型超级电容器,即一个电极采用具有法拉第赝电容电极材料或电池电极材料,而另一个电极则采用具有双电层电容的电极材料.同时介绍了由锂离子电池电极材料/活性炭作为正极,石墨作为负极组成的锂离子混合型超级电容器.最后,对超级电容器的发展方向进行了展望.     

超级电容器炭电极材料的研究

炭电极材料是超级电容器的核心,该领域的研究近年来相当活跃,活性炭粉、活性炭纤维、碳凝胶、碳纳米管、玻态炭、模板炭、碳化物衍生炭、石墨烯等各种多孔炭材料用作超级电容器电极材料的研究都有报道.本文概述了我们近年来在超级电容器炭电极材料方面的研究工作,主要介绍了强碱化学活化制备活性炭电极材料、纳米CaCO3模板法制备介孔炭电...     

碳基双电层电容器的结构、机理及研究进展

活性炭基双电层电容器是一种新型电化学能量储存装置,其储电机理是利用电极材料比较大的比表面积在电极和电解液之间形成双电层储存电荷,充放电过程中无化学反应发生。活性炭材料由于具有较大的比表面积、良好的孔结构分布、化学惰性表面等,一直是双电层电容器电极的首选材料。本文简要介绍了双电层电容器的制造工艺、应用及发展趋势。     

Characterization of Microporous Activated Carbon Electrodes for Electric Double-layer Capacitors

IntroductionElectric double layer capacitors( EDLCs) witha high power density can be used as memory back-up devices or electric vehicles.EDLCs store energyin the electric double layer by charge accumulationon the interface between the electrode and the elec-trolyte. In order to obtain reasonable energies andpower densities,the more suitable material forEDLCs musthave a high surface area with a signif-icant value of specific double layer capacitance,better pore size distribution and electro…     

Molecular Dynamics Simulation: Influence of External Electric Field on Bubble Interface in Air Flotation Process

Molecular dynamics(MD) simulation was performed to investigate the influence of external electric field on the vapour-liquid interface of the bubble during the process of toluene separation by air flotation. The physicochemical properties of vapour-liquid interface, surface tension, probability of a hydrogen bonding near the vapour-liquid interface and the viscosity of liquid phase caused by external electric field were analyzed. The results show that the angle between the water molecule dipole moment and the normal z axis in the vapour phase changes smaller when the external electric field is applied. The surface tension and the probability of hydrogen bonding near the vapour-liquid interface increase with the increase of electric field strength. And the viscosity also increases under an external electric field. The results confirm that the external electric field has a positive effect on the performance of bubbles in air flotation, which may provide useful guidance for the combination of electric field and air flotation technology.     

Application of Protonic Acid-Doped Silica Gels to Electric Double-Layer Capacitors

Silica gels doped with several protonic acids such as HClO₄, H₂SO₄ and H₃PO₄ have been prepared by the sol-gel method and totally solid electric double-layer capacitors have been successfully fabricated using the highly proton-conductive silica gels as an electrolyte and activated carbon powder (ACP) hybridized with the silica gels as a polarizable electrode. It was found that the addition of HClO₄, which had the highest value of acid dissociation constant among these three acids, most effectively increased the proton conductivity of the resultant acid-doped silica gels. Tablets of the HClO₄-doped silica gels exhibited conductivities as high as 10^–5–10^–2 S cm^–1 at room temperature in dry N₂ atmosphere. One of the capacitors fabricated using the protonic acid-doped silica gels had a capacitance of 44 F/(gram of total ACP in the capacitor), which was comparable to those of conventional capacitors using liquid electrolytes.     

A Study on Pre-Oxidation of Petroleum Pitch-Based Activated Carbons for Electric Double-Layer Capacitors

Electric double-layer capacitors (EDLCs) are an excellent electrochemical energy storage system (ESS) because of their superior power density, faster charge–discharge ability, and longer cycle life compared to those of other EES systems. Activated carbons (ACs) have been mainly used as the electrode materials for EDLCs because of their high specific surface area, superior chemical stability, and low cost. Petroleum pitch (PP) is a graphitizable carbon that is a promising precursor for ACs because of its high carbon content, which is obtained as an abundant by-product during the distillation of petroleum. However, the processibility of PP is poor because of its stable structure. In this study, pre-oxidized PP-derived AC (OPP-AC) was prepared to investigate the effects of pre-oxidation on the electrochemical behaviors of PP. The specific surface area and pore size distribution of OPP-AC were lower and narrower, respectively, compared to the textural properties of untreated PP-derived AC (PP-AC). On the other hand, the specific capacitance of OPP-AC was 25% higher than that of PP-AC. These results revealed that pre-oxidation of PP induces a highly developed micropore structure of ACs, resulting in improved electrochemical performance.     

电场下离子型聚合物复合囊泡结构变化的分子动力学模拟

利用粗粒化分子动力学模拟研究了电场作用下离子型聚合物复合囊泡形变与破裂的过程.定量分析了囊泡破裂过程中的结构变化,包括囊泡的形变程度、破裂速度、组分分布以及破裂后的结构.研究表明,电场强度较弱时,囊泡表面所吸附的聚电解质首先脱落,囊泡由球形结构转变为椭球结构.随着电场强度增大,离聚物的离子侧基发生重新排布,囊泡表面电荷的有序结构被破坏,导致囊泡的结构无法维持而破裂,囊泡塌缩,分裂形成离聚物团簇,并进一步破裂为小尺寸的离聚物聚集体,均匀分散于溶液中.本文利用分子动力学模拟明确了电场中离子型高分子复合囊泡破裂过程的分子机理,为药物释放技术的优化及发展提供了理论支持.     

新型活性炭材料在双电层电容器中的应用研究

以椰壳为原料,利用特定的物理 化学方法在一定条件下制得双电层电容器活性炭电极材料.实验表明,该活性炭经压制成型后制作的双电层电容器,具有大的比电容,文中同时研究了酸处理、二次活化以及电极冷压成型方法对电极性能的影响.     

纳米结构表面浸润性质的分子动力学研究

采用分子动力学方法研究了氩纳米液滴在铂金属及其模型固体表面的浸润现象,获得了液滴在平滑表面和三角纳米结构阵列表面的接触角和展布特性.研究表明,液滴与壁面的势能作用较强时,液滴与纳米结构表面为均匀浸润,但是由于迟滞效应,接触角受表面纳米结构的影响不明显;势能作用较弱时,纳米结构间隙中存在类似蒸汽的低密度相,液滴与纳米结构表面为非均匀浸润,接触角受纳米结构的影响而增大;表面纳米结构可以使表面具有超疏水性.     

分子动力学模拟研究外电场对咪唑类离子液体振动谱的影响

本文利用分子动力学模拟研究了外电场对咪唑类离子液体1-乙基-3-甲基咪唑六氟磷酸盐(EMIMPF₆)从0到4000 cm⁻¹范围内振动谱的影响。研究结果表明,在没有外电场时利用分子动力学模拟计算得到的从400到4000 cm⁻¹的振动带可以重现实验测得的谱。当外电场从0到9 V·nm⁻¹变化时,在50.0和199.8 cm⁻¹处的振动带强度持续增强然后趋于饱和,而从400到4000 cm⁻¹的振动带强度明显减弱并最终消失。此外,在外电场从0变到2 V·nm⁻¹时,50.0 cm⁻¹的振动带红移了16.7 cm⁻¹,然后当外电场变化到3 V·nm⁻¹及更大时,该振动带红移增大到33.3 cm⁻¹。在外电场从0变到3 V·nm⁻¹时,3396.6 cm⁻¹的振动带红移大约16.7 cm⁻¹,然后当外电场增大到4 V·nm⁻¹甚至更大时,该振动带红移33.3 cm⁻¹,但是从0到4000 cm⁻¹的其他振动带的位置几乎没有变化。基于对模拟结果和先前报道文献的进一步分析,对于50.0 cm⁻¹的振动带,增加的外电场增强了阳离子和阴离子之间的极性使阳离子和阴离子间的偶极矩增大,因此该振动带的强度不断增大然后达到饱和。对于199.8 cm⁻¹的振动带增加的外电场增强了乙基链的扭转,使该振动带的强度增大并达到饱和。对于从400到4000 cm⁻¹的其他振动带,增加的外电场使EMIMPF₆中的阳离子和阴离子的取向更一致,并且可以推测这种更一致的取向可能会削弱振动带的强度甚至使它们消失。50.0 cm⁻¹处振动带的红移可能是由于外电场破坏了EMIMPF₆内部的静电场分布进而减弱了阳离子和阴离子间的相互作用。3396.6 cm⁻¹处振动带的红移可归功于外电场减弱了氮原子与阳离子咪唑环上酸性氢原子间形成的氢键的拉伸振动。对于其他的振动带,由于官能团固有的拉伸、弯曲、转动振动不受外电场的影响,外电场没有改变振动带的位置。     

Surface Modification and Performance of Activated Carbon Electrode Material

A commercial activated carbon was modified by surface treatment using three chemicals, nitric acid, hydrogen peroxide, and ammonia, respectively. The modified carbons were characterized by N₂ adsorption-desorption isotherms and FTIR spectroscopy. The resultant carbon electrode-based electric double-layer capacitors (EDLCs) were assembled with 6 mol·L⁻¹ KOH as the electrolyte. The influence of surface modification on the performance of EDLCs was studied by galvanostatic charge-discharge, cyclic voltammetry, and alternating current impedance. The surface modification resulted in no big decrease in specific surface area and little decrease in average pore size, and introduced functional groups, such as hydroxyl, carbonyl, and amidogen, on the carbon surface. These functional groups significantly improved the wettability and reduced the resistance of the activated carbon. As a result, the specific capacitance of the carbon modified with 65% HNO₃ reached 250 F·g⁻¹, 72.4% higher than that of original carbon. The leakage current of testing EDLCs decreased unexpectedly to 3-18 μA, only 0.8%-4.9% that of the original carbon electrode-based EDLC (371 μA).