A Reversible Redox Strategy for SWCNT‐Based Supercapacitors Using a High‐Performance Electrolyte

In order to achieve pesudocapacitive performance of single‐wall carbon nanotube (SWCNT) electrodes, a high‐efficient and reversible redox strategy utilizing a redox‐mediated electrolyte for SWCNT‐based supercapacitors is reported. In this novel redox‐mediated electrolyte, the single‐electrode specific capacitance of the supercapacitor is heightened four times, reaching C=162.66 F g^?1 at 1 A g^?1. The quick charge‐discharge ability of the supercapacitor is also enhanced, and the relaxation time is as low as 0.58 s. Furthermore, the supercapacitor shows an excellent cycling performance of 96.51 % retention after 4000 cycles. The remarkable results presented here illustrate that the redox strategy is a facile and straightforward approach to improve the performances of SWCNT electrodes.     

Substituent effect on supercapacitive performances of conducting polymer‐based redox electrodes: Poly(3′,4′‐bis(alkyloxy) 2,2′:5′,2″‐terthiophene) derivatives

This work reports the synthesis of novel poly(3′,4′‐bis(alkyloxy)terthiophene) derivatives (PTTOBu, PTTOHex, and PTTOOct) and their supercapacitor applications as redox‐active electrodes. The terthiophene‐based conducting polymers have been derivatized with different alkyl pendant groups (butyl‐, hexyl‐, and octyl‐) to explore the effect of alkyl chain length on the surface morphologies and pseudocapacitive properties. The electrochemical performance tests have revealed that the length of alkyl substituent created a remarkable impact over the surface morphologies and charge storage properties of polymer electrodes. PTTOBu, PTTOHex, and PTTOOct‐based electrodes have reached up to specific capacitances of 94.3, 227.3, and 443 F g⁻¹ at 2.5 mA cm⁻² constant current density, respectively, in a three‐electrode configuration. Besides, these redox‐active electrodes have delivered satisfactory energy densities of 13.5, 29.3, and 60.7 W h kg⁻¹ and power densities of 0.98, 1, and 1.1 kW kg⁻¹ with good capacitance retentions after 10,000 charge/discharge cycles in symmetric solid‐state micro‐supercapacitor devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 480–495     

蟹壳基氮/氧共掺杂多孔炭的原位制备及其超级电容器性能

采用废弃蟹壳为碳源,KOH为活化剂原位制备了氮/氧共掺杂多孔炭,并研究其作为电极材料在超级电容器中的应用。 固定蟹壳与KOH的质量比为5:3,考察了煅烧温度对所得炭材料产率、孔结构和氮氧含量的影响。 结果表明,蟹壳基炭材料的孔结构和氮/氧含量可通过改变煅烧温度调变。 随着煅烧温度从500 ℃上升至700 ℃,多孔炭的比表面积和孔体积逐渐增大,而氮/氧含量随温度升高则降低。 采用循环伏安和恒流充放电对所得材料的电化学性能进行测试。 结果表明,所得多孔炭的电化学性能取决于其孔结构与氮/氧表面性质的协同作用,其中煅烧温度为600 ℃所得的多孔炭比表面积为612 m²/g,氮和氧含量分别为3.53%和32.8%,在50 mA/g的电流密度下比电容达到310 F/g,循环1000次比电容仍然保持95%以上,展现出良好的电化学性能。     

MnO2/煤基碳纳米纤维的制备及其在柔性超级电容器中的应用

采用静电纺丝技术制备了柔性煤基碳纳米纤维(CBCNFs)。利用低温等离子体技术对CBCNFs进行改性,并将改性后的CBCNFs作为还原剂与KMn O4反应,以实现Mn O2的原位还原负载制备CBCNFs/Mn O2复合材料。通过X射线衍射、扫描电镜和透射电镜等手段对复合材料的结构与形貌进行了表征;另外,研究了其作为柔性超级电容器电极材料的性能。结果表明,KMn O4∶CBCNFs=2∶1(质量比)条件下制备的复合材料(CBCNFs/Mn O2-2)具有良好的电化学性能。在0.1A·g-1电流密度下,CBCNFs/Mn O2-2的比电容高达118F·g-1,为CBCNFs比电容(26F·g-1)的4.5倍,在1A·g-1电流密度下,循环1000次后比容量保持率为97%,表现出良好的循环稳定性。     

以多层次聚苯胺颗粒为电极活性物质的超级电容器的电化学性能

以(NH₄)₂S₂O₈为氧化剂用化学氧化法合成了具有多层次结构的聚苯胺颗粒，其二次颗粒由一次颗粒集结而成，一次颗粒的粒径基本上在1 μm以下，一次颗粒由多层微小薄片叠合而成. 用这种聚苯胺为活性物质制成电极，以2 mol•L^-1的H₂SO₄水溶液作电解液，组装成了聚苯胺电极超级电容器. 用循环伏安法、电化学阻抗谱和恒电流充放电技术测试了该超级电容器的电化学性能.在7 mA的充放电电流下，它的比能量可达6.35 Wh•kg^-1，比功率可达132 W•kg^-1，电极材料的比容量可达408 F•g^-1. 在20 mA的充放电电流下，它的比能量可达4.39 Wh•kg^-1，比功率可达328 W•kg^-1，电极材料的比容量可达324 F•g^-1. 在100次的充放电循环中，聚苯胺电极超级电容器的电容量没有下降，电荷充放电效率一直保持在95%左右.     

Tin oxalate as a precursor of tin dioxide and electrode materials for lithium-ion batteries

Tin(II) oxalate was studied as a novel precursor for active electrode materials in lithium-ion batteries. The discharge of lithium cells using tin oxalate electrodes takes place by three irreversible steps: tin reduction, forming a lithium oxalate matrix; solvent decomposition to form a passivating layer; and oxalate reduction in a two-electron process. These are followed by reversible alloying of tin with lithium, leading to a maximum discharge of 11 F/mol. Cycling of the cells showed reversible capacities higher than 600 mAh/g during the first five cycles and ca. 200 mAh/g after 50 cycles. Tin oxalate was converted to tin dioxide by thermal decomposition at 450 °C and also by a chemical method by dissolving tin oxalate powder in 33% v/v hydrogen peroxide at room temperature. The ultrafine nature of the tin dioxide powders obtained by this procedure allow their use as electrodes in lithium cells. The best capacity retention during the first five cycles was achieved for a sample heat treated to 250 °C to eliminate surface water. Electronic Publication     

Co3O4纳米线的丙三醇辅助合成及其电化学性质

以硝酸钴和丙三醇为反应物通过反应条件的改变控制制备出Co3O4纳米线.利用粉末X射线衍射(XRD),扫描电子显微镜(SEM)和透射电子显微镜(TEM)对产物的形貌与结构进行了表征.实验发现,在低扫描速率下,Co3O4纳米线电极的循环伏安(CV)曲线呈现出两对氧化还原峰.恒电流充放电实验中,氧化钴纳米线电极在1A.g-1电流密度下的电容为163F.g-1;在1和4A.g-1条件下,其容量随循环次数的增加先上升后下降,1000次充放电循环后容量保持率分别在98%和80%以上,继续增加循环次数则容量下降比较明显.锂离子电池性质测试中,氧化钴纳米线的放电容量为1124mAh.g-1,然而放电容量随循环次数增加下降较快.基于实验结果,对Co3O4纳米线的形成机理及其结构与电化学性质之间的关系进行了探讨.     

基于三维花状五氧化二铌及活性炭的锂离子混合电容器

锂离子混合电容器由于兼备锂离子电池和超级电容器的优势,即较高的能量密度和功率密度,而成为当前能量存储体系的研究热点。本工作合成了具有三维花状微纳结构的正交相五氧化二铌(T-Nb_2O_5),并将其与活性炭(AC)相匹配,设计出一种新型的T-Nb_2O_5/AC锂离子混合电容器。循环伏安和恒电流充放电的测试结果表明该锂离子混合电容器具有较好的电化学性能,如在碳酸酯类的有机电解液中,工作电压可达到3.0 V;在100 m A·g~(-1)的电流密度下,电容器的比能量和比功率密度可达到53.79 Wh·kg~(-1)和294 W·kg~(-1);在200 m A·g~(-1)的电流密度下,经过1000次充放电循环后,该电容器的比能量保持率为73%。由此可见,本工作开发的T-Nb_2O_5/AC锂离子混合电容器将在高功率的储能设备中有很好地应用前景。     

高能量密度和功率密度炭电极材料

以核桃壳为原料, 采用同步物理-化学活化法制备活性炭(AC). 用氮气吸附法和傅立叶红外光谱(FTIR), 对活性炭的孔结构和表面官能团进行了分析. 以活性炭为电极材料制备炭电极, 6 mol·L-1 KOH溶液为电解液组装成超级电容器, 利用恒电流充放电、循环伏安、交流阻抗等电化学测试方法研究其电化学性能及其与活性炭材料结构的关系. 结果表明, 实验电容器的内电阻、漏电流小, 循环充放电稳定性好, 容量保持率高; 活性炭的比电容随比表面积的增加而增大, 且与BET比表面积呈线性相关; 孔径在1.5-4 nm之间的孔表面有利于形成有效的双电层. 中等比表面积1197 m2·g-1炭样的比电容高达292 F·g-1, 80 mA充放电时, 电容器能量密度高达7.3 Wh·kg-1, 功率密度超过770 W·kg-1,峰值功率密度为5.1 W·g-1.     

活性炭基Li2SO4水系电解液超级电容器

采用中性Li2SO4水溶液代替H2SO4和KOH作为电解液制备了活性炭(AC)基对称型超级电容器,使水系超级电容器的工作电压由1.0V提高到了1.6V.采用循环伏安和充放电测试研究了电容器的稳定电化学窗口.电化学充放电测试表明电容器在0.25A.g-1电流密度下单电极比容量可达129F.g-1,在功率密度为160W.kg-1时能量密度达到10Wh.kg-1(以正负极活性物质的总质量计).1.6V恒压充电1h后电容器漏电流为0.22mA.超级电容器的库仑效率接近100%,充放电循环5000次后容量仍可保持在92%以上.研究了电解液的浓度对电容器电化学性能的影响,发现随着Li2SO4浓度的增大电容器的电荷转移电阻显著减小,大电流充放电性能提高.活性炭基Li2SO4水系电解液超级电容器具有工作电压高、能量密度高和对环境友好等优点,因此有很好的产业化前景.     

Organic acid doped polythiophene nanoparticles as electrode material for redox supercapacitors

An organic acid doped electronically conducting polymer nanomaterial, polythiophene‐tartaric acid (PTh‐TA) nanoparticles, was prepared by cationic surfactant‐assisted dilute polymerization method. The physical properties of the synthesized polymer were characterized by FT‐IR, UV‐visible spectroscopy, X‐ray diffraction, SEM, and electrical conductivity studies. The symmetric type redox supercapacitor performances were studied in PVdF‐HFP in 1 M LiPF₆ containing EC&PC (1:1 v/v) based microporous polymer electrolyte. The specific capacitance of the capacitor was found to be 156 F g^?1. The energy and power densities were calculated as 14 Wh kg^?1 and 522 W kg^?1, respectively. The value of capacitance was found to be almost stable up to 1000 cycles and even more. Copyright © 2009 John Wiley & Sons, Ltd.     

聚吡咯/氧化石墨烯层状复合材料的制备及其在超级电容器中的应用(英文)

通过将吡咯单体在低温下与氧化石墨烯进行原位聚合,获得聚吡咯/石墨烯(Ppy/CRGO)复合材料.采用场发射电子显微镜(FESEM)、红外(FT-IR)和热重分析(TGA)对复合物的表面形貌、结构进行表征.FESEM结果表明,通过控制氧化石墨烯(GO)和吡咯单体的质量比例,可以对复合物的层状和厚度进行调控.FT-IR和TGA结果表明,聚吡咯(Ppy)是通过化学键合的方式与氧化石墨烯复合在一起.通过机械冷压法将粉末状Ppy/CRGO复合物压成圆片电极,并探讨了石墨烯和聚吡咯复合比例、反应时间、烘干温度和孔隙率等因素对Ppy/CRGO复合物电极的电学和电化学性能的影响.结果表明,Ppy与CRGO质量比为10∶1所制得的Ppy/CRGO复合物的电容量为421 F·g-1,通过在电极中引入孔隙,电容量能进一步提升为509 F·g-1.     

基于聚苯乙烯磺酸的锂金属负极界面保护层的设计

将聚苯乙烯磺酸(PSS)进行锂化处理后, 涂覆在锂箔表面, 在锂金属表面构筑一层均匀的聚苯乙烯磺酸锂(PSSLi)界面保护层, 形成PSSLi@Li复合电极. 通过红外光谱(FTIR)、 电化学阻抗谱(EIS)、 电池性能分析和有限元多物理场仿真模拟等方法, 对该复合电极进行了结构和性能研究. 结果表明, PSSLi界面保护层能有效地避免电解液与锂金属的直接接触, 抑制了“死锂”和锂枝晶的生成. 聚苯乙烯磺酸锂具有整齐排布的磺酸基团, 为锂离子提供了稳定的传输通道, 能够均匀化锂离子的迁移速率, 调节锂离子在电极表面的浓度分布, 并实现均匀的锂金属沉积/剥离. 电化学实验数据表明, 将该PSSLi界面层涂覆在铜箔表面进行库仑效率测试, 循环 350次实验后仍然能够保持在99.5%以上; 利用PSSLi@Li复合电极组装形成的对称电池, 在1 mA/cm²的电流密度、 1 mA·h/cm²的面积容量下, 能够稳定循环1200 h以上; PSSLi@Li与磷酸铁锂正极材料组装的全电池, 在1C倍率下循环500次后, 仍具有115 mA·h/g的容量, 容量保持率可达81%以上; 在8C的高倍率下, 该电池的容量可达到105 mA·h/g.     

Surface Modification Effect and Electrochemical Performance of LiOH-High Surface Activated Carbon as a Cathode Material in EDLC

This study aimed to improve the performance of the activated carbon-based cathode by increasing the Li content and to analyze the effect of the combination of carbon and oxidizing agent. The crystal structure and chemical structure phase of Li-high surface area activated carbon material (Li-HSAC) was analyzed by X-ray diffraction (XRD) and Raman spectroscopy, the surface state and quantitative element by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) and the surface properties with pore-size distribution by Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH) and t-plot methods. The specific surface area of the Li-YP80F is 1063.2 m²/g, micropore volume value is 0.511 cm³/g and mesopore volume is 0.143 cm³/g, and these all values are higher than other LiOH-treated carbon. The surface functional group was analyzed by a Boehm titration, and the higher number of acidic groups compared to the target facilitated the improved electrolyte permeability, reduced the interface resistance and increased the electrochemical properties of the cathode. The oxidizing agent of LiOH treated high surface area of activated carbon was used for the cathode material for EDLC (electric double layer capacitor) to determine its electrochemical properties and the as-prepared electrode retained excellent performance after 10 cycles and 100 cycles. The anodic and cathodic peak current value and peak segregation of Li-YP80F were better than those of the other two samples, due to the micropore-size and physical properties of the sample. The oxidation peak current value appeared at 0.0055 mA/cm² current density and the reduction peak value at –0.0014 mA/cm², when the Li-YP80F sample used to the Cu-foil surface. The redox peaks appeared at 0.0025 mA/cm² and –0.0009 mA/cm², in the case of using a Nickel foil, after 10 cycling test. The electrochemical stability of cathode materials was tested by 100 recycling tests. After 100 recycling tests, peak current drop decreased the peak profile became stable. The LiOH-treated high surface area of activated carbon had synergistically upgraded electrochemical activity and superior cycling stability that were demonstrated in EDLC.     

Rational Design of Porous Structured Nickel Manganese Sulfides Hexagonal Sheets-in-Cage Structures as an Advanced Electrode Material for High-Performance Electrochemical Capacitors

The design of hierarchical electrodes comprising multiple components with a high electrical conductivity and a large specific surface area has been recognized as a feasible strategy to remarkably boost pseudocapacitors. Herein, we delineate hexagonal sheets-in-cage shaped nickel–manganese sulfides (Ni-Mn-S) with nanosized open spaces for supercapacitor applications to realize faster redox reactions and a lower charge-transfer resistance with a markedly enhanced specific capacitance. The hybrid was facilely prepared through a two-step hydrothermal method. Benefiting from the synergistic effect between Ni and Mn active sites with the improvement of both ionic and electric conductivity, the resulting Ni-Mn-S hybrid displays a high specific capacitance of 1664 F g⁻¹ at a current density of 1 A g⁻¹ and a capacitance of 785 F g⁻¹ is maintained at a current density of 50 A g⁻¹, revealing an outstanding capacity and rate performance. The asymmetric supercapacitor device assembled with the Ni-Mn-S hexagonal sheets-in-cage as the positive electrode delivers a maximum energy density of 40.4 Wh kg⁻¹ at a power density of 750 W kg⁻¹. Impressively, the cycling retention of the as-fabricated device after 10 000 cycles at a current density of 10 A g⁻¹ reaches 85.5 %. Thus, this hybrid with superior capacitive performance holds great potential as an effective charge-storage material.     

低热固相法制备纳米MnO2/CNT超电容复合电极的循环稳定性

为了改善纳米MnO2超级电容器电极的充放电循环稳定性,以Mn(OAc)2·4H2O、NH4HCO3和碳纳米管(CNT)为原料,采用低热固相反应得到前驱体,再经焙烧和酸处理,制备了一系列CNT含量不同的纳米MnO2/CNT复合电极材料,并用X射线衍射(XRD)、透射电镜(TEM)和Brunauer-Emmett-Teller(BET)比表面积测定方法对其进行了表征.XRD分析结果表明,复合材料中的MnO2为纳米γ-MnO2.研究了复合电极在1 mol·L-1 LiOH电解质中的电化学性能,并与不含CNT的纯纳米MnO2电极进行了比较.结果表明,含CNTs为10%(w,质最分数,下同)和20%的MnO2/CNT复合电极的循环稳定性远优于纯纳米MnO2电极的循环稳定性,其中含10%CNTs的MnO2/CNT复合电极不仪具有良好的循环稳定性,而且在1000 mA·g-1高倍率充放电条件下仍具有200 F·g-1的高比电容.     

LiV3O8在Li2SO4水溶液中的电化学性能

采用低温固相法合成了具有纳米结构的LiV₃O₈材料.扫描电子显微镜（SEM）及透射电子显微镜（TEM）测试显示该材料具有纳米结构.X射线衍射（XRD）表明该材料属于单斜晶系,P2₁Im空间群.并采用循环伏安法（CV）及电化学阻抗谱图测试对该材料在1、2 mol·L^-1Li₂SO₄水溶液及饱和Li₂SO₄水溶液中的电化学行为进行了研究.结果表明,LiV₃O₈在饱和Li₂SO₄水溶液中具有最好的电化学性能.以LiV₃O₈作为负极材料,LiNi_1/3Co_1/3Mn_1/3O₂作为正极材料,饱和Li₂SO₄水溶液作为电解液组成了水性锂离子电池,进行恒流充放电测试,结果表明,在0.5C(1C=300 mA·g^-1)的充放电倍率下,该水性锂离子电池的首次放电比容量为95.2 mAh·g^-1,循环100次后仍具有37.0 mAh·g^-1的放电比容量.     

三维多孔还原氧化石墨烯气凝胶的制备及其在锂离子电池中的应用

以天然鳞片石墨为原料,采用改良的Hummers方法,制备了高纯度的薄层或单层氧化石墨(GO);并以抗坏血酸为还原剂,通过自组装还原的方式成功制备了具有三维多孔独巨石结构的还原氧化石墨烯(rGO)气凝胶,其形貌和结构经FT-IR, SEM, TEM, XRD和XPS表征。并对其作为锂离子电池负极材料的电化学性能进行了测试。结果表明：rGO气凝胶独特的形貌和结构提高了其比容量和循环性能,在100 mA·g^-1电流密度下首周放电比容量可达1 700 mAh·g^-1,首周充电比容量达710 mAh·g^-1,经过100周循环后放电比容量仍可保持在450 mAh·g^-1,库伦效率保持在98%。     

Facile Synthesis of Nitrogen‐Containing Mesoporous Carbon for High‐Performance Energy Storage Applications

Porous carbon with high specific surface area (SSA), a reasonable pore size distribution, and modified surface chemistry is highly desirable for application in energy storage devices. Herein, we report the synthesis of nitrogen‐containing mesoporous carbon with high SSA (1390 m² g^?1), a suitable pore size distribution (1.5–8.1 nm), and a nitrogen content of 4.7 wt % through a facile one‐step self‐assembly process. Owing to its unique physical characteristics and nitrogen doping, this material demonstrates great promise for application in both supercapacitors and encapsulating sulfur as a superior cathode material for lithium–sulfur batteries. When deployed as a supercapacitor electrode, it exhibited a high specific capacitance of 238.4 F g^?1 at 1 A g^?1 and an excellent rate capability (180 F g^?1, 10 A g^?1). Furthermore, when an NMC/S electrode was evaluated as the cathode material for lithium–sulfur batteries, it showed a high initial discharge capacity of 1143.6 mA h g^?1 at 837.5 mA g^?1 and an extraordinary cycling stability with 70.3 % capacity retention after 100 cycles.     

Nanosized Fe3O4-modified activated carbon for supercapacitor electrodes

Nanosized Fe₃O₄-modified activated carbon composites for supercapacitor electrodes have been investigated. Structural and morphological characterizations of activated materials are carried out using X-ray diffraction and scanning electron microscopy, respectively. The electrochemical performances of the composite electrodes are evaluated by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. The experimental results show that the specific capacitances of the 10 wt % Fe₃O₄-modified activated carbon composite electrode (154.3 F g^?1) is highly improved compared with that of Fe₃O₄ (78.5 F g^?1) and AC (79.2 F g^?1) at the current density of 5 mA cm^?2, respectively. The charge/discharge tests show that it could retain 79.6% of its initial capacitance over 1000 cycles, suggesting its potential application for the fabrication of high-quality supercapacitors.