Single-walled Carbon Nanotubes as Electrode Materials for Supercapacitors

Large-scale synthesized single-walled carbon nanotubes （SWNT） prepared by electric arc discharge method and a mixture of NiO and Y2O3 as catalyst have been used as electrode materials for supercapacitors. N2 adsorption/desorption measurement shows that the SWNT is a microporous and mesoporous material with specific surface area 435 m^2·g^-1. The specific capacitance of the nitric acid treated SWNT in aqueous electrolyte reaches as high as 105 F/g, which is a combination of electric double layer capacitance and pseudocapacitance. The SWNT-based capacitors also have good charge/discharge reversibility and cycling perdurability.     

导电聚合物超级电容器电极材料*

导电聚合物（聚苯胺,聚吡咯,聚噻吩）作为超级电容器电极材料的研究引起了人们广泛的兴趣,该类材料制备的超级电容器具有成本低、容量高、充放电时间短、环境友好和安全性高等优点。本文综述了近年来基于导电聚合物及其与无机材料（碳材料/金属氧化物材料）复合所得电极材料在超级电容器中的应用进展,指出具有纳米结构导电聚合物材料及导电聚合物与无机纳米材料的复合是超级电容器电极材料研究的重要发展方向。     

超级电容器用镍锰基二元金属氧化物电极材料

赝电容电容器相比于双电层电容器拥有更高的比容量(大约10~100倍),由于在充电/放电过程中法拉第反应同时在电极材料表面和内部发生。因此,会产生更多电子,拥有更大的比容量。目前,赝电容电极材料的研究主要集中在金属氧化物和导电聚合物。镍锰基金属氧化物具有较高的理论比容量、成本低、无毒、环境友好等优点,但是其实际的电化学性能远低于理论值。因此,为了提升材料的电化学表现,研究者提出许多有效的策略,例如:制备不同种类金属氧化物作为电极材料;采用不同的工艺制备高比表面积的材料以及不同材料之间的复合产生协同作用等。本文综述了镍锰基二元金属氧化物(NiMnO₃、NiMn₂O₄和Ni₆MnO₈)作为赝电容电极材料在超级电容器上的应用进展,同时结合目前研究方法进一步提出未来金属氧化物电极材料方面的发展方向,为继续深入研究提供一定的指导作用。     

氮掺杂碳片的模板诱导制备及其在超级电容器中的应用

兼具有优良的导电能力,高的比表面积和极佳的化学/机械稳定性,具有二维形貌的纳米碳材料近年来逐渐成为超级电容器电极材料的研究热点. 我们在此首次报道一种模板诱导方法以制备具有规整片状形貌的氮掺杂碳材料. 我们将作为硬模板的片状镁铝双金属氢氧化物与熔融的邻苯二胺混合后加入三氯化铁催化剂,进而通过加热使邻苯二胺聚合并碳化,随后刻蚀除去其中的氧化物成分即可以得到具有规整六边形片状氮掺杂碳材料. 通过改变碳化时的温度,可以有效的调节利用该方法所得到的氮掺杂碳片的形貌、结构、石墨化程度、氮含量以及比表面积. 更重要的是这些氮掺杂碳片在用作超级电容器电极材料时体现出优异的电化学性能,在0.5 A·g^-1的电流密度下其比容量可以达到290.0 F·g^-1的. 在1 A·g^-1的电流密度下经过10000周循环测试后,其容量仍然可以达到初始值83%.     

焦粉活性炭/Al-Ni(OH)2复合电极材料的制备及其超级容器性能

以焦粉为原料,用HNO3预处理除灰,采用KOH浸渍-煅烧活化法制备焦粉活性炭(CPAC),通过场发射扫描电子显微镜、X射线衍射等表征其形貌,采用BET测试其比表面积、孔结构及孔径分布。初步考察了活化温度、活化时间等对焦粉活性炭电极材料电化学性能的影响。采用共沉淀法制备CPAC/Al-Ni(OH)2复合电极材料,通过恒电流充放电测试及循环伏安测试表征CPAC/Al-Ni(OH)2复合电极材料的电化学性能。结果表明,当活化温度为800℃、活化时间为3 h制得的焦粉活性炭电极材料的电化学性能最佳,比电容达到211 F/g。CPAC-800℃-3 h/Al-Ni(OH)2复合电极材料随Al掺杂量的增大呈现先增大后减小的趋势。在固定Al质量掺杂量为4%,炭镍质量比为1∶1时所得复合材料的比电容量最大:1173.6 F/g。恒电流充放电及循环伏安测试表明Al掺杂量为4%、炭镍比为1∶1的复合材料具有较好的电化学性能。     

基于碳材料的超级电容器电极材料的研究

超级电容器作为一种新型的能源存储装置,因为其比容量大、充放电速度快、循环寿命长等优点,在储能领域引起了极为广泛的关注。电极材料是决定超级电容器性能的核心因素,其中,常用的超级电容器电极材料主要有如下三类:碳基材料、金属氧化物及氢氧化物材料和导电聚合物材料。本文综述了超级电容器的工作原理并详细介绍了基于碳材料及其二元、三元复合体系的电极材料的研究进展。     

Mesoporous Carbons Templated by PEO-PCL Block Copolymers as Electrode Materials for Supercapacitors

In this study, samples of activated mesoporous carbon are fabricated with pore structures with cylinder and gyroid nanostructures through the templating effect of amphiphilic poly(ethylene oxide-block-caprolactone) (PEO-PCL) and by using specific resol/PEO-PCL weight ratios (e.g., 60:40 for cylinders; 55:45 for gyroids). After carbonization and KOH activation, the activated mesoporous carbons were tested as electrode materials for electric double-layer capacitor (EDLC) supercapacitors. The electrochemical properties were examined by using three-electrode (6 m KOH_(aq) as electrolyte) and CR2032 coin-cell (1 m tetraethylammonium tetrafluoroborate (TEABF₄)/CN as the electrolyte) systems. The gyroid carbon samples provided specific capacitances higher than those of the cylinder carbon samples in both aqueous and organic systems: 155 F g⁻¹ compared with 135 F g⁻¹ in 6 m KOH_(aq), and 105.6 compared with 96 F g⁻¹ in 1 m TEABF₄/MeCN, after 100 charge/discharge cycles. It is suspected that the bi-continuous mesochannels of the gyroid-type activated mesoporous carbons provided a relatively higher effective adsorption surface area; in other words, the greater surface area for energy storage originated from a moderate pore size and an interconnected pore structure.     

Chemically Treated Carbon Nanofiber Materials for Supercapacitors

Doklady Chemistry - Carbon nanofibers obtained by catalytic decomposition of methane in a vibrated fluidized bed reactor were chemically treated to increase the specific capacitance of...     

花生壳制备微孔炭及其在电化学超级电容器中的应用

以未使用和使用氢氧化钠溶液处理的花生壳为碳源分别制备出微孔炭PSC-1和PSC-2.PSC-1和PSC-2的比表面积分别为552和726m2·g-1,其主要孔径都约为0.8nm.用PSC-1和PSC-2制备的电极和对称型超级电容器的循环伏安曲线均接近矩形,表明其具有良好的电容特性.在以微孔炭电极为工作电极、铂电极为对电极和银/氯化银电极为参比电极组成的三电极体系测量表明,在0.1A·g-1的电流密度下,PSC-1和PSC-2的比电容达到233和378F·g-1.经过1000次恒电流充放电循环后,在三电极体系和超级电容器中电极均表现出良好的稳定性和电容保持率.基于实验结果探讨了微孔炭的形成机理及其结构与电化学性质之间的联系.     

壳聚糖制备多孔炭及其在电化学超级电容器中的应用(英文)

以壳聚糖为原料在 600、700、800和900℃直接炭化制备多孔炭 C-600,C-700, C-800 和C-900,其BET比表面积分别为278、461、515和625 m2·g-1.用恒流充放电和循环伏安法表征了其电化学性能. 结果表明, 由 C-800 制备电极的循环伏安图形更接近矩形, 在恒电流充放电实验中阴极和阳极过程基本对称, 说明该电极具有较好的电容性能.在 50 mA·g-1 的电流密度下,C-600、C-700、C-800和C-900的电容分别为96、120、154 和 28 F·g-1.由 C-800 制备电极的循环充放电稳定性好, 电流密度为1 A·g-1循环1000次后电容损失小于2%,说明壳聚糖制备多孔碳具有作为超级电容器电极材料的潜在价值. 同时还考察了不同浓度的电解液对C-800电化学性质的影响,发现在KOH浓度为 30%时的电容最大.依据实验结果,对多孔炭制备及其电化学性质间的关系进行了探讨.     

静电纺纳米纤维基超级电容器无粘合剂电极材料的研究进展

对高性能超级电容器不断增长的需求促进了无粘合剂电极材料的快速发展。静电纺纳米纤维由于具有良好的柔性、大比表面积、高孔隙率、容易制备等优点引起了研究者们的强烈关注。本文综述了静电纺纳米纤维基无粘合剂电极材料在超级电容器领域的研究进展,阐述了不同材料的设计制备过程和提升电化学性能的诸多方法,并指明了静电纺纳米纤维基超级电容器无粘合剂电极材料的发展机遇与挑战,为性能优异的无粘合剂超级电容器电极材料的进一步开发与应用拓宽了思路。     

超级电容器用含氮碳与含氮碳/炭气凝胶复合电极材料的制备和性能研究

采用原位聚合法合成聚苯胺(PAIN)及聚苯胺/炭气凝胶(PAIN/CA)复合材料,经过高温裂解制备含氮碳(NC)及含氮碳/炭气凝胶复合材料(NC/CA),再以KOH为活化剂对其进行活化,制备活化含氮碳(ANC)及活化含氮碳/炭气凝胶复合材料(ANC/CA)。采用扫描电镜、循环伏安、恒流充放电以及电化学阻抗等方法进行性能测试,结果表明,由于KOH的活化作用,含氮碳材料的粒径明显变小,其比电容值为138 F/g,高于未活化含氮碳材料(98 F/g),ANC/AC3复合材料电极的比电容值比ACA电极(88 F/g)高,达到127 F/g。     

Nitrogen‐Doped Porous Graphitic Carbon as an Excellent Electrode Material for Advanced Supercapacitors

An advanced supercapacitor material based on nitrogen‐doped porous graphitic carbon (NPGC) with high a surface area was synthesized by means of a simple coordination–pyrolysis combination process, in which tetraethyl orthosilicate (TEOS), nickel nitrate, and glucose were adopted as porogent, graphitic catalyst precursor, and carbon source, respectively. In addition, melamine was selected as a nitrogen source owing to its nitrogen‐enriched structure and the strong interaction between the amine groups and the glucose unit. A low‐temperature treatment resulted in the formation of a NPGC precursor by combination of the catalytic precursor, hydrolyzed TEOS, and the melamine–glucose unit. Following pyrolysis and removal of the catalyst and porogent, the NPGC material showed excellent electrical conductivity owing to its high crystallinity, a large Brunauer–Emmett–Teller surface area (S_BET=1027 m² g^?1), and a high nitrogen level (7.72 wt %). The unusual microstructure of NPGC materials could provide electrochemical energy storage. The NPGC material, without the need for any conductive additives, showed excellent capacitive behavior (293 F g^?1 at 1 A g^?1), long‐term cycling stability, and high coulombic efficiency (>99.9 % over 5000 cycles) in KOH when used as an electrode. Notably, in a two‐electrode symmetric supercapacitor, NPGC energy densities as high as 8.1 and 47.5 Wh kg^?1, at a high power density (10.5 kW kg^?1), were achieved in 6 M KOH and 1 M Et₄NBF₄‐PC electrolytes, respectively. Thus, the synthesized NPGC material could be a highly promising electrode material for advanced supercapacitors and other conversion devices.     

Determining the Specific Surface Area of Carbon Electrode Materials for Electrodes of Supercapacitors via the Adsorption of Methylene Blue Dye

Russian Journal of Physical Chemistry A - An improved way of measuring the specific surface area of carbon materials that is based on the adsorption of methylene blue is proposed. It is found that...     

Microporous Carbon Nanofibers Derived from Poly(acrylonitrile-co-acrylic acid) for High-Performance Supercapacitors

Carbon nanofiber (CNF)-based supercapacitors have promising applications in the field of energy storage. It is desirable, but remains challenging, to develop CNF electrode materials with large specific surface area (SSA), high specific capacitance (SC), and high power density, as well as excellent cycling stability and high reliability. Herein, acrylonitrile–acrylic acid copolymer P(AN-co-AA) was synthesized for the preparation of nitrogen-doped microporous CNFs. Thermal degradation of the AA segment leads to the formation of micropores that are distributed not only on the CNF surface, but also inside the material. The microporous structure and nitrogen content can be manipulated at the molecular level by adjusting the weight ratio between AN and AA, and the SSA and SC could reach as high as 1099 m² g⁻¹ and 156 F g⁻¹, respectively. After KOH activation, the activated CNFs have an extremely high SSA of 2117 m² g⁻¹ and SC of 320 F g⁻¹, which are among the highest values ever reported for electric double-layer supercapacitors with an alkaline electrolyte. Furthermore, the capacitance retention, which can be maintained at 99 % even after 16 000 cyclic tests, reveals outstanding durability and repeatability.     

Carbon Electrode Materials for Advanced Potassium-Ion Storage

Tremendous progress has been made in the field of electrochemical energy storage devices that rely on potassium-ions as charge carriers due to their abundant resources and excellent ion transport properties. Nevertheless, future practical developments not only count on advanced electrode materials with superior electrochemical performance, but also on competitive costs of electrodes for scalable production. In the past few decades, advanced carbon materials have attracted great interest due to their low cost, high selectivity, and structural suitability and have been widely investigated as functional materials for potassium-ion storage. This article provides an up-to-date overview of this rapidly developing field, focusing on recent advanced and mechanistic understanding of carbon-based electrode materials for potassium-ion batteries. In addition, we also discuss recent achievements of dual-ion batteries and conversion-type K−X (X=O₂, CO₂, S, Se, I₂) batteries towards potential practical applications as high-voltage and high-power devices, and summarize carbon-based materials as the host for K-metal protection and possible directions for the development of potassium energy-related devices as well. Based on this, we bridge the gaps between various carbon-based functional materials structure and the related potassium-ion storage performance, especially provide guidance on carbon material design principles for next-generation potassium-ion storage devices.     

高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

柚子皮衍生的分级多孔碳作为高性能超级电容器的电极材料

使用CTAB作为软模板,水热处理柚子皮,再以碳化和KOH活化过程得到了分级多孔碳(HPC),这种分级多孔碳材料的比表面积高达1 813 m~2·g~(-1),相比于没有水热步骤制备的多孔碳(PC),拥有更加丰富的介孔结构和更大的比表面积。XPS分析结果表明HPC的氧掺杂量更高,会比PC贡献更大的赝电容。三电极测试体系中,HPC的比电容达到285 F·g~(-1)(0.5 A·g~(-1),1 mol·L~(-1)KOH)。同时,组装的两电极对称超级电容器拥有很好的倍率性能,循环12 000次充放电后,比电容依旧保留99%。HPC拥有这样优异的性能归结于较大的比表面积,高氧掺杂量和合理的孔径分布的协同作用。     

超级电容器用石墨烯/金属氧化物复合材料

超级电容器是一种具有高功率密度和长循环寿命的新型储能装置,碳材料、金属氧化物和导电聚合物是常见的三种超级电容器电极材料。在石墨烯/金属氧化物复合材料中,石墨烯和金属氧化物可以发挥各自的优点,结合石墨烯优异的循环稳定性能和金属氧化物的高容量特性,纳米复合材料的综合性能可以得到很大地提升。因此,石墨烯/金属氧化物复合物的研究是超级电容器领域的热点研究方向之一。本文以金属氧化物的种类、石墨烯的结构和复合物的制备方法为线索,综述了国内外应用于超级电容器方面的石墨烯/金属氧化物复合材料的研究进展,归纳总结出与石墨烯复合最优的金属氧化物类型和制备方法,并进一步对该类复合材料的发展趋势进行了展望。