Preparation and performance of polyvinyl alcohol-based activated carbon as electrode material in both aqueous and organic electrolytes

Porous carbon materials with high surface area and different pore structure have been successfully prepared by phenolic resin combined with polyvinyl alcohol (PVA) and KOH as activation agents. The surface morphology, structure, and specific surface area of the carbon materials were studied by scanning electron microscopy, X-ray diffraction, and nitrogen sorption measurement, respectively. Furthermore, the effects of specific surface area, pore structure, and electrolyte on electrochemical properties were investigated by galvanostatic charge–discharge measurement. The results show that KOH–PVA-activated carbon materials display specific capacitance as high as 218 F?g^?1 in 30 wt.% KOH aqueous electrolyte, 147 F?g^?1 in 1 M LiPF₆/(ethylene carbonate (EC) + dimethyl carbonate) (1:1?v/v), and 115 F?g^?1 in 1 M Et₃MeNBF₄/propylene carbonate organic electrolyte, respectively. In addition, the carbon materials demonstrate long-term cycle stability, especially the AK3P-0.30 in aqueous electrolyte and the AK2P-0.30 with excellent rate capability in organic electrolyte. These reveal that the existence of a micro-mesoporous structure of activated carbon is beneficial to store energy in an aqueous supercapacitor and broad pore size distribution of activated carbon is favorable to energy storage in an organic supercapacitor. The carbon materials with pore size distribution in different ranges improve the electrochemical performance of supercapacitor in different electrolytes. A new pore-expand agent (PVA combining with KOH) was used to obtain porous carbons with enhanced properties for supercapacitor.     

氢氧化钾活化制备超级电容器多孔碳电极材料

具有高比表面积、良好导电性的多孔碳材料在超级电容器中有着广泛的应用前景. 大量的研究工作致力于通过物理或者化学手段合成并调控多孔材料的微观结构. 在众多多孔碳材料的制备方式中,氢氧化钾作为一种高效的活化剂,常用于制备具有良好孔径分布和高比表面积多孔碳电极材料. 本文主要结合作者课题组的研究工作,着重概述利用氢氧化钾活化sp²碳纳米材料制备多孔碳材料的机理过程、结构形貌的转变以及所得材料的电化学性能,希望对发展新型的高性能基多孔碳材料的超级电容器电极材料有所帮助.     

多孔碳材料的化学气相后处理及其超级电容性能

以廉价的椰壳为原料制备了高比表面积的多孔碳材料,然后在密闭的反应釜中以硝酸蒸汽对多孔碳材料进行了后处理,制备了亲水性更好的多孔碳材料。采用扫描透射电子显微镜(TEM)、物理吸附、X射线粉末衍射(XRD)、拉曼光谱(Raman)和接触角测试对材料的微观形貌、孔道结构、组成和亲水性进行了表征,探究了不同温度下硝酸蒸汽对多孔碳材料的形貌、结构的影响,并采用循环伏安法、恒电流充放电法和交流阻抗法考察了多孔碳材料的超级电容性能。结果表明,经过硝酸蒸汽处理后的多孔碳材料的比表面积和孔体积均有所降低,且随着处理温度的升高,降低得更加明显,而亲水性却越来越好。电化学测试结果表明,经过100℃硝酸蒸汽处理的多孔碳材料(CSC-100)具有最佳的超级电容性能。在以6 mol·L^-1 KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时CSC-100的比电容可达452.9 F·g^-1,而未经硝酸蒸汽处理的多孔碳材料(CSC)的比电容仅为350.4 F·g^-1。电容贡献分析表明CSC-100良好的亲水性和表面官能团不仅提高了双电层电容,也提高了赝电容。     

基于聚多巴胺的氮掺杂碳材料的制备及其电化学性能

多孔碳材料由于高的比表面积、优异的电子传导率、良好的化学稳定性等优点在超级电容器电极材料领域被广泛研究。 碳材料的组成及表面孔结构直接影响其电化学性能,为进一步提高碳材料的电容性能,本文首次以聚多巴胺球为前体,KOH为活化剂,通过高温碳化成功制备了良好电化学性能的氮掺杂多孔碳材料。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)和Raman光谱等对所制备的氮掺杂多孔碳材料进行了形貌及结构组成的表征。 在6 mol/L KOH电解液中, 采用循环伏安、恒电流充放电对多孔碳材料的电化学性能进行了研究。 结果表明,由于双电层电容和赝电容的协同作用,在电流密度为1 A/g时,材料的比电容可达269 F/g,充放电循环1000圈后电容仍可保留初始值的93.5%。     

纤维素纳米晶模板法制备多级孔炭材料及其电化学性能

以纤维素纳米晶(CNC)为模板,酚醛树脂为碳源,KOH为活化剂,通过高温碳化制备了多级孔炭材料.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段对合成的一系列炭材料进行了表征.结果表明,前驱体中CNC的降解会形成与CNC直径相当的介孔,KOH活化则会导致炭材料产生大量的微孔和大孔,以及部分4 nm左右较小尺度的介孔,所制备炭材料呈现明显的多级孔特性,其比表面积达554.7 m²/g,总孔体积为0.323 cm³/g.以CNC为模板,KOH活化的炭材料作为电极材料时,在1.0 A/g电流密度下其比电容达202.8 F/g,当电流密度升高至40.0 A/g时,其电容保持率仍达69%,表明该炭材料具有优异的倍率性能;由该电极材料组装的超级电容器在10000次充放电循环后,电容保持率达95%以上,具有良好的循环稳定性.     

N-doped honeycomb-like porous carbon towards high-performance supercapacitor

Biomass-derived porous carbon with developed pore structure is critical to achieving high performance electrode materials. In this work, we report a grape-based honeycomb-like porous carbon (GHPC) prepared by KOH activation and carbonization, followed by N-doping (NGHPC). The obtained NGHPC exhibits a unique honeycomb-like structure with hierarchically interconnected micro/mesopores, and high specific surface area of 1268 m²/g. As a supercapacitor electrode, the NGPHC electrode exhibits a remarkable specific capacitance of 275 F/g at 0.5 A/g in a three-electrode cell. Moreover, the NGHPC//NGHPC symmetric supercapacitor displays a high energy density of 12.6 Wh/kg, and excellent cycling stability of approximately 95.2% capacitance retention after 5000 cycles at 5 A/g. The excellent electrochemical performance of NGHPC is ascribed to its high specific surface area, honeycomb-like structure and high-content of pyrodinic-N (36.29%). It is believed that grape-based carbon materials show great potential as advanced electrode materials for supercapacitors.     

Flexible Polyester Cellulose Paper Supercapacitor with a Gel Electrolyte

A low-cost polyester cellulose paper has been used as a substrate for a flexible supercapacitor device that contains aqueous carbon nanotube ink as the electrodes and a polyvinyl alcohol (PVA)-based gel as the electrolyte. Gel electrolytes have attracted much interest due to their solvent-holding capacity and good film-forming capability. The electrodes are characterized for their conductivity and morphology. Because of its high conductivity, the conductive paper is studied in supercapacitor applications as active electrodes and as separators after coating with polyvinylidene fluoride. Carbon nanotubes deposited on porous paper are more accessible to ions in the electrolyte than those on flat substrates, which results in higher power density. A simple fabrication process is achieved and paper supercapacitors are tested for their performance in both aqueous and PVA gel electrolytes by using galvanostatic and cyclic voltammetry methods. A high specific capacitance of 270 F g⁻¹ and an energy density value of 37 W h kg⁻¹ are achieved for devices with PVA gel electrolytes. Furthermore, this device can maintain excellent specific capacitance even under high currents. This is also confirmed by another counter experiment with aqueous sulfuric acid as the electrolyte. The cycle life, one of the most critical parameters in supercapacitor operations, is found to be excellent (6000 cycles) and less than 0.5 % capacitance loss is observed. Moreover, the supercapacitor device is flexible and even after twisting does not show any cracks or evidence of breakage, and shows almost the same specific capacitance of 267 F g⁻¹and energy density of 37 W h kg⁻¹. This work suggests that a paper substrate can be a highly scalable and low-cost solution for high-performance supercapacitors.     

Lignin derived porous carbon with favorable mesoporous contributions for highly efficient ionic liquid-based supercapacitors

Lignin and its derivatives hold great potential in developing high performance porous carbon materials for supercapacitors due to the versatile features of high carbon content, abundant multifunctional groups, low cost, and environmental benefits. Unfortunately, their derived porous carbon generally has the features of unfavorable microporous-dominated morphologies and low specific surface area (SSA) attributed from the highly-branched structure of lignin, which are hardly suitable for the supercapacitors with ionic liquid (IL) electrolyte, leading to poor energy density and rate capability. Herein, porous carbon materials with desirable mesoporous contributions from sodium lignosulphonate are designed via a facile template method. Such rich mesoporisity carbon materials not only possess with three-dimensional interconnected network, large SSA, as well as favorable pore size distribution for accelerated ion and electron mass transfer, but also feature low heteroatom content for high electrochemical stability. Consequently, the optimal electrode exhibits a high capacitance of 166 F/g at 0.5 A/g, superior rate performance (59 Wh/kg at 59 kW/kg), as well as impressive cycle life with good capacitance retention of 93.1% in EMIBF₄ electrolytes. The present work opens a new avenue to design porous carbon materials with high mesopore properties from lignin for effective compatibility with IL electrolyte in high-performance supercapacitors.     

植物基多孔炭材料在超级电容器中的应用

植物基多孔炭具有发达的孔结构、大的表面积、较为成熟的制备工艺、丰富的来源、低廉的价格,是目前商业应用范围最广的超级电容器电极材料。然而在实际应用中仍然存在着质量/体积比容量较低、倍率性能差等问题。本文针对先进电容器件的高能量密度、优异功率性能的要求,首先介绍了近年来发展的植物基多孔炭的制备方法,讨论了植物前驱体的组成和结构对其产物结构的影响以及与其电化学性能之间的构效关系,特别总结了近年来植物基超大比表面积多孔炭、中孔炭、层次化多孔炭的制备方法和电容储能性能。针对大比表面积多孔炭用于超级电容器时的体积性能不佳这一关键问题,本文还总结了提高植物基多孔炭体积电化学性能的方法。最后,对植物基多孔电极材料存在的问题进行了分析与总结,并展望了其研究前景。     

What are the practical limits for the specific surface area and capacitance of bulk sp~2 carbon materials?

The possible practical limits for the specific surface area and capacitance performance of bulk sp~2 carbon materials were investigated experimentally and theoretically using a variety of carbon materials. We find the limit for the specific surface area to be 3500–3700 m~2 g~(-1), and based on this, the corresponding best capacitance was predicted for various electrolyte systems. A model using an effective ionic diameter for the electrolyte ions was proposed and used to calculate the theoretical capacitance. A linear dependence of experimental capacitance versus effective specific surface area of various sp~2 carbon materials was obtained for all studied ionic liquid, organic and aqueous electrolyte systems. Furthermore, excellent agreement between the theoretical and experimental capacitance was observed for all the tested sp~2 carbon materials in these electrolyte systems, indicating that this model can be applied widely in the evaluation of various carbon materials for supercapacitors.     

Origins of Boosted Charge Storage on Heteroatom‐Doped Carbons

Although tremendous efforts have been devoted to understanding the origin of boosted charge storage on heteroatom‐doped carbons, none of the present studies has shown a whole landscape. Herein, by both experimental evidence and theoretical simulation, it is demonstrated that heteroatom doping not only results in a broadened operating voltage, but also successfully promotes the specific capacitance in aqueous supercapacitors. In particular, the electrolyte cations adsorbed on heteroatom‐doped carbon can effectively inhibit hydrogen evolution reaction, a key step of water decomposition during the charging process, which broadens the voltage window of aqueous electrolytes even beyond the thermodynamic limit of water (1.23 V). Furthermore, the reduced adsorption energy of heteroatom‐doped carbon consequently leads to more stored cations on the heteroatom‐doped carbon surface, thus yielding a boosted charge storage performance.     

Heteroatom‐Doped Porous Carbon Nanosheets: General Preparation and Enhanced Capacitive Properties

High‐performance electrical double‐layer capacitors (EDLCs) require carbon electrode materials with high specific surface area, short ion‐diffusion pathways, and outstanding electrical conductivity. Herein, a general approach combing the molten‐salt method and chemical activation to prepare N‐doped carbon nanosheets with high surface area (654 m² g^?1) and adjustable porous structure is presented. Owing to their structural features, the N‐doped carbon nanosheets exhibited superior capacitive performance, demonstrated by a maximum capacitance of 243 F g^?1 (area‐normalized capacitance up to 37 μF cm^?2) at a current density of 0.5 A g^?1 in aqueous electrolyte, high rate capability (179 F g^?1 at 20 A g^?1), and excellent cycle stability. This method provides a new route to prepare porous and heteroatom‐doped carbon nanosheets for high‐performance EDLCs, which could also be extended to other polymer precursors and even waste biomass.     

A study of ion charge transfer on electrochemical behaviors of poly(vinylidene fluoride)-derived carbon electrodes

In this work, porous carbon with a high specific surface area as electrode materials for supercapacitors are obtained by a carbonization process at various temperatures from 700 °C to 1000 °C without activation process using poly(vinylidene fluoride) (PVDF) as a carbon precursor. The electrochemical performance is characterized by cyclic voltammetry and galvanostatic charge–discharge cycling performance using two-electrode system in 6.0 M KOH as an aqueous electrolyte. The results indicate that carbonization temperature significantly affected the specific surface area and pore volume of the PVDF-derived carbons and their capacitive behavior. In particular, the electrochemical performance of the prepared PVDF-derived carbon is determined by both the electric double-layer capacitance and the pseudo-capacitance resulting from the residual surface functional groups on PVDF-derived carbons.     

Temperature stability of symmetric activated carbon supercapacitors assembled with in situ electrodeposited poly(vinyl alcohol) potassium borate hydrogel electrolyte

Temperature stability of symmetric activated carbon (AC) supercapacitors (SCs) assembled with in situ electrodeposited poly(vinyl alcohol) potassium borate hydrogel electrolyte was systematically studied and compared with that of AC SCs assembled with liquid aqueous electrolytes in the temperature range from -5℃ to 80℃.     

碳纳米管的活化处理及对其电化学容量影响的研究

采用KOH为活性剂,对碳纳米管进行活化处理,经透射电子显微镜和高分辨透射电子显微镜从不同角度观察,发现得到了两端开口,管长较短,管壁粗糙的活性碳纳米管．用氮气自动吸附仪测试了活化前后两种碳纳米管的比表面积,发现活性碳纳米管具有比活化前碳纳米管更高的有效比表面积,将这两种碳纳米管分别作为电极材料应用于电化学超级电容器,经测试,发现活化后的碳纳米管的电化学容量大大提高,在有机电解液中达到了50F／g．     

Supercapacitor Performance of Hollow Carbon Spheres by Direct Pyrolysis of Melamine-formaldehyde Resin Spheres

The nitrogen and oxygen co-doped hollow carbon spheres(HCSs) were prepared via a simple pyrolysis of solid melamine-formaldhyde resin spheres. The carbonization temperature has an important influence on the specific surface area, pore-size distribution and heteroatom contents of HCSs. The synergistic effects of those physical and chemical properties on supercapacitor performance were systematically investigated. Among the HCSs obtained at different temperatures, HCSs-800(co-doped HCSs at 800 ℃) exhibits the best reversible specific capacitance in 2 mol/L H₂SO₄ electrolyte and meanwhile maintains a high-class capacitance retention capability. The nitrogen heteroatoms were confirmed to play a crucial role in improving capacitance in an acid medium. This kind of nitrogen doped HCSs is a potential candidate for an efficient electrode material for supercapacitors.     

Improvement of capacitance activity for Cu‐doped Ni‐based metal–organic frameworks by adding potassium hexacyanoferrate into KOH electrolyte

Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K₃[Fe(CN)₆] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni_2.6Cu_0.4 MOFs material shows the highest specific capacitance (1282 F g^?1 at 1 A g^?1 in mixed 2 M KOH and 0.1 M K₃[Fe(CN)₆]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production.     

Symmetric electrochemical supercapacitor performance evaluation of N-doped graphene prepared via supercritical fluid processing

Here, the fast and shorter duration synthesis route was proposed for the production of N-doped graphene by supercritical fluid method involving ammonium oxalate as a source of nitrogen. Within the different proportions of graphene oxide and nitrogen source, the nitrogen-doped graphene formed from ammonium oxalate having nitrogen content of 3.3 wt% showed an enriched specific capacitance of 274 Fg^?1 at 1 A/g in 20% KOH electrolyte. The long-term stability results obtained from galvanostatic charge-discharge in ammonium oxalate-based N-doped graphene revealed that 90% specific capacitance retention was achieved up to 10,000 cycles at 10 A/g. To examine the device proficiency, a full cell was fabricated and the performance was evaluated in two different approaches. Among the different media in aqueous electrolytes, the fabricated symmetric supercapacitor has achieved a maximum specific capacitance value of 160 F/g at 1 A/g in alkaline medium (20% KOH solution). Between 20% KOH solution and 1 M NaClO₄ solution in acetonitrile, the fabricated symmetric supercapacitor exhibits an energy density of 26.5 Wh/kg as well as 5.5 Wh/kg in 1 M sodium perchlorate in acetonitrile solution and 20% KOH solution, respectively.     

Preparation of Hierarchical Porous Activated Carbon from Banana Leaves for High-performance Supercapacitor: Effect of Type of Electrolytes on Performance

We demonstrate a facile efficient way to fabricate activated carbon nanosheets (ACNSs) consisting of hierarchical porous carbon materials. Simply heating banana leaves with K₂CO₃ produce ACNSs having a unique combination of macro-, meso- and micropores with a high specific surface area of ∼1459 m² g⁻¹. The effects of different electrolytes on the electrochemical supercapacitor performance and stability of the ACNSs are tested using a two-electrode system. The specific capacitance (C_sp) values are 55, 114, and 190 F g⁻¹ in aqueous 0.5 M sodium sulfate, organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile, and pure ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) electrolytes, respectively. The ACNSs also shows the largest potential window of 3.0 V, the highest specific energy (59 Wh kg⁻¹) and specific power (750 W kg⁻¹) in [BMIM][PF₆]. A mini-prototype device is prepared to demonstrate the practicality of the ACNSs.     

萘基相互连接的多孔碳纳米囊的制备及超电容性能

以萘为碳源, 采用MgO模板诱导耦合KOH裁剪技术制备了相互连接的多孔碳纳米囊(ICNC). 结果表明所制备的ICNC₂具有大的比表面积(1811 m²/g)、 高的压实密度(1.38 g/cm³)和微孔孔容含量(58.93%). 在对称的超级电容器(SC)中, ICNC₂电极的体积比容在不同电流密度下分别高达420.8 F/cm³(0.069 A/cm³)和315 F/cm³(27.6 A/cm³), 容量保持率为74.82%. 在38 W/L功率密度下, ICNC₂基SC的体积能量密度为14.6 W?h/L. 经过20000次循环后, 其体积比容仅衰减1.4%, 库伦效率为99.1%, 为从萘基小分子制备储能用功能碳材料提供了一种可行的方法.