Composite MWCNT/carbon xerogel-nafion electrode for energy storage

In this paper, we report the preparation and characterization (morphological, structural, surface, and electrochemical) of multiwalled carbon nanotube (MWCNT)/carbon xerogel (CX) electrodes prepared by mixing. This research proposes the hypothesis that the use of a hydrophilic binder (nafion) and the use of MWCNTs enhance electrode capacitance and conductivity. Electrochemical measurements in 2 M NaCl solution were performed. The advantage of adding multiwalled carbon nanotubes to the array of xerogel-nafion was studied through different electrochemical methods. It was validated that the greater carbon nanotube mesoporosity allows less compaction of the electrode, thus effectively increasing the specific area and therefore capacitance. Furthermore, we observed the increase in electronic conductivity reported in numerous studies, a fact that is true for iR drop measurement cycles in both galvanostatic charging and discharging. The carbon composite proved to be viable for energy storage.     

Electrodeposition of MnO2 nanowires on carbon nanotube paper as free-standing,flexible electrode for supercapacitors

MnO₂ nanowires were electrodeposited onto carbon nanotube (CNT) paper by a cyclic voltammetric technique. The as-prepared MnO₂ nanowire/CNT composite paper (MNCCP) can be used as a flexible electrode for electrochemical supercapacitors. Electrochemical measurements showed that the MNCCP electrode displayed specific capacitances as high as 167.5 F g⁻¹ at a current density of 77 mA g⁻¹. After 3000 cycles, the composite paper can retain more than 88% of initial capacitance, showing good cyclability. The CNT paper in the composite acted as a good conductive and active substrate for flexible electrodes in supercapacitors, and the nanowire structure of the MnO₂ could facilitate the contact of the electrolyte with the active materials, and thus increase the capacitance.     

Dispersant Molecules with Functional Catechol Groups for Supercapacitor Fabrication

Cathodes for supercapacitors with enhanced capacitive performance are prepared using MnO₂ as a charge storage material and carbon nanotubes (CNT) as conductive additives. The enhanced capacitive properties are linked to the beneficial effects of catecholate molecules, such as chlorogenic acid and 3,4,5-trihydroxybenzamide, which are used as co-dispersants for MnO₂ and CNT. The dispersant interactions with MnO₂ and CNT are discussed in relation to the chemical structures of the dispersant molecules and their biomimetic adsorption mechanisms. The dispersant adsorption is a key factor for efficient co-dispersion in ethanol, which facilitated enhanced mixing of the nanostructured components and allowed for improved utilization of charge storage properties of the electrode materials with high active mass of 40 mg cm⁻². Structural peculiarities of the dispersant molecules are discussed, which facilitate dispersion and charging. Capacitive properties are analyzed using cyclic voltammetry, chronopotentiometry and impedance spectroscopy. A capacitance of 6.5 F cm⁻² is achieved at a low electrical resistance. The advanced capacitive properties of the electrodes are linked to the microstructures of the electrodes prepared in the presence of the dispersants.     

Copper sulfide nanoneedles on CNT backbone composite electrodes for high-performance supercapacitors and Li-S batteries

Hierarchical-structured copper sulfide nanoneedles were grown on multi-walled carbon nanotube backbone (denoted as CuS@CNT) as electrodes for supercapacitors via a facile template-based hydrothermal conversion approach and further by simply impregnating sulfur into CuS@CNT (S@CuS@CNT) as electrodes for Li-S batteries. The electrochemical measurements showed that the resultant CuS@CNT composite electrodes deliver outstanding electrochemical performance with a specific capacitance up to 566.4 F g^?1 and cyclic stability of 94.5 % of its initial capacitance after 5000 cycles at a current density of 1 A g^?1. A synergistic effect arising from the unique hierarchical structure was responsible for the electrode performance, including a large surface area of 49.3 m² g^?1 and active CuS ultrafine nanoneedles firmly bonded to the highly conductive carbon nanotube (CNT) backbone. When used as an electrode material for Li-S batteries, the S@CuS@CNT (S content 59 wt%) exhibited satisfying electrochemical performance. The S@CuS@CNT electrode showed that coulombic efficiency was close to 100 % and capacity maintained more than 500 mA h g^?1 with progressive cycling up to more than 100 cycles even at a high current density. This strategy of stabilizing S with a small amount of copper sulfide nanoneedles can be a very promising method to prepare free-standing cathode material for high-performance Li-S batteries. The fabrication strategy presented here is low cost, facile, and scalable, which can be considered as a promising material for large-scale energy storage device. In particular, the use of CNT as backbone for the growth of active materials presents many potential merits owing to its lightweight, biodegradable, and stretchable characteristics.     

Electrochemical capacitive properties of CNT fibers spun from vertically aligned CNT arrays

Due to their lightweight, large surface area; excellent electrical conductivity; and mechanical strength, carbon nanotube (CNT) fibers show great potentials in serving as both electrode materials and current collectors in supercapacitors. In this paper, the capacitive properties of both as-spun CNT fibers and electrochemically activated CNT fibers have been investigated using cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the as-spun CNT fibers exhibit a very low specific capacitance of 2.6 F g⁻¹, but electrochemically activated CNT fibers show considerably improved specific capacitance. The electrochemical activation has been realized by cyclic scanning in a wide potential window. Different electrolytes have also been examined to validate the applicability of our carbon materials and the activation mechanism. It is believed that such an activation process can significantly improve the surface wetting of the CNT fibers by electrolyte (aqueous Na₂SO₄ solution). The cycling stability and rate-dependence of the capacitance have been studied, and the results suggest practical applications of CNT fibers in electrochemical supercapacitors.     

Functionalized Cu‐MOF@CNT Hybrid: Synthesis,Crystal Structure and Applicability in Supercapacitors

The synthesis of a metal–organic framework (MOF) named IITI‐1 is reported by employing an H₂L linker with Cu(NO₃)₂?3 H₂O in a mixed solvent system of N,N‐dimethyl formamide (DMF) and H₂O. Further, in order to explore the energy storage application of IITI‐1 , a IITI‐1/CNT hybrid was prepared by a simple ultrasonication technique. Incorporation of a carbon nanotube (CNT) in the layered IITI‐1 MOF gave rise to enhanced electrolyte accessibility along with improved electrochemical storage capacity. The electrochemical investigations reveal a high specific capacitance (380 F g^?1 at 1.6 A g^?1) with a good rate performance for IITI‐1/CNT . The IITI‐1 MOF and the IITI‐1/CNT composite were characterized by PXRD, BET, SEM, and TEM techniques. Moreover, IITI‐1 MOF was also confirmed by single‐crystal XRD analysis.     

聚苯胺改性氮掺杂碳纳米管制备及其超级电容器性能

利用苯胺原位化学聚合合成聚苯胺包覆碳纳米管(CNTs), 再炭化处理制备氮掺杂碳纳米管(NCNTs).激光拉曼(Raman)光谱和X射线光电子谱(XPS)分析及透射电镜(TEM)观察表明, 苯胺包覆碳纳米管经炭化处理后, 得到以碳纳米管为核、氮掺杂碳层为壳, 具有核-壳结构的氮掺杂碳纳米管, 而碳纳米管本征结构未遭破坏. 研究表明, 随着苯胺用量的增大, 氮掺杂碳纳米管的氮掺杂碳层变厚, 氮含量从7.06%(质量分数)增加到8.64%, 而作为超级电容器电极材料, 随着氮掺杂碳层厚度降低, 氮掺杂碳纳米管在6 mol·L^-1氢氧化钾电解液中的比容量从107 F·g^-1增大到205 F·g^-1, 远高于原始碳纳米管10 F·g^-1的比容量, 且聚苯胺改性氮掺杂碳纳米管表现出较好的充放电循环性, 经1000次充放电循环后仍保持初始容量的92.8%~97.1%, 表明氮掺杂碳纳米管不仅通过表面氮杂原子引入大的法拉第电容和改善亲水性使电容量显著增大, 其具有的核壳结构特征也使循环稳定性增强。     

Effect of an activating agent on the physicochemical properties and supercapacitor performance of naturally nitrogen-enriched carbon derived from Albizia procera leaves

The present study reports the preparation of naturally nitrogen-doped carbon nanostructured materials from Albizia procera leaves with enhanced electrochemical supercapacitance properties. The doped carbon materials were prepared by the pyrolysis of Albizia procera leaves at 850 °C. The effect of using various activating agents such as NaHCO₃ and ZnCl₂ was checked and compared on the structural and textural properties, specific capacitance, surface functional groups, and surface area. The Brunauer–Emmett–Teller (BET) analysis shows that NaHCO₃-activated nitrogen-doped carbon (NaNC) has a higher specific surface area compare to ZnCl₂-activated nitrogen-doped carbon (ZnNC) and nitrogen-doped carbon prepared without an activating agent (WANC). Overall, the BET and microscopic analyses confirmed that NaNC is composed of carbon nanosheets with macropores and mesopores, as well as a large number of micropores, which is completely different from the composition of ZnNC and WANC. In addition, the XPS analysis confirmed the existence of higher amount of nitrogen in NaNC compared to that of ZnNC, and WANC. NaNC exhibits a specific capacitance of 231 F g⁻¹ at 1 A g⁻¹ current with good energy and power densities, and an outstanding charging-discharging stability thanks to its unique features such as the existence of high amounts of nitrogen, high SSA, and the nanosheet-type morphology.     

碳纳米管的功能化及其电化学性能

超级电容器作为一种新型的储能元件,以其快速储存、释放能量等优点,近年来成为各国科研工作的研究重点和焦点[1￣3],并在数据记忆存储系统、便携式仪器设备、后备电源、通讯设备、计算机、燃料电池、电动车混合电源等许多领域都有广泛的应用前景[4]。目前,超级电容器用的电极材     

Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).     

Electrochemical Introduction of Active Sites into Super-long Carbon Nanotubes for Enhanced Capacitance

Electrochemical cyclic voltammetric(CV)scan was applied to inducing the partial oxidation and defects of carbon nanotubes(CNTs).The electrochemically induced functional groups and physical defects were...     

Chitin and chitin-cellulose composite hydrogels prepared by ionic liquid-based process as the novel electrolytes for electrochemical capacitors

This paper reports on the preparation and electrochemical performance of chitin- and chitin-cellulose-based hydrogel electrolytes. The materials were prepared by a casting solution technique using ionic liquid-based solvents. The method of chitin dissolution in ionic liquid with the assistance of dimethyl sulfoxide co-solvent was investigated. The obtained membranes were soaked with 1-M lithium sulfate aqueous solution. The prepared materials were preliminarily characterized in terms of structural and physicochemical properties. Further, the most promising biopolymer membranes were assembled with activated carbon cloth electrodes in symmetric electrochemical capacitor cells. The electrochemical performances of these devices were studied in a 2-electrode system by commonly known electrochemical techniques, such as cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The devices operated at a maximum voltage of 0.8 V. All the investigated materials have shown high efficiency in terms of specific capacitance, power density, and cyclability. The studied capacitors exhibited specific capacitance values in the range of 92–98 F g⁻¹, with excellent capacitance retention (ca. 97–98%) after 20,000 galvanostatic charge and discharge cycles. Taking into account the above information and the eco-friendly nature of the biopolymer, it appears that the prepared chitin- and chitin-cellulose-based hydrogel electrolytes can be promising components for green electrochemical capacitors.

     

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.     

Hybrid porous Ni(OH)2-MnO2 nanosheets/plasma-grafted MWCNTs for boosted supercapacitor performance

The utilization of nickel hydroxide and manganese dioxide solely as high-performance supercapacitive materials is hindered by their low capacitance retention and electrical conductivity. As Ni(OH)₂ and MnO₂ give a synergistic effect, porous Ni(OH)₂-MnO₂ nanosheets with a thickness of 9 nm are successfully grown on carbon fiber (CF) via a single-step hydrothermal co-deposition method. Multi-walled carbon nanotubes (CNT) are grafted with maleic anhydride (MA) through plasma-grafted process, followed by thiol-ene reaction to synthesize CNT-MA−S (CMS) to increase their aqueous dispersion behavior. The electrochemical properties of Ni(OH)₂-MnO₂ are further enhanced by dip-coating CMS on nanosheets. The composition and morphology of CMS and Ni(OH)₂-MnO₂ nanosheets are characterized using scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), transmission electron microscopy (TEM), thermogravimetric analyses (TGA), nuclear magnetic resonance (NMR), and Raman spectroscopy. The electrochemical characteristics of fabricated electrodes are analyzed using cyclic voltammetry and chronopotentiometry methods. CF−Ni(OH)₂-MnO₂/CMS electrode is successfully synthesized without using any binder, exhibited ultrahigh specific capacitance (2049 F g⁻¹ at a current density of 1 A g⁻¹), and excellent capacitance retention (>80 %) at 2 A g⁻¹ charge/discharge rate after 5000 cycles.     

Highly stable performance of supercapacitors using microporous carbon derived from phenol–melamine–formaldehyde resin

A series of microporous carbons were prepared by simple carbonization and activation of phenol–melamine–formaldehyde resin. The morphology, surface area, and elemental composition of the samples were investigated by scanning electron microscope, Brunauer–Emmett–Teller measurement, Raman spectra, and elemental analysis, respectively. Electrochemical characteristics were evaluated by cyclic voltammograms, galvanostatic charge/discharge, and electrochemical impedance spectroscopy measurements in 6.0?mol?L^?1 KOH. The microporous carbon activated by KOH presented a high specific capacitance of 202?F?g^?1 at a scan rate of 2?mV?s^?1. Furthermore, the KOH-activated microporous carbon electrode exhibited durable operation, the total loss of capacitance after 20,000 cycles is 2% at a current density of 500?mA?g^?1. The good electrochemical performance of the activated carbon was ascribed to well-developed micropores, high surface area, larger pore volume as well as oxygen groups.     

Self-sustaining hybrid electrode prepared from polyaniline,carbon nanotubes,and carbon fibers: morphological,structural, and electrochemical analyses

The self-sustaining hybrid electrode was prepared via chemical polymerization of aniline in acid medium containing dispersed carbon nanotubes (CNT), using carbon fiber (CF) as conducting substrate. The ternary composites called PAni/CNT/CF were characterized in order to evaluate their morphologies, structures, and thermal properties. The influence of the polyaniline (PAni) layer in the ternary composite properties was studied considering different deposition times on CF samples (30, 60, and 90 min). The ternary composite morphologies were observed by scanning electron microscopy while thermal structural analyses were obtained using thermogravimetric measurements. The structural features were analyzed by Raman scattering spectroscopy and Fourier transform infrared spectroscopy (FTIR). The possible interactions between PAni and CNT were discussed on the basis of Raman and FTIR spectra. These spectroscopic analyses also confirmed that the PAni present in the composite is in the emeraldine (ES) salt form. Furthermore, the ternary composites were also evaluated by electrochemical measurements such as cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) techniques. The results showed good charge storage capacity for ternary composites, in particular, for PAni/CNT/CF obtained with 90 min of deposition time, which exhibited specific capacitance of around 500 F g^?1. Therefore, this electrode was selected to build a prototype of type I supercapacitor. This device presented specific capacitance of around 143 F g^?1 after 3200 charge/discharge cycles.     

Uranyl sensor based on a N,N′-bis(salicylidene)-2-hydroxy-phenylmethanediamine and multiwall carbon nanotube electrode

The electrochemical determination of uranyl was investigated by using carbon paste electrode modified with a Schiff base namely N,N??-bis(salicylidene)-2-hydroxy-phenylmethanediamine (SHPMD/CPE) and also in the presence of carbon nanotube (SHPMD/CNT/CPE). The both modified electrodes displayed an irreversible peak at E _pa?=?0.798?V versus Ag/AgCl. The electrocatalytic reduction of uranyl has been studied on SHPMD/CNT/CPE, using cyclic and differential pulse voltammetry, chronocoulometry and linear sweep techniques. Electrochemical parameters including the diffusion coefficient (D), the electron transfer coefficient (??), the ionic exchange current (i) and the redox reaction rate constant (K) were determined for the reduction of uranyl on the surface of the modified electrodes. Linear range concentration is 0.002?C0.6???mol?L^?1 and the detection limit of uranyl is 0.206?nmol?L^?1. The proposed method was used to detect uranyl in natural waters and good recovery was achieved.     

Scalable activated carbon/graphene based supercapacitors with improved capacitance retention at high current densities

Scalable, highly stable supercapacitor electrodes were developed from the mixture of a tea factory waste based activated carbon (AC) and a low-cost electrochemical exfoliated graphene (EEG). The hybrid electrodes showed notably enhanced stability at high current densities. The AC sample was prepared by chemical method and exposed to a further heat treatment to enhance electrochemical performance. Graphene used in the preparation of hybrid electrodes was obtained by direct electrochemical exfoliation of graphite in an aqueous solution. Detailed structural characterization of AC, EEG, and hybrid material was performed. The original electrochemical performances of AC and EEG were examined in button size cells using an aqueous electrolyte. The hybrid materials were prepared by mixing AC and EEG at different mass percentage ratios, and tested as supercapacitor electrodes under the same conditions. Capacitance stability of the electrodes developed from AC:EEG (70:30) at high currents increased by about 45% compared to the original AC. The highest gravimetric capacitance (110 F/g) was achieved by this hybrid electrode. The hybrid electrode was scaled up to the pouch size and tested using an organic electrolyte. The organic electrolyte was preferred for scaling up due to its wider voltage ranges. The pouch cell had a gravimetric capacitance of 85 F/g and exhibited as good performance as the coin cell in the organic electrolyte.     

High temperature all solid state supercapacitor based on multi-walled carbon nanotubes and poly[2,5 benzimidazole]

Supercapacitor containing multi-walled carbon nanotubes (MWCNT) as the electrode material and phosphoric acid-doped poly[2,5 benzimidazole] (ABPBI) as the solid electrolyte and separator membrane has been investigated in a wide temperature range. Supercapacitors with different solid electrolyte concentrations have been fabricated and evaluated for their electrochemical performance. Specific capacitance of supercapacitors at room temperature was found to increase after the first heating cycle. Supercapacitor containing 10?wt.% of solid electrolyte in the electrode shows higher specific capacitance than the supercapacitor with liquid electrolyte. Cyclic voltammetry analysis of supercapacitors indicates high rate capability. The linear increase in the specific capacitance with temperature implies that capacitance is predominantly due to electric double layer. Electrochemical impedance analysis indicates that the mass capacitance and Warburg parameter increase with temperature, while solution resistance and leakage resistance decrease with temperature. The complex capacitance of the supercapacitors shows that both real and loss capacitances increase with temperature. The phase angle of supercapacitors is found to be around 85.2?±?1° at room temperature and it decreases with temperature. Galvanostatic charge–discharge cycling exhibits almost constant specific capacitance of 28?F?g^?1 at room temperature. However, it increases sharply and then attains stable value of 52?F?g^?1 during cycling at 100?°C. The increase in specific capacitance has been attributed to increase in surface area of the carbon nanotube (CNT), due to activation by phosphoric acid and diffusion of free phosphoric acid into the central canal of MWCNT.     

Hierarchical mesoporous carbon materials: preparation by direct tri-constituent co-assembly and the electrochemical performance

Hierarchical mesoporous carbon materials with large microporosity were prepared by direct tri-constituent co-assembly with the use of resols as the carbon precursor, tetraethyl orthosilicate as the inorganic precursor, and triblock copolymer F127 as the soft template. Bimodal pore size distributions in the range of 1.5–4 and 7.5–12 nm were obtained in the synthesized hierarchical mesoporous carbon materials after etching of silica by HF acid, showing a high surface area of 1,675 m²?g^?1 with a large pore volume of 2.06 cm³?g^?1. The electrochemical performance of the hierarchical mesoporous carbons was evaluated as an electrode material for electrochemical supercapacitor, showing a specific capacitance as high as 152 F?g^?1 at a scan rate of 5 mV?s^?1 in 6 M KOH aqueous solution and a good cycling stability with capacitance retention of 99 % over 500 cycles.