Improving the electrochemical performances of active carbon-based supercapacitors through the combination of introducing functional groups and using redox additive electrolyte

High-performance and low-cost electrochemical capacitors (ECs) are essential for large-scale applications in energy storage. In this work, the specific capacitance of active carbon (AC) electrode was significantly improved through the combination of introducing functional groups on the surface of AC and adding redox-active molecules (K₃Fe(CN)₆) into 2?M KOH aqueous electrolytes. The surface-oxygen functionalized AC (FAC) was synthesized using HNO₃ echoed as the electrode and 2?M KOH with 0.1?M K₃Fe(CN)₆ as the electrolyte. The surface functional groups of the AC not only contribute to the pseudocapacitance but also increase the active sites of the electrode/electrolyte interface, which enhances the electrochemical activity of the Fe(CN)₆^3?/Fe(CN)₆^4? redox pair, thus leading to high capacitance. In the redox electrolyte, the specific capacitance was much higher in 229.17?F?g^?1 (1?A?g^?1) achieved for those FAC than in raw AC (only 147.06?F?g^?1). Similarly, the FAC electrode suggested high energy density and extended cycling stability in the KOH?+?K₃Fe(CN)₆ electrolyte.     

Perovskite SrCo0.9Nb0.1O3−δ as an Anion‐Intercalated Electrode Material for Supercapacitors with Ultrahigh Volumetric Energy Density

We have synthesized and characterized perovskite‐type SrCo_0.9Nb_0.1O_3−δ (SCN) as a novel anion‐intercalated electrode material for supercapacitors in an aqueous KOH electrolyte, demonstrating a very high volumetric capacitance of about 2034.6 F cm⁻³ (and gravimetric capacitance of ca. 773.6 F g⁻¹) at a current density of 0.5 A g⁻¹ while maintaining excellent cycling stability with a capacity retention of 95.7 % after 3000 cycles. When coupled with an activated carbon (AC) electrode, the SCN/AC asymmetric supercapacitor delivered a specific energy density as high as 37.6 Wh kg⁻¹ with robust long‐term stability.     

Converting eucalyptus leaves into mesoporous carbon for its application in quasi solid-state supercapacitors

A high performance activated carbon having pore diameter of 2.8 nm and specific surface area of 841.8 m² g^?1 is prepared by chemical activation of eucalyptus leaves using KOH as an activating agent. The chemically-treated eucalyptus leaves EL(T) as electrode material has a specific capacitance of 663.5 mF cm^?2 (equivalent to single electrode specific capacitance of 442.3 F g^?1) with solid polymer electrolyte. This active material has excellent rate capability and good cycle performance, over 95 % of the original capacitance is retained after 5,000 cycles. The energy density of 101.6 Wh kg^?1 and power density of 2.85 kW kg^?1 has been observed for EL(T) based quasi solid-state supercapacitors.     

Facile synthesis of CuO nanosheets as electrode for supercapacitor with long cyclic stability in novel methyl imidazole-based ionic liquid electrolyte

Hierarchical CuO nanosheets were synthesized through a facile, eco-friendly reflux deposition approach for supercapacitor electrode material for energy storage. The resultant CuO nanosheets were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption isotherm techniques. The supercapacitor behavior of CuO nanosheets was investigated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy in novel 0.1 M aqueous 1-(1′-methyl-2′-oxo-propyl)-3-dimethylimidazolium chloride [MOPMIM][Cl] ionic liquid as an electrolyte. The result demonstrate that CuO nanosheets exhibit specific capacitance of 180 F g^?1 at 10 mV s^?1 scan rate which is the highest value in ionic liquid electrolyte and 87% specific capacitance retention after 5000th cycle. The electrochemical performance proves CuO nanosheets as electrode with ionic liquid electrolyte for developing green chemistry approach in supercapacitor.

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Graphical abstract As-synthesized, CuO nanosheets demonstrate excellent supercapacitor electrode performance with high specific capacitance of 180 F g^?1 at 10 mV s^?1 scan rate and 87% specific capacitance retention in 0.1 M aqueous [MOPMIM][Cl] IL electrolyte

     

KOH direct treatment of kombucha and in situ activation to prepare hierarchical porous carbon for high-performance supercapacitor electrodes

Kombucha, a renewable biomass, has been successfully utilized as an accessible carbon source to fabricate kombucha-derived hierarchical porous carbon (KHPC) by KOH direct treatment and in situ activation. The prepared KHPC shows an interconnected hierarchical porous structure, a pore volume of 0.41 cm³ g^?1, and a specific surface area of 917 m² g^?1. Due to the multiple synergistic effects of these advantages, the KHPC-3 exhibits a high specific capacitance of 326 F g^?1 at a current density of 1 A g^?1 in 6 M KOH, good rate capability of 82% retention from 1 to 20 A g^?1, and cycling performance with 91.3% retention over 5000 cycles. Moreover, the KHPC-3 symmetric supercapacitor reveals a good energy density of 20.97 Wh kg^?1 at a power density of 871.2 W kg^?1 and retains 8.08 Wh kg^?1 at 6330 W kg^?1 in 1 M Na₂SO₄ electrolyte. Therefore, the KHPC obtained via the simple synthesis process shows great promise as an electrode material in energy storage devices.     

In situ synthesis of crosslinked-polyaniline nano-pillar arrays/reduced graphene oxide nanocomposites for supercapacitors

Crosslinked-polyaniline (CPA) nano-pillar arrays adsorbed on the surface of reduced graphene oxide (RGO) sheets were synthesized by in situ solution polymerization through two steps of reduction. The electrochemical analyses demonstrated that the befittingly reduced CPA/RGO composite exhibited high performance as electrode materials for supercapacitors. The CPA/RGO composite showed very high specific capacitance of 1532 F g^?1 at a scan rate of 10 mV s^?1 or 694 F g^?1 at a current density of 2 A g^?1 in 1 M H₂SO₄ electrolyte, as well as great energy density of 61.4 W h kg^?1 at a current density of 2 A g^?1. The electrode material also had decent power density of 4 kW kg^?1 at a current density of 10 A g^?1, and good cycling stability of 92.5 % capacitance retained after 500 cycles of cyclic voltammetry at 500 mV s^?1. The neat microstructures and super electrochemical properties suggest the potential use of the composites in supercapacitors.     

Enhanced energy density of asymmetric supercapacitors via optimizing negative electrode material and mass ratio of negative/positive electrodes

An asymmetric supercapacitor based on manganese dioxide/Au/nickel foam (MANF) electrode as positive electrode and graphene or commercial activated carbons (AC) as negative electrode was fabricated. The effect of different negative electrode materials and mass ratios of negative/positive electrodes on the electrochemical properties of the asymmetric supercapacitor was carefully investigated. The results suggest that the mass ratio of negative/positive electrode has a significant impact on the specific capacitance of the asymmetric supercapacitor. Especially, it is found that the optimal mass ratio of the negative/positive electrode is slightly lower than that calculated according to charge balance. On the other hand, the asymmetric supercapacitor with commercialized AC as negative electrode possesses higher specific capacitance and better rate capability than that of the asymmetric supercapacitor with graphene as negative electrode. The negative material has slight impact on the cycle stability of the asymmetric supercapacitor. In addition, the optimized asymmetric supercapacitor with MANF composite as positive electrode and AC as negative electrode can obtain an energy density as high as 65.9 Wh?kg^?1 at a power density of 180 W?kg^?1 and a cell voltage of 1.8 V in the neutral Na₂SO₄ aqueous solution.     

Reed straw derived active carbon/graphene hybrids as sustainable high-performance electrodes for advanced supercapacitors

Reed straw-derived active carbon@graphene (AC@GR) hybrids were prepared by one-step carbonization/activation process using a mixture of reed straw and graphene oxide (GO) as raw materials and ZnCl₂ as activation agent. The as-prepared hybrids exhibit high specific surface area in a range of 1971–2497 m² g^?1, abundant porosity, as well as excellent energy storage capability. The symmetric C//C supercapacitor using the hybrid obtained at 700 °C as electrodes demonstrates superior cycling durability, ca. 90 % retention after 6000 cycles at 2 A g^?1, and a high energy density of 6.12 Wh kg^?1 at a power density of up to 4660 W kg^?1 in 6 M KOH aqueous electrolyte. The excellent capacitive performance is attributed to the synergistic effect of AC and GR.     

Porous nitrogen-doped graphene for high energy density supercapacitors in an ionic liquid electrolyte

Porous nitrogen-doped graphene (PNG) has been prepared via simple thermal treatment of graphene oxide and urea, and the morphology and structure of the PNG have been characterized by using a range of electron microscopy, X-ray photoelectron spectroscopy, and other techniques. The electrochemical performances of the PNG have been investigated in an ionic liquid electrolyte by cyclic voltammetry and galvanostatic charge-discharge via both three-electrode and two-electrode configurations. The PNG electrode delivers a specific capacitance of 310 F g^?1 at 1 A g^?1 with good cycling stability over 4000 cycles. The high electrochemical performance is ascribed to the porous structure and nitrogen-doping in the PNG. The porous structure enables high specific surface area and rapid ion mobility, contributing to double layer capacitance, while the N-doping enhances electrochemical activity and electric conductivity, contributing to pseudocapacitance. Meanwhile, the ionic liquid electrolyte enables a very wide working voltage of 3 V, leading to a high energy density up to 163.8 W h kg^?1. The fabricated supercapacitor can light up a LED for a long while with low self-discharge, showing good potential for practical application.     

The effect of activation technology on the electrochemical performance of calcium carbide skeleton carbon

Porous CaC₂-derived carbon (CCDC) was synthesized by one-step route from CaC₂ in a freshly prepared chlorine environment at lower temperature. As-prepared CCDC was activated by H₃PO₄, ZnCl₂, and KOH, respectively. The effects of the activation technology on the structure and morphology of CCDC were studied by X-ray diffraction, physical N₂ adsorption/desorption, and transmission electron microscopy. It has been found that the pore structure and specific surface area of CCDC are apparently improved after activation; the CCDC activated by KOH especially showed an excellent specific surface area of 1,100?m²?g^?1. The electrochemical performance of supercapacitors using activated CCDC as electrode active material was studied by cyclic voltammery, galvanostatic charge/discharge, and cycle life measurements. The results indicated that the CCDCs activated by H₃PO₄, ZnCl₂, and KOH revealed enhanced capacitances of 172.6, 198.1, and 250.1?F?g^?1 in 6?M KOH electrolyte, which were increased by 11.4, 27.8, and 61.2?% compared with the pristine CCDC (155?F?g^?1), respectively. Furthermore, the supercapacitors using all activated CCDCs as electrode active material exhibited excellent cycle stability, and the specific capacitance for all activated CCDC samples had nearly no change after 5,000 cycles.     

Facile synthesis of biomass-derived hierarchical porous carbon microbeads for supercapacitors

Using the facile method of solvent evaporation, the leonardite fulvic acids (LFA)-based porous carbon microbeads (PCM) have been successfully prepared at ambient pressure, followed by carbonization and KOH activation (a low mass ratio alkali/LFA = 1.5) in an inert atmosphere. The effects of KOH treatment on pore structures and the formation mechanism of the PCM were discussed. The results showed that the sample exhibited remarkable improvement in textural properties. The activated carbon microbeads had high surface area (2269 m² g^?1), large pore volume (1.97 cm³ g^?1), and displayed excellent capacitive performances, compared with carbon powder. The porous carbon material electrodes with the “porous core structure” behaved superiorly at a specific capacitance of 320 F g^?1 at a current density of 0.05 A g^?1 in 6 M KOH electrolyte, which could still remain 193 F g^?1 when the current density increased to 100 A g^?1. Remarkably, in the 1 M TEABF₄/PC electrolyte, the PCM samples could reach 156 F g^?1 at 0.05 A g^?1, possess an outstanding energy density of 39.50 Wh kg^?1, and maintain at 22.05 Wh kg^?1 even when the power density rose up to 5880 W kg^?1. The balance of structural characteristic and high performance makes the porous carbon microbeads a competitive and promising supercapacitor electrode material.     

Functionalized graphene foam as electrode for improved electrochemical storage

We report on a non-covalent functionalization of graphene foam (GF) synthesized via chemical vapour deposition (CVD). The GF was treated with pyrene carboxylic acid (PCA) which acted as a source of oxygen and/or hydroxyl groups attached to the surface of the graphene foam for its electrochemical performance improvement. The modified graphene surface enabled a high pseudocapacitive effect on the GF. A specific capacitance of 133.3 F g^?1, power density ～ 145.3 kW kg^?1 and energy density ～ 4.7 W h kg^?1 were achieved based on the functionalized foam in 6 M KOH aqueous electrolyte. The results suggest that non-covalent functionalization might be an effective approach to overcome the restacking problem associated with graphene electrodes and also signify the importance of surface functionalities in graphene-based electrode materials.     

High Energy Density Heteroatom (O,N and S) Enriched Activated Carbon for Rational Design of Symmetric Supercapacitors

Carbon-based symmetric supercapacitors (SCs) are known for their high power density and long cyclability, making them an ideal candidate for power sources in new-generation electronic devices. To boost their electrochemical performances, deriving activated carbon doped with heteroatoms such as N, O, and S are highly desirable for increasing the specific capacitance. In this regard, activated carbon (AC) self-doped with heteroatoms is directly derived from bio-waste (lima-bean shell) using different KOH activation processes. The heteroatom-enriched AC synthesized using a pretreated carbon-to-KOH ratio of 1:2 (ONS@AC-2) shows excellent surface morphology with a large surface area of 1508 m² g⁻¹. As an SC electrode material, the presence of heteroatoms (N and S) reduces the interfacial charge-transfer resistance and increases the ion-accessible surface area, which inherently provides additional pseudocapacitance. The ONS@AC-2 electrode attains a maximum specific capacitance (C_sp) of 342 F g⁻¹ at a specific current of 1 Ag⁻¹ in 1 m NaClO₄ electrolyte at the wide potential window of 1.8 V. Moreover, as symmetric SCs the ONS@AC-2 electrode delivers a maximum specific capacitance (C_sc) of 191 F g⁻¹ with a maximum specific energy of 21.48 Wh kg⁻¹ and high specific power of 14 000 W kg⁻¹ and excellent retention of its initial capacitance (98 %) even after 10000 charge/discharge cycles. In addition, a flexible supercapacitor fabricated utilizing ONS@AC-2 electrodes and a LiCl/polyvinyl alcohol (PVA)-based polymer electrolyte shows a maximum C_sc of 119 F g⁻¹ with considerable specific energy and power.     

Mesopore-dominant porous carbon derived from bio-tars as an electrode material for high-performance supercapacitors

For the first time, toxic bio-tars collected from the gasification of pine sawdust are used as the precursor for activated carbons. Various types of activation agents including KOH, K₂CO₃, H₃PO₄ and ZnCl₂ were screened for obtaining superior activated carbons. When KOH was used as an activation agent, the obtained activated carbons exhibited high specific surface area and large mesopore volume. The activated carbons were further employed to be the electrode material of supercapacitors, and its specific capacitance reached up to 260 F g^?1 at 0.25 A g^?1 current density. Also, it showed an excellent rate performance from preserving a relatively high specific capacitance of 151 F g^?1 at 50 A g^?1. The assembled device also exhibited the good electrochemical stability with the capacity retention of 90% after 5000 cycles. Furthermore, the maximum energy density of the activated carbons in organic electrolyte reached 17.8 Wh kg^?1.     

Electrochemical capacitance performance of polypyrrole–titania nanotube hybrid

In this study, the polypyrrole–titania nanotube hybrid has been synthesized for an electrochemical supercapacitor application. The highly ordered and independent titania nanotube array is fabricated by an electro-oxidation of titanium sheet through an electrochemical anodization process in an aqueous solution containing ammonium fluoride, phosphoric acid and ethylene glycol. The polypyrrole–titania nanotube hybrid is then prepared by electrodepositing the conducting polypyrrole into well-aligned titania nanotubes through a normal pulse voltammetry deposition process in an organic acetonitrile solution containing pyrrole monomer and lithium perchlorate. The morphology and microstructure of polypyrrole–titania nanotube hybrid are characterized by scanning electron microscopy, infrared spectroscopy and Raman spectroscopy. The electrochemical capacitance performance is determined by cyclic voltammetry and charge/discharge measurement. It indicates that the polypyrrole film can been uniformly deposited on both surfaces of titania nanotube walls, demonstrating a heterogeneous coaxial nanotube structure. The specific capacitance of polypyrrole–titania nanotube hybrid is determined to be 179?F?g^?1 based on the polypyrrole mass. The specific energy and specific power are 7.8?Wh?kg^?1 and 2.8?kW?kg^?1 at a constant charge/discharge current of 1.85?mA?cm^?2, respectively. The retained specific capacitance still keeps 85% of the initial capacity even after 200 cycle numbers. This result demonstrates the satisfying stability and durability of PPy–TiO₂ nanotube hybrid electrode in a cyclic charge/discharge process. Such a composite electrode material with highly ordered and coaxial nanotube hybrid structure can contribute high energy storage for supercapacitor applications.     

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.     

Capacity of graphene anode in ionic liquid electrolyte

The graphene anode was investigated in an ionic liquid electrolyte (0.7 M lithium bis(trifluoromethanesulfonyl)imide (LiNTf₂)) in room temperature ionic liquid (N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPyrNTf₂)). SEM and TEM images suggested that the electrochemical intercalation/deintercalation process in the ionic liquid electrolyte without vinylene carbonate (VC) leads to small changes on the surface of graphene particles. However, a similar process in the presence of VC results in the formation of a coating (SEI—solid electrolyte interface) on the graphene surface. During charging/discharging tests, the graphene electrode working together with the 0.7 M LiNTf₂ in MPPyrNTf₂ electrolyte lost its capacity, during cycling and stabilizes at ca. 200 mAh g^?1 after 20 cycles. The addition of VC to the electrolyte (0.7 M LiNTf₂ in MPPyrNTf₂?+?10 wt.% VC) considerably increases the anode capacity. Electrodes were tested at different current regimes: ranging between 50 and 1,000 mA g^?1. The capacity of the anode, working at a low current regime of 50 mA g^?1, was ca. 1,250 mAh g^?1, while the current of 500 mA g^?1 resulted in capacity of 350 mAh g^?1. Coulombic efficiency was stable and close to 95 % during ca. 250 cycles. The exchange current density, obtained from impedance spectroscopy, was 1.3?×?10^?7 A cm^?2 (at 298 K). The effect of the anode capacity decrease with increasing current rate was interpreted as the result of kinetic limits of the electrode operation.     

Supercapacitor based on graphene and ionic liquid electrolyte

A new kind of supercapacitor by using chemical reduced graphene (CRG) as electrode material and ionic liquid with addition of acetonitrile as electrolyte is assembled and investigated. CRG materials with high surface area are prepared by chemical reduction of graphene oxide. The capacitive properties of the supercapacitor composed of the CRG and ionic liquid electrolyte are studied by electrical impedance spectroscopy, cyclic voltammetry and galvanostatic charge–discharge. With the combined advantages of graphene and ionic liquid, the supercapacitor shows perfect performance. The supercapacitor possesses wide cell voltage and good stability. The specific capacitance, energy density, and specific power density of the present supercapacitor are 132 Fg⁻¹, 143.7 Wh kg⁻¹, and 2.8 kW kg⁻¹, respectively. The results demonstrate the potential application of electrical energy storage devices with high performance based on this new kind of supercapacitor.

     

Carbon Electrode Material with High Densities of Energy and Power

Activated carbon (AC) samples as electrode materials were prepared by means of simultaneous physical-chemical activation using walnut shells as precursors. The porosity and surface chemistry of the resultant AC samples were studied by the nitrogen adsorption at 77 K, and FTIR spectrum. The testing supercapacitors were assembled with resultant carbon electrode and electrolyte of 6 mol·L⁻¹ KOH solution. Their electrochemical properties were investigated by charge-discharge of constant current, cyclic voltammogram, impedance spectrum and so on. The results showed that the capacitor had low inner resistance, low leakage current, high stability, and capacitance retainability. The specific capacitance of AC increased with increasing BET specific surface area. The specific capacitance of the AC sample with a specific area of 1197 m²·g⁻¹ could be as high as 292 F·g⁻¹. At a discharge current of 80 mA, the corresponding specific energy density, power density, and maximum power of the supercapacitor are 7.3 Wh·kg⁻¹, 770 W·kg⁻¹, and 5.1 W·g⁻¹, respectively.     

Extraordinary Supercapacitor Performance of a Multicomponent and Mixed‐Valence Oxyhydroxide

We report a novel multicomponent mixed‐valence oxyhydroxide‐based electrode synthesized by electrochemical polarization of a de‐alloyed nanoporous NiCuMn alloy. The multicomponent oxyhydroxide has a high specific capacitance larger than 627 F cm^?3 (1097±95 F g^?1) at a current density of 0.25 A cm^?3, originating from multiple redox reactions. More importantly, the oxyhydroxide electrode possesses an extraordinarily wide working‐potential window of 1.8 V in an aqueous electrolyte, which far exceeds the theoretically stable window of water. The realization of both high specific capacitance and high working‐potential windows gives rise to a high energy density, 51 mWh cm^?3, of the multicomponent oxyhydroxide‐based supercapacitor for high‐energy and high‐power applications.