Electrode Materials For Supercapacitors Research Articles

Ti3C2Tx/CDs@MnO2 composite as electrode materials for supercapacitors: synthesis and electrochemical performance

Ti3C2Tx/CDs@MnO2 composite as electrode materials for supercapacitors: synthesis and electrochemical performance

Tailoring microstructure and conductivity of porous hollow carbon spheres to enhance their performance as electrode materials for supercapacitors

Porous carbon materials are widely used in electrical double-layered capacitors for energy storage applications due to their abundant pores, high specific surface area and excellent electrochemical stability although their intrinsic electrical conductivity is generally low. Traditional high-temperature treatment was always adopted to boost the electrical conductivity of porous carbon materials by enhancing their graphitization degree, while this would always be accompanied by severe damage to pore structure and corresponding electrochemical performance. To solve the dilemma between boosting electrical conductivity and retaining pore structure, in this research, we proposed a low-temperature catalytic graphitization for hollow carbon spheres (HCSs) prepared by modified Stöber method accompanied with a special pore structure tailoring strategy. By altering the timing of adding carbon source, followed by secondary pore-forming and catalytic graphitization, HCSs with thin and porous shell walls along with enhanced conductivity were synthesized. Compared with the untreated HCSs or high-temperature graphitized HCSs, HCSs fabricated by the aforementioned combined strategies exhibited enhanced pore volume, specific surface area (2160.1 m2·g−1, 165.3 % of the untreated group) and conductivity (16.44±0.05 S·cm−2, 221.5 % of the untreated group), demonstrating much better electrochemical performance as the mass specific capacitance reached 256.7 F·g−1 and a volume specific capacitance reached 102.7 F·cm−3 at a current density of 1 A·g−1. Moreover, due to the largely promoted conductivity, the capacitance with the catalytic graphitized HCSs as the electrode material could be further boosted up to 273.4 F·g−1 at 1 A·g−1 by exempting the generally indispensable conductive agents and a high capacitance retention of 100.7 % was achieved after 5000 cycles at a relatively high current density of 10 A·g−1. This could be attributed to local graphitization brought by dispersed catalyst particles instead of entire atom rearrangement during high-temperature graphitization which would result in severe pore vanishing. The synergy of low-temperature catalytic graphitization and secondary pore-forming might be a novel strategy in electrode material fabrication for advanced supercapacitors or other energy storage devices.

Multicomponent hierarchical Ni-MOFs/MWCNTs@Ni/Co-LDH nanohybrid as advanced electrode material for supercapacitor

Layer double hydroxide (LDH) is a metal hydroxide with two or more metal components. It has promising prospects in supercapacitors (SCs) as electrode material due to the chemical composition adjustability, excellent ion exchangeability, good redox activity and high specific capacity. However, the further application of LDH is limited to the inferior electrochemical conductivity and slow reaction kinetics. Multiwalled carbon nanotubes (MWCNTs) as electrode materials possess excellent conductivity and distinctive hollow structure but the specific capacities are low. Metal-organic frameworks (MOFs) have abundant electrochemical active sites, multifunctionality and tunable porosity, which could accelerate the process of transporting and diffusing electrolyte ions, enhancing the specific capacitance as electrode material. Hence, in this work, MWCNTs decorated with Ni-MOFs were introduced into Ni/Co-LDH to fabricate multicomponent heterostructure Ni-MOFs/MWCNTs@Ni/Co-LDH nanohybrid by in situ chemical reaction. The specific capacity of Ni-MOFs/MWCNTs@Ni/Co-LDH was 1032.0 C g−1 at a current density of 1.0 A g−1 and retained 66.0 % initial capacity following 5000 cycles at 5 A g−1. A power density of 850.0 W kg−1 and an energy density of 28.9 Wh kg−1 were obtained for the assembled asymmetric supercapacitor.

Synthesis and characterisation of tamarind seed husk-derived carbon quantum dots incorporated polypyrrole nanosphere composite for energy storage applications

ABSTRACT In this study, the green synthesis of Tamarind Seed Husk-derived carbon quantum dots (TCQDs) by using a facile one-step hydrothermal technique and Tamarind Seed Husk-derived carbon quantum dots/Polypyrrole nanosphere composites (TCQDs/PPy-NS) was synthesised by using the facile in-situ chemical polymerisation method. These results suggest that the TCQDs/PPy-NS composite electrode is a promising electrode for high-energy storage applications. The TCQDs/PPy-NS composite offers an effective supercapacitor electrode material by blending the superior electrical conductivity of TCQDs with the increased pseudocapacitive capacity of polypyrrole nanospheres (PPy-NS). The TCQDs/PPy-NS composite exhibits a specific capacity (Csp) of 400 Fg−1 at a current density (CD) of 2 Ag−1, and a solid-state flexible symmetric supercapacitor (SSC) was developed using the TCQDs/PPy-NS composite to meet an excellent power density (PD) of 1008.19 Wkg−1 at an energy density (ED) of 31.02 Whkg−1 It also demonstrated excellent cycling stability with a capacity retention and coulombic efficiency of 84.57% and 98.06% after 4000 cycles at 2 Ag−1 respectively. This remarkable flexibility and stability make the TCQDs/PPy-NS SSC device highly suitable for applications in wearable electronics and flexible energy storage systems.

Ti2TaC2: A novel out-of-plane ordered MXene towards flexible and cytocompatible supercapacitors

Exploring biocompatible and flexible supercapacitor electrode material is crucial for expanding the development of health monitoring bioelectronics. MXene films, due to their low cost, high conductivity, and excellent durability under different deformation conditions, are highly competitive in bioelectronic device applications compared with traditional carbon-based materials. Herein, a novel out-of-plane ordered double transition metal MXene (Ti2TaC2) is elaborately designed and originally synthesized, where Ti atoms preferentially reside in the outer transition metal layer and Ta atoms occupy in the middle layer. Theoretical calculations prove that the introduction of Ta species into Ti3C2 MXene enlarges the work function, raises the d-band center close to Fermi level and increases the density of states of d-orbital. Consequently, the Ti2TaC2 film delivers high specific capacitance of 313 F g−1 at 2 mV s−1 and excellent cycling stability without capacitance loss after 10,000 cycles at 10 A/g. Furthermore, the safety and cytotoxicity of Ti2TaC2 material are innovatively evaluated in vitro multiple cell lines (e.g., 293T, bEnd.3, PC-12, BV2 and HUVEC cells) and implanted into the subcutaneous tissue of mice, proving its good biosafety and cytocompatibility. The results suggest that flexible Ti2TaC2 MXene film may be a promising cytocompatible electrode material for long-term health monitoring bioelectronics.

Computational investigation of quantum capacitance enhancement in Mg-substituted MgB[formula omitted]-based supercapacitor electrodes

The investigation into surface functionalization’s effect on magnesium diboride (MgB2) presents a captivating research direction, shedding light on the modifications in its electronic structure resulting from functionalization systematically analysed through density functional theory (DFT) calculations. This study systematically investigates the effects of varying functionalization concentrations on MgB2, unveiling a profound influence on its quantum capacitance(CQ). Maximum enhancement is found within an optimal doping range; however, impurity ad-atom interactions may cause quantum capacitance to decrease above this barrier. Notably, these ad-atoms act as magnetic impurities, generating a localized density of states near the Fermi energy, thereby increasing charge carrier density and resulting in a remarkable increase in quantum capacitance. We also emphasize the importance of functionalized MgB2 as an example of a two-dimensional supercapacitor electrode material in the advancement of energy storage technology. These materials promise improved charge storage capacities and tailored electronic properties, which will accelerate the development of effective energy storage technologies. This paper highlights the potential direction of two-dimensional electrode materials in developing supercapacitor technology towards superior energy storage systems by elucidating fundamental mechanisms using quantum capacitance enhancement.

Significantly Increased Specific Discharge Capacitance at Carbon Fibers Created via Architected Ultramicropores.

Carbon is commonly used as an electrode material for supercapacitors operating on an electrical double-layer energy storage mechanism. However, the low specific capacitance limits its application. Increasing the specific surface area is by far the most common expansion method, and surprisingly, they are not always positively correlated. The overmuch specific surface will show the characteristics of nanoconfinement, and the potential synergistic enhancement mechanism of various key parameters is still controversial. In this work, carbon fiber electrodes with different ultramicropore structures were designed in order to improve the utilization rate and the discharge capacitance. It has been found that when the ultramicropore entrance's surface is too small, it will lead to the decrease of the external charge of the pore transport channel, and then, the selectivity of the opposite ions will decrease. The numerical simulation based on Poisson and Nernst-Planck equations also indicates that ions have difficulty diffusing into the micropores when their entrance surface decreases. Surface properties within the nanocontainment space become critical factors influencing ion transport and adsorption. The specific discharge capacitance of carbon fiber is increased from 3 to 1430 mF cm-2.

Plasma Engineering of Co4N/CoN Heterostructure for Boosting Supercapacitor Performance.

Supercapacitor electrode materials play a decisive role in charge storage and significantly affect the cost and capacitive performance of the final device. Engineering of the heterostructure of metal-organic framework (MOF)-derived transition metal nitrides (TMNs) can be conducive to excellent electrochemical performance owing to the synergistic effect, optimized charge transport/mass transfer properties, and high electrical conductivity. In this study, a Co4N/CoN heterostructure was incorporated into a nitrogen-doped support by radio-frequency (RF) plasma after simple pyrolysis of Co-based formate frameworks (Co-MFFs), with the framework structure well retained. Plasma engineering can effectively increase the ratio of Co4N in the Co4N/CoN heterostructure, accelerating the electron transfer rate and resulting in a rough surface due to the reduction effect of high-energy electrons and the etching effect of ions. Benefiting from the plasma modification, the obtained electrode material Co4N/CoN@C-P exhibits a high specific capacitance of 346.2 F·g-1 at a current density of 1 A·g-1, approximately 1.7 times that of CoN/Co4N@C prepared by pyrolysis. The specific capacitance of Co4N/CoN@C-P reaches 335.6 F·g-1 at 10 A·g-1, approximately 96.9% of that at 1 A·g-1, indicating remarkable rate capability. Additionally, the capacitance retention remains at 100% even after 1000 cycles, suggesting excellent cycling stability. The rational design and plasma engineering of the TMN heterostructures at the nanoscale are responsible for the excellent electrochemical performance of this novel composite material.

Facile synthesis of samarium (Sm3+) doped cobalt-iron oxide nano ferrite as an advanced electrode material for possible supercapacitor applications

Herein, we present design and fabrication of Samarium (Sm3+) doped cobalt-iron oxide ferrites nanocomposite electrode as an efficient energy storage material for supercapacitors. We employed a simple, low cost and quick one step solution combustion method to synthesize CoFe2-xSmxO4 (x = 0.0, 0.050, 0.075 and 0.1) ferrites. The morphological and structural features of synthesized CoFe2-xSmxO4 ferrites were analysed through various analytical and spectroscopic characterization methods such as scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscope (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). These analytical techniques confirm the successful doping of Samarium (Sm3+) into cobalt-iron ferrite, and the doping does not affect the crystalline structure of pure ferrite. The electrochemical properties of the synthesized ferrites were significantly improved after Samarium (Sm3+) doping into the host cobalt-iron-oxide. The highest specific capacity about 314 F/g was achieved for CoFe2-xSmxO4 (x = 0.1) composite electrode material, in comparison to pure CoFe2-xSmxO4 (x = 0) which is about 125 F/g. However, CoFe2-xSmxO4 (x = 0.1) ferrite shows a superior capacitance retention of the order of 98 % even after 5000 cycles of operation at a scan rate of 250 mV/s. The electrode material fabricated by using CoFe2-xSmxO4 ferrite renders an energy density of 30.16 W h/kg at a power density of 400 W h/kg. The results obtained in presented studies opens new avenues for the fabrication high-performance electrode material for supercapacitor that could be well suited for light weight electronic devices, electric vehicles, and forthcoming generation supercapacitor applications.

High-performance asymmetric supercapacitor based on hierarchical hydrothermally grown CuS nanostructures

In this work, various hierarchical CuS were fabricated via an efficient one-step hydrothermal process with different surfactants (polyvinyl pyrrolidine (CS-P), Citric acid (CS-C), Oleic acid (CS-O)) and examined as electrode materials for supercapacitors. XRD, FESEM, HRTEM and BET analysis reveal the fabrication of a hexagonal crystal structure with porous microspheres of CuS-PVP having a BJH pore diameter of 16.241 nm. Among these, the CS-P electrode exhibits a superior specific capacitance of 414.28F/g at 1 A/g of current density in the KOH electrolyte. Additionally, an asymmetric supercapacitor built with CS-P as positive and Activated carbon as negative electrodes exhibited a specific energy of 27.95 Wh/kg at 624.96 W/kg of specific power at 2 A/g and demonstrated outstanding cycling stability with 80.6 % persistence of capacitance for 2500 GCD cycles at 10 A/g. Additionally, an ASC device created for use in real life and tested by charging it for 30 s managed to reach a 3-minute 50-second self-discharging duration. Hence, these favourable electrochemical findings indicate that the hydrothermally grown hierarchical CuS-PVP electrode is a bright potential material in energy storage applications.

Direct pyrolysis fabrication of N/O/S self-doping hierarchical porous carbon from Platycladus Orientali leaves for supercapacitor

To meet the growing market requirement for low-cost supercapacitor electrode materials, N/O/S self-doping hierarchical porous carbon is successfully fabricated by direct pyrolysis of platycladus orientalLeaves (POL). The obtained carbon material exhibits wide application prospects, because of simple and green-environmental technology, low-cost and satisfactory electrochemical properties, which avoided complex preparation routes and consumption of expensive chemical reagents in the traditional activation process. Under the optimum pyrolysis temperature (850 °C), the obtained POL-derived carbon (POL-850) possesses a high specific surface area (1140.2 m2g−1), sheet-like hierarchical porous microstructure, and uniform ternary heteroatoms co-doping (O: 6.79 at.%; N: 3.45 at.% and S: 2.20 at.%). As an electrode material for supercapacitor, the specific capacitance of the POL-850 reaches 224.4 Fg−1 of 0.5 Ag−1and 156.0 Fg−1 at 30 Ag−1, revealing excellent rate performance. The capacitance retention maintains 96.3 % after 10,000 consecutive charge-discharge cycles at 20 Ag−1, demonstrating superior cycling stability. Additionally, the assembled carbon-based symmetric supercapacitor device delivers a satisfied energy density of 11.0 Wh kg−1 with the power density of 65 W kg−1 and ultralong cycle-lifetime with 95.65 % capacitance retention after 10,000 charge/discharge cycles, while the Coulombic efficiency is retaining up to approximately 100 %. This work provides an easy and cost-effective way to rapidly prepare N/O/S co-doping hierarchical porous carbon for supercapacitors, which is very suitable for large-scale production.

Effect of hydrochloric acid on the properties of Ni-MOF nanostructures as supercapacitor electrode materials

In this paper, we investigate the effect of hydrochloric acid on the energy storage characteristics of nickel-based metal–organic framework (Ni-MOF) nanostructures. Electrochemical tests reveal that Ni-MOF exhibit high capacitance under hydrochloric acid regulation, achieving a current density of 2567.23 F/g at 2 A/g in 1 ml. Additionally, the synthesized Ni-MOF demonstrate low electrical resistance, with a resistance (Rs) of 1.209 Ω at a hydrochloric acid volume of 1 ml. After 5000 cycles of galvanostatic charge–discharge testing, the cycle retention efficiency of Ni-MOF-0.5 ml remains at 85.71 %.

Solvothermal synthesis of CuS nanosheets loaded porous carbon electrode composites for high performance supercapacitors

In this work, an electrode composite (CuS-NPC) for supercapacitors was synthesized by loading hexagonal nano-sheeted copper sulfide onto porous carbon through a solvothermal reaction using thiourea and copper acetate as the sulfur and copper sources, respectively. The synergistic effect of nanoscale copper sulfide sheet and hierarchical pore structure of porous carbon with high surface area achieves excellent capacitive performance in electrochemical reactions. CuS-NPC exhibited a large specific capacitance of 1298.7F g−1 at current density of 0.5 A/g and 766.3F g−1 at current density of 10 A/g, revealing that the electrode composite of copper sulfide and porous carbon have a great prospect as a supercapacitor electrode material.

Study on the properties of electrode materials for supercapacitors based on 1D Co-MOCPs

Three one-dimensional (1D) Co-MOCPs (23PCo–S1, 23PCo–S2, and 23PCo–S3; where 23P denotes the ligand, 2,3-pyridine dicarboxylic acid) were synthesized using a similar hydrothermal method. The molecular formulas for the isomers 23PCo–S1 and 23PCo–S2 are [Co(23P)3H2O], while that for 23PCo–S3 is [Co(23P)2H2O]. These single-crystal structures are classified into the P-1, Pca21, and P21/c space groups, displaying triclinic, orthogonal, and monoclinic symmetries, respectively. Techniques such as S-XRD, P-XRD, XPS, and SEM were applied to analyze the structures and valence states of the materials. Additionally, the electrochemical properties of the structures were evaluated using a three-electrode setup. Among these, 23P–Co–S2 demonstrated a remarkable specific capacitance of 458.5 F g−1 at a current density of 1 A g−1. In contrast, 23P–Co–S1 and 23P–Co–S2 showed specific capacitances of 192.2 and 270.6 F g−1, respectively, under the same experimental conditions.

In situ synthesis of M (Fe, Cu, Co and Ni)-MOF@MXene composites for enhanced specific capacitance and cyclic stability in supercapacitor electrodes

In this study, an in situ method was developed to synthesize a series of uniform 3D MOFs (Fe-, Cu-, Co-, Ni)-BTC@2D MXene (Ti3C2Tx) composites, and the experimental results show that a typical sample of Ni-MOF@MX 2 exhibits the highest specific capacitance of 1160.5 F·g−1 and 736 F·g−1 at a current density of 1 A·g−1 and 20 A·g−1, respectively, which is 2.3 times higher than the value of 320 F·g−1 at a current density of 20 A·g−1 on the bare Ni-MOF, and particularly maintains significant cyclic stability after 10,000 cycles at a high current density of 20 A·g−1. The improved electrochemical performance is ascribed to the synergistic interaction between layered MXene and MOFs, which were evidenced by experiments and theoretical calculations. The Ni-MOF@MX 2//AC asymmetric supercapacitor (ASC) device demonstrates a maximum energy density of 48.2 Wh kg−1 at 750 W kg−1. It retains 94 % capacity after 10,000 cycles. Moreover, the value still maintained at 23.3 Wh·kg−1 when elevating power density to 15000 W·kg−1. This indicates that the obtained MOF@MXene composites are probably alternative materials for supercapacitor electrodes in energy storage.

Conversion of cobalt from spent LIBs to Co3O4 electrode material for application in supercapacitors

ABSTRACT The cathode material of lithium-ion batteries (LIBs) is endowed with valuable metals, such as cobalt. The improper treatment of these batteries pollutes the environment and causes enormous resource waste. Therefore, the recovery of valuable metals from spent LIBs has attracted widespread attention. In this study, Co3O4 electrode materials were prepared by a simple homogeneous precipitation method and heat treatment using a leaching solution of spent LIBs-positive electrode material as the cobalt source. The crystal structure and morphology of the products were examined at different annealing temperatures, and their electrochemical performance was analyzed. The results show that low-temperature annealing contributes to grain refinement. The Co3O4 material prepared at 300°C annealing temperature has a rod-like structure with distinct pores and a specific surface area of 58.98 m2 g−1. Furthermore, electrochemical performance testing reveals that Co3O4 prepared at 300°C displays the best electrochemical performance as an electrode material, with a specific capacitance of 97.93 F g−1 and a cycle retention rate of 79.12% after 500 charge–discharge cycles. These findings demonstrate the feasibility of recycling valuable metal cobalt from spent LIBs cathode materials to produce Co3O4 materials for use as supercapacitor electrode materials, opening up new avenues for the recycling and utilisation of spent LIBs.

Advancing electrochemical activity: Insights from Li doped Ni-MOF synthesis and performance

This study presents the first-time synthesis of a novel Li doped Ni-MOF electrode material, achieved via a one-step hydrothermal strategy. Microstructural analysis using FESEM and HRTEM revealed hierarchical hollow spherical-like nanostructures within the Li doped Ni-MOF, providing abundant active sites for ion transport and storage. This structural feature resulted in enhanced specific capacity, exhibiting battery-like behaviors. Specifically, the Li doped Ni-MOF electrode displayed a notable specific capacity of 214.2 C/g in CV curves at 0.5 mV/s and 814 C/g in GCD curves at 1 A/g. These findings underscore the potential of the Li doped Ni-MOF as a superior electrode material for supercapacitors, indicating its promising prospects for advancing next-generation high-performance energy storage devices.

Oxalate and adipate mediated fabrication of CuO nanocrystallites for their electrochemical and supercapacitance studies

Cupric oxide (CuO) has been comprehensively studied in the field of electrochemistry due to its high Tc-Superconducting property. The present work focus on two different CuO materials i.e. CuO-1 and CuO-2 nanocrystallites which are successfully synthesized from their oxalate and adipate precursors respectively. The calcination temperature for the synthesis of CuO from their precursors is ascertained by TGA analysis of the dicarboxylates. Both the CuO materials are thoroughly characterized by SEM–EDS, XRD, IR and XPS spectroscopic techniques. As a candidate for supercapacitor electrode material, CuO-1/C and CuO-2/C showed a specific capacitance of 4.15 F/g and 22.24 F/g using cyclic voltammetry, 10.4 F/g and 46.6 F/g using GCD curves respectively at a current density of 1 A/g. Also, the CuO-1/C and CuO-2/C showed a specific energy density (Es) 1.59 Wh kg−1 and 0.36 Wh kg−1 at a specific power density (Ps) of 0.02 kW kg−1 and 0.025 kW kg−1 respectively. Moreover, the CuO-2/C exhibits ≈ 96.1% coulombic efficiency following 1000 cycles, whereas, CuO-1/C lags in coulombic efficiency with only 51.8%. As a better candidate, CuO-2/C exhibited excellent rate capability with an outstanding cycling stability of 93.7% retention after 1,000 cycles. The factors contributing to the significant specific capacitance of CuO-2/C along with better stability and reproducibility are its low electrolyte resistance Rs (2.47Ω) and charge transfer resistance Rct (1.01 Ω).

Nitrogen configuration modulation of porous graphitic carbon nanosheets for superior capacitive energy storage

Carbon nanosheets with layer-stacked porous structures and surface functionalized groups are beneficial for efficient ion storage in supercapacitor electrode materials, but achieving high cost-effectiveness and controllable surface groups remains a significant challenge. Herein, the biomass-derived chitosan and sodium alginate are selected as raw materials for self-assembly reaction with phytic acid as a cross-linking agent. The protonated chitosan and sodium alginate form a cross-linked network structure through hydrogen bonding and electrostatic adsorption, which is subsequently carbonized and activated to synthesize porous graphitic carbon nanosheets (PNPCN-X). PNPCN-X realizes an efficient distribution of porous and graphitic structures. It's noteworthy that phytic acid facilitates the fixation of N atoms, and various N configurations can be adjusted by altering the content of phytic acid. Optimized PNPCN-1.5 exhibits a high content of structurally stable pyridinic-N and graphitic-N configurations, which are confirmed to serve as active sites substantially augmenting the ion adsorption capacity through Density Functional Theory (DFT) calculations. Benefiting from its exceptional physicochemical properties, PNPCN-1.5 achieves 322 F g−1 as electrode materials in the three-electrode system, while the symmetrical supercapacitor assembled with EMIMBF4 electrolyte attains 56.29 W h kg−1. Furthermore, various kinetic analyses extensively elucidate its capacitance distribution characteristics and ion diffusion rates.

Recent Progress and Perspectives on Metal–Organic Framework-Based Electrode Materials for Metal-Ion Batteries and Supercapacitors

Recent Progress and Perspectives on Metal–Organic Framework-Based Electrode Materials for Metal-Ion Batteries and Supercapacitors