Self-supported Electrode Research Articles

C60 Fullerene-Reinforced Silicon Oxycarbide Composite Fiber Mats: Performance as Li-Ion Battery Electrodes.

Precursor-derived silicon oxycarbide (SiOC) has emerged as a potential high-capacity anode material for rechargeable Li-ion batteries. The polymer processing and pyrolysis route, a hallmark of polymer-derived ceramics, allows chemical interfacing with a variety of nanoprecursors and nanofiller phases to produce composites with low-dimensional structures such as fibers and coatings not readily attained in traditional sintered ceramics. Here, buckminsterfullerene or C60 was introduced as a filler phase in a hybrid precursor of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (TTCS) along with polyvinylpyrrolidone or PVP as a spinning agent to fabricate electrospun fiber mats, which upon a high-heat treatment transformed to a C60-reinforced SiOC ceramic composite. Tested as the self-supporting working electrode in a Li-ion half-cell, C60-reinforced fiber mats show a much-improved reversible capacity (825 mA h g-1), nearly 100% Coulombic efficiency, and superior rate capability with low-capacity decay at high currents (only 25.5% decay at 800 mA g-1) compared to neat C60 and neat carbonized fiber electrodes.

Superaerophobic Ni3N/Ni@W2N3 multi-heterointerfacial nanoarrays for efficient alkaline electrocatalytic hydrogen evolution reaction

The hydrogen evolution performances of electrocatalysts are greatly restricted by their unfavorable hydrogen evolution kinetics and the undesirable accumulation of as-evolved gas bubbles on the electrocatalysts surface. Herein, we present the fabrication of self-supporting multi-heterointerfacial nanoarrays electrode toward addressing these challenges simultaneously. A monolith Ni3N/Ni@W2N3 electrode is prepared, which exhibits a multi-heterojunction interface between the different components. The construction of this multi-heterojunction interface allows for the redistribution of the electrons, thus alleviating the strong Ni-H bond and optimizing the hydrogen adsorption free energy toward more efficient HER catalysis. Moreover, by virtue of the distinct nanoarray structure, the Ni3N/Ni@W2N3 nanoarrays exhibit improved hydrophilicity and superaerophobicity compared with Ni/Ni3N, facilitating water contact and enabling more efficient detachment of the as-evolved H2 bubbles from the surface. Benefiting from these attractive features, the Ni3N/Ni@W2N3 nanoarrays deliver an attractive alkaline HER catalytic activity with a low overpotential of 66 mV to achieve a current density of 10 mA cm−2, which is comparable with that of the benchmark Pt/C electrode. Moreover, the electrode exhibits remarkable stability during long-term electrolysis. The simultaneous interface and nanostructure engineering provide a feasible pathway for obtaining high-performance electrodes and beyond for various electrochemical reactions.

Flower-like B-FeNiCoP/NF prepared by NaBH4 treatment for water splitting

This paper presents the preparation of a flower-like heterostructure self-supporting working electrode for the purpose of designing an electrolytic water catalyst with high stability and catalytic activity. The study investigates the impact of different ratios of nickel, cobalt, and iron on the microstructure and catalytic performance of the electrode. It was found that a Fe:Ni:Co ratio of 1:1:1 resulted in fluffy nanowires dispersed on nanosheets of flower-like nanoflowers, leading to an increase in specific surface area. Additionally, the heterogeneous structure of NiCoP and Fe2P significantly enhanced the catalytic performance of the electrode. The exceptional electrocatalytic performance of B-FeNiCoP/NF can be attributed to the synergistic interface effect and the presence of numerous exposed active sites. In the electrochemical evaluation of the hydrogen evolution reaction (HER), an overpotential of 185.5 mV at a current density of 100 mA cm−2 has been identified as sufficient, with a difference of 35.9 mV compared to Pt-C and a Tafel slope of 58.3 mV/dec. In the assessment of the oxygen evolution reaction (OER), an overpotential of 301.8 mV at a current density of 100 mA cm−2 was found necessary, with a discrepancy of 18.2 mV compared to RuO2 and a Tafel slope of 69.5 mV/dec. The stability assessment of the HER and OER at a current density of 100 mA cm−2 over a duration of 48 hours demonstrated exceptional stability. This study introduces a hydrothermal pretreatment method for sodium borohydride, which has the potential to enhance the phosphorylation of catalytic application systems.

Constructing nitrogen-doped graphene quantum dots embedded in CNT supported layered (Ni0.5Co0.5)3V2O8 self-supporting film for high-performance supercapacitor

To improve the electrochemical performance of positive electrode materials, constructing graded nanostructures is a worthwhile approach. This study successfully synthesized nitrogen-doped graphene quantum dots (NGQD) modified (Ni0.5Co0.5)3V2O8 on a carbon nanotube (CNT) substrate to construct self-supporting electrodes for high-performance supercapacitors. The (Ni0.5Co0.5)3V2O8 nanosheets were successfully wrapped onto the CNT surface through a solution impregnation process, which increased the specific surface area and interlayer spacing of the material. Furthermore, the electrochemical properties of the electrode material underwent significant enhancement due to the synergistic interplay between metal ions and the numerous redox centers. The embedding of the NGQD enriched the materials with active sites and further improved its specific capacity without compromising the structure intergrity of the layer configuration. Using CNT as the substrate ensured the self-supporting nature of the electrode. Consequently, the (Ni0.5Co0.5)3V2O8/NGQD@CNT composite exhibits an ultra-high specific capacitance of 3018.2 F g−1 at 1 A g−1 and 2332 F g−1 at 10 A g−1. The asymmetric supercapacitor constructed with (Ni0.5Co0.5)3V2O8/NGQD@CNT and activated carbon (AC) presented an impressive energy density of 160.2 Wh kg−1 at a power density of 800 W kg−1. After 8000 charge–discharge cycles, the capacity retention rate was 78.5 %, with a Coulo mbic efficiency consistently above 98 %.

Interface Engineering of Transition Metal-Based Heterostructure Electrocatalysts for Enhanced Hydrogen Evolution Reaction

Electrochemical water splitting to produce clean hydrogen plays a significant role in the development of the hydrogen economy. The rational design of highly efficient and inexpensive electrocatalysts is critical for improving water electrolysis efficiency. Herein, we report the fabrication of heterostructure monometallic, bimetallic, and trimetallic sulfides on Ni foam (NF) as porous self-supported electrodes for hydrogen evolution reaction (HER) via an energy-saving electrodeposition process. Molybdenum-cobalt-nickel sulfide electrode (MoCoNiS@NF) only requires a low overpotential of 114 mV to produce a current density of 10 mA cm-2 for HER, compared with nickel sulfides (NiS@NF, 142 mV) and cobalt-nickel sulfides (CoNiS@NF, 129 mV). The desirable HER performance of MoCoNiS@NF results from the synergistic effect of heterostructure interfaces of multi-metal sulfides, providing high intrinsic catalytic activity and a large amount of catalytic active sites. Electrochemical impedance spectroscopy and Tafel slope analysis proved the fast reaction kinetics of MoCoNiS@NF toward HER. Our present work provides valuable insights into the working mechanisms behind the HER catalytic process and new perspectives for the future design of cost-effective electrocatalysts for HER.

A robust polyaniline hydrogel electrode enables superior rate capability at ultrahigh mass loadings

Simultaneously achieving high mass loading and superior rate capability in electrodes is challenging due to their often mutually constrained nature, especially for pseudocapacitors for high-power density applications. Here, we report a robust porous polyaniline hydrogel (PPH) prepared using a facile ice-templated in situ polymerization approach. Owing to the conductive, robust, and porous nanostructures suitable for ultrafast electron and ion transport, the self-supporting pure polyaniline hydrogel electrode exhibits superior areal capacitance without sacrificing rate capability and gravimetric capacitance at an ultrahigh mass loading and notable current density. It achieves a high areal capacitance (15.2 F·cm−2 at 500 mA·cm−2) and excellent rate capability (~92.7% retention from 20 to 500 mA·cm−2) with an ultrahigh mass loading of 43.2 mg cm−2. Our polyaniline hydrogel highlights the potential of designing porous nanostructures to boost the performance of electrode materials and inspires the development of other ultrafast pseudocapacitive electrodes with ultrahigh loadings and fast charge/discharge capabilities.

Melamine foam scaffolded 3D porous polyaniline/reduced graphene oxide composite electrode for flexible supercapacitor

Graphene composite foam with enhanced mechanical and electrochemical properties holds great promise for flexible supercapacitors. This work developed a cost-effective method for massive production of three-dimensional (3D) porous graphene composite using melamine foam (MF) as a flexible scaffold. The MF was coated reduced graphene oxide (RGO) to form an interconnected conductive layer by dip-coating and vapor reduction, and loaded with polyaniline (PANI) by in-situ polymerization. The resulted PANI/RGO/MF, as self-supporting electrode, exhibits extraordinary mechanical flexibility and a high specific capacitance of 806.2 mF cm−2 at 0.5 mA cm−2. Furthermore, the assembled solid-state supercapacitor exhibits an outstanding capacity of 299.1 mF cm−2 at 0.5 mA cm−2, a high energy density of 26.6 μWh cm−2 at 200 μW cm−2, nearly 100 % capacitance retention at 0°–180°, and good cycling stability. This study provides a scalable strategy for fabricating graphene composite foam suitable for flexible energy storage application.

Interface reconstruction of NiCoP@NiMoP self-supported electrodes for highly efficient alkaline water/seawater electrolysis

Electrocatalytic water splitting is considered a feasible hydrogen generation technique. However, their sluggish kinetics and poor stability remains a huge challenge for alkaline water electrolysis. Herein, we report a corrosion-resistant NiCoP@NiMoP micro-pillar arrays for catalysts. It indicates that a layer of amorphous film on the surface of catalysts exposes many active sites and accelerates the species reconstruction. The prepared hybrid catalysts present an overpotential of 76 mV at −10 mA cm−2 for hydrogen evolution reaction (HER) and 268 mV@100 mA cm−2 for oxygen evolution reaction (OER). Furthermore, the assembled cell realizes a stable and high-efficiency water splitting with cycling life of 100 h in seawater media. This work provides a universal approach toward highly active and durable electrocatalysts.

Construction of electron-interactive CoMoO4 @ CoP core–shell structure on boron-doped graphene aerogel as strongly interface coupled hybrid electrodes for high flexible supercapacitor

Exploring high energy density, lightweight and self-supporting flexible electrodes is essentially significant to flexible energy storage equipment. Herein, boron-doped three-dimensional porous graphene aerogel (BGA) is engineered and novel flake-like CoP encapsulating flower-like CoMoO4 core–shell structure is arranged on it (CoMoO4@CoP/BGA) utilizing a combination of solvothermal, freeze-drying and vapor deposition techniques. Boron-doped graphene aerogel as flexible self-supporting positrode creates a unique three-dimensional porous interface with a larger specific surface area, which is conducive to exposing more active sites and avoids the additional process of adding binders and conductive agents. The heterointerface engineering of CoP epitaxial growth on CoMoO4 can efficiently enhance electrolyte ions adsorption ability and fast reaction kinetics. As expected, the fabricated CoMoO4@CoP/BGA demonstrates a better specific capacitance of 3056.4F/g than that of CoMoO4/BGA (1582.4F/g) and pure CoMoO4 (669.2F/g), apart from retains the remarkable cyclic stability of 88.4 % after 10,000 cycles. Furthermore, a hybrid supercapacitor composed of CoMoO4@CoP/BGA and BGA can provide a high energy density of 50.2 Wh kg−1 at 800.0 W kg−1, and retains good capacitance retention of 95.6 % after 10,000 cycles, which can be attributed to the large specific surface of B doping 3D porous graphene aerogel and the rich strong coupling interface synergy between CoP and CoMoO4. More importantly, this work provides important guidance for the design of heterojunction electrodes based on heteroatom doped graphene aerogel and phosphides @ oxide based flexible energy storage devices.

Electrochemical Detection of Ammonia in Water Using NiCu Carbonate Hydroxide-Modified Carbon Cloth Electrodes: A Simple Sensing Method.

Excessive ammonia nitrogen can potentially compromise the safety of drinking water. Therefore, developing a rapid and simple detection method for ammonia nitrogen in drinking water is of great importance. Nickel-copper hydroxides exhibit strong catalytic capabilities and are widely applied in ammonia nitrogen oxidation. In this study, a self-supported electrode made of nickel-copper carbonate hydroxide was synthesized on a carbon cloth collector via a straightforward one-step hydrothermal method for rapid ammonia nitrogen detection in water. It exhibits sensitivities of 3.9 μA μM-1 cm-2 and 3.13 μA μM-1 cm-2 within linear ranges of 1 μM to 100 μM and 100 μM to 400 μM, respectively, using a simple and rapid i-t method. The detection limit is as low as 0.62 μM, highlighting its excellent anti-interference properties against various anions and cations. The methodology's simplicity and effectiveness suggest broad applicability in water quality monitoring and environmental protection, particularly due to its significant cost-effectiveness.

Construction of nitrite electrochemical sensor by in-situ deposition of FeOOH nanomaterials on carbon cloth modified with green DBD technology

The treatment of carbon cloth with concentrated or dilute acid to produce hydrophilic carbon-based flexible electrodes raises environmental pollution concerns. This study utilized a green, rapid, and cost-effective dielectric barrier discharge (DBD) technique was utilized for the hydrophilic modification of conductive hydrophobic carbon cloth. A nitrite electrochemical sensor was constructed by depositing high specific surface area pom-pom FeOOH on modified carbon cloth through a constant potential electrochemical in-situ deposition method. The FeOOH/CC binder-free self-supporting electrode demonstrates nitrite detection capabilities within linear ranges of 0.5–900 µM and 1 mM–10 mM, boasting a detection limit of 0.154 µM (S/N = 3). This sensor exhibits excellent interference immunity, stability, and reproducibility. Its application in detecting nitrite in ham sausage and tap water samples yields 97.00 % to 101.33 % recovery rates, respectively, comparable to UV spectrophotometry results, affirming the sensor’s accuracy and practical feasibility. This straightforward and swift carbon material modification technique presents a novel approach for crafting carbon cloth electrochemical sensors.

Conjugated polyimides modified self-supported carbon electrodes for electrochemical conversion of CO2 to CO

Conjugated polyimides modified self-supported carbon electrodes for electrochemical conversion of CO₂ to CO

Rational Construction of a 3D Self-Supported Electrode Based on ZIF-67 and Amorphous NiCoP for an Enhanced Oxygen Evolution Reaction.

The development of efficient and Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is an urgent requirement in the field of electrochemical water splitting. The electrocatalytic performance of the OER can be greatly enhanced by the synergistic combination of zeolite imidazolate frameworks (ZIFs) and transition-metal phosphides, both of which individually exhibit promising capabilities in this regard. In this study, a novel amorphous NiCoP deposited on ZIF-67 sheets supported on Ni foam (labeled as NiCoP/ZIF-67/NF) as an OER electrocatalytic material was successfully synthesized using a simple, secure, and time-efficient two-step strategy. The experimental results demonstrate that NiCoP/ZIF-67/NF possesses a large active surface area with abundant active sites. Also, the synergistic effect and interaction between NiCoP and ZIF-67, as well as between Ni and Co within NiCoP, effectively enhance its electrochemical performance under alkaline conditions. Consequently, NiCoP/ZIF-67/NF exhibits outstanding catalytic activity for OER with an overpotential (η) of 175 mV at a current density of 10 mA cm-2 and a long-term stability over 40 h at 20 mA cm-2 in a 1.0 M KOH electrolyte. The corresponding analyses suggest that the real active sites responsible for the OER are identified as NiOOH and CoOOH species within the structure of NiCoP/ZIF-67/NF. Additionally, the catalytic function and stability of ZIF-67 toward the OER under alkaline conditions were also briefly discussed. This work provides a novel catalytic material for the OER along with a facile strategy to fabricate superior, efficient, and noble metal-free catalysts suitable for energy-related applications.

MOF-Derived Zn/N-Doped Porous Carbon Film on a Carbon Nanotube for High-Performance Supercapacitors.

Designing high-performance binder-free electrochemical electrodes is crucially important toward supercapacitors. In this paper, a Zn/N-doped porous carbon film coating on flexible carbon nanotubes (ZIF-8@CT-800) derived from the epitaxial Zn-MOF film growth on cotton textile was successfully fabricated via a combination of the liquid-phase epitaxial (LPE) method and calcination treatments. The ZIF-8@CT-800 serves directly as a self-supported electrode for supercapacitors and exhibits a high areal capacitance of 930 mF·cm-2 at a current density of 1 mA·cm-2 and a good recyclability of 86% after 2000 cycles. The excellent supercapacitor property is ascribed to the unique structural design of ZIF-8@CT-800, which provides appropriate channels for enhanced electronic and ionic transport as well as increased surface area for accessing more electrolyte ions. This work will provide significant guidance for designing MOF-derived porous carbon to construct flexible binder-free electrode materials with high electrochemical performance.

Self-Reconstructed Metal-Organic Framework-Based Hybrid Electrocatalysts for Efficient Oxygen Evolution.

Refining synthesis strategies for metal-organic framework (MOF)-based catalysts to improve their performance and stability in an oxygen evolution reaction (OER) is a big challenge. In this study, a series of nanostructured electrocatalysts were synthesized through a solvothermal method by growing MOFs and metal-triazolates (METs) on nickel foam (NF) substrates (named MET-M/NF, M = Fe, Co, Cu), and these electrocatalysts could be used directly as OER self-supporting electrodes. Among these electrocatalysts, MET-Fe/NF exhibited the best OER performance, requiring only an overpotential of 122 mV at a current density of 10 mA cm-2 and showing remarkable stability over 15 h. The experimental results uncovered that MET-Fe/NF underwent an in situ structural reconstruction, resulting in the formation of numerous iron/nickel (oxy)hydroxides with high OER activity. Furthermore, in a two-electrode water-splitting setup, MET-Fe/NF only required 1.463 V to achieve a current density of 10 mA cm-2. Highlighting its potential for practical applications. This work provides insight into the design and development of efficient MOF-based OER catalysts.

Highly selective electrochemical reduction of nitrate-to-ammonia using iron phosphide self-supported electrode

Highly selective electrochemical reduction of nitrate-to-ammonia using iron phosphide self-supported electrode

A highly efficient and self-supporting nanoporous FeMoC catalyst for enhanced hydrogen evolution reaction

Optimizing structure and surface morphologies in electrocatalyst design are important to enhance the intrinsic activity of the hydrogen evolution reaction (HER). Mo-based phosphides and carbides have been confirmed as the widely-reported catalysts for HER. However, the origin of their enhanced catalytic activity is not fully clarified. Herein, the np-FeMoC and np-FeMoP with a self-supporting nanoporous structure were prepared using the melt-spinning and dealloying methods. Benefiting from the self-supporting electrode, nanoporous structure, abundant active species, low charge-transfer resistance and electron synergy, the np-FeMoC exhibits good catalytic performance. The np-FeMoC performs a low overpotential of 50.8 mV at 10 mA cm−2 current density for HER in 1 M KOH. This value is 2.7 times lower than that of the np-FeMoP sample, indicating a synergistic effect between Mo2C and Fe. From XPS and in-situ Raman results, it was observed that the dissolution of Mo2C occurs accompanied by dynamic evolution during the HER process on the np-FeMoC surface. This work unveils the intrinsic activity of Mo-based carbide and phosphide, providing valuable guidance for reasonable exploit of high-performance HER catalysts.

Controlled synthesized of ternary Cu-Co-Ni-S sulfides nanoporous network structure on carbon fiber paper: a superior catalytic electrode for highly-sensitive glucose sensing

BackgroundEfficient monitoring of glucose concentration in the human body necessitates the utilization of electrochemically active sensing materials in nonenzymatic glucose sensors. However, prevailing limitations such as intricate fabrication processes, lower sensitivity, and instability impede their practical application. Herein, ternary Cu-Co-Ni-S sulfides nanoporous network structure was synthesized on carbon fiber paper (CP) by an ultrafast, facile, and controllable technique through on-step cyclic voltammetry, serving as a superior self-supporting catalytic electrode for the high-performance glucose sensor.ResultsThe direct growth of free-standing Cu-Co-Ni-S on the interconnected three-dimensional (3D) network of CP boosted the active site of the composites, improved ion diffusion kinetics, and significantly promoted the electron transfer rate. The multiple oxidation states and synergistic effects among Co, Ni, Cu, and S further promoted glucose electrooxidation. The well-architected Cu-Co-Ni-S/CP presented exceptional electrocatalytic properties for glucose with satisfied linearity of a broad range from 0.3 to 16,000 μM and high sensitivity of 6829 μA mM− 1 cm− 2. Furthermore, the novel sensor demonstrated excellent selectivity and storage stability, which could successfully evaluate the glucose levels in human serum. Notably, the novel Cu-Co-Ni-S/CP showed favorable biocompatibility, proving its potential for in vivo glucose monitoring.ConclusionThe proposed 3D hierarchical morphology self-supported electrode sensor, which demonstrates appealing analysis behavior for glucose electrooxidation, holds great promise for the next generation of high-performance glucose sensors.

Rational Design of Flexible, Self-Supporting, and Binder-Free Prussian White/KetjenBlack/MXene Composite Electrode for Sodium-Ion Batteries with Boosted Electrochemical Performance.

Due to their cost-effectiveness, abundant resources, and suitable working potential, sodium-ion batteries are anticipated to establish themselves as a leading technology in the realm of grid energy storage. However, sodium-ion batteries still encounter challenges, including issues related to low energy density and constrained cycling performance. In this study, a self-supported electrode composed of Prussian white/KetjenBlack/MXene (TK-PW) is proposed. In the TK-PW electrode, the MXene layer is coated with Prussian white nanoparticles and KetjenBlack with high conductivity, which is conducive to rapid Na+ dynamics and effectively alleviates the expansion of the electrode. Notably, the electrode preparation method is uncomplicated and economically efficient, enabling large-scale production. Electrochemical testing demonstrates that the TK-PW electrode retains 74.9% of capacity after 200 cycles, with a discharge capacity of 69.7 mAh·g-1 at 1000 mA·g-1. Furthermore, a full cell is constructed, employing a hard carbon anode and TK-PW cathode to validate the practical application potential of the TK-PW electrode.

Facile preparation of CoFe-MnO2@titania nanotube array bifunctional electrodes for high-current-density water splitting at industrial temperatures

The development of bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at high current density under industrial temperatures is crucial for large-scale industrial hydrogen production from water splitting. In this work, M-MnO2@TNTA composite electrodes were prepared by depositing various metal ion-doped manganese oxide nanoparticles on the titania nanotube array (TNTA) by successive ionic layer adsorption reaction (SILAR) method, and their HER and OER electrocatalytic performances were investigated in 1 M KOH. Results show that the CoFe-MnO2@TNTA composite electrode prepared by simultaneous doping of Co3+ and Fe3+ in MnO2 exhibits optimal catalytic performance. Compared with MnO2@TNTA without ion doping, the overpotentials of CoFe-MnO2@TNTA at 10 mA cm−2 (η10) for HER and OER are reduced by 571 and 665 mV. In addition, the electrode performance can be significantly enhanced by increasing the test temperature, and the porous array structure enables CoFe-MnO2@TNTA to exhibit better performance at high current densities. At 50 °C, which is the common industrial electrolytic water temperature, the η10 of CoFe-MnO2@TNTA for HER is almost equal to that of the Pt/C electrode. The η100 of CoFe-MnO2@TNTA for HER is reduced by 35 mV compared with the Pt/C electrode. Moreover, η200 of CoFe-MnO2@TNTA for OER is significantly lowered by 111 and 184 mV compared with IrO2 and RuO2 electrodes. Utilizing CoFe-MnO2@TNTA as both the cathode and anode for overall water splitting, the electrolysis voltage is merely 2.33 V under the current density of 200 mA cm−2, much lower than that of IrO2 (+)||Pt/C (–) (2.68 V). The present work may provide a valuable reference for the development of self-supporting bifunctional electrodes suitable for high-current-density water splitting at industrial temperatures.