RESUMO
The demand for high-performance energy storage devices to power Internet of Things applications has driven intensive research on micro-supercapacitors (MSCs). In this study, RuN films made by magnetron sputtering as an efficient electrode material for MSCs are investigated. The sputtering parameters are carefully studied in order to maximize film porosity while maintaining high electrical conductivity, enabling a fast charging process. Using a combination of advanced techniques, the relationships among the morphology, structure, and electrochemical properties of the RuN films are investigated. The films are shown to have a complex structure containing a mixture of crystallized Ru and RuN phases with an amorphous oxide layer. The combination of high electrical conductivity and pseudocapacitive charge storage properties enabled a 16 µm-thick RuN film to achieve a capacitance value of 0.8 F cm-2 in 1 m KOH with ultra-high rate capability.
RESUMO
The voluntary introduction of defects can be considered an effective strategy for enhancing the electrochemical properties of metal oxide electrodes. In this study, the enhanced pseudocapacitive properties of an acceptor (Gd) doped cerium oxide nanoparticle-a sustainable metal oxide with low environmental and human toxicity-are investigated in depth using ex situ X-ray photoemission spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Interestingly, with 15 at% Gd doping (15GDC), the specific capacitance of the nanoparticles measured at 1 A g-1 enhanced to 547.8 F g-1, which is fivefold higher than undoped CeO2 (98.7 F g-1 at 1 A g-1). The rate-dependent capacitance is also improved for 15GDC, which showed a 31.0% decrease in the specific capacitance upon a tenfold increase in the current density, while CeO2 showed a 49.9% decrease. The enhanced electrochemical properties are studied in depth via ex situ XPS and EIS analysis, which revealed that the oxygen vacancies at the surface of the nanoparticles played important roles in enhancing both the specific capacitance and the high-rate performance of 15GDC by acting as the active site for pseudocapacitive redox reaction and allowing fast diffusion of oxygen ions at the surface of 15GDC nanoparticles.
RESUMO
Fluorides are viewed as promising conversion-type Li-ion battery cathodes to meet the desired high energy density. FeOF is a typical member of conversion-type fluorides, but its major drawback is sluggish kinetics upon deep discharge. Herein, a heterostructured FeOF-MXene composite (FeOF-MX) is demonstrated to overcome this limitation. The rationally designed FeOF-MX electrode features a microsphere morphology consisting of closely packed FeOF nanoparticles, providing fast transport pathways for lithium ions while a continuous wrapping network of MXene nanosheets ensures unobstructed electron transport, thus enabling high-rate lithium storage with enhanced pseudocapacitive contribution. In/ex situ characterization techniques and theoretical calculations, both reveal that the lithium storage mechanism in FeOF arises from a hybrid intercalation-conversion process, and strong interfacial interactions between FeOF and MXene promote Li-ion adsorption and migration. Remarkably, through demarcating the conversion-type reaction with a controlled potential window, a symmetric full battery with prelithiated FeOF-MX as both cathode and anode is fabricated, achieving a high energy density of 185.5 Wh kg-1 and impressive capacity retention of 88.9% after 3000 cycles at 1 A g-1. This work showcases an effective route toward high-performance MXene engineered fluoride-based electrodes and provides new insights into constructing symmetric batteries yet with high-energy/power densities.
RESUMO
Exploiting pseudocapacitance in rationally engineered nanomaterials offers greater energy storage capacities at faster rates. The present research reports a high-performance Molybdenum Oxynitride (MoON) nanostructured material deposited directly over stainless-steel mesh (SSM) via reactive magnetron sputtering technique for flexible symmetric supercapacitor (FSSC) application. The MoON/SSM flexible electrode manifests remarkable Na+-ion pseudocapacitive kinetics, delivering exceptional ≈881.83 F g-1 capacitance, thanks to the synergistically coupled interfaces and junctions between nanostructures of Mo2N, MoO2, and MoO3 co-existing phases, resulting in enhanced specific surface area, increased electroactive sites, improved ionic and electronic conductivity. Employing 3D Bode plots, b-value, and Dunn's analysis, a comprehensive insight into the charge-storage mechanism has been presented, revealing the superiority of surface-controlled capacitive and pseudocapacitive kinetics. Utilizing PVA-Na2SO4 gel electrolyte, the assembled all-solid-state FSSC (MoON/SSM||MoON/SSM) exhibits impressive cell capacitance of 30.7 mF cm-2 (438.59 F g-1) at 0.125 mA cm-2. Moreover, the FSSC device outputs a superior energy density of 4.26 µWh cm-2 (60.92 Wh kg-1) and high power density of 2.5 mW cm-2 (35.71 kW kg-1). The device manifests remarkable flexibility and excellent electrochemical cyclability of ≈91.94% over 10,000 continuous charge-discharge cycles. These intriguing pseudocapacitive performances combined with lightweight, cost-effective, industry-feasible, and environmentally sustainable attributes make the present MoON-based FSSC a potential candidate for energy-storage applications in flexible electronics.
RESUMO
Owing to its pseudocapacitive, unidimensional, rapid ion channels, TiO2(B) is a promising material for application to battery electrodes. In this study, we align these channels by epitaxially growing TiO2(B) films with the assistance of an isostructural VO2(B) template layer. In a liquid electrolyte, binder-free TiO2(B) epitaxial electrodes exhibit a supercapacity near the theoretical value of 335 mA h g-1 and an excellent charge-discharge reproducibility for ≥200 cycles, which outperform those of other TiO2(B) nanostructures. For the all-solid-state configuration employing the LiPON solid electrolyte, excellent stability persists. Our findings suggest excellent potential for miniaturizing all-solid-state nanobatteries in self-powered integrated circuits.
RESUMO
2D transition metal carbides and nitrides (MXenes) are actively pursued as pseudocapacitive materials for supercapacitors owing to their advantages in electronic conductivity and surface reactivity. Increasing the fraction of âO terminal groups in Ti3 C2 Tx is a promising approach to improve the pseudocapacitive charge storage in H2 SO4 electrolytes, but it suffers from a lack of effective functionalization methods and stability of the groups in practical operation. Here a low-temperature and environment-friendly approach via the interaction of nonequilibrium plasmas with Ti3 C2 Tx dispersion is demonstrated to generate abundant and stable surface-terminating O groups. The impact of the discharge environment (Ar, O2 , and H2 ) on the structural characteristics and electrochemical performance of Ti3 C2 Tx nanosheets is studied. The Ti3 C2 Tx modified in Ar and H2 maintains their original morphology but a significantly lower F content. Consequently, an extraordinarily high content (78.5%) of surface-terminating O groups is revealed by the high-resolution X-ray photoelectron spectroscopy spectra for the Ti3 C2 Tx samples modified in H2 plasma-treated solutions. Additionally, the Ti3 C2 Tx treated using H2 plasmas exhibits the best capacitive performance of 418.3 F g-1 at 2 mV s-1 , which can maintain 95.88% capacity after 10 000 cycles. These results contribute to the development of advanced nanostructured pseudocapacitive electrode materials for renewable energy storage applications.
RESUMO
Carbonaceous materials are widely investigated as anodes for potassium-ion batteries (PIBs). However, the inferior rate capability, low areal capacity, and limited working temperature caused by sluggish K-ions diffusion kinetics are still primary challenges for carbon-based anodes. Herein, a simple temperature-programmed co-pyrolysis strategy is proposed for the efficient synthesis of topologically defective soft carbon (TDSC) based on inexpensive pitch and melamine. The skeletons of TDSC are optimized with shortened graphite-like microcrystals, enlarged interlayer spacing, and abundant topological defects (e.g., pentagons, heptagons, and octagons), which endow TDSC with fast pseudocapacitive K-ion intercalation behavior. Meanwhile, micrometer-sized structure can reduce the electrolyte degradation over particle surface and avoid unnecessary voids, ensuring a high initial Coulombic efficiency as well as high energy density. These synergistic structural advantages contribute to excellent rate capability (116 mA h g-1 at 20 C), impressive areal capacity (1.83 mA h cm-2 with a mass loading of 8.32 mg cm-2 ), long-term cycling stability (capacity retention of 91.8% after 1200 h cycling), and low working temperature (-10 °C) of TDSC anodes, demonstrating great potential for the practical application of PIBs.
RESUMO
Ni(OH)2 nanosheet, acting as a potential active material for supercapacitors, commonly suffers from sluggish reaction kinetics and low intrinsic conductivity, which results in suboptimal energy density and long cycle life. Herein, a convenient electrochemical halogen functionalization strategy is applied for the preparation of mono/bihalogen engineered Ni(OH)2 electrode materials. The theoretical calculations and experimental results found that thanks to the extraordinarily high electronegativity, optimal reversibility, electronic conductivity, and reaction kinetics could be achieved through F functionalization . However, benefiting from the largest ionic radius, INi(OH)2 contributes the best specific capacity and morphology transformation, which is a new finding that distinguishes it from previous reports in the literature. The exploration of the interaction effect of halogens (F, INi(OH)2 , F, BrNi(OH)2 , and Cl, INi(OH)2 ) manifests that F, INi(OH)2 delivers a higher specific capacity of 200.6 mAh g-1 and an excellent rate capability of 58.2% due to the weaker electrostatic repulsion, abundant defect structure, and large layer spacing. Moreover, the F, INi(OH)2 //FeOOH@NrGO device achieves a high energy density of 97.4 Wh kg-1 and an extremely high power density of 32426.7 W kg-1 , as well as good cycling stability. This work develops a pioneering tactic for designing energy storage materials to meet various demands.
RESUMO
Nickel sulfides are promising anode candidates in sodium ion batteries (SIBs) due to high capacity and abundant reserves. However, their applications are restricted by poor cycling stability and slow reaction kinetics. Thus, mesoporous nickel sulfide microsphere encapsulated in nitrogen, sulfur dual-doped carbon (MNS@NSC) is prepared. The packaged structure and carbon matrix restrain the volume variation together, the N, S dual-doping improves the electronic conductivity and offers extra active sites for sodium storage. Ex-situ X-ray diffraction appeals copper collector adsorbs polysulfide to inhibit the polysulfide accumulation and enhance conductivity. Moreover, the large subsurface attributed to C-S-S-C bonding further boosts pseudocapacitive capacity, conducive to charge transfer. As a result, MNS@NSC delivers a high reversible capacity of 640.2 mAh g-1 after 100 cycles at 0.1 A g-1 , an excellent rate capability (569.8 mAh g-1 at 5 A g-1 ), and a remained capacity of 513.8 mAh g-1 after undergoing 10000 circulations at 10 A g-1 . The MNS@NSC|| Na3 V2 (PO4 )3 full cell shows a cycling performance of specific capacity of 230.8 mAh g-1 after 100 cycles at 1 A g-1 . This work puts forward a valid strategy of combing structural design and heteroatom doping to synthesize high-performance nickel sulfide materials in SIBs.
RESUMO
Conducting polymers show attractive characteristics as electrode materials for micro-electrochemical energy storage (MEES). However, there is a lack of characterization techniques to study conjugated/conducting polymer-based nanostructured electrodes. Here, scanning electrochemical microscopy (SECM) is introduced as a new technique for in situ characterization and acceleration of degradation processes of conducting polymers. Electrodes of PEDOT:PSS on flat silicon, silicon nanowires (SiNWs) and silicon nanotrees (SiNTrs) are analyzed by SECM in feedback mode with approach curves and chronoamperometry. The innovative degradation method using SECM reduces the time required to locally degrade polymer samples to a few thousand seconds, which is significantly shorter than the time usually required for such studies. The degradation rate is modeled using Comsol Multiphysics. The model provides an understanding of the phenomena that occur during degradation of the polymer electrode and describes them using a mathematical constant A0 and a time constant τ.
RESUMO
Electroactive biofilms (EBs) engage in complex electron transfer and storage processes involving intracellular and extracellular mediators with temporary electron storage capabilities. Consequently, electroactive biofilms exhibit pseudocapacitive behaviors during substrate degradation processes. However, comprehensive systematic research in this area has been lacking. This study demonstrated that the pseudocapacitive property was an intrinsic characteristic of EBs. This property represents dynamic-controlled electron transfer and is critical in current generation, unlike noncapacitive responses. Nontransient charge and discharge experiments revealed a correlation between capacitive charge accumulation and current generation in EBs. Additionally, analysis of substrate degradation suggested that the maximum power density (Pmax) changed with the kinetic constants of COD degradation, with pseudocapacitances of EBs directly proportional to Pmax. The interaction networks of key latent variables were evaluated through partial least-squares path modeling analysis. The results indicated that cytochrome c was closely associated with the formation of pseudocapacitance in EBs. In conclusion, pseudocapacitance can be considered a valuable indicator for assessing the complex electron transfer behavior of EBs. Pseudocapacitive biofilms have the potential to efficiently regulate biological reactions and serve as a promising carbon-neutral and renewable strategy for energy generation and storage. An in-depth understanding of the intrinsic property of pseudocapacitive behavior in EBs can undoubtedly advance the development of this concept in the future.
Assuntos
Elétrons , Purificação da Água , Transporte de Elétrons , Biofilmes , Carbono , EletrodosRESUMO
The study of planar energy storage devices, characterized by low-cost, high capacity, and satisfactory flexibility, is becoming a valuable research hotspot. Graphene, monolayer sp2 hybrid carbon atoms with a large surface area, always acts as its active component, yet there is a tension between its high conductivity and ease of implementation. Although the difficult-to-assemble graphene can easily achieve planar assemblies in its highly oxidized form (GO), the undesirable conductivity, even after proper reduction, still restricts its further applications. Here, a facile "Top-down" method has been proposed to prepare the graphene planar electrode via in situ electro-exfoliation of graphite supported on a piece of laser-cutting patterned scotch tape. Detailed characterizations have been performed to study its physiochemical property evolution during electro-exfoliation. The obtained flexible graphene planar electrodes show decent energy storage performance, e.g., 40.8 mF cm-2 at a current density of 0.5 mA cm-2 and an 81% capacity retention at a current density of 8 mA cm-2 for the optimized sample G-240. Their high conductivity also makes it possible to couple them with other redox-active materials through electrodeposition to improve their performance, e.g., ferrocene-functionalized mesoporous silica film (Fc-MS), MnO2, and polyaniline (PANI). The highest capacity was achieved with the PANI functionalized sample, which achieved a 22-fold capacity increase. In a word, the versatility, practicality, and adaptability of the protocol to prepare the planar graphene electrode proposed in this work make it a potential candidate to meet the continuously growing energy storage demands.
Assuntos
Grafite , Grafite/química , Óxidos/química , Compostos de Manganês/química , Dióxido de Silício , EletrodosRESUMO
The most prominent and highly visible advantage attributed to supercapacitors of any type and application, beyond their most notable feature of high current capability, is their high stability in terms of lifetime, number of possible charge/discharge cycles or other stability-related properties. Unfortunately, actual devices show more or less pronounced deterioration of performance parameters during time and use. Causes for this in the material and component levels, as well as on the device level, have only been addressed and discussed infrequently in published reports. The present review attempts a complete coverage on these levels; it adds in modelling approaches and provides suggestions for slowing down ag(e)ing and degradation.
Assuntos
Líquidos Corporais , Antígenos do Grupo Sanguíneo de LewisRESUMO
Sluggish storage kinetics and insufficient performance are the major challenges that restrict the transition metal dichalcogenides (TMDs) applied for zinc ion storage, especially at the extreme temperature conditions. Herein, a multiscale interface structure-integrated modulation concept was presented, to unlock the omnidirectional storage kinetics-enhanced porous VSe2-x â n H2 O host. Theory research indicated that the co-modulation of H2 O intercalation and selenium vacancy enables enhancing the interfacial zinc ion capture ability and decreasing the zinc ion diffusion barrier. Moreover, an interfacial adsorption-intercalation pseudocapacitive storage mechanism was uncovered. Such cathode displayed remarkable storage performance at the wide temperature range (-40-60 °C) in aqueous and solid electrolytes. In particular, it can retain a high specific capacity of 173â mAh g-1 after 5000â cycles at 10â A g-1 , as well as a high energy density of 290â Wh kg-1 and a power density of 15.8â kW kg-1 at room temperature. Unexpectedly, a remarkably energy density of 465â Wh kg-1 and power density of 21.26â kW kg-1 at 60 °C also can be achieved, as well as 258â Wh kg-1 and 10.8â kW kg-1 at -20 °C. This work realizes a conceptual breakthrough for extending the interfacial storage limit of layered TMDs to construct all-climate high-performance Zn-ion batteries.
RESUMO
A pseudocapacitive electrode with a large surface area is critical for the construction of a high-performance supercapacitor. A 3D and interconnected network composed of W18 O49 nanoflowers and Ti3 C2 Tx MXene nanosheets is thus synthesized using an electrostatic attraction strategy. This composite effectively prevents the restacking of Ti3 C2 Tx MXene nanosheets and meanwhile sufficiently exposes electrochemically active sites of W18 O49 nanoflowers. Namely, this self-assembled composite owns abundant oxygen vacancies from W18 O49 nanoflowers and enough active sites from Ti3 C2 Tx MXene nanosheets. As a pseudocapacitive electrode, it shows a big specific capacitance, superior rate capability and good cycle stability. A quasi-solid-state asymmetric supercapacitor (ASC) is then fabricated using this pseudocapacitive anode and the cathode of activated carbon coupled with a redox electrolyte of FeBr3 . This ASC displays a cell voltage of 1.8 V, a capacitance of 101 F g-1 at a current density of 1 A g-1 , a maximum energy density of 45.4 Wh kg-1 at a power density of 900 W kg-1 , and a maximum power density of 18 000 W kg-1 at an energy density of 10.8 Wh kg-1 . The proposed strategies are promising to synthesize different pseudocapacitive electrodes as well as to fabricate high-performance supercapacitor devices.
RESUMO
Secondary lithium-ion batteries are restricted in large-scale applications including power grids and long driving electric vehicles owing to the low specific capacity of conventional intercalation anodes possessing sluggish Li-ion diffusion kinetics. Herein, we demonstrate an unusual pseudocapacitive lithium-ion storage on defective Co3O4nanosheet anodes for high-performance rechargeable batteries. Cobalt-oxide nanosheets presented here composed of various defects including vacancies, dislocations and grain boundaries. Unique 2D holey microstructure enabled efficient charge transport as well as provided room for volume expansions associated with lithiation-delithiation process. These defective anodes exhibited outstanding pseudocapacitance (up to 87%), reversible capacities (1490 mAh g-1@ 25 mA g-1), rate capability (592 mAh g-1@ 30 A g-1), stable cycling (85% after 500 cycles @ 1 A g-1) and columbic efficiency (â¼100%). Exceptional Li-ion storage phenomena in defective Co3O4nanosheets is accredited to the pseudocapacitive nature of conversion reaction resulting from ultrafast Li-ion diffusion through various crystal defects. The demonstrated approach of defect-induced pseudocapacitance can also be protracted for various low-cost and/or eco-friendly transition metal-oxides for next-generation rechargeable batteries.
RESUMO
Cobalt oxide (Co3O4) is a low-cost material exhibiting excellent physicochemical and photocatalytic properties indicating its potential use for next-generation eco-friendly energy storage and photocatalytic degradation applications. In this study, Co3O4 nanoarcs were synthesized using SBA-15 as a template by microwave-assisted method to form an S15/m-Co3O4 product. Characterization was done by low and wide-angle X-Ray diffraction, and Fourier transformed infra-red spectroscopic studies confirming the presence of S15/m-Co3O4. Scanning Electron Microscope images proved the agglomerated nanotube and nanoarcs like the structure of SBA-15 and S15/m- Co3O4, respectively. Electrochemical studies included cyclic voltammetry, charge/discharge, retention capacity, and electron impedance spectroscopy studies in a 3-electrode system. S15/m-Co3O4 nanoarcs, as the electrode material, was revealed to have a specific capacity of 87.5 C/g in 1 M KOH solution. Upon running 1000 cycles, the material had excellent capacity retention of 87%. The S15/m-Co3O4 product also underwent photocatalytic degradation studies. The Rhodamine R6G dye degradation by S15/m-Co3O4 under UV irradiation exhibited a high degradation percentage of 97.7%, following the first-order kinetics. S15/m-Co3O4 has proven to be biocompatible and can be used to enhance supercapacitors which are an ideal alternative to conventional batteries for energy storage applications. Thus, the data produced proves S15/m-Co3O4 nanoarcs is an excellent electrode material for pseudocapacitive application and a catalyst for photocatalytic degradation of dye molecules.
Assuntos
Óxidos , Catálise , Cobalto , Eletrodos , Óxidos/química , Dióxido de SilícioRESUMO
Comprised of a battery anode and a supercapacitor cathode, hybrid lithium-ion capacitors (HLICs) are found to be an effective solution to realize both high power density and high energy density at the same time. Organic-inorganic hybrid materials with well-organized framework guided by the reticular chemistry are one of the promising anode materials for HLICs because of rich active sites and ordered porosity. Herein, metal-organic framework consisting of Zr4+ metal ions and tetrathiafulvalene-based ligands (Zr-MOF) is proposed as the pseudocapacitive anode of HLICs. The Zr-MOF possesses high stability, high crystallinity, and multiple meso-microporous channels favorable for ion transport. The as-prepared Zr-MOF||activated carbon HLICs present high energy density (122.5 Wh kg-1 ), high power density (12.5 kW kg-1 ), and stable cycling performance (86% capacity retention after 1000 cycles at 2000 mA g-1 ) within the operating voltage range of 1.0-4.0 V. The results expand the direct application of MOF for bridging the performance gap between batteries and supercapacitors.
RESUMO
In this study, a strategy that can result in the polyaniline (PANI) solely confined within the nanopores of a metal-organic framework (MOF) without forming obvious bulk PANI between MOF crystals is developed. A water-stable zirconium-based MOF, UiO-66-NH2 , is selected as the MOF material. The polymerization of aniline is initiated in the acidic suspension of UiO-66-NH2 nanocrystals in the presence of excess poly(sodium 4-styrenesulfonate) (PSS). Since the pore size of UiO-66-NH2 is too small to enable the insertion of the bulky PSS, the quick formation of pore-confined solid PANI and the slower formation of well dispersed PANI:PSS occur within the MOF crystals and in the bulk solution, respectively. By taking advantage of the resulting homogeneous PANI:PSS polymer solution, the bulk PANI:PSS can be removed from the PANI/UiO-66-NH2 solid by successive washing the sample with fresh acidic solutions through centrifugation. As this is the first time reporting the PANI solely confined in the pores of a MOF, as a demonstration, the obtained PANI/UiO-66-NH2 composite material is applied as the electrode material for supercapacitors. The PANI/UiO-66-NH2 thin films exhibit a pseudocapacitive electrochemical characteristic, and their resulting electrochemical activity and charge-storage capacities are remarkably higher than those of the bulk PANI thin films.
RESUMO
Herein, a novel conductive poly(N-phenylglycine) (PNPG) polymer was successfully prepared, byin situelectrochemical polymerization method (+0.75 VversusAg/AgCl) for 10 min, on flexible stainless-steel plate coated with a thin Au film (Au/SS) to serve as a binder-free pseudocapacitive PNPG/Au/SS electrode for energy storage devices. Compared to the electrode without Au coating, PNPG/Au/SS electrode exhibited better electrochemical performance with larger specific capacitance (495 F g-1at a current density of 2 A g-1), higher rate performance and lower resistance, which are good indications to act as a positive electrode for asymmetric supercapacitor devices. Combined with activated carbon as a negative electrode, an asymmetric supercapacitor device was constructed. It displayed a specific capacitance of 38 F g-1at a current density of 0.5 A g-1and an energy density of 5.3 Wh kg-1at a power density of 250 W kg-1. Experimentally, two asymmetric supercapacitor devices were connected in series to power a home-made windmill continuously for 8 s, revealing the high potential of this novel conductive polymer material for energy storage application.