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1.
Nitrogen-doped transition metal materials display promising potential as bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, Fe/N co-doped three-dimensional (3D) porous graphene (FeN-3D-PG) is prepared via a template method using sodium alginate as the carbon source and low polymerization degree melamine resin as the nitrogen source. The low polymerization degree melamine resin can form complexes with Fe3+ in the aqueous solution and further forms high density Fe-Nx active sites during pyrolysis. Meanwhile, the formed 3D porous structure efficiently promotes the uniform distribution of Fe-Nx active sites. The FeN-3D-PG catalyst exhibits pH-independent ORR activity. For OER, the catalyst possesses a low over potential (370 mV at 10 mA cm−2) in alkaline electrolyte. The Zn-air batteries (ZABs) using FeN-3D-PG as cathode exhibits a power density up to 212 mW cm−2, a high specific capacity of 651 mAh g−1, and the charge-discharge stability of 80 h. This work provides new sight to transition metal materials based ZABs with excellent performance.  相似文献   

2.
Perovskite oxides are widely regarded as the promising air electrode catalytic materials for zinc-air batteries (ZABs). In the present work, A-site Y and B-site Fe co-doped La0.85Y0.15Ni0.7Fe0.3O3 perovskite catalyst was prepared by self-propagating high-temperature synthesis, and this material was evaluated as a bifunctional electrocatalyst for ZABs. The effect of co-doping on crystal structure and reaction activities, which can promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), was investigated. Results show that Y and Fe co-doping substantially improved the ORR and OER of LaNiO3. In comparison with LaNiO3, the ORR performance of La0.85Y0.15Ni0.7Fe0.3O3 exhibited a higher limiting current density (3.8 mA cm?2 at 0.4 V vs. RHE) and more positive onset potential (0.75 V vs. RHE) at 1600 rpm. It also had an excellent OER performance of 1.74 V vs. RHE at 10 mA cm?2. When La0.85Y0.15Ni0.7Fe0.3O3 was used as an air electrode catalyst for ZABs, it exhibited a high power density of 93.6 mW cm?2, which increased by 84.8% compared with that of LaNiO3. Moreover, the full cell with La0.85Y0.15Ni0.7Fe0.3O3 air electrode catalyst was operated for more than 80 h, maintaining good stability. Therefore, La0.85Y0.15Ni0.7Fe0.3O3 can be used as a promising bifunctional air electrode catalyst for ZABs. The characterization analysis reveals that A-site Y and B-site Fe co-doped catalyst transforms crystal structure from trigonal system to cubic system, retain the valence state of Ni3+ and increases the contents of O22?/O?, and these properties are more conducive for LaNiO3 catalysis.  相似文献   

3.
This study assessed the feasibility of vanadium pentoxide (V2O5) as a novel cathode catalyst material in air-cathode single chamber microbial fuel cells (SCMFCs). The V2O5 nanorod catalyst was synthesized using a hydrothermal method. MFCs with different cathode catalyst loadings were studied. Cyclic voltammetry (CV) was used to examine the electrochemical behavior of the catalysts in the MFCs. The V2O5 cathode catalyst constructed with a double loading MFC exhibited the highest maximum power density of 1073 ± 18 mW m−2 (OCP; 691±4 mV) compared with 447 ± 12 mW m−2 (OCP; 594 ± 5 mV) and 936 ± 15 mW m−2 (OCP; 647±5 mV) for the single loading MFC and triple loading MFC, respectively. The power density of MFC with double loaded V2O5 is comparable to the traditional Pt/C cathode (2067 ± 25 mW m−2, OCP; 821 ± 4 mV), which covers up to 55% of the performance of Pt/C. This finding highlights the potential of the V2O5 cathode as an inexpensive catalyst material for MFCs that may have commercial applications.  相似文献   

4.
One of the most promising ways to produce high purity hydrogen is electrocatalytic water splitting, the slow rate of oxygen evolution reaction (OER) limited the whole water splitting process under alkaline conditions. Here, NiCo2O4@NiWO4/NF is firstly acted as a metal tungstate dominated bifunctional water splitting catalyst, which a very low cell voltage of 1.59 V is obtained with 10 mA cm−2 in alkaline media. Remarkably, the catalytic performance of NiCo2O4@NiWO4/NF is also kept for at least 12 h, which shows long time electrochemical stability.  相似文献   

5.
Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the core reaction processes of rechargeable Zn-air battery (ZAB) cathode. Therefore, exploring a bifunctional catalyst with excellent electrochemical performance, high durability, and low cost is essential for rechargeable ZAB. In this work, amino functionalized carbon nanotubes supported core/shell nanoparticles composed of CoNi alloy core and CoO–NiO shell (CoNi@CoO–NiO/NH2-CNTs-1) is synthesized through a simple and efficient hydrothermal reaction and calcination method, which shows higher ORR/OER bifunctional catalytic performance than the single metal-based catalyst, such as Ni@NiO/NH2-CNTs and Co@CoO/NH2-CNTs. The fabricated bimetallic alloy based catalyst CoNi@CoO–NiO/NH2-CNTs-3 with the optimized loading content of CoNi@CoO–NiO core/shell nanoparticles, presents the best bifunctional catalytic performance for ORR/OER. Experimental studies reveal that CoNi@CoO–NiO/NH2-CNTs-3 exhibits the onset potential of 0.956 V and 1.423 V vs. RHE for ORR and OER, respectively. It also exhibits a low overpotential of 377 mV to achieve a 10 mA cm?2 current density for OER, and positive half-wave potentials of 0.794 V for ORR. And the potential difference between half-wave potential of ORR (E1/2) and the potential at 10 mA cm?2 for OER (Ej10) is 0.813 V. In addition, when CoNi@CoO–NiO/NH2-CNTs-3 is used as an air electrode catalyst of rechargeable ZAB, its maximum power density and open circuit voltage (OCV) can reach 128.7 mW cm?2 and 1.458 V (The commercially available catalyst of Pt/C–RuO2 is 88.1 mW cm?2), which strongly demonstrates that the fabricated catalyst CoNi@CoO–NiO/NH2-CNTs-3 can be used as a highly efficient bifunctional catalyst for ZABs, and is expected to replace those expensive precious metal electrocatalysts to meet the growing demand for new energy devices.  相似文献   

6.
Synthesis of highly efficient, non-noble and bi-functional electrocatalysts is exceedingly challenging and necessary for water splitting devices. In this work, three-dimensional spherical Ni(OH)2/NiCo2O4 heterojunctions are prepared by a one-step hydrothermal method and the hybrids are explored as efficient electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in an alkaline electrolyte via tuning different Ni/Co atomic ratios of heterojunctions. The optimized Ni(OH)2/NiCo2O4 (S (1:1)) exhibits high electrocatalytic activity with an ultralow over-potential of 189 mV at 10 mA cm−2 for the HER. With regard to the OER, the over-potential of the as-synthesized S (1:1) heterojunction is only 224 mV at the current density of 10 mA cm−2. The improved catalytic performance of the Ni(OH)2/NiCo2O4 heterojunctions is attributed to the chemical synergic combining of Ni(OH)2 and NiCo2O4, large specific surface area for exposing more accessible active sites, and heterointerface for activating the intermediates that facilitates electron/electrolyte transport. The prepared catalyst exhibits good durability and stability in HER and OER catalyzing conditions. This study provides a feasible approach for the building of highly efficient bifunctional water splitting electrocatalysts and stimulates the development of renewable energy conversion and storage devices.  相似文献   

7.
The rational design and preparation of bifunctional electrocatalysts with pleasant oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance is crucial for extensive commercial applications of rechargeable Zn–air batteries (ZABs). Herein, we report a simple method to obtain multi-metal (Fe, Ni, Zn) embedded in N-doped carbon sheets entangled with carbon nanotubes (CNTs) as superior oxygen electrocatalysts (FeNi-NCS-2). The resultant FeNi-NCS-2 exhibits an impressive electrochemical performance, providing a reversible oxygen overpotential as low as 0.758 V. The ZAB with FeNi-NCS-2 as the air cathode shows a promising capacity of 639.71 mAh g?1 at 20 mA cm?2, a power density of 109.8 mW cm?2 and cycling stability of over 130 cycles at 10 mA cm?2 with an energy efficiency of about 55%, superior to the ZAB based on Pt/C–IrO2. The satisfactory electrocatalytic performance is mainly due to the Fe, Ni-based nanoparticles protected by graphitic carbon layers, hierarchical porous lamellar structures that promote the accessibility between the active centers and the electrolyte as well as self-growing tangled carbon nanotubes that provide fast transmission channels. This study presents a facile way for the synthesis of highly efficient ORR/OER bifunctional electrocatalysts for high-performance rechargeable ZABs.  相似文献   

8.
It is highly critical to explore efficient bifunctional oxygen electrocatalysts for regenerative fuel cells and metal-air batteries. Herein, N, F co-doped carbon material (NF@CB) was synthesized as metal-free efficient bifunctional electrocatalysts by directly pyrolyzing a mixture of carbon black, polytetrafluoroethylene and melamine. Benefiting from the synergistic effects between N and F atoms, NF@CB exhibits a positive half-wave potential (E1/2) of 0.814 V (vs. RHE) for oxygen reduction reaction, and an operating potential (E10) of 1.609 V at 10 mA cm−2 for oxygen evolution reaction in alkaline electrolyte. The bifunctional oxygen electrocatalytic activity index (ΔE = E10E1/2) is 0.795 V, which is notably better than that of the single N-doped carbon (1.238 V), and similar to that of the commercial Pt/C and RuO2 mixture catalyst (0.793 V). Impressively, the assembled Zn-air battery (ZAB) with NF@CB as an air-electrode catalyst displays a small charge/discharge voltage gap of 0.852 V at 20 mA cm−2. Moreover, the NF@CB catalyzed ZAB exhibits good rechargeability and long-lasting cycling stability with over 49 h. This investigation introduces a cheap and simple way to develop highly efficient bifunctional N, F co-doped electrocatalysts.  相似文献   

9.
Developing efficient nonprecious electrocatalysts that can drive the oxygen electrode reactions in zinc-air batteries (ZABs) is important but remains challenging. In this work, novel materials comprising Mn/Cu nanoclusters-grafted N-doped carbon nanotubes are synthesized by preparing and then pyrolyzing Mn/Cu polyphthalocyanine-encapsulated carbon nanotubes (CNTs), followed by treating the products with acidic solution. The materials are named CNTs@(Mn,Cu)PPc-T, where T denotes the pyrolysis temperature in °C, and they are demonstrated to serve as efficient oxygen electrode catalysts for zinc-air batteries (ZABs). Among them, the one synthesized at 900 °C, CNTs@(Mn,Cu)PPc-900, requires more positive onset and half-wave potentials for reduction of oxygen and a low overpotential for the evolution of oxygen. A rechargeable ZAB assembled with CNTs@(Mn,Cu)PPc-900 electrocatalyst delivers a high power density (158.5 mW cm−2) and displays an excellent stability in 200 cycles of charge/discharge (in over 33 h). Such performance is even superior to that of a ZAB containing the benchmark Pt/C + RuO2 catalyst as an air cathode under identical testing condition.  相似文献   

10.
It is very important to exploit robust electrocatalysts for the urea splitting in an alkaline medium. Hence, the NiCo2S4@NiCoP nanoarrays on Ni foam (NiCo2S4@NiCoP/NF) was successfully synthesized for the first time and used as an efficient and stable difunctional electrocatalyst for the overall urea splitting. As one of the most promising bifunctional electrocatalysts reported, NiCo2S4@NiCoP only needs 108 mV to reach current density of 10 mA cm−2 for hydrogen evolution reaction. Moreover, such NiCo2S4@NiCoP//NiCo2S4@NiCoP electrodes couple display superior urea splitting performance with the requirement of a cell voltage of 1.53 V to drive a catalytic current density of 10 mA cm−2. In addition, the NiCo2S4@NiCoP material presents high long-term electrocatalytic stability keeping its performance at 11 mA cm−2 for 12 h. The experimental results demonstrate that the sluggish Volmer step has been improved by incorporating the NiCoP to the NiCo2S4.  相似文献   

11.
Spinel-type nickel cobaltite with numerous oxygen vacancies is successfully synthesized by hydrothermal and thermal reduction using hydrogen. The effects of oxygen vacancies on the electrochemical activity and stability for the oxygen reduction reaction are investigated. The prepared catalyst displays significantly enhanced oxygen reduction reaction (ORR) catalytic performance under alkaline conditions, which is comparable to that of commercial Pt/C. The oxygen-deficient NiCo2O4 exhibits a very high limiting current density of −5.44 mA cm−2 with onset and half-wave potentials of 0.93 and 0.78 V versus the reversible hydrogen electrode (RHE), respectively. Additionally, it shows excellent durability and resistance to methanol. The enhanced ORR activity and stability of the catalyst can be ascribed to the synergistic effects of the relatively large electrochemical surface area, more exposed active sites, and good electrical conductivity derived from abundant oxygen vacancies.  相似文献   

12.
Spinel oxides have been considered as promising precious metal-free catalysts for oxygen reduction reaction (ORR). However, the poor intrinsic conductivity and moderate electrocatalytic performance hinder their practical applications. Hence, various strategies have been explored and reported in addressing the issues. Herein, an elaborate approach for enhancing the ORR performance of spinel NiCo2O4 is proposed, by combining the decoration of NiCo2O4 nanoparticles on electrospun carbon nanofibers and defect engineering with rich oxygen vacancies on NiCo2O4 nanoparticles through a facilely controlling on calcination circumstance, which could not only increase more active sites and improve the intrinsic catalytic activity, but also render an excellent stability for long-term operation. Thus, the as-prepared hybrid exhibits significantly improved ORR electrocatalytic performance, including a high limited current density of −5.8 mA cm−2, a positively shifting of the onset potential at 0.88 V and half-wave potential at 0.76 V (vs. RHE). The performance of rechargeable Zn-air battery based on the as-prepared catalyst surpasses the one based on Pt/C catalyst significantly. This work can be also applied to other metal oxides based electrocatalysts, and then provided an avenue for the realization of metal-air batteries and fuel cells with high efficient and cost-effective.  相似文献   

13.
Silver nanocatalyst (40 wt%) is deposited on commercial mesoporous carbon support material (Ag/C) using two different wet chemical methods, to obtain high electrochemically active surface area. The catalyst materials are characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis and are evaluated toward the oxygen reduction reaction (ORR) in alkaline media employing the rotating disk electrode method. It is worth noting that the Ag/C leads to oxygen reduction through a direct four-electron pathway in alkaline medium. The silver catalyst on mesoporous carbon exhibits relatively higher mass activity for ORR (38 A g−1) compared to that with Vulcan carbon (32 A g−1) at −0.2 V vs SCE at room temperature. Anion exchange membrane fuel cell shows maximum power density of 310 mW cm−2 with Ag/C cathode catalyst using H2 and O2 gases at 65% RH conditions at 65 °C.  相似文献   

14.
Heterostructured materials with special interfaces and features give a unique character for much electrocatalytic process. In this work, the introduction of exogenous modifier Ni-MOF improved the reaction kinetics and morphology of the NiCo2O4@Ni-MOF/NF catalyst. As-obtained NiCo2O4@Ni-MOF/NF has excellent oxygen evolution reaction (OER) performance and urea oxidation reaction (UOR) performance. The catalyst need overpotential of 340 mV at a current density of 100 mA cm?2 for OER and a potential of 1.31 V at the same current density for UOR. The Tafel slopes of NiCo2O4@Ni-MOF/NF is 38.34 and 15.33 mV dec?1 for OER and UOR respectively, which is more superior than 78.58 and 66.73 mV dec?1 of NiCo2O4/NF. The nanosheets microstructure is beneficial to the adsorption and transport of electrolyte and the presence of a large number of mesoporous channels can also accelerate gas release, and then improves activity of the catalyst. Density functional theory calculation demonstrate that NiCo2O4 plays a role in absorbing water, while the existence of in situ generated NiOOH can promote the electron transfer efficiency. It is synergies of NiCo2O4 and in situ generated NiOOH that enhance the decomposition of water on the surface of the NiCo2O4@Ni-MOF/NF. This investigation provides a new strategy for the application of spinel oxide and MOF materials.  相似文献   

15.
W–Co was cathodically electrodeposited on gas diffusion layer (GDL) electrodes for application as a bifunctional catalyst for Zn-air batteries. The electrodes were synthesized galvanostatically at various pH values (4.5 and 7.5) and deposition times (5, 15 and 25 min). Transmission electron microscopy (TEM) analysis showed that the deposits oxidized in contact with air, forming a conformal layer of W–Co oxide with a thickness of ~10 nm. During battery cycling, most of the W dissolved in the electrolyte. The remaining Co oxide agglomerated, forming nanoparticles less than 100 nm in size. Zinc (present in the electrolyte as ZnO) was incorporated into the Co oxide nanoparticles. As such, the conformal layer of W–Co oxide transformed into cubic spinel ZnCo2O4 nanoparticles which provided excellent bifunctional catalytic activity. The W in the original deposit acted as a conduit to facilitate formation of the ZnCo2O4 nanoparticles. The ZnCo2O4 catalyst demonstrated good performance in two-electrode and three-electrode full-cell Zn-air battery tests. In three-electrode tests at 10 mA cm−2, a round trip efficiency of 62% was achieved, exceeding the efficiency of Pt/Ru–C (61%). The final efficiencies were 59% for the three-electrode configuration (after 100 cycles). A high maximum power density of 216 mW cm−2 was also achieved.  相似文献   

16.
The effect of Ag particle size on oxygen reduction reaction (ORR) at the cathode was investigated in anion exchange membrane direct glycerol fuel cells (AEM-DGFC) with oxygen as an oxidant. At the anode, high purity glycerol (99.8 wt%) or crude glycerol (88 wt%, from soybean biodiesel) was used as fuel, and commercial Pt/C served as the anode catalyst. A solution phase-based nanocapsule synthesis method was successfully developed to prepare the non-precious Ag/C cathode catalyst, with LiBEt3H as a reducing agent. XRD and TEM characterizations show that as-synthesized Ag nanoparticles (NP) with a size of 2–9 nm are well dispersed on the Vulcan XC-72 carbon black support. Commercial Ag nanoparticles with a size of 20–40 nm were also supported on carbon black as a control sample. The results show that higher peak power density was obtained in AEM-DGFC employing an Ag-NP catalyst with smaller particle size: nanocapsule made Ag-NP > commercial Ag-NP (Alfa Aesar, 99.9%). With the nanocapsule Ag-NP cathode catalyst, the peak power density and open circuit voltage (OCV) of AEM-DGFC with high-purity glycerol at 80 °C are 86 mW cm−2 and 0.73 V, respectively. These are much higher than 45 mW cm−2 and 0.68 V for the AEM-DGFC with the commercial Ag/C cathode catalyst, which can be attributed to the enhanced kinetics and reduced internal resistance. Directly fed with crude glycerol, the AEM-DGFC with the nanocapsule Ag-NP cathode catalyst shows an encouraging peak power density of 66 mW cm−2, which shows great potential of direct use of biodiesel waste fuel for electricity generation.  相似文献   

17.
The development of bifunctional catalysts that can be applied to both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is widely regarded as a key factor in the production of sustainable hydrogen fuel by electrochemical water splitting. In this work, we present a high-performance electrocatalyst based on nickel-cobalt metal-organic frameworks for overall water splitting. The as-obtained catalyst shows low overpotential to reaches the current density of 10 mA cm−2 with 249 mV for OER and 143 mV for HER in alkaline media, respectively. More importantly, when the electrolyzer was assembled with the as-prepared catalyst as anode and cathode simultaneously, it demonstrates excellent activity just applies a potential of 1.68 V to achieve 10 mA cm−2 current density for overall water splitting.  相似文献   

18.
This work reports on the synthesis of tin-nitrogen/carbon (Sn–N/C) catalysts suitable for the electroreduction of molecular oxygen at the cathode of proton exchange membrane fuel cells. The catalysts were synthesized through a simple pyrolysis process of folic acid as the carbon and nitrogen source, tin chloride as a tin source and Vulcan carbon as the substrate. The synthesized catalyst exhibited excellent oxygen reduction activity with a half wave potential of 0.82 V and a mass activity of 15.5 mA mg−1. Successful application at the cathode of a self-breathing fuel cell further confirmed the superior performance of this catalyst leading to a power density of 29.4 mW cm−2. This is very comparable to the reference platinum/Vulcan carbon catalyst (28.4 mW cm−2). In addition, this Sn–N/C catalyst showed good stability under accelerated stress tests with only a 12% decrease in fuel cell performance after 10,000 cycles. The superior performance was assumed to be due to the presence of both metal-nitrogen and nitrogen-carbon active sites, which facilitate the four-electron path of the oxygen reduction reaction.  相似文献   

19.
Developing the low-cost, durable, and efficient bifunctional electrocatalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) plays an important role in the commercial implementation of the Zn-air batteries. Herein, we design and synthesize the MnO and Co nanoparticles coated with N-doped carbon (MC@NC) as an excellent bifunctional oxygen electrocatalyst. It is found that the optimal MC@NC-0.3 exhibits outstanding ORR performance with a positive half-wave potential of 0.82 V and excellent OER activity with a small overpotential of 360 mV at 10 mA cm−2. When applied in the liquid Zn-air battery, MC@NC-0.3 displays a high maximum power density of 153 mW cm−2, a large specific capacity of 776 mAh g−1 and the excellent cycling stability with a negligible increase after 300 h. Furthermore, the fiber-shaped all-solid-state Zn-air battery also displays remarkable stability at high current density. This study offers a facile strategy to construct a high-efficient, low-cost, and durable transitional metal-based bifunctional electrode for renewable energy applications.  相似文献   

20.
The development of non-precious metal catalysts to replace scarce and expensive Pt-based catalysts is critical for oxygen reduction reactions (ORR), where zeolitic-imidazolate-framework-derived (ZIF-derived) iron-based electrocatalysts hold a promising prospect. Herein, Fe3O4 was used as Fe source, and ZIF-8 was used as C and N source to prepare Fe-NC catalysts. Specifically, the half-wave potential (E1/2) of the Fe-NC reached 0.90 V, which was higher than commercial Pt/C catalysts (0.87 V), and the overpotential of OER reached 327 mV. In addition, the power density tested in Zn-air batteries upped to 129.59 mW cm−2, surpassing that of the Pt/C (108.93 mW cm−2). The superior performance was attributed to the effective introduction of Fe, the large specific surface area (851.6 m2 g−1), relatively regular porous structure and the high degree of graphitization.  相似文献   

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