Highly Dispersed Cobalt Nanoparticles Embedded in Nitrogen-Doped Graphitized Carbon for Fast and Durable Potassium Storage.
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ABSTRACT: Potassium-ion batteries (KIBs) have great potential for applications in large-scale energy storage devices. However, the larger radius of K+ leads to sluggish kinetics and inferior cycling performance, severely restricting its practical applicability. Herein, we propose a rational strategy involving a Prussian blue analogue-derived graphitized carbon anode with fast and durable potassium storage capability, which is constructed by encapsulating cobalt nanoparticles in nitrogen-doped graphitized carbon (Co-NC). Both experimental and theoretical results show that N-doping effectively promotes the uniform dispersion of cobalt nanoparticles in the carbon matrix through Co-N bonds. Moreover, the cobalt nanoparticles and strong Co-N bonds synergistically form a three-dimensional conductive network, increase the number of adsorption sites, and reduce the diffusion energy barrier, thereby facilitating the adsorption and the diffusion kinetics. These multiple effects lead to enhanced reversible capacities of 305 and 208.6 mAh g-1 after 100 and 300 cycles at 0.05 and 0.1 A g-1, respectively, demonstrating the applicability of the Co-NC anode for KIBs.
Project description:Developing single-site catalysts featuring maximum atom utilization efficiency is urgently desired to improve oxidation-reduction efficiency and cycling capability of lithium-oxygen batteries. Here, we report a green method to synthesize isolated cobalt atoms embedded ultrathin nitrogen-rich carbon as a dual-catalyst for lithium-oxygen batteries. The achieved electrode with maximized exposed atomic active sites is beneficial for tailoring formation/decomposition mechanisms of uniformly distributed nano-sized lithium peroxide during oxygen reduction/evolution reactions due to abundant cobalt-nitrogen coordinate catalytic sites, thus demonstrating greatly enhanced redox kinetics and efficiently ameliorated over-potentials. Critically, theoretical simulations disclose that rich cobalt-nitrogen moieties as the driving force centers can drastically enhance the intrinsic affinity of intermediate species and thus fundamentally tune the evolution mechanism of the size and distribution of final lithium peroxide. In the lithium-oxygen battery, the electrode affords remarkably decreased charge/discharge polarization (0.40 V) and long-term cyclability (260 cycles at 400 mA g-1).
Project description:As a promising energy storage system, potassium (K) ion batteries (KIBs) have received extensive attention due to the abundance of potassium resource in the Earth's crust and the similar properties of K to Li. However, the electrode always presents poor stability for K-ion storage due to the large radius of K-ions. In our work, we develop a nitrogen-doped carbon nanofiber (N-CNF) derived from bacterial cellulose by a simple pyrolysis process, which allows ultra-stable K-ion storage. Even at a large current density of 1 A g-1, our electrode exhibits a reversible specific capacity of 81 mAh g-1 after 3000 cycles for KIBs, with a capacity retention ratio of 71%. To investigate the electrochemical enhancement performance of our N-CNF, we provide the calculation results according to density functional theory, demonstrating that nitrogen doping in carbon is in favor of the K-ion adsorption during the potassiation process. This behavior will contribute to the enhancement of electrochemical performance for KIBs. In addition, our electrode exhibits a low voltage plateau during the potassiation-depotassiation process. To further evaluate this performance, we calculate the "relative energy density" for comparison. The results illustrate that our electrode presents a high "relative energy density", indicating that our N-CNF is a promising anode material for KIBs.
Project description:The more apparent specific heat release at a lower high-temperature decomposition (HTD) temperature of ammonium perchlorate (AP) poses a challenge for the development of highly active catalysts. In this work, a well-designed cobalt-embedded N-doped porous graphitized carbon (Co@NC) catalyst is obtained by high-temperature calcination of a zeolite imidazolate frameworks-67 precursor, in which the cobalt catalytic active center realizes effective nanoscale dispersion; meanwhile, the cobalt and N-doped porous graphitized carbon can release considerable heat after oxidation, and the cobalt oxides have an excellent catalytic effect on reducing the HTD temperature of AP. The catalytic activity of Co@NC was tested by a differential thermal analytical method. The results indicated that the HTD peak of AP was significantly decreased by 100.5 °C, the apparent activation energy of the HTD reaction of AP was reduced by 82.0 kJ mol-1, and the heat release compared with pure AP increased 2.9 times. On teh basis of these findings, Co@NC is expected to be one of the best candidate materials for AP thermal decomposition.
Project description:Multipores engineering composed of micro/mesopores is an effective strategy to improve potassium storage performance via providing enormous adsorption sites and shortened ions diffusion distance. However, a detailed exploration of the role played by macropores in potassium storage is still lacking and has been barely reported until now. Herein, a superstructure carbon hexahedron (DGN-900) is synthesized using poly tannic acid (PTA) as precursor. Due to the spatially confined two-step local contraction of PTA along different directions and dimensions during pyrolysis, defective nanosheets with macropores are formed, while realizing a balance between defects content and graphitization degree by regulating temperature. The presence of macropores is conducive to accelerating electrolyte ions rapid infiltration within electrode, and its pore volume can accommodate electrode structure fluctuation upon cycling, while the most suitable ratio of defects to graphitic provides rich ions adsorption sites and sufficient electrons transfer channels, simultaneously. These advantages enable a prominent electrochemical performance in DGN-900 electrode, including high rate (202.9 mAh g-1 at 2 A g-1 ) and long cycling stability over 2000 cycles. This unique fabrication strategy, that is, defects engineering coupled with macropores structure, makes fast and durable potassium storage possible.
Project description:For the electrochemical reduction of oxygen the development of heteroatom-doped carbon-based transition metal catalysts has become a recognized strategy to replace traditional noble metal catalysts. In this work a catalyst consisting of CoFe nanoparticles encapsulated in N-doped carbon-based materials (NC) supported by carbon nanotubes (CNTs), i.e. Fe3Co1@NC/CNTs, was modified via treatment with a phosphate salt to synthesize a P-Fe3Co1@NC/CNTs catalyst. The P-Fe3Co1@NC/CNTs exhibits with 5.29 mA cm-2 an enhanced current density which is comparable to a Pt/C catalyst. In addition, a stability and methanol resistance better than the Pt/C catalyst were observed which is ascribed to the carbon encapsulation and the synergies between the two transition metals. Finally, the reaction mechanism of P-doping was studied and discussed. These results provide possible directions for carbon-based catalysts and doping with heteroatoms for the improvement of catalytic activity. Moreover, the zinc-air battery assembled with P-Fe3Co1@NC/CNTs as the air-cathode exhibited a high-power density of 73 mW cm-2, which is comparable to that of Pt/C (71 mW cm-2) and a specific capacity of 763 mA h g-1. The prepared catalyst could potentially serve to take the place of precious metal catalysts in rechargeable Zn-air batteries.
Project description:Construction of a suitable hybrid structure has been considered an important approach to address the defects of metal sulfide anode materials. V3S4 nanosheets anchored on an N, S co-coped graphene (VS/NSG) aerogel were successfully fabricated by an efficient self-assembled strategy. During the heat treatment process, decomposition, sulfuration and N, S co-doping occurred. This hybrid structure was not only endowed with an enhanced capability to buffer the volume expansion, but also improved electron conductivity as a result of the conductive network that had been constructed. The dominating pseudocapacitive contribution (57.78% at 1 mV s-1) enhanced the electrochemical performance effectively. When serving as anode material for lithium ion batteries, VS/NSG exhibits excellent lithium storage properties, including high rate capacity (480 and 330 mAh g-1 at 5 and 10 A g-1, respectively) and stable cyclic performance (692 mAh g-1 after 400 cycles at 2 A g-1).
Project description:In view of rich potassium resources and their working potential, potassium-ion batteries (PIBs) are deemed as next generation rechargeable batteries. Owing to carbon materials with the preponderance of durability and economic price, they are widely employed in PIBs anode materials. Currently, porosity design and heteroatom doping as efficacious improvement strategies have been applied to the structural design of carbon materials to improve their electrochemical performances. Herein, nitrogen-doped mesoporous carbon spheres (MCS) are synthesized by a facile hard template method. The MCS demonstrate larger interlayer spacing in a short range, high specific surface area, abundant mesoporous structures and active sites, enhancing K-ion migration and diffusion. Furthermore, we screen out the pyrolysis temperature of 900 °C and the pore diameter of 7 nm as optimized conditions for MCS to improve performances. In detail, the optimized MCS-7-900 electrode achieves high rate capacity (107.9 mAh g-1 at 5000 mA g-1) and stably brings about 3600 cycles at 1000 mA g-1. According to electrochemical kinetic analysis, the capacitive-controlled effects play dominant roles in total storage mechanism. Additionally, the full-cell equipped MCS-7-900 as anode is successfully constructed to evaluate the practicality of MCS.
Project description:Potassium-ion batteries (PIBs) are attractive for grid-scale energy storage due to the abundant potassium resource and high energy density. The key to achieving high-performance and large-scale energy storage technology lies in seeking eco-efficient synthetic processes to the design of suitable anode materials. Herein, a spherical sponge-like carbon superstructure (NCS) assembled by 2D nanosheets is rationally and efficiently designed for K+ storage. The optimized NCS electrode exhibits an outstanding rate capability, high reversible specific capacity (250 mAh g-1 at 200 mA g-1 after 300 cycles), and promising cycling performance (205 mAh g-1 at 1000 mA g-1 after 2000 cycles). The superior performance can be attributed to the unique robust spherical structure and 3D electrical transfer network together with nitrogen-rich nanosheets. Moreover, the regulation of the nitrogen doping types and morphology of NCS-5 is also discussed in detail based on the experiments results and density functional theory calculations. This strategy for manipulating the structure and properties of 3D materials is expected to meet the grand challenges for advanced carbon materials as high-performance PIB anodes in practical applications.
Project description:Exploring efficient and cost-effective catalysts to replace precious metal catalysts, such as Pt, for electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) holds great promise for renewable energy technologies. Herein, we prepare a type of Co catalyst with single-atomic Co sites embedded in hierarchically ordered porous N-doped carbon (Co-SAS/HOPNC) through a facile dual-template cooperative pyrolysis approach. The desirable combination of highly dispersed isolated atomic Co-N4 active sites, large surface area, high porosity, and good conductivity gives rise to an excellent catalytic performance. The catalyst exhibits outstanding performance for ORR in alkaline medium with a half-wave potential (E 1/2) of 0.892 V, which is 53 mV more positive than that of Pt/C, as well as a high tolerance of methanol and great stability. The catalyst also shows a remarkable catalytic performance for HER with distinctly high turnover frequencies of 0.41 and 3.8 s-1 at an overpotential of 100 and 200 mV, respectively, together with a long-term durability in acidic condition. Experiments and density functional theory (DFT) calculations reveal that the atomically isolated single Co sites and the structural advantages of the unique 3D hierarchical porous architecture synergistically contribute to the high catalytic activity.