Project description:Cu2Se with high theoretical capacity and good electronic conductivity have attracted particular attention as anode materials for sodium ion batteries (SIBs). However, during electrochemical reactions, the large volume change of Cu2Se results in poor rate performance and cycling stability. To solve this issue, nanosized-Cu2Se is encapsulated in 1D nitrogen-doped carbon nanofibers (Cu2Se-NC) so that the unique structure of 1D carbon fiber network ensures a high contact area between the electrolyte and Cu2Se with a short Na+ diffusion path and provides a protective matrix to accommodate the volume variation. The kinetic analysis and DNa+ calculation indicates that the dominant contribution to the capacity is surface pseudocapacitance with fast Na+ migration, which guarantees the favorable rate performance of Cu2Se-NC for SIBs.
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: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:Sodium ion batteries (SIBs) have been considered as a promising alternative to lithium ion batteries (LIBs) for large scale energy storage in the future. However, the commercial graphite anode is not suitable for SIBs because of its low Na+ ions storage capability and poor cycling stability. Recently, another alternative as anode for SIBs, amorphous carbon materials, have attracted tremendous attention because of their abundant resource, nontoxicity, and most importantly, stability. Here, N-doped hierarchical porous carbon microspheres (NHPCS) derived from Ni-MOF have been prepared and used as anode for SIBs. Benefiting from the open porous structure and expanded interlayer distance, the diffusion of Na+ is greatly facilitated and the Na+ storage capacity is significantly enhanced concurrently. The NHPCS exhibit high reversible capacity (291 mA h g-1 at current of 200 mA g-1), excellent rate performance (256 mA h g-1 at high current of 1,000 mA g-1), and outstanding cycling stability (204 mA h g-1 after 200 cycles).
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:Sodium ion batteries have drawn extensive attentions for large-scale energy storage to replace lithium ion batteries primarily due to the natural abundance of sodium resource and low cost, but their energy density and electrochemical performance are hindered by the sluggish diffusion kinetics of sodium ion. Herein, free-standing nitrogen-doped graphene aerogel has been fabricated via hydrothermal reaction as the potential anode material for sodium ion batteries. The three dimensional porous network structure of the graphene aerogel provides sufficient interstitial space for sodium ion accommodation, allowing fast and reversible ion intercalation/de-intercalation. The nitrogen doping could introduce defects on the graphene sheets, making the feasible transport of large-sized sodium ion. Benefiting from the effective structure and nitrogen doping, the obtained material demonstrates high reversible capacities, good cycling performance (287.9?mA h g-1 after 200 cycles at a current density of 100?mA?g-1), especially superior rate capability (151.9?mA h g-1 at a high current density of 5?A g-1).
Project description:Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.
Project description:Pyrolyzing metal-organic frameworks (MOFs) typically yield composites consisting of metal/metal oxide nanoparticles finely dispersed on carbon matrices. The blend of pseudocapacitive metal oxides and conductive metals, as well as highly porous carbon networks, offer unique opportunities to obtain supercapacitor electrodes with mutually high capacitances and excellent rate capabilities. Herein, we demonstrate nitrogen-doped carbon nanocuboid arrays grown on carbon fibers and incorporating cobalt metal and cobalt metal oxides. This composite was synthesized via pyrolysis of a chemical bath deposited MOF, cobalt-containing zeolite imidazole framework (Co-ZIF). The active materials for charge storage are the cobalt oxide and nitrogen-doped carbon. Additionally, the Co metal and the nanoporous carbon network facilitated electron transport and the rich nanopores in each nanocuboid shortened ion diffusion distance. Benefited from these merits, our Co-ZIF-derived electrode delivered an areal capacitance of 1177 mF cm-2 and excellent cycling stability of ~94% capacitance retained after 20,000 continuous charge-discharge cycles. An asymmetric supercapacitor prototype having the Co-ZIF-derived hybrid material (positive electrode) and activated carbon (negative electrode) achieved a maximal volumetric energy density of 1.32 mWh cm-3 and the highest volumetric power density of 376 mW cm-3. This work highlights the promise of metal-metal oxide-carbon nanostructured composites as electrodes in electrochemical energy storage devices.
Project description:Lithium-ion capacitors (LICs) have been proposed as an emerging technological innovation that integrates the advantages of lithium-ion batteries and supercapacitors. However, the high-power output of LICs still suffers from intractable challenges due to the sluggish reaction kinetics of battery-type anodes. Herein, polypyrrole-coated nitrogen and phosphorus co-doped hollow carbon nanospheres (NPHCS@PPy) were synthesized by a facile method and employed as anode materials for LICs. The unique hybrid architecture composed of porous hollow carbon nanospheres and PPy coating layer can expedite the mass/charge transport and enhance the structural stability during repetitive lithiation/delithiation process. The N and P dual doping plays a significant role on expanding the carbon layer spacing, enhancing electrode wettability, and increasing active sites for pseudocapacitive reactions. Benefiting from these merits, the NPHCS@PPy composite exhibits excellent lithium-storage performances including high rate capability and good cycling stability. Furthermore, a novel LIC device based on the NPHCS@PPy anode and the nitrogen-doped porous carbon cathode delivers a high energy density of 149 Wh kg-1 and a high power density of 22,500 W kg-1 as well as decent cycling stability with a capacity retention rate of 92% after 7,500 cycles. This work offers an applicable and alternative way for the development of high-performance LICs.
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).