Rose-like NiCo2O4 with Atomic-Scale Controllable Oxygen Vacancies for Modulating Sulfur Redox Kinetics in Lithium-Sulfur Batteries.

The long-term stability of Li-S batteries is significantly compromised by the shuttle effect and insulating nature of active substance S, constraining their commercialization. Developing efficient catalysts to mitigate the shuttle effect of lithium polysulfides (LiPSs) is still a challenge. Herein, we designed and synthesized a rose-like cobalt-nickel bimetallic oxide catalyst NiCo2O4-OV enriched with oxygen vacancies (OV) and verified the controllable synthesis of different contents of OV. Introducing the OV proved to be an efficient approach for controlling the electronic structure of the electrocatalyst and managing the absorption/desorption processes on the reactant surface, thereby addressing the challenges posed by the LiPS shuttle effect and sluggish transformation kinetics in Li-S batteries. In addition, we investigated the effect of OV in NiCo2O4 on the adsorption capacity of LiPSs using adsorption experiments and density functional theory (DFT) simulations. With the increase in the level of OV, the binding energy between the two is enhanced, and the adsorption effect is more obvious. NiCo2O4-OV contributes to the decomposition of Li2S and diffusion of Li+ in Li-S batteries, which promotes the kinetic process of the batteries.

Enhancing Electron Conductivity and Electron Density of Single Atom Based Core-Shell Nanoboxes for High Redox Activity in Lithium Sulfur Batteries.

Herein, an integrated structure of single Fe atom doped core-shell carbon nanoboxes wrapped by self-growing carbon nanotubes (CNTs) is designed. Within the nanoboxes, the single Fe atom doped hollow cores are bonded to the shells via the carbon needles, which act as the highways for the electron transport between cores and shells. Moreover, the single Fe atom doped nanobox shells is further wrapped and connected by self-growing carbon nanotubes. Simultaneously, the needles and carbon nanotubes act as the highways for electron transport, which can improve the overall electron conductivity and electron density within the nanoboxes. Finite element analysis verifies the unique structure including both internal and external connections realize the integration of active sites in nano scale, and results in significant increase in electron transfer and the catalytic performance of Fe-N4 sites in both Li2 Sn lithiation and Li2 S delithiation. The Li-S batteries with the double-shelled single atom catalyst delivered the specific capacity of 702.2 mAh g-1 after 550 cycles at 1.0 C. The regional structure design and evaluation method provide a new strategy for the further development of single atom catalysts for more electrochemical processes.

Shaping droplet by semiflexible micro crystallizer for high quality crystal harvest.

Droplet crystallization behavior held great potential in crystal preparation, micromaterial engineering, and molecular assembly. However, restricted by natural surface tension, the intrinsic crystallization regulation and efficient harvest of high quality crystal in diverse droplet features were still a great challenge. Herein, we developed a 3D printed semiflexible micro crystallizer with two aspectant sessile platforms that could simultaneously construct a series of heteromorphic droplets (HDs) and controllable HD shape. By shaping HD on the interface of the platform, central-converging micro-flows were generated by coordinating the gas-liquid interface and flow intensity (i.e., Ra/Ma) during HD crystallization from 'barrel', 'can', to 'sand clock' shape, which was validated via simulative and experimental research. Therefore, HDs, constructed in semiflexible micro crystallizer, exhibited efficient screening (>70 %) of single cubic crystal just at the center zone of platform, even under wide ranges of concentration and volume, manifesting excellent repeatability on high quality crystal harvest and relevant interfacial science research.

Increasing N active sites by in-situ growing conformal C3N4 layer in hierarchical porous carbon-based networks for fast Li+ transfer and polysulfide anchoring in lithium-sulfur batteries.

Various challenges remain to be overcome in lithium-sulfur (Li-S) batteries, including the volume expansion and low conductivity of sulfur, the shuttle effect of lithium polysulfides and the sluggish redox reaction in the cell. Herein, we propose a multilayered conductive framework by the in situ growth of a conformal graphene-like C3N4 (GCN) coating on porous CNT@NC networks with carbon nanotubes (CNTs) as the core and N-doped carbon (NC) as the crosslinking shell. The abundant N in the GCN coating increased the surface N concentration of the framework from 14.38% to 18.77%, which enriched the active sites in the frameworks for the adsorption and catalysis conversion of LiPSs and Li2S with a low energy barrier. Furthermore, the scalable frameworks can provide an 85% porosity for a sufficient reaction interface and accommodate the volume expansion of sulfur. The synergistic effect between GCN and the highly conductive hierarchical structure can accelerate the transport of Li+ and electrons as well as the diffusion of electrolyte. Benefitting from the above advantages, the Al-free CNT@NC@GCN electrode exhibits a reversible capacity of 647.6 mAh g-1 after cycling for 450 cycles at 1C with a low capacity fading rate of 0.09% per cycle. This proposed facile strategy creates inspiring insights into the design of novel cathode materials for Li-S batteries.

Thiophilic-Lithiophilic Hierarchically Porous Membrane-Enabled Full Lithium-Sulfur Battery with a Low N/P Ratio.

Lithium-sulfur batteries stand out as the next-generation batteries because of their high energy density and low cost. However, the shuttle effect of lithium polysulfides (LiPSs), growth of lithium dendrites, and overuse of lithium resources still hinder their further application. To address these problems, we constructed a porous network structure in which Sn is melted and coated on a frame that has a carbon nanotube (CNT) core and a nitrogen-doped carbon (NC) coating as cross-linking shell (CNT@NC@Sn). This hierarchically porous membrane electrode, which has an ultrahigh porosity of approximately 90%, works as a matrix to strengthen the conductivity of Li+ and electrons and provides enough space for the conversion between sulfur and LiPSs. Moreover, the in situ thin coating of Sn not only promotes the adsorption and catalytic conversion of LiPSs but also provides lithiophilic binding sites and induces uniform lithium deposition. Thus, the thiophilic-lithiophilic porous membrane electrode with lithium loaded on the frame (in the form of Sn-Li alloy) by electroplating can replace lithium sheets, reduce the use of Li, and improve the safety performance of the battery. Additionally, these dual-functional membranes boost the reaction kinetics and conductivity of the cathode by dispersing the sulfur slurry in the porous membrane framework. As a result, the lithium-sulfur full battery assembled with the CNT@NC@Sn integrated membrane electrode exhibits stable cycling with a reversible capacity of 617.1 mAh g-1 after 200 cycles at 1 C. The capacity decay rate per cycle is 0.105%, and the N/P ratio is as low as 2.98.

A Covalent Organic Framework Membrane with Homo Hierarchical Pores for Confined Reactive Crystallization.

Gas-liquid (G-L) reactive crystallization is a major technology for advanced materials construction, which requires a short diffusion path on the interface to ensure the reactant supply and stable crystal nucleation under ultrahigh supersaturation. Herein, a covalent organic framework (COF) membrane with homo hierarchical pore structures was proposed as an effective interfacial material for the regulation of confined reactive crystallization. By combining the ordered nanopores of COFs and micropores of anodic aluminum oxide (AAO), the COF membrane simultaneously provided an excellent nanoscale diffusion-reaction regulation network as the molecular-level confined G-L reactive interface and adjustable submicrometer gas mass transfer channels. The highly selective construction of CaCO3 superstructures was then achieved. When the submicrometer primary pore size rp of the constructed COF membrane ranged from 120 to 1.6 nm, the diffusion mechanism of CO2 varied from viscous flow diffusion to Knudsen diffusion. The growth orientation of CaCO3 crystals was well confined to obtain spindle-shaped crystals with high selectivity. Meanwhile, the crystal selectivity factor (cube/sphere) increased from 0 to 3.53 under the low interfacial nuclear barrier. Thus, the COF membrane with coupled micro-nanostructures successfully screened the directional preparation conditions for diverse CaCO3 superstructures, which also paved a meaningful path for the functional application of COFs in accurate mass transfer control and confined chemical reactions.

N-Doped Hierarchically Porous CNT@C Membranes for Accelerating Polysulfide Redox Conversion for High-Energy Lithium-Sulfur Batteries.

To improve the structural design of electrodes and interlayers for practical applications of Li-S batteries, we report two scalable porous CNT@C membranes for high-energy Li-S batteries. The asymmetric CNT@C (1:2) membrane with both dense and macroporous layers can act as an Al-free cathode for current collection and high sulfur loading, while the symmetric CNT@C (1:1) membrane with hierarchically porous networks can be used as an interlayer to trap lithium polysulfides (LiPSs), thus weakening the shuttle effect by strong adsorption of the N atoms toward LiPSs. The doped N sites in carbon membranes are identified as bifunctional active centers that electrocatalytically accelerate the oxidation of Li2S and polysulfide conversion. First-principles calculations reveal that the pyridinic and pyrrolic N sites exhibit favorable reactivity for strong adsorption/dissociation of polysulfide species. They lead to greatly reduced energy and kinetic barrier for polysulfide conversion without weakening the polysulfide adsorption on the membrane. Using the synergistic circulation groove with the two membranes, the practical S loading can be tailored from 1.2 to 6.1 mg cm-2. The Li-S battery can deliver an areal capacity of 4.6 mA h cm-2 (684 mA h g-1) at 0.2 C even at an ultrahigh S loading of 6.1 mg cm-2 and a lean electrolyte to sulfur ratio of 5.3 µL mg-1. Our work for scalable membrane fabrication and structural design provides a promising strategy for practical applications of high-energy Li-S batteries.

Bioinspired Hybrid Micro/Nanostructure Composited Membrane with Intensified Mass Transfer and Antifouling for High Saline Water Membrane Distillation.

Membrane distillation (MD) holds great promise for high-saline solution treatment, but it is typically impeded by the trade-off between the high mass transfer and antifouling properties of the membrane. Herein, a new MD utilized membrane with bioinspired micro/nanostructure (lotus leaf and fish gill) was constructed on commercial PP membrane, which can simultaneously enhance the permeation flux and antifouling in the hypersaline MD operation. On the basis of the classic nucleation theory and hydrodynamics simulation, the nanoscale structure can intensify the interfacial nanoscale turbulent flow and hinder the crystal deposition, which works like the fish gill. In addition, the optimized nanoscale feature size renders the membrane with the heterogeneous nucleation barrier very similar to the homogeneous system, which works like the lotus leaf and hinders the induced nucleation effectively. The microscale structure as the supporting platform of nanostructure can additionally enlarge the effective evaporative surface with superior hydrophobicity and then promote the permeation transfer through the membrane. The hybrid micro/nanostructures render the fabricated membrane with excellent high-permeation flux and significantly prolonged fouling induction time, which sheds light on a new approach for the development of ideal MD utilized membrane.

Scalable High-Areal-Capacity Li-S Batteries Enabled by Sandwich-Structured Hierarchically Porous Membranes with Intrinsic Polysulfide Adsorption.

The key to realizing practical applications of Li-S batteries lies in scalable fabrication of cathode materials with high sulfur-loading and strong binding of lithium polysulfides (LiPSs). We report a scalable CeO2-CNT@C porous membrane with a large porosity of 90%. Introducing CNTs is critical to increase the porosity and construct porous networks with CNTs as the skeleton and CeO2-doped carbon as the shell. The macropores can improve the transport of Li+ and electrolyte, while the porous networks possess high polysulfide-adsorbing and electron-transferring ability. The CeO2-CNT@C membrane can serve as an Al foil-free cathode and an interlayer for Li-S batteries. Moreover, CeO2 can immobilize LiPSs and can alleviate its shuttle effect. The Li-S batteries with a sulfur loading of 6.2 mg cm-2 deliver a capacity of 847 mA h g-1 after 100 cycles, showing a high areal capacity of 5.25 mA h cm-2 at a low electrolyte/sulfur ratio of 5.2 µL mg-1.

Hierarchically Porous C/Fe3C Membranes with Fast Ion-Transporting Channels and Polysulfide-Trapping Networks for High-Areal-Capacity Li-S Batteries.

We report here highly scalable yet stackable C/Fe3C membranes with fast ion-transport micro-/nanochannels and polysulfide-trapping networks via a facile phase-inversion process for high-areal-capacity Li-S batteries. The membrane cathodes with aligned channels and hierarchically porous networks significantly promote Li+ and electron transportation and meanwhile trap soluble polysulfide intermediates (LiPSs) effectively via strong chemical adsorption of the doped Fe3C nanoparticles in the membrane toward LiPSs. We further demonstrated that five-layer membrane electrodes with high S loading of 7.1 mg cm-2 were readily prepared via layer-by-layer stacking of the C/Fe3C membrane, which can deliver a high capacity of 726 mA h g-1 after 100 cycles, corresponding to an ultra-high-areal-capacity of 5.15 mA h cm-2 at a low electrolyte/sulfur (E/S) ratio of 6.4 µL mg-1. The scalable multifunctional membrane electrodes with excellent electrochemical performance under high-sulfur-loading and lean electrolyte conditions reveal its promising applications in practical Li-S batteries.

Constructing Patch-Ni-Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li-S Batteries.

Reducing the deposit of discharge products and suppressing the polysulfide shuttle are critical to enhancing reaction kinetics in Li-S batteries. Herein, a Pt@Ni core-shell bimetallic catalyst with a patch-like or complete Ni shell based on a confined catalysis reaction in porous carbon spheres is reported. The Pt nanodots can effectively direct and catalyze in situ reduction of Ni2+ ions to form core-shell catalysts with a seamless interface that facilitates the charge transfer between the two metals. Thus, the bimetallic catalysts offer a synergic effect on catalyzing reactions, which shows dual functions for catalytic oxidation of insoluble polysulfides to soluble polysulfides by effectively reducing the energy barrier with simultaneous strong adsorption, ensuring a high reversible capacity and cycling stability. A novel process based on the Pt@Ni core-shell bimetallic catalyst with a patch-like Ni shell is proposed: electronic migration from Ni to Pt forces Ni to activate Li2 S2 /Li2 S molecules by promoting the transformation of Li-S-Li to Ni-S-Li, consequently releasing Li+ and free electrons, simultaneously enhancing protonic/electronic conductivity. The presence of the intermediate state Ni-S-Li is more active to oxidize Li2 S to polysulfides. The Li2 S bound to adjacent Pt sites reacts with abundant -S-Li species and then releases the Pt sites for the next round of reactions.

Quantitative real-time PCR with high-throughput automatable DNA preparation for molecular screening of Nosema spp. in Antheraea pernyi.

Accurate diagnosis of pathogenic Nosema spp. in Antheraea pernyi samples is considered especially useful for reducing economic losses in sericulture and improving food safety by maintaining pathogen-free pupae. However, microscopy and immunologic methods have poor diagnostic sensitivity, while the more sensitive PCR methods remain costly and time-consuming for template preparation. To address this issue, we introduce a sensitive ALMS-qPCR method that combines fast, simple DNA extraction using Alkali Lysis followed by Magnetic bead Separation (ALMS) and quantitative real-time PCR (qPCR). This approach is especially fit for large-scale pathogen molecular screening, because the DNA preparation procedure is fast (<0.94 min per sample) and is high-throughput (performs on a 96-well plate). It is cost-effective, since the most expensive materials can be made in the lab and can be recycled, while the automated procedure can help to minimize labor cost. Though the DNA preparation procedure was substantially simplified, common PCR inhibitory factors were not observed. The sensitivity of ALMS-qPCR is high and the limit of detection is 0.045 parasites/µL. Large-scale screening of Nosema spp. in 3000 Antheraea pernyi samples confirmed the efficacy of the ALMS-qPCR method. Sensitivity is much higher than clinical microscopy, especially for host groups with low infection prevalence and levels. High-throughput ALMS-qPCR, combining automated DNA preparation and sensitive qPCR, provides an enhanced approach for pébrine screening and epidemiological studies. The application of ALMS-qPCR in the sericulture industry will help to strengthen pébrine control and breed pathogen-free species, which means much safer food provision and better genetic resource conservation.

Triple-Layered Carbon-SiO2 Composite Membrane for High Energy Density and Long Cycling Li-S Batteries.

Here we report a highly scalable yet flexible triple-layer structured porous C/SiO2 membrane via a facile phase inversion method for advancing Li-sulfur battery technology. As a multifunctional current-collector-free cathode, the conductive dense layer of the C/SiO2 membrane offers hierarchical macropores as an ideal sulfur host to alleviate the volume expansion of sulfur species and facilitate ion/electrolyte transport for fast kinetics, as well as spongelike pores to enable high sulfur loading. The triple-layer structured membrane cathode enables the filling of most sulfur species in the macropores and additional loading of a thin sulfur slurry on the membrane surface, which facilitates ion/electrolyte transport with faster kinetics than the conventional S/C slurry-based cathode. Furthermore, density functional theory simulations and visual adsorption measurements confirm the critical role of the doped SiO2 nanoparticles (∼10 nm) in the asymmetric C membrane in suppressing the shuttle effect of polysulfides via chemisorption and electrocatalysis. The rationally designed C/SiO2 membrane cathodes demonstrate long-term cycling stability of 300 cycles at a high sulfur loading of 2.8 mg cm-2 with a sulfur content of ∼75%. This scalable yet flexible self-supporting cathode design presents a useful strategy for realizing practical applications of high-performance Li-S batteries.

Multishelled Transition Metal-Based Microspheres: Synthesis and Applications for Batteries and Supercapacitors.

With the rapid growth of material innovations, multishelled hollow nanostructures are of tremendous interest due to their unique structural features and attractive physicochemical properties. Continued effort has been made in the geometric manipulation, composition complexity, and construction diversity of this material, expanding its applications. Energy storage technology has benefited from the large surface area, short transport path, and excellent buffering ability of the nanostructures. In this work, the general synthesis of multishelled hollow structures, especially with architecture versatility, is summarized. A wealth of attractive properties is also discussed for a wide area of potential applications based on energy storage systems, including Li-ion/Na-ion batteries, supercapacitors, and Li-S batteries. Finally, the emerging challenges and outlook for multishelled hollow structures are mentioned.

Tailored 3D printed micro-crystallization chip for versatile and high-efficiency droplet evaporative crystallization.

Droplet evaporative crystallization on a micro-structured platform with limited interfacial area has potential applications in crystallization theory, bioengineering, and particle drug preparation. Here, an efficient and versatile approach is discussed for multiple drop-evaporative crystallization processes on a micro-crystallization chip fabricated via three-dimensional printing. A chip with limited interfacial area could be fabricated on a highly controlled crystallizer interface. During liquid injection, various drop locations and evaporative conditions can be used, which enables flexible and distinct crystallization processes. This reveals controlling mechanisms and identifies nucleation locations and growth paths. Various classic crystallization systems were introduced to evaluate the chip performance. Controlled nucleation and growth mechanisms at stable evaporative rates were revealed. From the final crystal morphologies, particle locations, and distributions, the effects of the initial concentration and droplet contact conditions at the triple-phase interface could be investigated with high adjustability. Moreover, the results can provide insights into the 'coffee ring' formation during evaporative crystallization, dendritic crystal growth, and hydrate crystallization mechanisms. In the limited microstructure, the capillary flow of a liquid drop can spontaneously drive the crystal distribution and morphology. Finally, incorrect liquid drop locations that led to unpredictable crystal formation and distributions were discussed to improve repeatability and efficiency. Applications include the manufacture of particle drugs and flow chemistry.

Tailored Robust Hydrogel Composite Membranes for Continuous Protein Crystallization with Ultrahigh Morphology Selectivity.

The tailored and robust hydrogel composite membranes (HCMs) with diverse ion adsorption and interfacial nucleation property are prepared and successfully used in the continuous lysozyme crystallization. Beyond the heterogeneous supporter, the HCMs functioning as an interface ion concentration controller and nucleation generator are demonstrated. By constructing accurately controlled nucleation and growth circumstances in the HCM-equipped membrane crystallizer, the target desired morphology (hexagon cube) and brand-new morphology (multiple flower shape) that differ from the ones created in the conventional crystallizer are continuously and repetitively generated with ultrahigh morphology selectivity. These tailored robust HCMs show great potential for improving current approaches to continuous protein crystallization with specific crystal targets from laboratorial research to actual engineering applications.

Pulverization Control by Confining Fe3O4 Nanoparticles Individually into Macropores of Hollow Carbon Spheres for High-Performance Li-Ion Batteries.

In this article, double carbon shell hollow spheres which provide macropores (mC) for ultrasmall Fe3O4 nanoparticle (10-20 nm) encapsulation individually were first prepared (Fe3O4@mC). The well-constructed Fe3O4@mC electrode materials offer the feasibility to study the volume change, aggregation, and pulverization process of the active Fe3O4 nanoparticles for Li-ion storage in a confined space. Fe3O4@mC exhibits excellent electrochemical performances and delivers a high capacity of 645 mA h g-1 at 2 A g-1 after 1000 cycles. Even at 10 A g-1 or after 1000 cycles at 2 A g-1, the porous carbon structure was well maintained and no obvious aggregation and pulverization of the Fe3O4 nanoparticles was observed, although the volume of the active Fe3O4 particles was expanded to 40-60 nm compared to that of the original particles (10-20 nm). This can be due to the in situ embedment of one Fe3O4 nanoparticle into one macropore individually. The uniform dispersion and confinement of the Fe3O4 nanoparticles in the macropores of the carbon shell could effectively accommodate severe volume variations upon cycling and prevent self-aggregation and spreading out from the carbon shell during the expansion process of the nanoscale Fe3O4 particles, leading to improved capacity retention. Our work confirms the effectiveness for pulverization control by confining Fe3O4 nanoparticles individually into macropores to improve its Li-ion storage properties, providing a novel strategy for the design of new-structured anode materials for Li-ion batteries.

Interpenetrated Networks between Graphitic Carbon Infilling and Ultrafine TiO2 Nanocrystals with Patterned Macroporous Structure for High-Performance Lithium Ion Batteries.

Interpenetrated networks between graphitic carbon infilling and ultrafine TiO2 nanocrystals with patterned macropores (100-200 nm) were successfully synthesized. Polypyrrole layer was conformably coated on the primary TiO2 nanoparticles (∼8 nm) by a photosensitive reaction and was then transformed into carbon infilling in the interparticle mesopores of the TiO2 nanoparticles. Compared to the carbon/graphene supported TiO2 nanoparticles or carbon coated TiO2 nanostructures, the carbon infilling would provide a conductive medium and buffer layer for volume expansion of the encapsulated TiO2 nanoparticles, thus enhancing conductivity and cycle stability of the C-TiO2 anode materials for lithium ion batteries (LIBs). In addition, the macropores with diameters of 100-200 nm in the C-TiO2 anode and the mesopores in carbon infilling could improve electrolyte transportation in the electrodes and shorten the lithium ion diffusion length. The C-TiO2 electrode can provide a large capacity of 192.8 mA h g-1 after 100 cycles at 200 mA g-1, which is higher than those of the pure macroporous TiO2 electrode (144.8 mA h g-1), C-TiO2 composite electrode without macroporous structure (128 mA h g-1), and most of the TiO2 based electrodes in the literature. Importantly, the C-TiO2 electrode exhibits a high rate performance and still delivers a high capacity of ∼140 mA h g-1 after 1000 cycles at 1000 mA g-1 (∼5.88 C), suggesting good lithium storage properties of the macroporous C-TiO2 composites with high capacity, cycle stability, and rate capability. This work would be instructive for designing hierarchical porous TiO2 based anodes for high-performance LIBs.

Multishelled NiO Hollow Microspheres for High-performance Supercapacitors with Ultrahigh Energy Density and Robust Cycle Life.

Multishelled NiO hollow microspheres for high-performance supercapacitors have been prepared and the formation mechanism has been investigated. By using resin microspheres to absorb Ni(2+) and subsequent proper calcinations, the shell numbers, shell spacing and exterior shell structure were facilely controlled via varying synthetic parameters. Particularly, the exterior shell structure that accurately associated with the ion transfer is finely controlled by forming a single shell or closed exterior double-shells. Among multishelled NiO hollow microspheres, the triple-shelled NiO with an outer single-shelled microspheres show a remarkable capacity of 1280 F g(-1) at 1 A g(-1), and still keep a high value of 704 F g(-1) even at 20 A g(-1). The outstanding performances are attributed to its fast ion/electron transfer, high specific surface area and large shell space. The specific capacitance gradually increases to 108% of its initial value after 2500 cycles, demonstrating its high stability. Importantly, the 3S-NiO-HMS//RGO@Fe3O4 asymmetric supercapacitor shows an ultrahigh energy density of 51.0 Wh kg(-1) at a power density of 800 W kg(-1), and 78.8% capacitance retention after 10,000 cycles. Furthermore, multishelled NiO can be transferred into multishelled Ni microspheres with high-efficient H2 generation rate of 598.5 mL H2 min(-1) g(-1)Ni for catalytic hydrolysis of NH3BH3 (AB).

Multishelled Nickel-Cobalt Oxide Hollow Microspheres with Optimized Compositions and Shell Porosity for High-Performance Pseudocapacitors.

Nickel-cobalt oxides/hydroxides have been considered as promising electrode materials for a high-performance supercapacitor. However, their energy density and cycle stability are still very poor at high current density. Moreover, there are few reports on the fabrication of mixed transition-metal oxides with multishelled hollow structures. Here, we demonstrate a new and flexible strategy for the preparation of hollow Ni-Co-O microspheres with optimized Ni/Co ratios, controlled shell porosity, shell numbers, and shell thickness. Owing to its high effective electrode area and electron transfer number (n(3/2) A), mesoporous shells, and fast electron/ion transfer, the triple-shelled Ni-Co1.5-O electrode exhibits an ultrahigh capacitance (1884 F/g at 3A/g) and rate capability (77.7%, 3-30A/g). Moreover, the assembled sandwiched Ni-Co1.5-O//RGO@Fe3O4 asymmetric supercapacitor (ACS) retains 79.4% of its initial capacitance after 10 000 cycles and shows a high energy density of 41.5 W h kg(-1) at 505 W kg(-1). Importantly, the ACS device delivers a high energy density of 22.8 W h kg(-1) even at 7600 W kg(-1), which is superior to most of the reported asymmetric capacitors. This study has provided a facile and general approach to fabricate Ni/Co mixed transition-metal oxides for energy storage.