Sodium Stoichiometry Tuning of the Biphasic-Nax MnO2 Cathode for High-Performance Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are promising alternatives for large-scale energy storage owing to the rich resource and cost effectiveness. However, there are limitations of suitable low-cost, high-rate cathode materials for fast charging and high-power delivery in grid systems. Herein, a biphasic tunnel/layered 0.80Na0.44 MnO2 /0.20Na0.70 MnO2 (80T/20L) cathode delivering exceptional rate performance through subtly regulating the sodium and manganese stoichiometry is reported. It delivers a reversible capacity of 87 mAh g-1 at 4 A g-1 (33 C), much higher than that of tunnel Na0.44 MnO2 (72 mAh g-1 ) and layered Na0.70 MnO2 (36 mAh g-1 ). It proves that the one-pot synthesized 80T/20L is able to suppress the deactivation of L-Na0.70 MnO2 under air-exposure, which improves the specific capacity and cycling stability. Based on electrochemical kinetics analysis, the electrochemical storage of 80T/20L is mainly based on pseudocapacitive surface-controlled process. The thick film of 80T/20L cathode (a single-side mass loading over 10 mg cm-2 ) also has superior properties of pseudocapacitive response (over 83.5% at a low sweep rate of 1 mV s-1 ) and excellent rate performance. In this sense, the 80T/20L cathode with outstanding comprehensive performance could meet the requirements of high-performance SIBs.

Understanding the origin of the improved sodium ion storage performance of the transition metal oxide@carbon nanocomposite anodes.

Transition metal oxide (TMO) anodes show inferior sodium ion storage performance compared with that of lithium ion storage owing to the larger radium size and heavier elemental mass of Na+ than Li+. Effective strategies are highly desired to improve the Na+ storage performance of TMOs for applications. In this work, using ZnFe2O4@xC nanocomposites as model materials for investigation, we found that by manipulating the particle sizes of the inner TMOs core and the features of outer carbon coating, the Na+ storage performance can be significantly improved. The ZnFe2O4@1C with a diameter of the inner ZnFe2O4 core of around 200 nm coated by a thin carbon layer of around 3 nm shows a specific capacity of only 120 mA h g-1. The ZnFe2O4@6.5C with a diameter of the inner ZnFe2O4 core of around 110 nm embedding in a porous interconnected carbon matrix displays a significantly improved specific capacity of 420 mA h g-1 at the same specific current. Furthermore, the latter shows an excellent cycling stability of 1000 cycles with a capacity retention of 90% of the initial 220 mA h g-1 specific capacity at 1.0 A g-1. TEM, electrochemical impedance spectroscopy, and kinetic analysis show that the inner ZnFe2O4 core with reduced particle size and the outer thicker and interconnected carbon matrix synergistically improve the active reaction sites, integrity, electric conductivity, and pseudocapacitive-controlled contribution of ZnFe2O4@xC nanocomposites, thus leading to an overall enhanced Na+ storage performance. Our findings create a universal, facile, and effective method to enhance the Na+ storage performance of the TMO@C nanomaterials.

Mo2 C Nanoparticles Embedded in Carbon Nanowires with Surface Pseudocapacitance Enables High-Energy and High-Power Sodium Ion Capacitors.

Electrochemical sodium-ion storage technologies have become an indispensable part in the field of large-scale energy storage systems owing to the widespread and low-cost sodium resources. Molybdenum carbides with high electron conductivity are regarded as potential sodium storage anode materials, but the comprehensive sodium storage mechanism has not been studied in depth. Herein, Mo2 C nanowires (MC-NWs) in which Mo2 C nanoparticles are embedded in carbon substrate are synthesized. The sodium-ion storage mechanism is further systematically studied by in/ex situ experimental characterizations and diffusion kinetics analysis. Briefly, it is discovered that a faradaic redox reaction occurs in the surface amorphous molybdenum oxides on Mo2 C nanoparticles, while the inner Mo2 C is unreactive. Thus, the as-synthesized MC-NWs with surface pseudocapacitance display excellent rate capability (a high specific capacity of 76.5 mAh g-1 at 20 A g-1 ) and long cycling stability (a high specific capacity of 331.2 mAh g-1 at 1 A g-1 over 1500 cycles). The assembled original sodium ion capacitor displays remarkable power density and energy density. This work provides a comprehensive understanding of the sodium storage mechanism of Mo2 C materials, and constructing pseudocapacitive materials is an effective way to achieve sodium-ion storage devices with high power and energy density.

Versatile Synthesis of Mesoporous Crystalline TiO2 Materials by Monomicelle Assembly.

Mesoscale TiO2 structures have realized many technological applications-ranging from catalysis and biomedicine to energy storage and conversion-because of their large mesoporosities offering desirable accessibility and mass transport. Tailoring mesoporous TiO2 structures with novel mesoscopic and microscopic configurations is envisaged to offer ample opportunities for further applications. In this Review, we explain how to synthesize novel mesoporous TiO2 materials and present recent examples. An emphasis is placed on a "monomicelle assembly" strategy as an emerging and powerful approach to direct the formation of mesostructured TiO2 with precise control over its structural orientations and architectures. Furthermore, typical examples of mesoporous TiO2 for applications in batteries and photocatalysis are highlighted. The Review ends with an outlook towards the synthesis of mesoporous TiO2 with tailored architectures by self-assembly, which could pave the way for developing advanced energy conversion and storage devices.

Precisely Designed Mesoscopic Titania for High-Volumetric-Density Pseudocapacitance.

Surface redox pseudocapacitance, which enables short charging times and high power delivery, is very attractive in a wide range of sites. To achieve maximized specific capacity, nanostructuring of active materials with high surface area is indispensable. However, one key limitation for capacitive materials is their low volumetric capacity due to the low tap density of nanomaterials. Here, we present a promising mesoscale TiO2 structure with precisely controlled mesoporous frameworks as a high-density pseudocapacitive model system. The dense-packed mesoscopic TiO2 in micrometer size offers a high accessible surface area (124 m2 g-1) and radially aligned mesopore channels, but high tap density (1.7 g cm-3) that is much higher than TiO2 nanoparticles (0.47 g cm-3). As a pseudocapacitive sodium-ion storage anode, the precisely designed mesoscopic TiO2 model achieved maximized gravimetric capacity (240 mAh g-1) and volumetric capacity (350 mAh cm-3) at 0.025 A g-1. Such a designed pseudocapacitive mesostructure further realized a commercially comparable areal capacity (2.1 mAh cm-2) at a high mass loading of 9.47 mg cm-2. This mesostructured electrode that enables fast sodiation in dense nanostructures has implications for high-power applications, fast-charging devices, and pseudocapacitive electrode design.

Stable Ti3+ Defects in Oriented Mesoporous Titania Frameworks for Efficient Photocatalysis.

By introducing a compatible reducing agent (2-ethylimidazole) into a mono-micelle assembly process, we present a type of ordered mesoporous TiO2 microspheres that combines radially aligned mesostructure with Ti3+ defects in mesoporous frameworks. Such reductant acts as a building block of mesostructured frameworks and reduces Ti4+ in situ to generate defects during calcination, giving rise to the coexistence of bulk Ti3+ defects and an ordered mesostructure. The mesoporous TiO2 has both excellent mesoporosity (a high surface area of 106 m2 g-1 , a mean pore size of 18.4 nm) and stable defects with an extended photoresponse. Such integration of unique mesoscopic architecture and atomic vacancies provide both effective mass transportation and enhanced light utilization, leading to a remarkable increase in H2 generation rate. A maximum H2 evolution rate of 19.8 mmol g-1 h-1 can be achieved, along with outstanding stability under solar light.

Two-Dimensional Mesoporous Heterostructure Delivering Superior Pseudocapacitive Sodium Storage via Bottom-Up Monomicelle Assembly.

Two-dimensional (2D) heterostructures endowed with mesoporosities offer exciting opportunities in electrocatalysis, photocatalysis, energy storage, and conversion technologies due to their integrated functionalities, abundant active sites and shortened diffusion distance. However, layered mesostructures have not been combined due to the immense difficulties by conventional chemical, mechanical exfoliation or self-assembly approaches. Herein, we explore a bottom-up strategy, carried out under mild conditions, for the facile synthesis of monolayered mesoporous-titania-mesoporous-carbon vertical heterostructure with uniform mesopore size, which enables ultrahigh rate capability and cycling longevity for pseudocapacitive sodium-ion storage in nonaqueous electrolyte. Such a brand-new type of heterostructure consists of well-ordered monolayered mesoporous titania nanosheets and surrounding two mesoporous carbon monolayers assembled at both sides. Remarkably, the combination of interconnected large mesoporosity and heterointerface leads to highly promoted reversible pseudocapacitance (96.4% of total charge storage at a sweep rate of 1 mV s-1), and it enables the material to retain strong mechanical stability during the rapid sodiation and desodiation processes. This study reveals the importance of incorporating mesopores into heterointerface as a strategy for enhancing charge storage kinetics of electroactive materials.

Strongly Coupled Pyridine-V2 O5 ·nH2 O Nanowires with Intercalation Pseudocapacitance and Stabilized Layer for High Energy Sodium Ion Capacitors.

Developing pseudocapacitive cathodes for sodium ion capacitors (SICs) is very significant for enhancing energy density of SICs. Vanadium oxides cathodes with pseudocapacitive behavior are able to offer high capacity. However, the capacity fading caused by the irreversible collapse of layer structure remains a major issue. Herein, based on the Acid-Base Proton theory, a strongly coupled layered pyridine-V2 O5 ·nH2 O nanowires cathode is reported for highly efficient sodium ion storage. By density functional theory calculations, in situ X-ray diffraction, and ex situ Fourier-transform infrared spectroscopy, a strong interaction between protonated pyridine and VO group is confirmed and stable during cycling. The pyridine-V2 O5 ·nH2 O nanowires deliver long-term cyclability (over 3000 cycles), large pseudocapacitive behavior (78% capacitive contribution at 1 mV s-1 ) and outstanding rate capability. The assembled pyridine-V2 O5 ·nH2 O//graphitic mesocarbon microbead SIC delivers high energy density of ≈96 Wh kg-1 (at 59 W kg-1 ) and power density of 14 kW kg-1 (at 37.5 Wh kg-1 ). The present work highlights the strategy of realizing strong interaction in the interlayer of V2 O5 ·nH2 O to enhance the electrochemical performance of vanadium oxides cathodes. The strategy could be extended for improving the electrochemical performance of other layered materials.

Polyol Solvation Effect on Tuning the Universal Growth of Binary Metal Oxide Nanodots@Graphene Oxide Heterostructures for Electrochemical Applications.

Tuning the uniformity and size of binary metal oxide nanodots on graphene oxide (BMO NDs@GO) is significant but full of challenges in wet-chemistry, owing to the difficulties of controlling the complicated cation/anion co-adsorption, heterogeneous nucleation, and overgrowth processes. Herein, the aim is to tune these processes by understanding the functions of various alcohol solvents for NDs growth on GO. It is found that the polyol solvation effect is beneficial for obtaining highly uniform BMO NDs@GO. Polyol shell capped metal ions exhibit stronger hydrogen-bond interactions with the GO surface, leading to a uniform cation/anion co-adsorption and followed heterogeneous nucleation. The polyol-solvated ions with large diffusion energy barrier drastically limit the ion diffusion kinetics in liquids and at the solid/liquid interface, resulting in a slow and controllable growth. Moreover, the synthesis in polyol systems is highly controllable and universal, thus eleven BMO and polynary metal oxide NDs@GO are obtained by this method. The synthetic strategy provides improved prospects for the manufacture of inorganic NDs and their expanding electrochemical applications.

Mesoporous NiS2 Nanospheres Anode with Pseudocapacitance for High-Rate and Long-Life Sodium-Ion Battery.

It is of great importance to exploit electrode materials for sodium-ion batteries (SIBs) with low cost, long life, and high-rate capability. However, achieving quick charge and high power density is still a major challenge for most SIBs electrodes because of the sluggish sodiation kinetics. Herein, uniform and mesoporous NiS2 nanospheres are synthesized via a facile one-step polyvinylpyrrolidone assisted method. By controlling the voltage window, the mesoporous NiS2 nanospheres present excellent electrochemical performance in SIBs. It delivers a high reversible specific capacity of 692 mA h g-1 . The NiS2 anode also exhibits excellent high-rate capability (253 mA h g-1 at 5 A g-1 ) and long-term cycling performance (319 mA h g-1 capacity remained even after 1000 cycles at 0.5 A g-1 ). A dominant pseudocapacitance contribution is identified and verified by kinetics analysis. In addition, the amorphization and conversion reactions during the electrochemical process of the mesoporous NiS2 nanospheres is also investigated by in situ X-ray diffraction. The impressive electrochemical performance reveals that the NiS2 offers great potential toward the development of next generation large scale energy storage.

Methyl-functionalized MoS2 nanosheets with reduced lattice breathing for enhanced pseudocapacitive sodium storage.

Sodium ion batteries (SIBs) possess the potential to realize low-cost and large-scale energy storage due to the abundance of sodium. However, the large ionic radius of sodium often leads to sluggish kinetics and large volume change, limiting the further development of SIBs. Layered MoS2, with a large interlayer distance, is a promising intercalation anode material for SIBs. In this work, we report the synthesis of methyl-functionalized MoS2 (M-MoS2) nanosheets through a facile second solvothermal method. During the second solvothermal treatment, the pristine MoS2 is mostly converted from the 2H to 1T phase and the interlayer distance is expanded from 0.65 to 0.80 nm. When evaluated as the anode for SIBs, the M-MoS2 exhibits superior cycling stability and rate capability. Kinetic analysis shows that the capacity is mainly contributed from a pseudocapacitive process. Ex situ XRD shows that the M-MoS2 exhibits inhibited lattice breathing and thus reduced volume change during cycling. This work demonstrates that the M-MoS2 is a promising candidate for pseudocapacitive sodium storage.

Single-Nanowire Electrochemical Probe Detection for Internally Optimized Mechanism of Porous Graphene in Electrochemical Devices.

Graphene has been widely used to enhance the performance of energy storage devices due to its high conductivity, large surface area, and excellent mechanical flexibility. However, it is still unclear how graphene influences the electrochemical performance and reaction mechanisms of electrode materials. The single-nanowire electrochemical probe is an effective tool to explore the intrinsic mechanisms of the electrochemical reactions in situ. Here, pure MnO2 nanowires, reduced graphene oxide/MnO2 wire-in-scroll nanowires, and porous graphene oxide/MnO2 wire-in-scroll nanowires are employed to investigate the capacitance, ion diffusion coefficient, and charge storage mechanisms in single-nanowire electrochemical devices. The porous graphene oxide/MnO2 wire-in-scroll nanowire delivers an areal capacitance of 104 nF/µm(2), which is 4.0 and 2.8 times as high as those of reduced graphene oxide/MnO2 wire-in-scroll nanowire and MnO2 nanowire, respectively, at a scan rate of 20 mV/s. It is demonstrated that the reduced graphene oxide wrapping around the MnO2 nanowire greatly increases the electronic conductivity of the active materials, but decreases the ion diffusion coefficient because of the shielding effect of graphene. By creating pores in the graphene, the ion diffusion coefficient is recovered without degradation of the electron transport rate, which significantly improves the capacitance. Such single-nanowire electrochemical probes, which can detect electrochemical processes and behavior in situ, can also be fabricated with other active materials for energy storage and other applications in related fields.

A High-Rate V2 O5 Hollow Microclew Cathode for an All-Vanadium-Based Lithium-Ion Full Cell.

V2O5 hollow microclews (V2O5-HMs) have been fabricated through a facile solvothermal method with subsequent calcination. The synthesized V2O5-HMs exhibit a 3D hierarchical structure constructed by intertangled nanowires, which could realize superior ion transport, good structural stability, and significantly improved tap density. When used as the cathodes for lithium-ion batteries (LIBs), the V2O5-HMs deliver a high capacity (145.3 mAh g(-1)) and a superior rate capability (94.8 mAh g(-1) at 65 C). When coupled with a lithiated Li3VO4 anode, the all-vanadium-based lithium-ion full cell exhibits remarkable cycling stability with a capacity retention of 71.7% over 1500 cycles at 6.7 C. The excellent electrochemical performance demonstrates that the V2O5-HM is a promising candidate for LIBs. The insight obtained from this work also provides a novel strategy for assembling 1D materials into hierarchical microarchitectures with anti-pulverization ability, excellent electrochemical kinetics, and enhanced tap density.

Flexible additive free H2V3O8 nanowire membrane as cathode for sodium ion batteries.

Sodium ion batteries (SIBs) have emerged as a potential candidate to succeed lithium ion batteries (LIBs), because of the abundant sodium resources on earth. Layered vanadium oxides are regarded as the promising candidates for SIBs because of their large interlayer spacing, high theoretical specific capacity, abundant sources and low cost. In this paper, a vanadium oxide hydrate (H2V3O8) nanowire membrane is presented as a flexible cathode for SIBs without addition of any other additives (binders or conductive compounds). Such a freestanding flexible membrane exhibits a high specific capacity of 168 mA h g(-1) at 10 mA g(-1), and its high capacity is maintained well after 100 cycles. It is found that the capacitive charge storage accounts for a relatively large proportion of the total capacity, whereas the crystal structure of H2V3O8 is highly reversible during the sodiation/desodiation processes. This research demonstrates that the H2V3O8 nanowire is an exceptional candidate for SIBs.

In Situ Investigation of Li and Na Ion Transport with Single Nanowire Electrochemical Devices.

In the past decades, Li ion batteries are widely considered to be the most promising rechargeable batteries for the rapid development of mobile devices and electric vehicles. There arouses great interest in Na ion batteries, especially in the field of static grid storage due to their much lower production cost compared with Li ion batteries. However, the fundamental mechanism of Li and Na ion transport in nanoscale electrodes of batteries has been rarely experimentally explored. This insight can guide the development and optimization of high-performance electrode materials. In this work, single nanowire devices with multicontacts are designed to obtain detailed information during the electrochemical reactions. This unique platform is employed to in situ investigate and compare the transport properties of Li and Na ions at a single nanowire level. To give different confinement for ions and electrons during the electrochemical processes, two different configurations of nanowire electrode are proposed; one is to fully immerse the nanowire in the electrolyte, and the other is by using photoresist to cover the nanowire with only one end exposed. For both configurations, the conductivity of nanowire decreases after intercalation/deintercalation for both Li and Na ions, indicating that they share the similar electrochemical reaction mechanisms in layered electrodes. However, the conductivity degradation and structure destruction for Na ions is more severe than those of Li ions during the electrochemical processes, which mainly results from the much larger volume of Na ions and greater energy barrier encountered by the limited layered spaces. Moreover, the battery performances of coin cells are compared to further confirm this conclusion. The present work provides a unique platform for in situ electrochemical and electrical probing, which will push the fundamental and practical research of nanowire electrode materials for energy storage applications.

Three-Dimensional Interconnected Vanadium Pentoxide Nanonetwork Cathode for High-Rate Long-Life Lithium Batteries.

Three-dimensional interconnected vanadium pentoxide nanonetworks as cathodes for rechargable lithium batteries are successfully synthesized via a quick gelation followed by annealing. The interconnected structure ensures the electron transport of each unit. And their inner porous structure buffer the volume change over long-term repeated lithium ion insertion/extraction cycles, leading to the high-rate long-life cycling performance.

Integrated SnO2 nanorod array with polypyrrole coverage for high-rate and long-life lithium batteries.

Conversion/alloying reactions, in which more lithium ions are involved, are severely handicapped by the dramatic volume changes. A facile and versatile strategy has been developed for integrating the SnO2 nanorod array in the PPy nanofilm for providing a flexible confinement for anchoring each nanorod and maintaining the entire structural integrity and providing sustainable contact; therefore, exhibiting much more stable cycling stability (701 mA h g(-1) after 300 cycles) and better high-rate capability (512 mA h g(-1) at 3 A g(-1)) when compared with the core-shell SnO2-PPy NA.

Amorphous vanadium oxide matrixes supporting hierarchical porous Fe3O4/graphene nanowires as a high-rate lithium storage anode.

Developing electrode materials with both high energy and power densities holds the key for satisfying the urgent demand of energy storage worldwide. In order to realize the fast and efficient transport of ions/electrons and the stable structure during the charge/discharge process, hierarchical porous Fe3O4/graphene nanowires supported by amorphous vanadium oxide matrixes have been rationally synthesized through a facile phase separation process. The porous structure is directly in situ constructed from the FeVO4·1.1H2O@graphene nanowires along with the crystallization of Fe3O4 and the amorphization of vanadium oxide without using any hard templates. The hierarchical porous Fe3O4/VOx/graphene nanowires exhibit a high Coulombic efficiency and outstanding reversible specific capacity (1146 mAh g(-1)). Even at the high current density of 5 A g(-1), the porous nanowires maintain a reversible capacity of ∼500 mAh g(-1). Moreover, the amorphization and conversion reactions between Fe and Fe3O4 of the hierarchical porous Fe3O4/VOx/graphene nanowires were also investigated by in situ X-ray diffraction and X-ray photoelectron spectroscopy. Our work demonstrates that the amorphous vanadium oxides matrixes supporting hierarchical porous Fe3O4/graphene nanowires are one of the most attractive anodes in energy storage applications.

One-Pot synthesized bicontinuous hierarchical Li3V2(PO4)3/C mesoporous nanowires for high-rate and ultralong-life lithium-ion batteries.

Lithium-ion batteries have attracted enormous attention for large-scale and sustainable energy storage applications. Here we present a design of hierarchical Li3V2(PO4)3/C mesoporous nanowires via one-pot synthesis process. The mesoporous structure is directly in situ carbonized from the surfactants (CTAB and oxalic acid) along with the crystallization of Li3V2(PO4)3 without using any hard templates. As a cathode for lithium-ion battery, the Li3V2(PO4)3/C mesoporous nanowires exhibit outstanding high-rate and ultralong-life performance with capacity retention of 80.0% after 3000 cycles at 5 C in 3-4.3 V. Even at 10 C, it still delivers 88.0% of its theoretical capacity. The ability to provide this level of performance is attributed to the hierarchical mesoporous nanowires with bicontinuous electron/ion pathways, large electrode-electrolyte contact area, low charge transfer resistance, and robust structure stability upon prolonged cycling. Our work demonstrates that the unique mesoporous nanowires structure is favorable for improving the cyclability and rate capability in energy storage applications.

Nanoflakes-assembled three-dimensional hollow-porous v2 o5 as lithium storage cathodes with high-rate capacity.

Three-dimensional (3D) hollow-porous vanadium pentoxide (V2 O5 ) quasi-microspheres are synthesized by a facile solvothermal method followed by annealing at 450 °C in air. The interconnected hollow-porous networks facilitate the kinetics of lithium-ion diffusion and improve the performance of V2 O5 to achieve a high capacity and remarkable rate capability as a cathode material for lithium batteries.