Overcoming copper-induced conversion reactions in nickel disulphide anodes for sodium-ion batteries.

Employing copper (Cu) as an anode current collector for metal sulphides is perceived as a general strategy to achieve stable cycle performance in sodium-ion batteries, despite the compatibility of the aluminium current collector with sodium at low voltages. The capacity retention is attributed to the formation of copper sulphide with the slow corrosion of the current collector during cycling which is not ideal. Conventional reports on metal sulphides demonstrate excellent electrochemical performances using excessive carbon coatings/additives, reducing the overall energy density of the cells and making it difficult to understand the underlying side reaction with Cu. In this report, the negative influence of the Cu current collector is demonstrated with in-house synthesised, scalable NiS2 nanoparticles without any carbon coating as opposed to previous works on NiS2 anodes. Ex situ TEM and XPS experiments revealed the formation of Cu2S, further to which various current collectors were employed for NiS2 anode to rule out the parasitic reaction and to understand the true performance of the material. Overall, this study proposes the utilisation of carbon-coated aluminium foil (C/Al) as a suitable current collector for high active material content NiS2 anodes and metal sulphides in general with minimal carbon contents as it remains completely inert during the cycling process. Using a C/Al current collector, the NiS2 anode exhibits stable cycling performance for 5000 cycles at 50 A g-1, maintaining a capacity of 238 mA h g-1 with a capacity decay rate of 8.47 × 10-3% per cycle.

Enabling 100C Fast-Charging Bulk Bi Anodes for Na-Ion Batteries.

It is challenging to develop alloying anodes with ultrafast charging and large energy storage using bulk anode materials because of the difficulty of carrier-ion diffusion and fragmentation of the active electrode material. Herein, a rational strategy is reported to design bulk Bi anodes for Na-ion batteries that feature ultrafast charging, long cyclability, and large energy storage without using expensive nanomaterials and surface modifications. It is found that bulk Bi particles gradually transform into a porous nanostructure during cycling in a glyme-based electrolyte, whereas the resultant structure stores Na ions by forming phases with high Na diffusivity. These features allow the anodes to exhibit unprecedented electrochemical properties; the developed Na-Bi half-cell delivers 379 mA h g-1 (97% of that measured at 1C) at 7.7 A g-1 (20C) during 3500 cycles. It also retained 94% and 93% of the capacity measured at 1C even at extremely fast-charging rates of 80C and 100C, respectively. The structural origins of the measured properties are verified by experiments and first-principles calculations. The findings of this study not only broaden understanding of the underlying mechanisms of fast-charging anodes, but also provide basic guidelines for searching battery anodes that simultaneously exhibit high capacities, fast kinetics, and long cycling stabilities.

Development and Evaluation of Sn Foil Anode for Sodium-Ion Batteries.

Metal foil electrodes are simple to prepare and have a high active material loading, making them well suited for the fabrication of inexpensive high-energy-density batteries. Herein, Sn metal foil is used as a binder- and conductive additive-free anode for sodium-ion batteries, achieving a high reversible specific capacity of 692 mAh g-1 and coulombic efficiency of 99% after 100 cycles at a rate of 0.1 C. During the first discharge process, the anode undergoes area expansion. It then splits into multiple parts during the first-charge process. Upon cycling, the separated parts reconnect and form a single piece with a porous and robust coral structure owing to the self-healing nature of the anode. A full cell with a Sn foil anode and Na3 V2 (PO4 )3 cathode shows a stable cycle life of 100 mAh g-1 for 300 cycles. Thus, the cracking or pulverization of the Sn anode is not the principal origin of poor cycling properties. The adopted strategy will promote the development and commercialization of high-capacity metal foil anodes that undergo volume changes during charge/discharge cycling.

Self-Assembly of Pulverized Nanoparticles: An Approach to Realize Large-Capacity, Long-Lasting, and Ultra-Fast-Chargeable Na-Ion Batteries.

The fabrication of battery anodes simultaneously exhibiting large capacity, fast charging capability, and high cyclic stability is challenging because these properties are mutually contrasting in nature. Here, we report a rational strategy to design anodes outperforming the current anodes by simultaneous provision of the above characteristics without utilizing nanomaterials and surface modifications. This is achieved by promoting spontaneous structural evolution of coarse Sn particles to 3D-networked nanostructures during battery cycling in an appropriate electrolyte. The anode steadily exhibits large capacity (∼480 mAhg-1) and energy retention capability (99.9%) during >1500 cycles even at an ultrafast charging rate of 12 690 mAg-1 (15C). The structural and chemical origins of the measured properties are explained using multiscale simulations combining molecular dynamics and density functional theory calculations. The developed method is simple, scalable, and expandable to other systems and provides an alternative robust route to obtain nanostructured anode materials in large quantities.

Deflection Estimation Based on the Thermal Characteristics of Composite Deck Slabs Containing Macro-Synthetic Fibers.

The purpose of this study was to evaluate the structural performance of composite deck slabs containing macro-synthetic fibers. after a fire by proposing a deflection estimation method for non-fireproof structural decks. Therefore, this study evaluated the fire resistance performance and deflection of deck slabs mixed with macro-synthetic fibers. Afterward, the deflection estimation method considering the thermal characteristics of concrete and deck plates was proposed. A material test was first conducted to evaluate the mechanical properties of concrete mixed with macro-synthetic fibers. This test found that the compressive strength and elasticity modulus of concrete mixed with macro-synthetic fibers was greater than that of general concrete. A flexural tensile test confirmed that residual strength was maintained after the maximum strength was achieved. The fire resistance of the deck slab was adequate even when a fire-resistant coating was not applied. The internal temperature was lowest for the specimen with macro-synthetic fibers. Deflection was evaluated using previously published equations and standards. The deflection evaluation confirmed that the temperature distribution should be applied differently in the estimation method that uses the thermal load of the deck slab.

Ultrahigh-rate nickel monosulfide anodes for sodium/potassium-ion storage.

Transition-metal sulfides have been extensively studied as anode materials for use in sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) due to their multi-electron reactions, high rate performance, and abundant available resources. However, the practical capacities of metal sulfides remain low due to conductivity issues, volume expansion, and the use of traditional carbonate electrolytes. To overcome these drawbacks, ether electrolytes can be combined with nanoparticle-based metal sulfide anodes. Herein, a nanoparticle-based nickel monosulfide (NiS) anode with high rate performance in the ether electrolytes of SIBs/PIBs was prepared by heating a mixture of nickel nanoparticles with sulfur. In SIBs, the NiS anode capacity was 286 mA h g-1 at a high current density of 100 A g-1, and excellent cycling performance was observed at 25 A g-1 with a capacity of 468 mA h g-1 after 1000 cycles. Moreover, a full-cell containing a Na3V2(PO4) cathode demonstrated a rate performance of 65 mA h g-1 at a high current density of 100 A g-1. In PIBs, the NiS electrode capacity was 642 and 37 mA h g-1 at 0.5 and 100 A g-1, respectively. Hence, the synthesised NiS nanoparticles possessed excellent storage capability, regardless of the alkali-ion type, suggesting their potential use as robust NiS anodes for advanced battery systems.

Realizing High-Performance Li/Na-Ion Half/Full Batteries via the Synergistic Coupling of Nano-Iron Sulfide and S-doped Graphene.

Iron sulfide (FeS) anodes are plagued by severe irreversibility and volume changes that limit cycle performances. Here, a synergistically coupled hybrid composite, nanoengineered iron sulfide/S-doped graphene aerogel, was developed as high-capacity anode material for Li/Na-ion half/full batteries. The rational coupling of in situ generated FeS nanocrystals and the S-doped rGO aerogel matrix boosted the electronic conductivity, Li+ /Na+ diffusion kinetics, and accommodated the volume changes in FeS. This anode system exhibited excellent long-term cyclability retaining high reversible capacities of 422 (1100 cycles) and 382 mAh g-1 (1600 cycles), respectively, for Li+ and Na+ storage at 5 A g-1 . Full batteries designed with this anode system exhibited 435 (FeS/srGOA||LiCoO2 ) and 455 mAh g-1 (FeS/srGOA||Na0.64 Co0.1 Mn0.9 O2 ). The proposed low-cost anode system is competent with the current Li-ion battery technology and extends its utility for Na+ storage.

Binder-free and high-loading sulfurized polyacrylonitrile cathode for lithium/sulfur batteries.

Sulfurized polyacrylonitrile (SPAN) is a promising active material for Li/S batteries owing to its high sulfur utilization and long-term cyclability. However, because SPAN electrodes are synthesized using powder, they require large amounts of electrolyte, conducting agents, and binder, which reduces the practical energy density. Herein, to improve the practical energy density, we fabricated bulk-type SPAN disk cathodes from pressed sulfur and polyacrylonitrile powders using a simple heating process. The SPAN disks could be used directly as cathode materials because their π-π structures provide molecular-level electrical connectivity. In addition, the electrodes had interconnected pores, which improved the mobility of Li+ ions by allowing homogeneous adsorption of the electrolyte. The specific capacity of the optimal electrode was very high (517 mA h gelectrode -1). Furthermore, considering the weights of the anode, separator, cathode, and electrolyte, the Li/S cell exhibited a high practical energy density of 250 W h kg-1. The areal capacity was also high (8.5 mA h cm-2) owing to the high SPAN loading of 16.37 mg cm-2. After the introduction of 10 wt% multi-walled carbon nanotubes as a conducting agent, the SPAN disk electrode exhibited excellent cyclability while maintaining a high energy density. This strategy offers a potential candidate for Li/S batteries with high practical energy densities.

Effect of Ordered Carbon Structures on Electrochemical Properties of Carbon/Sulfur Composites in Lithium-Sulfur Batteries.

In this paper, the relationship between the pore spatial structures, pore sizes, and pore types of highly ordered mesoporous CMK-based carbons (CMK-1, CMK-3, and CMK-5) and their electrochemical performance in Li-S batteries is investigated. CMK-1 has a complex spatial structure and small pores. The structure is good for limiting polysulfide in the pores, but not for rapid transfer of Li+ ions in the cell. CMK-3 and CMK-5 have similar spatial structures and pore sizes, but different pore types. Compared to the single pore structure of CMK-3, the bimodal pore structure of CMK-5 not only improves the electrolyte accessibility, but also increases the number of reaction sites, resulting in better electrochemical performance. Studying the correlation between the physical structure of carbon-based materials and their electrochemical performance in Li-S batteries will provide new insights for optimizing porous electrode materials.

Synthesis and Electrochemical Properties of MoS2/rGO/S Composite as a Cathode Material for Lithium-Sulfur Batteries.

To develop the next-generation energy storage systems, lithium-sulfur batteries represent an attractive option due to its high theoretical capacity, and energy density. In this work, MoS2/rGO (reduced graphene oxide) was prepared by hydrothermal synthesis and sulfur added by the melt diffusion method. The as-prepared MoS2/rGO has strong polysulfides entrapping, high conductivity, large surface area, and high catalytic activity, consequently resulting in enhanced rate performance and cycling capability of Li-S batteries. The coin cells were constructed with the MoS2/rGO/S cathode material, exhibit a high reversible capacity of nearly 1380 mAh/g at 0.1 C, outstanding cycling stability with a low capacity fading rate. Present work reveals that the hierarchal MoS2/rGO/S cathodes are potential candidate materials for future high-performance lithium-sulfur batteries.

Fabrication and Electrochemical Characterization of Sulfurized-Polyacrylonitrile Nanofiber Electrodes for Na/S Batteries Using Various Polyacrylonitrile Solutions.

A polyacrylonitrile (PAN) nanofiber web was prepared by electrospinning PAN solutions with dimethyl sulfoxide (DMSO) or Dimethylformamide (DMF) as solvent. The PAN web was heated with sulfur to synthesize a sulfurized polyacrylonitrile (SPAN) nanofiber web. The shape of the SPAN web was found to depend on concentration of the PAN solution and properties of the solvent. The SPAN web synthesized using 8 wt% PAN solution in DMSO showed the highest capacity of 1053.3 mAh g-1sulfur under a current density of 526 mA g-1sulfur. Thus, we determined that DMSO could be a potential solvent for preparation of SPAN web electrodes.

Free-Standing NiS2 Electrode as High-Rate Anode Material for Sodium-Ion Batteries.

Owing to the speculated price hike and scarcity of lithium resources, sodium-ion batteries are attracting significant research interest these days. However, sodium-ion battery anodes do not deliver good electrochemical performance, particularly rate performance. Herein, we report the facile electrospinning synthesis of a free-standing nickel disulfide (NiS²) embedded on carbon nanofiber. This electrode did not require a conducting agent, current collector, and binder, and typically delivered high capacity and rate performance. The electrode delivered a high initial capacity of 603 mAh g-1 at the current density of 500 mA g-1. Moreover, the electrode delivered the capacity of 271 mAh g-1 at the high current density of 15 A g-1. The excellent rate performance and high coulombic efficiency of the electrode were attributed to its low charge transfer resistance and unique structure.

High power Na3V2(PO4)3 symmetric full cell for sodium-ion batteries.

Sodium-ion batteries (SIBs) are a viable substitute for lithium-ion batteries due to the low cost and wide availability of sodium. However, practical applications require the development of fast charging sodium-ion-based full-cells with high power densities. Na3V2(PO4)3 (NVP) is a bipolar material with excellent characteristics as both a cathode and an anode material in SIBs. Designing symmetric cells with NVP results in a single voltage plateau with significant specific capacity which is ideal for a full cell. Here we demonstrate for the first time a tremendous improvement in the performance of NVP symmetric full cells by introducing an ether-based electrolyte which favors fast reaction kinetics. In a symmetric full cell configuration, 75.5% of the initial capacity was retained even after 4000 cycles at 2 A g-1, revealing ultra-long cyclability. Excellent rate performances were obtained at current densities as high as 1000C, based on the cathode mass, revealing ultrafast Na+ transfer. The power density obtained for this NVP symmetric cell (48 250 W kg-1) is the best among those of all the sodium-ion-based full cells reported to date.

An ionic liquid incorporated in a quasi-solid-state electrolyte for high-temperature supercapacitor applications.

An ionic liquid (IL) incorporated in a quasi-solid-state electrolyte (ILQSE) is prepared using 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and poly (ethylene glycol dimethacrylayte) (PEGDMA) for high-temperature application of supercapacitors. The prepared ILQSE displays a thermal stability up to 150 °C and the supercapacitors exhibit a specific capacitance of 134 F g-1.

Boosting High Energy Density Lithium-Ion Storage via the Rational Design of an FeS-Incorporated Sulfurized Polyacrylonitrile Fiber Hybrid Cathode.

In order to satisfy the escalating energy demands, it is inevitable to improve the energy density of current Li-ion batteries. As the development of high-capacity cathode materials is of paramount significance compared to anode materials, here we have designed for the first time a unique synergistic hybrid cathode material with enhanced specific capacity, incorporating cost-effective iron sulfide (FeS) nanoparticles in a sulfurized polyacrylonitrile (SPAN) nanofiber matrix through a rational in situ synthesis strategy. Previous reports on FeS cathodes are scarce and consist of an amorphous carbon matrix to accommodate the volume changes encountered during the cycling process. However, this inactive buffering matrix eventually increases the weight of the cell, reducing the overall energy density. By the rational design of this hybrid composite cathode, we ensure that the presence of covalently bonded sulfur in SPAN guarantees high sulfur utilization, while effectively buffering the volume changes in FeS. Meanwhile, FeS can compensate for the conductivity issues in the SPAN, thereby realizing a synergistically driven dual-active cathode material improving the overall energy density of the composite. Simultaneous in situ generation of FeS nanoparticles within the SPAN fiber matrix was carried out via electrospinning followed by a one-step heating procedure. The developed hybrid cathode material displays enhanced lithium-ion storage, retaining 688.6 mA h g(FeS@SPAN composite)-1 at the end of 500 cycles at 1 A g-1 even within a narrow voltage range of 1-3.0 V. A high discharge energy density > 900 W h kg(FeS@SPAN composite)-1, much higher than the theoretical energy density of the commercial LiCoO2 cathode, was also achieved, revealing the promising prospects of this hybrid cathode material for high energy density applications.

Carbon-Coated Ordered Mesoporous SnO2 Composite Based Anode Material for High Performance Lithium-Ion Batteries.

Recently, tin oxide (SnO2) has received significant attention for use as an anode material for next generation lithium-ion batteries (LIBs) owing to its high theoretical capacity (782 mAh g-1), which is more than twice of that of the commercialized graphite (372 mAh g-1). Several additional advantages, such as low cost, environmental friendliness, easy fabrication and natural abundance improve its promise. Although the theoretical capacity of SnO2 is high, volume expansion during cycling causes issue with cycling stability. In this study, an ordered mesoporous SnO2 was synthesized using a hard template (SBA-15), such that its mesoporous structure can buffer SnO2 particles from cracks caused by volume expansion. It can also allow effective electrolyte infiltration to ensure better reactivity of the active material with Li+ ions. The capacity of synthesized mesoporous SnO2 improved to 218.4 mAh g-1 compared regular SnO2 nanoparticles (69.6 mAh g-1) after 50 cycles at a rate of 0.1 C. Furthermore, carbon-coated mesoporous SnO2 enhanced capacity retention upon cycling (844.6 mAh g-1 after 50 cycles at 0.1 C) by insulating and preventing the cracking of the active material during lithiation and delithiation.

Electrochemical Properties of Micron-Sized SnO Anode Using a Glyme-Based Electrolyte for Sodium-Ion Battery.

Tin monoxide (SnO) anodes are promising candidates for use in sodium-ion batteries because of their high theoretical capacities and stable cycle performance. In previous reports, electrodes with excellent performance have been prepared by using nano-sized SnO particles. However, the synthesis of nano-sized SnO particles is complex, time-consuming, and expensive. In this paper, an anode of micron-sized SnO is prepared by using commercial micron-sized SnO particles. The electrode exhibits a reversible capacity of 450 mAh g-1 in the 1st cycle at a current rate of 100 mA g-1. We used a tetraethylene glycol dimethyl ether (TEGDME)-based electrolyte, which is well known for its superior electrochemical performance in sodium-ion batteries. The mechanism of operation of the anode containing micron-sized SnO particles has been confirmed by a detailed study using X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). During initial discharge, the SnO changed to Sn and sodium oxide, and the surface of the electrode became covered with a film. The electrode composed of micron-sized SnO is a potential candidate for use in sodium-ion batteries.

Initial Discharge Behavior of an Ultra High Loading 3D Sulfur Cathode for a Room-Temperature Na/S Battery.

A 3D sulfur cathode for a large-scale room-temperature (RT) Na/S battery with a high sulfur loading of 14.63 mg cm-2 was fabricated. The first discharge was tested in order to understand the macroscopic changes. A first discharge capacity of 865 mAh g-1 was obtained at 1/1000 C-rate along with a discharge curve with two clear plateaus at 2.29 V and 1.78 V, respectively. A visual change occurs in the 3D sulfur cathode. A thick layer of discharge products at the solid electrolyte separator face of the 3D sulfur cathode was observed and analyzed using a scanning electron microscope (SEM) coupled with energy dispersive X-ray spectroscopy (EDS).

Nitrogen-Doped Mesoporous Carbon: A Top-Down Strategy to Promote Sulfur Immobilization for Lithium-Sulfur Batteries.

The loss of active sulfur material is a challenge in the application of lithium-sulfur (Li-S) batteries. To immobilize sulfur, a nitrogen-doped mesoporous carbon (PMC) was synthesized with polyaniline (PANi) as the carbon source, which was used for development of Li-S batteries. The nitrogen content and pore system of the PMCs were modulated by varying the pyrolysis temperature to impart good electrochemical properties to the Li-S cells. As a result, the optimal capacity reversibility was obtained with the PMC synthesized at 700 °C that consisted of 12.8 % nitrogen. The enhanced cycle performance of Li-S cells was also validated at high sulfur contents up to 70 % and high C-rates up to 2 C. Furthermore, such sulfur/PMC cathodes could alleviate volume expansion during the discharge process. The results suggest that our synthesized nitrogen-doped PMCs prepared by this top-down strategy are promising materials to immobilize active sulfur in Li-S batteries.

MoS2 Nanosheets Supported on 3D Graphene Aerogel as a Highly Efficient Catalyst for Hydrogen Evolution.

The development of efficient catalysts for electrochemical hydrogen evolution is essential for energy conversion technologies. Molybdenum disulfide (MoS2 ) has emerged as a promising electrocatalyst for hydrogen evolution reaction, and its performance greatly depends on its exposed edge sites and conductivity. Layered MoS2 nanosheets supported on a 3D graphene aerogel network (GA-MoS2 ) exhibit significant catalytic activity in hydrogen evolution. The GA-MoS2 composite displays a unique 3D architecture with large active surface areas, leading to high catalytic performance with low overpotential, high current density, and good stability.