Building High-Rate Nickel-Rich Cathodes by Self-Organization of Structurally Stable Macrovoid.

Nickel-rich materials, as a front-running cathode for lithium-ion batteries suffer from inherent degradation issues such as inter/intragranular cracks and phase transition under the high-current density condition. Although vigorous efforts have mitigated these current issues, the practical applications are not successfully achieved due to the material instability and complex synthesis process. Herein, a structurally stable, macrovoid-containing, nickel-rich material is developed using an affordable, scalable, and one-pot coprecipitation method without using surfactants/etching agents/complex-ion forming agents. The strategically developed macrovoid-induced cathode via a self-organization process exhibits excellent full-cell rate capability, cycle life at discharge rate of 5 C, and structural stability even at the industrial electrode conditions, owing to the fast Li-ion diffusion, the internal macrovoid acting as "buffer zones" for stress relief, and highly stable nanostructure around the void during cycling. This strategy for nickel-rich cathodes can be viable for industries in the preparation of high-performance lithium-ion cells.

Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries.

Cathode material degradation during cycling is one of the key obstacles to upgrading lithium-ion and beyond-lithium-ion batteries for high-energy and varied-temperature applications. Herein, we highlight recent progress in material surface-coating as the foremost solution to resist the surface phase-transitions and cracking in cathode particles in mono-valent (Li, Na, K) and multi-valent (Mg, Ca, Al) ion batteries under high-voltage and varied-temperature conditions. Importantly, we shed light on the future of materials surface-coating technology with possible research directions. In this regard, we provide our viewpoint on a novel hybrid surface-coating strategy, which has been successfully evaluated in LiCoO2 -based-Li-ion cells under adverse conditions with industrial specifications for customer-demanding applications. The proposed coating strategy includes a first surface-coating of the as-prepared cathode powders (by sol-gel) and then an ultra-thin ceramic-oxide coating on their electrodes (by atomic-layer deposition). What makes it appealing for industry applications is that such a coating strategy can effectively maintain the integrity of materials under electro-mechanical stress, at the cathode particle and electrode- levels. Furthermore, it leads to improved energy-density and voltage retention at 4.55 V and 45 °C with highly loaded electrodes (≈24 mg.cm-2 ). Finally, the development of this coating technology for beyond-lithium-ion batteries could be a major research challenge, but one that is viable.

Hydrogen Adsorption in Flame Synthesized and Lithium Intercalated Carbon Nanofibers--A Comparative Study.

Carbon nanofibers (CNF) have been synthesized under partial combustion conditions in a flame reactor using different mixtures of hydrocarbon gases in the presence and absence of precursors. The hydrogen (H2) adsorption studies have been carried out using a high pressure Sievert's apparatus maintained at a constant temperature (24 degrees C). The flame synthesized CNFs showed high degree of H2 adsorption capacities at 100 atm pressure. The highest H2 capacities recorded have been 4.1 wt% [for CNF produced by liquefied petroleum gas (LPG)-Air (E-17)], 3.7 wt% [for nano carbons produced by Methane-Acetylene-Air (EMAC-4)] and 5.04 wt% for [Lithium intercalated sample (Li-EMAC-4)] respectively.

Sodium and Lithium Storage Properties of Spray-Dried Molybdenum Disulfide-Graphene Hierarchical Microspheres.

Developing nano/micro-structures which can effectively upgrade the intriguing properties of electrode materials for energy storage devices is always a key research topic. Ultrathin nanosheets were proved to be one of the potential nanostructures due to their high specific surface area, good active contact areas and porous channels. Herein, we report a unique hierarchical micro-spherical morphology of well-stacked and completely miscible molybdenum disulfide (MoS2) nanosheets and graphene sheets, were successfully synthesized via a simple and industrial scale spray-drying technique to take the advantages of both MoS2 and graphene in terms of their high practical capacity values and high electronic conductivity, respectively. Computational studies were performed to understand the interfacial behaviour of MoS2 and graphene, which proves high stability of the composite with high interfacial binding energy (-2.02 eV) among them. Further, the lithium and sodium storage properties have been tested and reveal excellent cyclic stability over 250 and 500 cycles, respectively, with the highest initial capacity values of 1300 mAh g(-1) and 640 mAh g(-1) at 0.1 A g(-1).

Electrochemistry and structure of the cobalt-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode.

The development of cathode materials with high capacity and cycle stability is essential to emerging electric-vehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wet-chemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b). We find Ni(2+)/Ni(3+)/Ni(4+) to be the active redox-center of the cathode with lithiation/delithiation occurring via a solid-solution reaction where the lattice responds approximately linearly with cycling, differing to that observed for iso-structural commercial cathodes with a lower level of cation mixing. The composite cathode has ∼75% active material and delivers an initial discharge-capacity of ∼103 mA h g(-1) with a reasonable capacity retention of ∼84.4% after 100 cycles. Notably, the electrochemically-active component possesses a capacity of ∼139 mA h g(-1), approaching that of the commercialized LiCoO2 and Li(Ni1/3Mn1/3Co1/3)O2 materials. Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ∼80% less change in its stacking-axis than for LiCoO2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials.

Electrospun P2-type Na(2/3)(Fe(1/2)Mn(1/2))O2 hierarchical nanofibers as cathode material for sodium-ion batteries.

Sodium-ion batteries can be the best alternative to lithium-ion batteries, because of their similar electrochemistry, nontoxicity, and elemental abundance and the low cost of sodium. They still stand in need of better cathodes in terms of their structural and electrochemical aspects. Accordingly, the present study reports the first example of the preparation of Na2/3(Fe1/2Mn1/2)O2 hierarchical nanofibers by electrospinning. The nanofibers with aggregated nanocrystallites along the fiber direction have been characterized structurally and electrochemically, resulting in enhanced cyclability when compared to nanoparticles, with initial discharge capacity of ∼195 mAh g(-1). This is attributed to the good interconnection among the fibers, with well-guided charge transfers and better electrolyte contacts.

Effect of surface nanomorphology and interfacial galvanic coupling of PEDOT-titanium counter electrodes on the stability of dye-sensitized solar cell.

The present study demonstrates a novel approach by which titanium foils coated with electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT) in combination with sputtered platinum can be processed into a high-surface area cathodes for dye-sensitized solar cells (DSSCs). A detailed study has been performed to elucidate how surface nanomorphology and I(-)/I(3-) redox reaction behaviors underlying these photocathodes impact the DSSC performances. From the analysis of the relevant electrochemical parameters, an intrinsic correlation between the photovoltaic performances and the cathode surface area has been deduced for such a system and explained on the basis of relative contributions of the galvanic coupling properties of the nanomorphology PEDOT film and platinum. Depending on the type of photocathodes incorporated, it was observed that these PEDOT coated cathodes can exhibit higher stability over a given time range and photo-conversion efficiencies 12-40%, higher than that achievable in absence of the intermediate PEDOT coatings. It has been shown that DSSCs based on such metal-polymer hybrid photo-cathodes allow significant room for improvement in the catalytic performance at the electrode/electrolyte interface.

Effect of embedded plasmonic Au nanoparticles on photocatalysis of electrospun TiO2 nanofibers.

The present study demonstrates an original approach by which Au nanoparticles (approximately 10 nm) are embedded into TiO2 fibers via electrospinning. The photocatalytic performance of the resultant fibrous material was studied and related to the architecture and the nature of the internal interfaces in the composite. It was found that embedment of nano Au particles into the TiO2 fiber significantly improved the photocatalytic performance as compared to non-embedded ones. Electrospun fibers with the Au nanoparticles (approximately 10 nm) showed an average fiber diameter of approximately 380 nm. The photocatalytic studies of Au embedded TiO2 fibers using ultra-violet (UV) visible spectroscopy showed approximately 35% increase in photocatalytic activity when compared to the TiO2 fibers without the Au nanoparticles after 7 hrs of UV irradiation. This increase in photocatalysis was attributed to the ability of Au to increase charge separation in TiO2 and also to the ability of Au to transfer plasmonic energy to the dye.