Understanding the Improved Kinetics and Cyclability of a Li2MnSiO4 Cathode with Calcium Substitution.

Limited practical capacity and poor cyclability caused by sluggish kinetics and structural instability are essential aspects that constrain the potential application of Li2MnSiO4 cathode materials. Herein, Li2Mn1- xCa xSiO4/C nanoplates are synthesized using a diethylene-glycol-assisted solvothermal method, targeting to circumvent its drawbacks. Compared with the pristine material, the Ca-substituted material exhibits enhanced electrochemical kinetics and improved cycle life performance. In combination with experimental studies and first-principles calculations, we reveal that Ca incorporation enhances electronic conductivity and the Li-ion diffusion coefficient of the Ca-substituted material, and it improves the structural stability by reducing the lattice distortion. It also shrinks the crystal size and alleviates structure collapse to enhance cycling performance. It is demonstrated that Ca can alleviate the two detrimental factors and shed lights on the further searching for suitable dopants.

Microwave-assisted synthesis and prototype oxygen reduction electrocatalyst application of N-doped carbon-coated Fe3O4 nanorods.

Fe3O4 nanorods coated with nitrogen-doped mesoporous carbon (ND-Fe3O4@mC) shells of defined thicknesses have been prepared via a new microwave-assisted approach. Microstructural characterization of these ND-Fe3O4@mC structures was performed using x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. Following identification, the electrochemical performance of the catalysts was evaluated using linear sweep voltammetry with a rotating disc electrode system. The present investigation reveals enhanced oxygen reduction reaction catalytic activity and the carbon layer thickness influences oxygen diffusion to the active Fe3O4 nanorod core.

Nucleation and growth of electrodeposited Mn oxide rods for supercapacitor electrodes.

The nucleation and growth of electrodeposited Mn oxide rods has been investigated by preparing deposits on Au coated Si at varying deposition times between 0.5 s and 10 min. The deposits were investigated using high resolution scanning and transmission electron microscopy. A model for the nucleation and growth of Mn oxide rods has been proposed. Nucleation begins as thin sheets along Au grain boundaries and triple points. As these nucleation sites are consumed, nucleation spreads across the grains. Nucleation of sheets in close proximity causes agglomeration and the formation of rounded particles. Some of these rounded particles then accelerate in growth, initially in all directions and then primarily in the direction normal to the sample surface. Accelerated growth normal to the sample surface leads to the formation of rods. As rods grow, the growth of other particles accelerates and they become rods themselves. Eventually the entire sample surface is covered with rods 15-20 µm long and about 2 µm wide. The sheet-like morphology of the deposits is retained at all stages of deposition. Electron diffraction analysis of 3 s and 6 s deposits shows that the sheets are initially amorphous and then begin to crystallize into a cubic spinel Mn3O4 crystal structure. High resolution imaging of the 6 s sample shows small crystalline regions (∼5 nm in size) within an amorphous matrix.

Salt-Assisted Recovery of Sodium Metal Anodes for High-Rate Capability Sodium Batteries.

Rechargeable sodium metal batteries are considered to be one of the most promising high energy density and cost-effective electrochemical energy storage systems. However, their practicality is constrained by the high reactivity of sodium metal anodes that readily brings about excessive accumulation of inactive Na species on the surface, either by chemical reactions with oxygen and moisture during electrode handling or through electrochemical processes with electrolytes during battery operation. Herein, this paper reports on an alkali, salt-assisted, assembly-polymerization strategy to recover Na activity and to reinforce the solid-electrolyte interphase (SEI) of sodium metal anodes. To achieve this, an alkali-reactive coupling agent 3-glycidoxypropyltrimethoxysilane (GPTMS) is applied to convert inactive Na species into Si-O-Na coordination with a self-assembly GPTMS layer that consists of inner O-Si-O networks and outer hydrophobic epoxides. As a result, the electrochemical activity of Na metal anodes can be fully recovered and the robust GPTMS-derived SEI layer ensures high capacity and long-term cycling under an ultrahigh rate of 30 C (93.1 mAh g-1, 94.8% after 3000 cycles). This novel process provides surface engineering clues on designing high power density and cost-effective alkaline metal batteries.

Manganese oxide-based materials as electrochemical supercapacitor electrodes.

Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high energy densities, have become a versatile solution to various emerging energy applications. This critical review describes some materials science aspects on manganese oxide-based materials for these applications, primarily including the strategic design and fabrication of these electrode materials. Nanostructurization, chemical modification and incorporation with high surface area, conductive nanoarchitectures are the three major strategies in the development of high-performance manganese oxide-based electrodes for EC applications. Numerous works reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based electrode materials. However, many fundamental questions remain unanswered, particularly with respect to characterization and understanding of electron transfer and atomic transport of the electrochemical interface processes within the manganese oxide-based electrodes. In order to fully exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation of these basic questions and optimization of synthesis parameters and material properties are critical for the further development of EC devices (233 references).

Reaction mechanisms for electrolytic manganese dioxide in rechargeable aqueous zinc-ion batteries.

This study reports the phase transformation behaviour associated with electrolytic manganese dioxide (EMD) utilized as the positive electrode active material for aqueous zinc-ion batteries. Electrochemical techniques, including galvanostatic charge-discharge and rotating ring-disk electrode measurements, and microstructural techniques, using X-ray powder diffraction, scanning electron microscopy, and transmission/scanning transmission electron microscopy, were utilized to characterize the positive electrode at different stages of discharge and charge of zinc-ion cells. The results indicate that, during discharge, a fraction of EMD undergoes a transformation to ZnMn2O4 (spinel-type) and Zn2+ is intercalated into the tunnels of the γ- and ε-MnO2 phases, forming ZnxMnO2 (tunnel-type). When a critical concentration of Mn3+ in the intercalated ZnxMnO2 species is reached, a disproportionation/dissolution reaction is triggered leading to the formation of soluble Mn2+ and hydroxide (OH-) ions; the latter precipitates as zinc hydroxide sulfate (ZHS, Zn4(OH)6(SO4)·5H2O) by combination with the ZnSO4/H2O electrolyte. During charge, Zn2+ is reversibly deintercalated from the intergrown tunneled phases (γ-/ε-ZnxMnO2), Mn2+ is redeposited as layered chalcophanite (ZnMn3O7·3H2O), and ZHS is decomposed by protons (H+) formed during the electrochemical deposition of chalcophanite.

Mn3O4 nanoparticle-decorated hollow mesoporous carbon spheres as an efficient catalyst for oxygen reduction reaction in Zn-air batteries.

Hybrids of Mn3O4 nanoparticles and hollow carbon spheres prepared from templated pyrolysis of polydopamine were assembled via a straightforward sonication procedure. The resulting hybrids exhibit excellent catalytic activity toward the oxygen reduction reaction (ORR) in prototype Zn-air batteries. Impressively, these catalysts exhibit higher discharge potential and exceptional stability when compared to commercial Pt-Ru catalysts while simultaneously showing comparable onset potential and maximum current density.

Enhancing the Structural Stability of Ni-Rich Layered Oxide Cathodes with a Preformed Zr-Concentrated Defective Nanolayer.

Nickel-rich layered oxides (NLOs) exhibit great potential to meet the ever-growing demand for further increases in the energy density of Li-ion batteries because of their high specific capacities. However, NLOs usually suffer from severe structural degradation and undesired side reactions when cycled above 4.3 V. These effects are strongly correlated with the surface structure and chemistry of the active NLO materials. Herein, we demonstrate a preformed cation-mixed ( Fm3̅ m) surface nanolayer (∼5 nm) that shares a consistent oxygen framework with the layered lattice through Zr modification, in which Ni cations reside in Li slabs and play the role of a "pillar". This preformed nanolayer alleviates the detrimental phase transformations upon electrochemical cycling, effectively enhancing the structural stability. As a result, the Zr-modified Li(Ni0.8Co0.1Mn0.1)0.985Zr0.015O2 material exhibits a high reversible discharge capacity of ∼210 mA h/g at 0.1 C (1 C = 200 mA/g) and outstanding cycling stability with a capacity retention of 93.2% after 100 cycles between 2.8 and 4.5 V. This strategy may be further extended to design and prepare other high-performance layered oxide cathode materials.

Electrochemical Property-Structure Correlation for Ni-Based Layered Na-Ion Cathodes.

A class of Ni-based layered Na xNi0.5Mn0.3Co0.2O2 oxide composites is prepared via a solid-state process. Mixed P-, O-, and P-/O-type phases can be obtained by tuning the Na content and annealing temperature, as demonstrated by structural and chemical characterization. Among these materials, the triphase P2/P'3/O'3-type composite exhibits the best overall electrochemical performance. Specifically, this triphase composite delivers a high specific capacity of 126 mA h g-1 in the potential range of 1.5-4.2 V, high rate capability (∼72% of its initial capacity at a rate of 5 C), and good capacity retention after 100 cycles at 0.5 C. The structural transition mechanism for each phase upon electrochemical cycling is investigated, providing insights into the correlation between electrochemical properties and the crystal structure of Ni-rich layered Na xNi0.5Mn0.3Co0.2O2 oxide composites.

High Ion-Conducting Solid-State Composite Electrolytes with Carbon Quantum Dot Nanofillers.

Solid-state polymer electrolytes (SPEs) with high ionic conductivity are desirable for next generation lithium- and sodium-ion batteries with enhanced safety and energy density. Nanoscale fillers such as alumina, silica, and titania nanoparticles are known to improve the ionic conduction of SPEs and the conductivity enhancement is more favorable for nanofillers with a smaller size. However, aggregation of nanoscale fillers in SPEs limits particle size reduction and, in turn, hinders ionic conductivity improvement. Here, a novel poly(ethylene oxide) (PEO)-based nanocomposite polymer electrolyte (NPE) is exploited with carbon quantum dots (CQDs) that are enriched with oxygen-containing functional groups. Well-dispersed, 2.0-3.0 nm diameter CQDs offer numerous Lewis acid sites that effectively increase the dissociation degree of lithium and sodium salts, adsorption of anions, and the amorphicity of the PEO matrix. Thus, the PEO/CQDs-Li electrolyte exhibits an exceptionally high ionic conductivity of 1.39 × 10-4 S cm-1 and a high lithium transference number of 0.48. In addition, the PEO/CQDs-Na electrolyte has ionic conductivity and sodium ion transference number values of 7.17 × 10-5 S cm-1 and 0.42, respectively. It is further showed that all solid-state lithium/sodium rechargeable batteries assembled with PEO/CQDs NPEs display excellent rate performance and cycling stability.

Crystallographic Habit Tuning of Li2MnSiO4 Nanoplates for High-Capacity Lithium Battery Cathodes.

Li2MnSiO4 has attracted significant attention as a cathode material for lithium ion batteries because of its high theoretical capacity (330 mA h g-1 with two Li+ ions per formula unit), low cost, and environmentally friendly nature. However, its intrinsically poor Li diffusion, low electronic conductivity, and structural instability preclude its use in practical applications. Herein, elongated hexagonal prism-shaped Li2MnSiO4 nanoplates with preferentially exposed {001} and {210} facets have been successfully synthesized via a solvothermal method. Density functional theory calculations and experimental characterization reveal that the formation mechanism involves the decomposition of solid precursors to nanosheets, self-assembly into nanoplates, and Ostwald ripening. Hydroxyl-containing solvents such as ethylene glycol and diethylene glycol play a crucial role as capping agents in tuning the preferential growth. Li2MnSiO4@C nanoplates demonstrate a near theoretical discharge capacity of 326.7 mA h g-1 at 0.05 C (1 C = 160 mA h g-1), superior rate capability, and good cycling stability. The enhanced electrochemical performance is ascribed to the electrochemically active {001} and {210} exposed facets, which provide short and fast Li+ diffusion pathways along the [001] and [100] axes, a conformal carbon nanocoating, and a nanoscaled platelike structure, which offers a large electrode/electrolyte contact interface for Li+ extraction/insertion processes.

Understanding the Enhanced Kinetics of Gradient-Chemical-Doped Lithium-Rich Cathode Material.

Although chemical doping has been extensively employed to improve the electrochemical performance of Li-rich layered oxide (LLO) cathodes for Li ion batteries, the correlation between the electrochemical kinetics and local structure and chemistry of these materials after chemical doping is still not fully understood. Herein, gradient surface Si/Sn-doped LLOs with improved kinetics are demonstrated. The atomic local structure and surface chemistry are determined using electron microscopy and spectroscopy techniques, and remarkably, the correlation of local structure-enhanced kinetics is clearly described in this work. The experimental results suggest that Si/Sn substitution decreases the TMO2 slab thickness and enlarges the interslab spacing, and the concentration gradient of Si/Sn affects the magnitude of these structural changes. The expanded interslab spacing accounts for the enhanced Li+ diffusivity and rate performance observed in Si/Sn-doped materials. The improved understanding of the local structure-enhanced kinetic relationship for doped LLOs demonstrates the potential for the design and development of other high-rate intercalated electrode materials.

Hierarchical Nanocomposite of Hollow N-Doped Carbon Spheres Decorated with Ultrathin WS2 Nanosheets for High-Performance Lithium-Ion Battery Anode.

Hierarchical nanocomposite of ultrathin WS2 nanosheets uniformly attached on the surface of hollow nitrogen-doped carbon spheres (WS2@HNCSs) were successfully fabricated via a facile synthesis strategy. When evaluated as an anode material for LIBs, the hierarchical WS2@HNCSs exhibit a high specific capacity of 801.4 mA h g(-1) at 0.1 A g(-1), excellent rate capability (545.6 mA h g(-1) at a high current density of 2 A g(-1)), and great cycling stability with a capacity retention of 95.8% after 150 cycles at 0.5 A g(-1). The Li-ion storage properties of our WS2@HNCSs nanocomposite are much better than those of the previously most reported WS2-based anode materials. The impressive electrochemical performance is attributed to the robust nanostructure and the favorable synergistic effect between the ultrathin (3-5 layers) WS2 nanosheets and the highly conductive hollow N-doped carbon spheres. The hierarchical hybrid can simultaneously facilitate fast electron/ion transfer, effectively accommodate mechanical stress from cycling, restrain agglomeration, and enable full utilization of the active materials. These characteristics make WS2@HNCSs a promising anode material for high-performance LIBs.

Spherical nitrogen-doped hollow mesoporous carbon as an efficient bifunctional electrocatalyst for Zn-air batteries.

Materials based upon porous carbon have gained considerable attention due to their high surface area, electric conductivity, thermal and chemical stability, low density, and availability. These superior properties make them ideal for diverse applications. Doping these carbon nanostructures holds promise of designing the properties of these structures and opening the door to practical applications. Herein, we report the preparation of hollow N-doped mesoporous carbon (HMC) spheres fabricated via polymerization and carbonization of dopamine on a sacrificial spherical SiO(2) template that is removed upon hydrofluoric acid etching. The morphology and structural features of these HMCs were evaluated using scanning electron microscopy and transmission electron microscopy and the N-doping (7.1 at%) was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen reduction/evolution reaction (ORR/OER) performance of N-doped HMC was evaluated using rotating disk electrode (RDE) voltammetry in an alkaline electrolyte. N-doped HMC demonstrated a high ORR onset potential of -0.055 V (vs. Hg/HgO) and excellent stability. The outstanding bifunctional activity was implemented in a practical Zn-air battery (ZAB), which exhibited a small charge-discharge voltage polarization of 0.89 V and high stability over repeated cycling.

In situ TEM study of stability of TaRhx diffusion barriers using a novel sample preparation method.

The atomic diffusion mechanisms associated with metallurgical failure of TaRhx diffusion barriers for Cu metallizations were studied by in situ transmission electron microscopy (TEM). The issues related to in situ heating of focused ion beam (FIB) prepared cross-sectional TEM samples that contain Cu thin films are discussed. The Cu layer in Si/(13 nm)TaRhx/Cu stacks showed grain growth and formation of voids at temperatures exceeding 550°C. For Si/(43 nm)TaRhx/Cu stacks, grain growth of Cu was delayed to higher temperatures, i.e., 700°C, and void formation was not observed. Extensive surface diffusion of Cu, however, preceded bulk diffusion. Therefore, a 10 nm film of electron beam evaporated C was deposited on both sides of the TEM lamellae to limit surface diffusion. This processing technique allowed for direct observation of atomic diffusion and reaction mechanisms across the TaRhx interface. Failure occurred by nucleation of orthorhombic RhSi particles at the Si/TaRhx interface. Subsequently, the barrier at areas adjacent to RhSi particles was depleted in Rh. This created lower density areas in the barrier, which facilitated diffusion of Cu to the Si substrate to form Cu3Si. The morphology of an in situ annealed lamella was compared with an ex situ bulk annealed sample, which showed similar reaction morphology. The sample preparation method developed in this study successfully prevented surface diffusion/delamination of the Cu layer and can be employed to understand the metallurgical failure of other potential diffusion barriers.