Encapsulating lithium at the microscale: selective deposition in carbon-doped graphitic carbon nitride spheres.

For stable lithium deposition without dendrites, three-dimensional (3D) porous structure has been intensively investigated. Here, we report the use of carbon-doped graphitic carbon nitride (C-doped g-C3N4) microspheres as a 3D host for lithium to suppress dendrite formation, which is crucial for stable lithium deposition. The C-doped g-C3N4microspheres have a high surface area and porosity, allowing for efficient lithium accommodation with high accessibility. The carbon-doping of the g-C3N4microspheres confers lithiophilic properties, which facilitate the regulation of Li+flux and dense filling of cavities with nucleated lithium, thereby preventing volume expansion and promoting dendrite-free Li deposition. The electrochemical performance was improved with cyclic stability and high Coulombic efficiency over 260 cycles at 1.0 mA cm-2for 1.0 mAh cm-2, and even over 70 cycles at 5.0 mA cm-2for 3.0 mAh cm-2. The use of C-doped g-C3N4microspheres as a 3D Li host shows promising results for stable lithium deposition without dendrite formation.

Effect of Highly Periodic Au Nanopatterns on Dendrite Suppression in Lithium Metal Batteries.

Despite the extremely high energy density of the lithium metal, dendritic lithium growth caused by nonuniform lithium deposition can result in low Coulombic efficiency and safety hazards, thereby inhibiting its practical applications. Here, we report a new strategy for adopting a nanopatterned gold (Au) seed on a copper current collector for uniform lithium deposition. We find that Au nanopatterns enhance lithium metal battery performance, which is strongly affected by the feature dimensions of Au nanopatterns (diameter and height). Ex situ scanning electron microscopy images confirm that this can be attributed to the perfectly selective lithium nucleation and uniform growth resulting from the spatial confinement effect. The spatial arrangement of Au dot seeds homogenizes the Li+ flux and electric field, and the size-controlled Au seeds prevent both seed-/substrate-induced agglomeration and interseed-induced lithium growth, leading to uniform lithium deposition. This dendrite-free lithium deposition results in the improvement of electrochemical performance, and the system showed cyclic stability over 300 cycles at 0.5 mA cm-2 and 200 cycles at 1.0 mA cm-2 (1 mA h cm-2) and a high rate capability. This study provides in-depth insights into the more complicated and diverse seed geometry control of seed materials for the development of high-performance lithium metal batteries.

The Effect of Combined Superheated Steam Roasting and Smoking on the Quality Characteristic of Alaska Pollack (Gadus chalcogrammus) Roe.

Alaska pollack roe (APR) is a protein source that is usually salted and fermented, containing a high salt content. Using a combination of superheated steam roasting and smoking, we developed a new low-salt ready-to-eat APR variant, whose quality characteristics we analyzed. The optimal conditions for roasting (216 °C for 4 min) and smoking (64 °C for 14 min) were obtained from sensorial attributes using response surface methodology. Under the optimal conditions, smoke-roasted APR had an overall acceptance (OA) score of 8.89. The combination of roasting and smoking significantly increased volatile basic nitrogen (VBN, 18.6%) and decreased the total bacterial count (TBC, 38.6%), while thiobarbituric acid reactive substances (TBARS) were not affected. Smoke-roasting APR also increased its nutritional content to 30% protein with 44% essential amino acids, and more than 40% DHA and EPA in 4.3% fat. During 30 days of storage, the OA, VBN, TBARS, and TBC values significantly changed with time and storage temperature (p < 0.05). The shelf life of the product was estimated to be 24 d. In conclusion, the combination of roasting and smoking APR could improve product quality and may be an alternative to diversify processed APR.

Polyelemental Nanoparticles as Catalysts for a Li-O2 Battery.

The development of highly efficient catalysts in the cathodes of rechargeable Li-O2 batteries is a considerable challenge. Polyelemental catalysts consisting of two or more kinds of hybridized catalysts are particularly interesting because the combination of the electrochemical properties of each catalyst component can significantly facilitate oxygen evolution and oxygen reduction reactions. Despite the recent advances that have been made in this field, the number of elements in the catalysts has been largely limited to two metals. In this study, we demonstrate the electrochemical behavior of Li-O2 batteries containing a wide range of catalytic element combinations. Fourteen different combinations with single, binary, ternary, and quaternary combinations of Pt, Pd, Au, and Ru were prepared on carbon nanofibers (CNFs) via a joule heating route. Importantly, the Li-O2 battery performance could be significantly improved when using a polyelemental catalyst with four elements. The cathode containing quaternary nanoparticles (Pt-Pd-Au-Ru) exhibited a reduced overpotential (0.45 V) and a high discharge capacity based on total cathode weight at 9130 mAh g-1, which was ∼3 times higher than that of the pristine CNF electrode. This superior electrochemical performance is be attributed to an increased catalytic activity associated with an enhanced O2 adsorbability by the quaternary nanoparticles.

Mechanism for Preserving Volatile Nitrogen Dioxide and Sustainable Redox Mediation in the Nonaqueous Lithium-Oxygen Battery.

Excessive overpotential during charging is a major hurdle in lithium-oxygen (Li-O2) battery technology. NO2-/NO2 redox mediation is an efficient way to substantially reduce the overpotential and to enhance oxygen efficiency and cycle life by suppressing parasitic reactions. Considering that nitrogen dioxide (NO2) is a gas, it is quite surprising that NO2-/NO2 redox reactions can be sustained for a long cycle life in Li-O2 batteries with such an open structure. A detailed study with in situ differential electrochemical mass spectrometry (DEMS) elucidated that NO2 could follow three reaction pathways during charging: (1) oxidation of Li2O2 to evolve oxygen, (2) vaporization, and (3) conversion into NO3-. Among the pathways, Li2O2 oxidation occurs exclusively in the presence of Li2O2, which suggests that NO2 has high reactivity to Li2O2. At the end of the charging process, most of the volatile oxidized couple (NO2) is stored by conversion to a stable third species (NO3-), which is then reused for producing the reduced couple (NO2-) in the next cycle. The dominant reaction of Li2O2 oxidation involves the temporary storage of NO2 as a stable third species during charging, which is an innovative way for preserving the volatile redox couple, resulting in a sustainable redox mediation for a high-performance Li-O2 battery.

Nanoscale Wrinkled Cu as a Current Collector for High-Loading Graphite Anode in Solid-State Lithium Batteries.

Solid-state lithium batteries have been intensively studied as part of research activities to develop energy storage systems with high safety and stability characteristics. Despite the advantages of solid-state lithium batteries, their application is currently limited by poor reversible capacity arising from their high resistance. In this study, we significantly improve the reversible capacity of solid-state lithium batteries by lowering the resistance through the introduction of a graphene and wrinkle structure on the surface of the copper (Cu) current collector. This is achieved through a process of chemical vapor deposition (CVD) facilitating graphene-growth synthesis. The modified graphene/wrinkled Cu current collector exhibits a periodic wrinkled pattern 420 nm in width and 22 nm in depth, and we apply it to a graphite composite electrode to obtain an improved areal loading average value of ∼2.5 mg cm-2. The surface-modified Cu current collector is associated with a significant increase in discharge capacity of 347 mAh g-1 at 0.2 C when used with a solid polymer electrolyte. Peel test results show that the observed enhancement is due to the improved strength of adhesion occurring between the graphite composite anode and the Cu current collector, which is attributed to mechanical interlocking. The surface-modified Cu current collector structure effectively reduces resistance by improving adhesion, which subsequently improves the performance of the solid-state lithium batteries. Our study can provide perspective and emphasize the importance of electrode design in achieving enhancements in battery performance.

Understanding Reaction Pathways in High Dielectric Electrolytes Using ß-Mo2C as a Catalyst for Li-CO2 Batteries.

The rechargeable Li-CO2 battery has attracted considerable attention in recent years because of its carbon dioxide (CO2) utilization and because it represents a practical Li-air battery. As with other battery systems such as the Li-ion, Li-O2, and Li-S battery systems, understanding the reaction pathway is the first step to achieving high battery performance because the performance is strongly affected by reaction intermediates. Despite intensive efforts in this area, the effect of material parameters (e.g., the electrolyte, the cathode, and the catalyst) on the reaction pathway in Li-CO2 batteries is not yet fully understood. Here, we show for the first time that the discharge reaction pathway of a Li-CO2 battery composed of graphene nanoplatelets/beta phase of molybdenum carbide (GNPs/ß-Mo2C) is strongly influenced by the dielectric constant of its electrolyte. Calculations using the continuum solvents model show that the energy of adsorption of oxalate (C2O42-) onto Mo2C under the low-dielectric electrolyte tetraethylene glycol dimethyl ether is lower than that under the high-dielectric electrolyte N,N-dimethylacetamide (DMA), indicating that the electrolyte plays a critical role in determining the reaction pathway. The experimental results show that under the high-dielectric DMA electrolyte, the formation of lithium carbonate (Li2CO3) as a discharge product is favorable because of the instability of the oxalate species, confirming that the dielectric properties of the electrolyte play an important role in the formation of the discharge product. The resulting Li-CO2 battery exhibits improved battery performance, including a reduced overpotential and a remarkable discharge capacity as high as 14,000 mA h g-1 because of its lower internal resistance. We believe that this work provides insights for the design of Li-CO2 batteries with enhanced performance for practical Li-air battery applications.

Synthesis of Single-Crystalline Hexagonal Graphene Quantum Dots from Solution Chemistry.

Graphene-based carbon nanostructures with nanometer dimensions have been of great interest due to the existence of a bandgap. So far, well-ordered edge structure and uniformly synthesized graphene quantum dots (GQDs) with a hexagonal single-crystalline structure have not been directly observed owing to the limited precision of current synthesis approaches. Herein, we report on a novel approach not just for the synthesis of the size-controlled single-crystalline GQDs with hexagonal shape but also for a new discovery on constructing 2D and 3D graphene single crystal structures from d-glucose via catalytic solution chemistry. With size-controlled single-crystalline GQDs, we elucidated the crucial role of edge states on luminescence from the correlation between their crystalline size and exciton lifetime. Furthermore, blue-emissive single-crystalline GQDs were used as an emitter on light-emitting diodes and exhibit stable deep-blue emission regardless of the voltage and doping level.

Formation of toroidal Li2O2 in non-aqueous Li-O2 batteries with Mo2CT x MXene/CNT composite.

Due to the growing demand for high energy density devices, Li-O2 batteries are considered as a next generation energy storage system. The battery performance is highly dependent on the Li2O2 morphology, which arises from formation pathways such as the surface growth and the solution growth models. Thus, controlling the formation pathway is important in designing cathode materials. Herein for the first time, we controlled the Li2O2 formation pathway by using Mo2CT x MXene on a catalyst support. The cathode was fabricated by mixing the positively charged CNT/CTAB solution with the negatively charged Mo2CT x solution. After introducing Mo2CT x , important battery performance metrics were considerably enhanced. More importantly, the discharge product analysis showed that the functional groups on the surface of Mo2CT x inhibit the adsorption of O2 on the cathode surface, resulting in the formation of toroidal Li2O2 via the solution growth model. It was supported by density functional theory (DFT) calculations that adsorption of O2 on the Mo2CT x surface is implausible due to the large energy penalty for the O2 adsorption. Therefore, the introduction of MXene with abundant functional groups to the cathode surface can provide a cathode design strategy and can be considered as a universal method in generating toroidal Li2O2 morphology.

High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

To fabricate a sustainable lithium-oxygen (Li-O2) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO3) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO3 electrolyte efficiently produces NO2-, which initiates a redox shuttle reaction. Interestingly, this NO2-/NO2 redox reaction derived from the LiNO3 salt is not very effective in solvents other than TMS. Compared with other common Li-O2 solvents, TMS seems optimum solvent for the efficient use of LiNO3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO2-/NO2 redox reaction, which results in a high-performance Li-O2 battery.

Facile Synthesis of Composition-Controlled Graphene-Supported PtPd Alloy Nanocatalysts and Their Applications in Methanol Electro-Oxidation and Lithium-Oxygen Batteries.

A new and simple approach is reported for the synthesis of uniformly dispersed PtPd alloy nanocatalysts supported on graphene nanoplatelets (GNPs) (PtPd-GNPs) through the introduction of bifunctional materials, which can modify the GNP surface and simultaneously reduce metal ions. With the use of poly(4-styrenesulfonic acid), poly(vinyl pyrrolidone), poly(diallyldimethylammonium chloride), and poly(vinyl alcohol) as bifunctional materials, PtPd-GNPs can be produced through a procedure that is far simpler than previously reported methods. The as-prepared nanocrystals on GNPs clearly exhibit uniform PtPd alloy structures of around 2 nm in size, which are strongly anchored and well distributed on the GNP sheets. The Pt/Pd atomic ratio and loading density of the nanocrystals on the GNPs are controlled easily by changing the metal precursor feed ratio and the mass ratio of GNP to the metal precursor, respectively. As a result of the synergism between Pt and Pd, the as-prepared PtPd-GNPs exhibit markedly enhanced electrocatalytic performance during methanol electro-oxidation compared with monometallic Pt-GNP or commercially available Pt/C. Furthermore, the PtPd-GNP nanocatalysts also show greatly enhanced catalytic activity toward the oxygen reduction/evolution reaction in a lithium-oxygen (Li-O2 ) process, resulting in greatly improved cycling stability of a Li-O2 battery.

Synthesis of chestnut-bur-like palladium nanostructures and their enhanced electrocatalytic activities for ethanol oxidation.

We report a facile method for the synthesis of Pd nanostructures with highly open structure and huge surface area by reducing Na2PdCl4 with ascorbic acid and using cetylpyridinium chloride (CPC) as a surfactant in an aqueous solution. The prepared Pd nanostructures had an average overall size of 70 nm and were composed of dozens of needle-like thin arms, originating from the same core, with an average thickness of 2.3 nm; the arms looked like chestnut-burs. Time evolution of Pd nanostructures implied that small Pd particles generated at the early stage of the reaction by fast reduction grew via the particle attachment growth mechanism. The morphology and size of the Pd nanostructures could be readily controlled by varying the concentration of CPC; depending on the amount of CPC, the reduction rates varied the morphology of the Pd nanostructures. Because of the huge surface area and possible catalytically active sites, the prepared chestnut-bur-like Pd nanostructures exhibited greater electrocatalytic activity toward ethanol electrooxidation compared to other Pd nanocatalysts, including cubic and octahedral Pd nanocrystals, and even commercial Pd/C.

Seed-mediated synthesis of gold octahedra in high purity and with well-controlled sizes and optical properties.

We report a facile method for the synthesis of uniform Au octahedra with well-controlled sizes and optical properties by seed-mediated growth. Starting from single-crystal seeds of Au spheres with a uniform size, we could reproducibly obtain Au octahedra with a narrow size distribution (<7% in standard deviation) and in high purity (>90%). Moreover, the edge lengths of these Au octahedra could be readily tuned in a controllable fashion from 16 to 77 nm by varying the amount of seeds, the concentration of HAuCl(4) , or both. We have also investigated the effects of water and poly(vinyl pyrrolidone) (PVP) in the system, as well as the reaction temperature, on the evolution of octahedral shape.