Photo-Rechargeable Asymmetric Supercapacitors Exceeding Light-to-Charge Storage Efficiency over 21% under Indoor Light.

Photo-rechargeable energy storage devices are appealing for substantial research attention because of their possible applications in the Internet of Things (IoT) and low-powered miniaturized portable electronics. However, due to the incompatibility of the photovoltaics and energy storage systems (ESSs), the overall light-to-storage efficiency is limited under indoor light conditions. Herein, a porous carbon scaffold MnO-Mn3 O4 /C microsphere-based monolithic dye-sensitized photo-rechargeable asymmetric supercapacitor (DSPC) is fabricated. The integrated DSPC has a high areal specific capacitance of 281.9 mF cm-2 at the discharge rate of 0.01 mA cm-2 . The light-to-electrical conversion efficiency of the DSSC is 27.6% under the 1000 lux compact fluorescent lamp (CFL). The DSPC shows an outstanding light-to-charge storage efficiency of 21.6%, which is higher than that reported ever. Furthermore, the fabricated polymer gel electrolyte-based quasi-solid state (QSS) DSPC shows similar overall conversion efficiency with superior cycling capability. This work shows a convenient fabrication process for a wireless power pack of interest with outstanding performance.

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.

Stable Cycling of a 4 V Class Lithium Polymer Battery Enabled by In Situ Cross-Linked Ethylene Oxide/Propylene Oxide Copolymer Electrolytes with Controlled Molecular Structures.

Commercial lithium-ion batteries are vulnerable to fire accidents, mainly due to volatile and flammable liquid electrolytes. Although solid polymer electrolytes (SPEs) are considered promising alternatives with antiflammability and processability for roll-to-roll mass production, several requirements have not yet been fulfilled for a viable lithium polymer battery. Such requirements include ionic conductivity, electrochemical stability, and interfacial resistance. In this work, the ionic conductivity of the SPEs is optimized by controlling the molecular weight and structural morphology of the plasticizers as well as introducing propylene oxide (PO) groups. Electrochemical stability is also enhanced using ethylene oxide (EO)/PO copolymer electrolytes, making the SPEs compatible with high-Ni LiNixCoyMn1-x-yO2 cathodes. The in situ cross-linking method, in which a liquid precursor first wets the electrode and is then solidified by a subsequent thermal treatment, enables the SPEs to soak into the 60 µm thick electrode with a high loading density of more than 8 mg cm-2. Thus, interfacial resistance between the SPE and the electrode is minimized. By using the in situ cross-linked EO/PO copolymer electrolytes, we successfully demonstrate a 4 V class lithium polymer battery, which performs stable cycling with a marginal capacity fading even over 100 cycles.

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.

Investigation of suitable seed sizes, segregation of ripe seeds, and improved germination rate for the commercial production of hemp sprouts (Cannabis sativa L.).

BACKGROUND: With a growing market for functional foods, the nutraceutical properties of hemp sprouts have been investigated in recent studies. However, commercial mass production methods have yet to be developed. This study aimed to identify seed sizes suitable for segregating ripe seeds, which would improve the low germination rate in the high seed densities used in commercial hemp sprout production. RESULTS: Seeds ranging in size from 2.80 to 3.3 mm, collected by sieving, were the most suitable for sprouting, based on the distribution rate (74.9%) and germination rate (70.0%) at a low seed density (0.016 grains mm-2 ). Seed segregation by sinking the seeds in 70% ethanol after 2 h or more of water infiltration generated high germination rates of 86.3% to 94.3% at low seed density, compared to a 64.0% germination rate in non-segregated seeds. The hemp seed germination rate decreased geometrically with increasing sowing density. The germination rate with a high seed density (0.29 grains mm-2 ) was increased from 19.9% when seeds were not mixed with sand to 58.7% when mixed with sand in a 3:1 ratio. The sprouting yield significantly increased from 1.64 kg kg-1 when seeds were not mixed with sand to 9.55 kg kg-1 in seeds germinating when mixed with sand. Delta-9-tetrahydrocannabinol was not detected in hemp sprout. CONCLUSION: The production of hemp sprouts may be improved by identifying suitable seed sizes, segregating ripe seeds, and germinating seeds mixed with sand. This can be used in the commercial production of hemp sprouts. The sprouts were also found to be safe and without hallucinogenic effects. © 2020 Society of Chemical Industry.

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.

Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

Lithium-oxygen (Li-O2) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

Room-Temperature, Ambient-Pressure Chemical Synthesis of Amine-Functionalized Hierarchical Carbon-Sulfur Composites for Lithium-Sulfur Battery Cathodes.

Recently, the achievement of newly designed carbon-sulfur composite materials has attracted a tremendous amount of attention as high-performance cathode materials for lithium-sulfur batteries. To date, sulfur materials have been generally synthesized by a sublimation technique in sealed containers. This is a well-developed technique for the synthesizing of well-ordered sulfur materials, but it is limited when used to scale up synthetic procedures for practical applications. In this study, we suggest an easily scalable, room-temperature/ambient-pressure chemical pathway for the synthesis of highly functioning cathode materials using electrostatically assembled, amine-terminated carbon materials. It is demonstrated that stable cycling performance outcomes are achievable with a capacity of 730 mAhg-1 at a current density of 1 C with good cycling stability by a virtue of the characteristic chemical/physical properties (a high conductivity for efficient charge conduction and the presence of a number of amine groups that can interact with sulfur atoms during electrochemical reactions) of composite materials. The critical roles of conductive carbon moieties and amine functional groups inside composite materials are clarified with combinatorial analyses by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy.

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.

Mesoporous amorphous binary Ru-Ti oxides as bifunctional catalysts for non-aqueous Li-O2 batteries.

Mesoporous amorphous binary Ru-Ti oxides were prepared as bifunctional catalysts for non-aqueous Li-O2 batteries, and their electrochemical performance was investigated for the first time. A Li-O2 battery with mesoporous amorphous binary Ru-Ti oxides exhibited a remarkably high capacity of 27100 mAh g-1 as well as a reduced overpotential. A GITT analysis suggested that the introduction of amorphous TiO2 to amorphous RuO2 was responsible for the enhanced kinetics toward both the oxygen reduction reaction and oxygen evolution reaction. Excellent cyclic stability up to 230 cycles was achieved, confirming the applicability of the new bifunctional catalyst in non-aqueous Li-O2 batteries.

High-rate performance of Ti(3+) self-doped TiO2 prepared by imidazole reduction for Li-ion batteries.

Ti(3+) self-doped TiO2 nanoparticles were prepared via a simple imidazole reduction process and developed as an anode material for Li-ion batteries. Introducing the Ti(3+)-state on TiO2 nanoparticles resulted in superior rate performances that the capacity retention of 88% at 50 C. The enhanced electrochemical performances were attributed to the resulting lower internal resistance and improved electronic conductivity, based on galvanostatic intermittent titration technique and electrochemical impedance spectroscopy analyses.

A morphology, porosity and surface conductive layer optimized MnCo2O4 microsphere for compatible superior Li(+) ion/air rechargeable battery electrode materials.

Uniform surface conductive layers with porous morphology-conserved MnCo2O4 microspheres are successfully synthesized, and their electrochemical performances are thoroughly investigated. It is found that the microwave-assisted hydrothermally grown MnCo2O4 using citric acid as the carbon source shows a maximum Li(+) ion lithiation/delithiation capacity of 501 mA h g(-1) at 500 mA g(-1) with stable capacity retention. Besides, the given microsphere compounds are effectively activated as air cathode catalysts in Li-O2 batteries with reduced charge overpotentials and improved cycling performance. We believe that such an affordable enhanced performance results from the appropriate quasi-hollow nature of MnCo2O4 microspheres, which can effectively mitigate the large volume change of electrodes during Li(+) migration and/or enhance the surface transport of the LiOx species in Li-air batteries. Thus, the rationally designed porous media for the improved Li(+) electrochemical reaction highlight the importance of the 3D macropores, the high specific area and uniformly overcoated conductive layer for the promising Li(+) redox reaction platforms.

Superior lithium storage performance using sequentially stacked MnO2/reduced graphene oxide composite electrodes.

Hybrid nanostructures based on graphene and metal oxides hold great potential for use in high-performance electrode materials for next-generation lithium-ion batteries. Herein, a new strategy to fabricate sequentially stacked α-MnO2 /reduced graphene oxide composites driven by surface-charge-induced mutual electrostatic interactions is proposed. The resultant composite anode exhibits an excellent reversible charge/discharge capacity as high as 1100 mA h g(-1) without any traceable capacity fading, even after 100 cycles, which leads to a high rate capability electrode performance for lithium ion batteries. Thus, the proposed synthetic procedures guarantee a synergistic effect of multidimensional nanoscale media between one (metal oxide nanowire) and two dimensions (graphene sheet) for superior energy-storage electrodes.

Determination of Li(+) diffusion coefficients in the LixV2O5 (x = 0 - 1) nanocrystals of composite film cathodes.

The Li(+) ion diffusion coefficients (DLi+) in V2O5 (2.12 × 10(-12) cm(2) s(-1)) and in the intermediate α-, ε-, and δ-LixV2O5 phases (1.6 × 10(-14), 8.0 × 10(-15), and 8.5 × 10(-15) cm(2) s(-1), respectively), reversibly formed during charging/discharging processes of the crystalline-V2O5 and PEDOT (poly-3,4-ethylenedioxythiophene) composite-film electrode, are precisely determined by the galvanostatic intermittent titration technique. The specific surface area of the composite film is estimated to be 13.600 m(2) g(-1), where the external surface area and the nanopore area are 10.704 and 2.896 m(2) g(-1), respectively. The V2O5 crystals are coated and interconnected by a conductive polymer network in the composite film, thereby improving the electrode characteristics. V2O5 and PEDOT composite-film cathodes showed high specific capacities (290 mA h g(-1) at a 1 C rate), excellent rate capabilities (178 mA h g(-1) at a 10 C rate), and superior cycling stabilities (ca. 15% degradation after 500 consecutive cycles).

Organic sensitizers containing julolidine moiety for dye-sensitized solar cells.

We prepared organic sensitizers (S1 and S2) containing julolidine moiety as a donor, phenyl or phenylene thiophene units as a conjugation bridge, and cyano acetic acid as an acceptor for dye sensitized solar cells. S1 exhibited two absorption maxima at 441 nm (epsilon = 26,200) and 317 nm (epsilon = 15,500) due to the pi-pi transition of the dye molecule. S2 dyes with an additional thiophene unit showed the absorption maximum extended by 18 nm. DSSCs based on S1 dye achieved 2.66% of power conversion efficiency with 8.3 mA cm(-2) of short circuit current, 576 mV of open circuit voltage, and 0.56 of fill factor. DSSCs using S2 dye with a longer conjugation attained only 1.48% of power conversion efficiency. The 0.21 V lower driving force for regeneration of the S2 dye compared to the Si dye is one of the reasons for low conversion efficiency of the S2 dye.