Electrochemically active porous carbon nanospheres prepared by inhibition of pyrolytic condensation of polymers.

Porous carbon is a pivotal material for electrochemical applications. The manufacture of porous carbon has relied on chemical treatments (etching or template) that require processing in all areas of the carbon/carbon precursor. We present a unique approach to preparing porous carbon nanospheres by inhibiting the pyrolytic condensation of polymers. Specifically, the porous carbon nanospheres are obtained by coating a thin film of ZnO on polystyrene spheres. The porosity of the porous carbon nanospheres is controlled by the thickness of the ZnO shell, achieving a BET-specific area of 1,124 m2/g with a specific volume of 1.09 cm3/g. We confirm that under the support force by the ZnO shell, a hierarchical pore structure in which small mesopores are connected by large mesopores is formed and that the pore-associated sp3 defects are enriched. These features allow full utilization of the surface area of the carbon pores. The electrochemical capacitive performance of porous carbon nanospheres was evaluated, achieving a high capacitance of 389 F/g at 1 A/g, capacitance retention of 71% at a 20-fold increase in current density, and stability up to 30,000 cycles. In particular, we achieve a specific area-normalized capacitance of 34.6 µF/cm2, which overcomes the limitations of conventional carbon materials.

The Polysulfide-Cathode Binding Energy Landscape for Lithium Sulfide Growth in Lithium-Sulfur Batteries.

A cathode substrate with strong adsorption of lithium polysulfides (LiPSs) has been preferred for lithium-sulfur (Li-S) batteries. However, the recent finding that controlled growth of lithium sulfides (Li2 S) during discharge is crucial for S utilization stimulates improvement of this preference. Here, the Li2 S growth and cell capacity in the LiPS binding energy landscape of cathode substrates are investigated. Specifically, Co-based ternary oxides are employed to obtain binding energies in the range of 4.0-7.4 eV. Of these substrates, only the MnCo2 O4 substrate with moderate LiPS affinity exhibits 3D Li2 S growth. The MnCo2 O4 cells achieve high sulfur utilization up to 84% at 0.2 C and excellent performance even under high sulfur loading/lean electrolyte conditions. In contrast, weak affinity substrates such as ZnCo2 O4 and strong affinity substrates such as NiCo2 O4 and CuCo2 O4 exhibit low discharge capacity with 2D Li2 S growth. For optimal LiPS affinity driving 3D growth, a balance between promoting LiPS adsorption and diffusion limitation in the LiPS adsorption layer is suggested.

Discovery of Dual-Functional Amorphous Titanium Suboxide to Promote Polysulfide Adsorption and Regulate Sulfide Growth in Li-S Batteries.

Lithium-sulfur (Li-S) batteries are promising as next-generation energy storage systems. Adsorbents for sulfide species are favorably applied to the cathode, but this substrate often results in a surface-passivating lithium sulfide(Li2 S) film with a strong adsorption of Li2 S. Here, an amorphous titanium suboxide (a-TiOx) is presented that strongly adsorbs lithium polysulfides (Li2 Sx , x < 6) but relatively weakly adsorbs to Li2 S. With these characteristics, the a-TiOx achieves high conversion of Li2 Sx and high sulfur utilization accompanying the growth of particulate Li2 S. The DFT calculations present a mechanism for particulate growth driven by the promoted diffusion and favorable clustering of Li2 S. The a-TiOx -coated carbon nanotube-assembled film (CNTF) cathode substrate cell achieves a high discharge capacity equivalent to 90% sulfur utilization at 0.2 C. The cell also delivers a high capacity of 850 mAh g-1 even at the ultra-high-speed of 10 C and also exhibits high stability of capacity loss of 0.0226% per cycle up to 500 cycles. The a-TiOx /CNTF is stacked to achieve a high loading of 7.5 mg S cm-2 , achieving a practical areal capacity of 10.1 mAh cm-2 .

Balancing Electrolyte Donicity and Cathode Adsorption Capacity for High-Performance LiS Batteries.

LiS batteries with high theoretical capacity are attracting attention as next-generation energy storage systems. Much effort has been devoted to the introduction of cathode materials with strong adsorption to sulfide species, but it is presented that this selection should be refined in the application of high donicity electrolytes. The oxides with different adsorption capacities are explored while controlling the electrolyte donicity, confirming the trade-off effect between the donicity and the adsorption capacity for sulfur conversion. Specifically, a cathode substrate containing oxide nanoparticles of MgO, NiO, Fe2 O3 , Co3 O4 , and V2 O5 is prepared with spectra in adsorption capacity as well as low and high donicity electrolytes by controlling the concentration of LiNO3 salt. Strong adsorbent oxides such as Co3 O4 and V2 O5 cause competitive adsorption of electrolyte salts in high donicity electrolytes, resulting in poor cell performance. High cell performance is achieved on weakly adsorbing oxides of MgO or NiO with high donicity electrolytes; the MgO-containing cathode cell delivers a high discharge capacity of 1394 mAh g-1 at 0.2 C. It is believed that understanding the interactions between electrolytes and adsorbent substrates will be the cornerstone of high-performance LiS batteries.

A Layer-by-Layer Assembly Route to Electroplated Fibril-Based 3D Porous Current Collectors for Energy Storage Devices.

Electrical conductivity, mechanical flexibility, and large electroactive surface areas are the most important factors in determining the performance of various flexible electrodes in energy storage devices. Herein, a layer-by-layer (LbL) assembly-induced metal electrodeposition approach is introduced to prepare a variety of highly porous 3D-current collectors with high flexibility, metallic conductivity, and large surface area. In this study, a few metal nanoparticle (NP) layers are LbL-assembled onto insulating paper for the preparation of conductive paper. Subsequent Ni electroplating of the metal NP-coated substrates reduces the sheet resistance from ≈103 to <0.1 Ω sq-1 while maintaining the porous structure of the pristine paper. Particularly, this approach is completely compatible with commercial electroplating processes, and thus can be directly extended to electroplating applications using a variety of other metals in addition to Ni. After depositing high-energy MnO NPs onto Ni-electroplated papers, the areal capacitance increases from 68 to 811 mF cm-2 as the mass loading of MnO NPs increases from 0.16 to 4.31 mg cm-2 . When metal NPs are periodically LbL-assembled with the MnO NPs, the areal capacitance increases to 1710 mF cm-2 .

Colloidal assembly in droplets: structures and optical properties.

Colloidal assembly in emulsion drops provides fundamental tools for studying optimum particle arrangement under spherical confinement and practical means for producing photonic microparticles. Recent progress has revealed that energetically favored cluster configurations are different from conventional supraballs, which could enhance optical performance. This paper reviews state-of-the-art emulsion-templated colloidal clusters, and particularly focuses on recently reported novel structures such as icosahedral, decahedral, and single-crystalline face-centered cubic (fcc) clusters. We classify the clusters according to the number of component particles as small (N < O(102)), medium (O(102) ≤N≤O(104)), and large (N≥O(105)). For each size of clusters, we discuss the detailed structures, mechanisms of cluster formation, and optical properties and potential applications. Finally, we outline current challenges and questions that require further investigation.

Photon upconversion-assisted dual-band luminescence solar concentrators coupled with perovskite solar cells for highly efficient semi-transparent photovoltaic systems.

A luminescent solar concentrator-based photovoltaic system (LSC-PVs) is highly transparent because it harvests solar light via the LSC, a transparent panel containing only fluorophores, and is, therefore, promising as a PV window. However, for the practical use of LSC-PV, achieving high efficiency remains a challenge. Here, we demonstrate an LSC-PV, which is based on the combination of an upconversion (UC)-assisted dual band harvesting LSC and perovskite solar cells (PSCs). We prepare a dual LSC panel consisting of a downshift (DS) LSC that absorbs violet light and an LSC that upconverts the red light. We apply a highly efficient mixed halide PSC with an efficiency of 17.22%. We control the thickness of the LSC panel as well as the dye concentration to maximize the emission from dual LSCs. The dual LSCs coupled with a PSC exhibit a high average-visible-transmittance of 82% and achieve a maximum efficiency of 7.53% at 1 sun (AM 1.5G) illumination. The dual LSC-PSC exhibits a constant efficiency even under oblique solar light illumination and a stable operation with an efficiency retention of 80%.

Unveiling the Effects of Nanostructures and Core Materials on Charge-Transport Dynamics in Heterojunction Electrodes for Photoelectrochemical Water Splitting.

Understanding the photogenerated charge-transport dynamics of metal oxide electrodes is the key to providing a strategy for practical improvement in the photoelectrochemical reaction activity. Here, we analyze the electron transport of a 3D bicontinuous SnO2/BiVO4 nanostructured photoelectrode by intensity-modulated photocurrent spectroscopy. We compare this electrode with 3D WO3/BiVO4 and planar-type bilayer SnO2/BiVO4 electrodes. In the results, we observe an order of magnitude faster electron transport in the 3D electrodes relative to the bilayer electrode. Moreover, we observe trap-limited transport on widely applied WO3/BiVO4 electrodes but confirm rapid trap-free transport on 3D SnO2/BiVO4. We also characterize the effect of electron transport on the water-splitting reaction. The electron-transport rate is directly related to the charge-separation efficiency in the water-splitting reaction. The fast transport time of the 3D SnO2/BiVO4 leads to the achievement of a significantly higher charge separation efficiency of 94%.

Dual-sensitized upconversion-assisted, triple-band absorbing luminescent solar concentrators.

Luminescent solar concentrator-photovoltaic systems (LSC-PV) harvest solar light by using transparent photoluminescent plates, which is expected to be particularly useful for building-integrated PV applications. LSC panels that absorb multiple wavelength bands are required to achieve high power conversion efficiency (PCE). In this study, we demonstrate a pair of downshift LSC and photon upconversion (UC) LSC, absorbing triple bands (violet, green, and red light). The UC is obtained by energy transfer and triplet-triplet annihilation between sensitizer and emitter dyes. In particular, we exploit the dual sensitizer to obtain absorption of the dual wavelength band. The couple with the UC LSC obtains photoluminescence of a single visible wavelength band from the LSC, which enables the use of wide bandgap solar cells to absorb it. Here, we apply mixed-cation perovskite solar cells (PSCs) with high absorption coefficients, especially at visible wavelengths. In our triple-band-absorbing LSC-PSC, we achieve a maximum PCE of 8.99%.

Complete encapsulation of sulfur through interfacial energy control of sulfur solutions for high-performance Li-S batteries.

Complete encapsulation of high-content sulfur in porous carbon is crucial for high performance Li-S batteries. To this end, unlike conventional approaches to control the pore of carbon hosts, we demonstrate controlling the interfacial energy of the solution in the process of penetrating the sulfur-dissolved solution. We unveil, experimentally and theoretically, that the interfacial energy with the carbon surface of the sulfur solution is the key to driving complete encapsulation of sulfur. In the infiltration of sulfur solutions with N-methyl-2-pyrrolidone, we achieve complete encapsulation of sulfur, even up to 85 wt %. The sulfur fully encapsulated cathode achieves markedly high volumetric capacity and stable cycle operation in its Li-S battery applications. We achieve a volumetric capacity of 855 mAh/cm3 at 0.2C and a capacity reduction of 0.071% per cycle up to 300 cycles at 1C.

Enhanced Photoelectrochemical Water Splitting through Bismuth Vanadate with a Photon Upconversion Luminescent Reflector.

As the performance of photoanodes for solar water splitting steadily improves, the extension of the absorption wavelength in the photoanodes is highly necessary to substantially improve the water splitting. We use a luminescent back reflector (LBR) capable of photon upconversion (UC) to improve the light harvesting capabilities of Mo:BiVO4 photoelectrodes. The LBR is prepared by dispersing the organic dye pair meso-tetraphenyltetrabenzoporphine palladium and perylene capable of triplet-triplet annhilation-based UC in a polymer film. The LBR converts the wavelengths of 600-650 nm corresponding to the sub-band gap of Mo:BiVO4 and the wavelengths of 350-450 nm that are not sufficiently absorbed in Mo:BiVO4 to a wavelength that can be absorbed by a Mo:BiVO4 photoelectrode. The LBR improves the water splitting reaction of Mo:BiVO4 photoelectrodes by 17 %, and consequently, the Mo:BiVO4 /LBR exhibits a photocurrent density of 5.25 mA cm-2 at 1.23 V versus the reversible hydrogen electrode. The Mo:BiVO4 /LBR exhibits hydrogen/oxygen evolution corresponding to the increased photocurrent density and long-term operational stability for the water splitting reaction.

Polydopamine-wrapped, silicon nanoparticle-impregnated macroporous CNT particles: rational design of high-performance lithium-ion battery anodes.

We present a simple but rationally designed anode composed of polydopamine-wrapped, Si nanoparticle-impregnated macroporous CNT particles for lithium-ion batteries; this anode is mass-producible and at the same time achieves an excellent capacity and its retention by effective stress relaxation and surface passivation.

Three-Dimensional Bicontinuous BiVO4/ZnO Photoanodes for High Solar Water-Splitting Performance at Low Bias Potential.

A photoanode capable of high-efficiency water oxidation at low bias potential is essential for its practical application for photocathode-coupled tandem systems. To address this issue, a photoanode with low turn-on voltage for water oxidation and high charge separation efficiency at low bias potential is essential. In this study, we demonstrate the photoanode of the BiVO4/ZnO three-dimensional (3D) bicontinuous (BC) structure. ZnO has a relatively cathodic flat-band potential, which leads to low turn-on potential; the BiVO4/ZnO 3D BC photoanode shows an onset potential of 0.09 V versus the reversible hydrogen electrode ( VRHE). Moreover, we achieve remarkably high charge separation efficiency at low bias potential (78% at 0.6 VRHE); this is attributed to the application of thin-film BiVO4 shells by high light-scattering properties of the 3D BC structure. As a result, the BiVO4/ZnO 3D BC photoanode generates a high water oxidation photocurrent of up to 3.4 ± 0.2 mA cm-2 (with CoPi catalyst coating). This photocurrent value is reproducible, and the photocurrent-to-O2 conversion efficiency is over 90%. To the best of our knowledge, this is the highest value among the values of the photocurrent at 0.6 VRHE in previous BiVO4-based heterojunction photoanodes.

Hierarchical Pore-Patterned Carbon Electrodes for High-Volumetric Energy Density Micro-Supercapacitors.

Micro-supercapacitors (MSCs) are attractive for applications in next-generation mobile and wearable devices and have the potential to complement or even replace lithium batteries. However, many previous MSCs have often exhibited a low volumetric energy density with high-loading electrodes because of the nonuniform pore structure of the electrodes. To address this issue, we introduced a uniform-pore carbon electrode fabricated by 3D interference lithography. Furthermore, a hierarchical pore-patterned carbon (hPC) electrode was formed by introducing a micropore by chemical etching into the macropore carbon skeleton. The hPC electrodes were applied to solid-state MSCs. We achieved a constant volumetric capacitance and a corresponding volumetric energy density for electrodes of various thicknesses. The hPC MSC reached a volumetric energy density of approximately 1.43 mW h/cm3. The power density of the hPC MSC was 1.69 W/cm3. We could control the capacitance and voltage additionally by connecting the unit MSC cells in series or parallel, and we confirmed the operation of a light-emitting diode. We believe that our pore-patterned electrodes will provide a new platform for compact but high-performance energy storage devices.

Spherical Macroporous Carbon Nanotube Particles with Ultrahigh Sulfur Loading for Lithium-Sulfur Battery Cathodes.

A carbon host capable of effective and uniform sulfur loading is the key for lithium-sulfur batteries (LSBs). Despite the application of porous carbon materials of various morphologies, the carbon hosts capable of uniformly impregnating highly active sulfur is still challenging. To address this issue, we demonstrate a hierarchical pore-structured CNT particle host containing spherical macropores of several hundred nanometers. The macropore CNT particles (M-CNTPs) are prepared by drying the aerosol droplets in which CNTs and polymer particles are dispersed. The spherical macropore greatly improves the penetration of sulfur into the carbon host in the melt diffusion of sulfur. In addition, the formation of macropores greatly develops the volume of the micropore between CNT strands. As a result, we uniformly impregnate 70 wt % sulfur without sulfur residue. The S-M-CNTP cathode shows a highly reversible capacity of 1343 mA h g-1 at a current density of 0.2 C even at a high sulfur content of 70 wt %. Upon a 10-fold current density increase, a high capacity retention of 74% is observed. These cathodes have a higher sulfur content than those of conventional CNT hosts but nevertheless exhibit excellent performance. Our CNTPs and pore control technology will advance the commercialization of CNT hosts for LSBs.

In Situ Observation of Carbon Dioxide Capture on Pseudo-Liquid Eutectic Mixture-Promoted Magnesium Oxide.

Eutectic mixtures of alkali nitrates are known to increase the sorption capacity and kinetics of MgO-based sorbents. Underlying principles and mechanisms for CO2 capture on such sorbents have already been established; however, real-time observation of the system was not yet accomplished. In this work, we present the direct-observation of the CO2 capture phenomenon on a KNO3-LiNO3 eutectic mixture (EM)-promoted MgO sample, denoted as KLM, via in situ transmission electron microscopy (in situ TEM). Results revealed that the pseudoliquid EM undergoes structural rearrangement as MgCO3 evolves from the surface of MgO, resulting in surface roughening and evolution of cloudy structures that stay finely distributed after regeneration. From this, we propose a nucleation and structural rearrangement scheme for MgCO3 and EM, which involves the rearrangement of bulk EM to evenly distributed EM clusters due to MgCO3 saturation as adsorption proceeds. We also conducted studies on the interface between EM over solid MgO and MgCO3 formed during sorption, which further clarifies the interaction between MgO and EM. This study provides better insight into the sorption and regeneration mechanism, as well as the structural rearrangements involved in EM-promoted sorbents by basing not only on intrinsic evolutions but also on real-time observation of the system as a whole.

Ultrahigh Electrocatalytic Conversion of Methane at Room Temperature.

Due to the greenhouse effect, enormous efforts are done for carbon dioxide reduction. By contrast, more attention should be paid for the methane oxidation and conversion, which can help the effective utilization of methane without emission. However, methane conversion and utilization under ambient conditions remains a challenge. Here, this study designs a Co3O4/ZrO2 nanocomposite for the electrochemical oxidation of methane gas using a carbonate electrolyte at room temperature. Co3O4 activated the highly efficient oxidation of methane under mild electric energy with the help of carbonate as an oxidant, which is delivered by ZrO2. Based on the experimental results, acetaldehyde is the key intermediate product. Subsequent nucleophilic addition and free radical addition reactions accounted for the generation of 2-propanol and 1-propanol, respectively. Surprisingly, this work achieves a production efficiency of over 60% in the conversion of methane to produce these long-term stable products. The as-proposed regional electrochemical methane oxidation provides a new pathway for the synthesis of higher alcohols with high production efficiencies under ambient conditions.

Highly N-doped microporous carbon nanospheres with high energy storage and conversion efficiency.

Porous carbon spheres (CSs) have distinct advantages in energy storage and conversion applications. We report the preparation of highly monodisperse N-doped microporous CSs through the carbonization of polystyrene-based polymer spheres and subsequent activation. The N-doped microporous CSs have a remarkably high N-doping content, over 10%, and high BET surface area of 884.9 m2 g-1. We characterize the synergistic effects of the micropores and N doping on the energy storage performance of a supercapacitor electrode consisting of the CSs and on the performance in an electrocatalytic reaction of a CS counter electrode in a photovoltaic cell. The N-doped microporous CSs exhibit a maximum capacitance of 373 F g-1 at a current density of 0.2 Ag-1, a high capacitance retention up to 62% with a 10-fold increase in current density, and excellent stability over 10,000 charge/discharge cycles. A counter electrode consisting of N-doped microporous CSs was found to exhibit superior electrocatalytic behavior to an electrode consisting of conventional Pt nanoparticles. These CSs derived from polymer spheres synthesized by addition polymerization will be new platform materials with high electrochemical performance.

Monolithic Two-Dimensional Photonic Crystal Reflectors for the Fabrication of Highly Efficient and Highly Transparent Dye-Sensitized Solar Cells.

The transparent characteristic of dye-sensitized solar cells (DSCs) makes them suitable for building integrated photovoltaic (BIPV) devices. However, the diffusive scattering layer, which is usually used to increase the efficiency of these devices, greatly lowers the transparency of the DSC. This paper described a two-dimensional (2D) photonic crystal (PC) reflector with a sub-micrometer characteristic length that can improve the efficiency of these devices while maintaining transparency. This 2D PCs were fabricated directly onto TiO2 photoelectrodes using colloidal lithography and have the structure of a nanopillar array. A nanopillar with a height of 430 nm was observed to selectively reflect up to 40% of the light of 400-500 nm wavelength. The perceived transparency of the 2D PC electrode was 52%, which is much higher than 0.3% of the conventional scattering layer. The DSC fabricated using the 2D PC electrode demonstrated a maximum photon-to-electric conversion efficiency of 8.23%, which is 18% higher than the pristine electrode. The 2D PC is a highly efficient and wavelength-selective reflector that can be applied to various photoelectric conversion devices.

In Situ Gelation of Poly(vinylidene fluoride) Nanospheres for Dye-Sensitized Solar Cells: The Analysis on the Efficiency Enhancement upon Gelation.

The in situ gelation that utilizes the dissolution of polymers inside the cell is allowed high concentration polymer gel without concerns regarding high viscous electrolyte incorporation into the cell as in the conventional approach. We demonstrate the in situ gelation of polymer composite electrolytes using poly(vinylidene fluoride) nanospheres (PVdF NSs). The PVdF NSs were synthesized by high pressure emulsion polymerization using gaseous vinylidene fluoride monomers. Compared to the liquid electrolyte (LE) DSCs without PVdF gelation, the PVdF polymer gel electrolyte (PGE) DSCs displayed higher η than the LE DSCs; specifically, the 10 wt % PVdF PGE DSCs display 8.1% of the η, while the LE DSCs only display 6.5%. We characterized the effect of PVdF PGE on the photovoltaic parameters in detail. We also compared the long-term stability of DSCs containing LE and PVdF PGE. The DSCs with PVdF PGE exhibited high stability compared to the LE DSCs, similar to a conventional PGE system. We believe that this facile in situ gelation approach could be utilized for not only the practical application of polymer gel electrolytes DSCs but also for various energy-storage devices.