Exceptionally high proton conductivity in Eu2O3 by proton-coupled electron transfer mechanism.

Proton conductors are typically developed by doping to introduce structural defects such as oxygen vacancies to facilitate ionic transport through structural bulk conduction mechanism. In this study, we present a novel electrochemical proton injection method via an in situ fuel cell process, demonstrating proton conduction in europium oxide (Eu2O3) through a surficial conduction mechanism for the first time. By tuning Eu2O3 into a protonated form, H-Eu2O3, we achieved an exceptionally high proton conductivity of 0.16 S cm-1. Distribution of relaxation time (DRT) analysis was employed to investigate the proton transport behavior and reveal the significant contribution of surface proton transport to the overall conductivity of Eu2O3. Remarkably, H-Eu2O3 exhibited a low activation energy for ionic transport, comparable to the best ceramic electrolytes available. The proton-coupled electron transfer (PCET) mechanism describes this novel surficial proton conduction mechanism. These findings provide new possibilities for developing advanced proton conductors with improved performance.

Toward next-generation fuel cell materials.

The fuel cell's three layers-anode/electrolyte/cathode-convert fuel's chemical energy into electricity. Electrolyte membranes determine fuel cell types. Solid-state and ceramic electrolyte SOFC/PCFC and polymer based PEMFC fuel cells dominate fuel cell research. We present a new fuel cell concept using next-generation ceramic nanocomposites made of semiconductor-ionic material combinations. A built-in electric field driving mechanism boosts ionic (O2- or H+ or both) conductivity in these materials. In a fuel cell device, non-doped ceria or its heterostructure might attain 1 Wcm-2 power density. We reviewed promising functional nanocomposites for that range. Ceria-based and multifunctional semiconductor-ionic electrolytes will be highlighted. Owing to their simplicity and abundant resources, these materials might be used to make fuel cells cheaper and more accessible.

A-site deficient semiconductor electrolyte Sr1-x Co x FeO3-δ for low-temperature (450-550 °C) solid oxide fuel cells.

Fast ionic conduction at low operating temperatures is a key factor for the high electrochemical performance of solid oxide fuel cells (SOFCs). Here an A-site deficient semiconductor electrolyte Sr1-x Co x FeO3-δ is proposed for low-temperature solid oxide fuel cells (LT-SOFCs). A fuel cell with a structure of Ni/NCAL-Sr0.7Co0.3FeO3-δ -NCAL/Ni reached a promising performance of 771 mW cm-2 at 550 °C. Moreover, appropriate doping of cobalt at the A-site resulted in enhanced charge carrier transportation yielding an ionic conductivity of >0.1 S cm-1 at 550 °C. A high OCV of 1.05 V confirmed that neither short-circuiting nor power loss occurred during the operation of the prepared SOFC device. A modified composition of Sr0.5Co0.5FeO3-δ and Sr0.3Co0.7FeO3-δ also reached good fuel cell performance of 542 and 345 mW cm-2, respectively. The energy bandgap analysis confirmed optimal cobalt doping into the A-site of the prepared perovskite structure improved the charge transportation effect. Moreover, XPS spectra showed how the Co-doping into the A-site enhanced O-vacancies, which improve the transport of oxide ions. The present work shows that Sr0.7Co0.3FeO3-δ is a promising electrolyte for LT-SOFCs. Its performance can be boosted with Co-doping to tune the energy band structure.

Systematic Analysis on the Effect of Sintering Temperature for Optimized Performance of Li0.15Ni0.45Zn0.4O2-Gd0.2Ce0.8O2-Li2CO3-Na2CO3-K2CO3 Based 3D Printed Single-Layer Ceramic Fuel Cell.

Single-layer ceramic fuel cells consisting of Li0.15Ni0.45Zn0.4O2, Gd0.2Ce0.8O2 and a eutectic mixture of Li2CO3, Na2CO3 and K2CO3, were fabricated through extrusion-based 3D printing. The sintering temperature of the printed cells was varied from 700 °C to 1000 °C to identify the optimal thermal treatment to maximize the cell performance. It was found that the 3D printed single-layer cell sintered at 900 °C produced the highest power density (230 mW/cm2) at 550 °C, which is quite close to the performance (240 mW/cm2) of the single-layer cell fabricated through a conventional pressing method. The best printed cell still had high ohmic (0.46 Ω·cm2) and polarization losses (0.32 Ω·cm2) based on EIS measurements conducted in an open-circuit condition. The XRD spectra showed the characteristic peaks of the crystalline structures in the composite material. HR-TEM, SEM and EDS measurements revealed the morphological information of the composite materials and the distribution of the elements, respectively. The BET surface area of the single-layer cells was found to decrease from 2.93 m2/g to 0.18 m2/g as the sintering temperature increased from 700 °C to 1000 °C. The printed cell sintered at 900 °C had a BET surface area of 0.34 m2/g. The fabrication of single-layer ceramic cells through up-scalable 3D technology could facilitate the scaling up and commercialization of this promising fuel cell technology.

Application of a Triple-Conducting Heterostructure Electrolyte of Ba0.5Sr0.5Co0.1Fe0.7Zr0.1Y0.1O3-δ and Ca0.04Ce0.80Sm0.16O2-δ in a High-Performance Low-Temperature Solid Oxide Fuel Cell.

Dual-ion electrolytes with oxygen ion and proton-conducting properties are among the innovative solid oxide electrolytes, which exhibit a low Ohmic resistance at temperatures below 550 °C. BaCo0.4Fe0.4Zr0.1Y0.1O3-δ with a perovskite-phase cathode has demonstrated efficient triple-charge conduction (H+/O2-/e-) in a high-performance low-temperature solid oxide fuel cell (LT-SOFC). Here, we designed another type of triple-charge conducting perovskite oxide based on Ba0.5Sr0.5Co0.1Fe0.7Zr0.1Y0.1O3-δ (BSCFZY), which formed a heterostructure with ionic conductor Ca0.04Ce0.80Sm0.16O2-δ (SCDC), showing both a high ionic conductivity of 0.22 S cm-1 and an excellent power output of 900 mW cm-2 in a hybrid-ion LT-SOFC. In addition to demonstrating that a heterostructure BSCFZY-SCDC can be a good functional electrolyte, the existence of hybrid H+/O2- conducting species in BSCFZY-SCDC was confirmed. The heterointerface formation between BSCFZY and SCDC can be explained by energy band alignment, which was verified through UV-vis spectroscopy and UV photoelectron spectroscopy (UPS). The interface may help in providing a pathway to enhance the ionic conductivities and to avoid short-circuiting. Various characterization techniques are used to probe the electrochemical and physical properties of the material containing dual-ion characteristics. The results indicate that the triple-charge conducting electrolyte is a potential candidate to further reduce the operating temperature of SOFC while simultaneously maintaining high performance.

Deep decarbonization of urban energy systems through renewable energy and sector-coupling flexibility strategies.

This paper presents deep decarbonization strategies for city-level energy systems. Helsinki city is used as a case in the analysis. The strategies are mainly based on extensive electrification employing renewable electricity, storage, and sector-coupling strategies. We perform energy, economic, and resilience analyses for the different cases. An energy balance model with 1-h resolution is used to optimize the energy system on macro-scale, while a MILP-algorithm is used for micro-level optimization of operation of individual plants against different criteria. The results indicate that a zero-carbon energy system is feasible by 2050, but it would also require coupling to the exogenous energy system (national electricity market) to balance mismatches. Power-to-heat coupling, or storage alone would not be adequate. As an example of system dynamics limitations, with a wind power capacity of 1.5 GW corresponding to 56% of the annual electricity demand in Helsinki, 90% of the wind electricity can be used locally in the different sectors, but the rest needs coupling to the exogenous market due to mismatch and plant limitations. The decarbonization strategies with increasing variable renewable energy production generally improve the resilience of the energy system, but with some concerns to adequacy of peak production and electricity dependency of heating.

Adhesion of Single-Walled Carbon Nanotube Thin Films with Different Materials.

Single-walled carbon nanotubes (SWCNTs) possess extraordinary physical and chemical properties. Thin films of randomly oriented SWCNTs have great potential in many opto-electro-mechanical applications. However, good adhesion of SWCNT films with a substrate material is pivotal for their practical use. Here, for the first time, we systematically investigate the adhesion properties of SWCNT thin films with commonly used substrates such as glass (SiO2), indium tin oxide (ITO), crystalline silicon (C-Si), amorphous silicon (a-Si:H), zirconium oxide (ZrO2), platinum (Pt), polydimethylsiloxane (PDMS), and SWCNTs for self-adhesion using atomic force microscopy. By comparing the results obtained in air and inert Ar atmospheres, we observed that the surface state of the materials greatly contributes to their adhesion properties. We found that the SWCNT thin films have stronger adhesion in an inert atmosphere. The adhesion in the air can be greatly improved by a fluorination process. Experimental and theoretical analyses suggest that adhesion depends on the atmospheric conditions and surface functionalization.

Data for global power demand and solar PV output matching.

Increasing use of solar energy necessitates better data sets for analyzing matching of solar photovoltaic output and power demand. Data source information presented in this article is useful to analyze the self-consumption rates of photovoltaic systems on global scale. The data is provided in figure format. The time resolution is basically one hour, but 1-min data is also included. The geographical range of selected sites is lat. 26-60 deg. (Europe, Asia, Latin-America). The power demand data ranges from a single household to national scale. Both measured and simulated data are included. The data sets are linked to a recent article by Lund [1].

Impact of Film Thickness of Ultrathin Dip-Coated Compact TiO2 Layers on the Performance of Mesoscopic Perovskite Solar Cells.

Uniform and pinhole-free electron-selective TiO2 layers are of utmost importance for efficient perovskite solar cells. Here we used a scalable and low-cost dip-coating method to prepare uniform and ultrathin (5-50 nm) compact TiO2 films on fluorine-doped tin oxide (FTO) glass substrates. The thickness of the film was tuned by changing the TiCl4 precursor concentration. The formed TiO2 follows the texture of the underlying FTO substrates, but at higher TiCl4 concentrations, the surface roughness is substantially decreased. This change occurs at a film thickness close to 20-30 nm. A similar TiCl4 concentration is needed to produce crystalline TiO2 films. Furthermore, below this film thickness, the underlying FTO might be exposed resulting in pinholes in the compact TiO2 layer. When integrated into mesoscopic perovskite solar cells there appears to be a similar critical compact TiO2 layer thickness above which the devices perform more optimally. The power conversion efficiency was improved by more than 50% (from 5.5% to ∼8.6%) when inserting a compact TiO2 layer. Devices without or with very thin compact TiO2 layers display J-V curves with an "s-shaped" feature in the negative voltage range, which could be attributed to immobilized negative ions at the electron-extracting interface. A strong correlation between the magnitude of the s-shaped feature and the exposed FTO seen in the X-ray photoelectron spectroscopy measurements indicates that the s-shape is related to pinholes in the compact TiO2 layer when it is too thin.

Frugal energy innovations for developing countries - a framework.

Frugal innovations have recently emerged to feature low-cost technologies and business innovations to serve consumers in emerging markets and improve their quality of life. Although the concept of frugality is well known, the present literature on frugal energy innovations, or energy frugality, is scarce, which could lead to overlooking its true characteristics. Therefore, we propose a framework for defining energy frugality based on a detailed analysis of several low-cost sustainable energy technologies. The five-criteria assessment method developed will help to identify potential frugal energy innovations and will increase the adoption of these technologies through better matching to local needs. Fuel-efficient biomass cooking stoves, small-scale photovoltaic systems, and pico-grids are examples of such frugal energy technologies.

An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.