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1.
Free‐standing electrolyte membranes for low‐temperature micro‐solid oxide fuel cells (micro‐SOFCs) are prepared by aerosol‐assisted chemical vapor deposition (AA‐CVD), a cost‐effective, non‐vacuum thin‐film deposition technique. Thin, yttria‐stabilized zirconia (YSZ) membranes (50–400 nm) as well as bilayer membranes of YSZ and gadolinia‐doped ceria are prepared at temperatures of 600 °C and below. AA‐CVD, which is a gas‐phase deposition method, allows for the synthesis of precursor‐free crystalline layers, thereby limiting the development of tensile stress. High membrane survival rates of around 90% are thus obtained. The columnar structure of the electrolyte ensures high oxygen‐ion conductivity and results in negligible ohmic losses. Using sputtered platinum electrodes, the demonstration of a micro‐SOFC based on AA‐CVD electrolyte is achieved and first power density data of 166 mW cm‐2 at 410 °C is obtained.  相似文献   

2.
Membranes with precise control of selective layer are designed and prepared by adjusting diffusion of solvents. Combining experiments and theoretical calculations, the formation mechanism of ion conductive membranes prepared by a non‐solvent induced phase separation (NIPS) method is found to be related to internal diffusion flux of solvent to the non‐solvent bath and external diffusion flux of non‐solvent to the casting solution. By regulating the internal and external diffusion rates via a two‐step NIPS method, a series of polybenzimidazole (PBI) porous membranes with independently controlled thin selective skin layers and highly porous support layers are fabricated, which achieve a simultaneous improvement in ion selectivity and proton conductivity. A vanadium flow battery assembled with a PBI membrane demonstrates an energy efficiency of 80% at a current density of 220 mA cm?2, which is the highest value among the reported PBI membranes. This provides a simple and effective way to fabricate membranes with well‐defined morphologies.  相似文献   

3.
Strontium (Sr) diffusion in magnetron sputtered gadolinia‐doped ceria (CGO) thin films is investigated. For this purpose, a model system consisting of a screen printed (La,Sr)(Co,Fe)O3?δ (LSCF) layer, and thin films of CGO and yttria‐stabilized zirconia (YSZ) is prepared to simulate a solid oxide fuel cell. This setup allows observation of Sr diffusion by observing SrZrO3 formation using X‐ray diffraction while annealing. Subsequent electron microscopy confirms the results. This approach presents a simple method for assessing the quality of CGO barriers without the need for a complete fuel cell test setup. CGO films with thicknesses ranging from 250 nm to 1.2 μm are tested at temperatures from 850 °C to 1000 °C which yields an in‐depth understanding of Sr diffusion through CGO thin films that may be of high scientific and technical interest for implementation of novel fuel cell materials. Sr is found to diffuse along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier can be increased.  相似文献   

4.
An effective separation of CO2 from H2 can be achieved using currently known polyethylene oxide (PEO)‐based membranes at low temperatures but the CO2 permeability is inadequate for commerical operations. For commercial‐scale CO2/H2 separation, CO2 permeability of these membranes must be significantly enhanced without compromising CO2/H2 selectivity. We report here exceptional CO2/H2 separation properties of a nanohybrid membrane comprising polyethylene glycol methacrylate (PEGMA) grafts on an organic‐inorganic membrane (OIM) consisting of a low molecular weight polypropylene oxide (PPO)‐PEO‐PPO diamine and 3‐glycidyloxypropyltrimethoxysilane (GOTMS), an alkoxysilane. The CO2 gas permeability of this nanohybrid membrane can reach 1990 Barrer with a CO2/H2 selectivity of 11 at 35 °C for a mixed gas mixture comprising 50% CO2 ‐ 50% H2 at 3.5 atm. The transformation of the inorganic silica phase from a well‐dispersed network of finely defined nanoparticles to rough porous clusters appears to be responsible for this OIM membrane exceeding the performance of other state‐of‐the‐art PEO‐based membranes.  相似文献   

5.
The catalyst layer of the cathode is arguably the most critical component of low‐temperature fuel cells and carbon dioxide (CO2) electrolysis cells because their performance is typically limited by slow oxygen (O2) and CO2 reduction kinetics. While significant efforts have focused on developing cathode catalysts with improved activity and stability, fewer efforts have focused on engineering the catalyst layer structure to maximize catalyst utilization and overall electrode and system performance. Here, we study the performance of cathodes for O2 reduction and CO2 reduction as a function of three common catalyst layer preparation methods: hand‐painting, air‐brushing, and screen‐printing. We employed ex‐situ X‐ray micro‐computed tomography (MicroCT) to visualize the catalyst layer structure and established data processing procedures to quantify catalyst uniformity. By coupling structural analysis with in‐situ electrochemical characterization, we directly correlate variation in catalyst layer morphology to electrode performance. MicroCT and SEM analyses indicate that, as expected, more uniform catalyst distribution and less particle agglomeration, lead to better performance. Most importantly, the analyses reported here allow for the observed differences over a large geometric volume as a function of preparation methods to be quantified and explained for the first time. Depositing catalyst layers via a fully‐automated air‐brushing method led to a 56% improvement in fuel cell performance and a significant reduction in electrode‐to‐electrode variability. Furthermore, air‐brushing catalyst layers for CO2 reduction led to a 3‐fold increase in partial CO current density and enhanced product selectivity (94% CO) at similar cathode potential but a 10‐fold decrease in catalyst loading as compared to previous reports.  相似文献   

6.
A novel scheme to fabricate polybenzimidazole (PBI) hollow fiber membranes with a thin skin loaded with fully dispersed palladium nanoparticles is proposed for the first time. Palladium is added to the membrane during the spinning process in the form of ions that coordinate to the imidazole groups of the polymer. This is attractive for membrane production because agglomeration of nanoparticles is minimized and the high‐cost metal is incorporated in only the selective layer—where it is required. Pd‐containing membranes achieve three orders of magnitude higher H2 permeances and a twofold improvement in H2/CO2 selectivity compared to pure PBI hollow fiber membranes.  相似文献   

7.
An artificial photosynthesis system based on N‐doped ZnTe nanorods decorated with an N‐doped carbon electrocatalyst layer is fabricated via an all‐solution process for the selective conversion of CO2 to CO. Substitutional N‐doping into the ZnTe lattice decreases the bandgap slightly and improves the charge transfer characteristics, leading to enhanced photoelectrochemical activity. Remarkable N‐doping effects are also demonstrated by the N‐doped carbon layer that promotes selective CO2‐to‐CO conversion instead of undesired water‐to‐H2 reduction by providing active sites for CO2 adsorption and activation, even in the absence of metallic redox centers. The photocathode shows promising performance in photocurrent generation (?1.21 mA cm?2 at ?0.11 VRHE), CO selectivity (dominant CO production of ≈72%), minor H2 reduction (≈20%), and stability (corrosion suppression). The metal‐free electrocatalyst/photocatalyst combination prepared via a cost‐effective solution process exhibits high performance due to synergistic effects between them, and thus may find application in practical solar fuel production.  相似文献   

8.
Efficient CO2 utilization is key to limit global climate change. Carbon monoxide, which is a crucial feedstock for chemical synthesis, can be produced by splitting CO2. However, existing thermochemical routes are energy intensive requiring high operating temperatures. A hybrid redox process (HRP) involving CO2‐to‐CO conversion using a lattice oxygen‐deprived redox catalyst at relatively low temperatures (<700 °C) is reported. The lattice oxygen of the redox catalyst, restored during CO2‐splitting, is subsequently used to convert methane to syngas. Operated at temperatures significantly lower than a number of industrial waste heat sources, this cyclic redox process allows for efficient waste heat‐utilization to convert CO2. To enable the low temperature operation, lanthanum modified ceria (1:1 Ce:La) promoted by rhodium (0.5 wt%) is reported as an effective redox catalyst. Near‐complete CO2 conversion with a syngas yield of up to 83% at low temperatures is achieved using Rh‐promoted LaCeO4?x. While La improves low‐temperature bulk redox properties of ceria, Rh considerably enhances the surface catalytic properties for methane activation. Density functional theory calculations further illustrate the underlying functions of La‐substitution. The highly effective redox catalyst and HRP scheme provide a potentially attractive route for chemical production using CO2, industrial waste heat, and methane, with appreciably lowered CO2 emissions.  相似文献   

9.
Polymers of intrinsic microporosity (PIM‐1) have been known for their super high permeability but average selectivity for medium‐size gas pairs. They have unimpressive selectivity for H2 and CO2 separation (i.e., α (H2/CO2) = 0.6). For the first time, we have discovered that ultraviolet (UV)‐rearranged polymers of PIM‐1 membranes can be used for H2/CO2 separation with far superior separation performance to others in literatures. The PIM‐1 membrane after UV radiation for 4 hours shows H2 permeability of 452 barrer with H2/CO2 selectivity of 7.3. Experimental data and molecular simulation reveal that the polymer chains of PIM‐1 undergo 1,2‐migration reaction and transform to close‐to‐planar like rearranged structure after UV radiation. As a result, the UV‐irradiated PIM‐1 membrane shows considerable drops in both fractional free volume (FFV) and size of micro‐pores. Positron annihilation lifetime (PAL) results have confirmed the chemical and structural changes, suggesting the FFV and pore size drops are mainly ascribed to the destructed spiro‐carbon centre during UV radiation. Sorption and x‐ray diffractor (XRD) analyses indicate that the impressive H2/CO2 selectivity arises from the significantly enhanced diffusivity selectivity induced by UV radiation, followed by molecular rearrangement, conformation change and chain packing.  相似文献   

10.
High‐performance zeolitic imidazolate frameworks (ZIFs)/polybenzimidazole (PBI) nanocomposites are molecularly designed for hydrogen separation at high temperatures, and demonstrate it in a useful configuration as dual‐layer hollow fibers for the first time. By incorporating as‐synthesized nanoporous ZIF‐8 nanoparticles into the high thermal stability but extremely low permeability polybenzimidazole (PBI), the resultant mixed matrix membranes show an impressive enhancement in H2 permeability as high as a hundred times without any significant deduction in H2/CO2 selectivity. The 30/70 ZIF‐8/PBI dense membrane has a H2 permeability of 105.4 Barrer and a H2/CO2 selectivity of 12.3. This performance is far superior to ZIF‐7/PBI membranes and is the best ever reported data for H2‐selective polymeric materials in the literature. Meanwhile, defect‐free ZIF‐8‐PBI/Matrimid dual‐layer hollow fibers are successfully fabricated, without post‐annealing and coating, by optimizing ZIF‐8 nanoparticle loadings, spinning conditions, and solvent‐exchange procedures. Two types of hollow fibers targeted at either high H2/CO2 selectivity or high H2 permeance are developed: i) PZM10‐I B fibers with a medium H2 permeance of 64.5 GPU (2.16 ×10?8 mol m?2 s?1 Pa?1) at 180°C and a high H2/CO2 selectivity of 12.3, and, ii) PZM33‐I B fibers with a high H2 permeance of 202 GPU (6.77 ×10?8 mol m?2 s?1 Pa?1) at 180°C and a medium H2/CO2 selectivity of 7.7. This work not only molecularly designs novel nanocomposite materials for harsh industrial applications, such as syngas and hydrogen production, but also, for the first time, synergistically combines the strengths of both ZIF‐8 and PBI for energy‐related applications.  相似文献   

11.
It is shown that an electrochemically‐driven oxide overcoating substantially improves the performance of metal electrodes in high‐temperature electrochemical applications. As a case study, Pt thin films are overcoated with (Pr,Ce)O2?δ (PCO) by means of a cathodic electrochemical deposition process that produces nanostructured oxide layers with a high specific surface area and uniform metal coverage and then the coated films are examined as an O2‐electrode for thin‐film‐based solid oxide fuel cells. The combination of excellent conductivity, reactivity, and durability of PCO dramatically improves the oxygen reduction reaction rate while maintaining the nanoscale architecture of PCO layers and thus the performance of the PCO‐coated Pt thin‐film electrodes at high temperatures. As a result, with an oxide coating step lasting only 5 min, the electrode resistance is successfully reduced by more than 1000 times at 500 °C in air. These observations provide a new direction for the design of high‐performance electrodes for high‐temperature electrochemical cells.  相似文献   

12.
The environmental benefits of fuel cells and electrolyzers have become increasingly recognized in recent years. Fuel cells and electrolyzers that can operate at intermediate temperatures (300–450 °C) require, in principle, neither the precious metal catalysts that are typically used in polymer‐electrolyte‐membrane systems nor the costly heat‐resistant alloys used in balance‐of‐plant components of high‐temperature solid oxide electrochemical cells. These devices require an electrolyte with high ionic conductivity, typically more than 0.01 S cm?1, and high chemical stability. To date, however, high ionic conductivities have been found in chemically unstable materials such as CsH2PO4, In‐doped SnP2O7, BaH2, and LaH3?2xOx. Here, fast and stable proton conduction in 60‐at% Sc‐doped barium zirconate polycrystal, with a total conductivity of 0.01 S cm?1 at 396 °C for 200 h is demonstrated. Heavy doping of Sc in barium zirconate simultaneously enhances the proton concentration, bulk proton diffusivity, specific grain boundary conductivity, and grain growth. An accelerated stability test under a highly concentrated and humidified CO2 stream using in situ X‐ray diffraction shows that the perovskite phase is stable over 240 h at 400 °C under 0.98 atm of CO2. These results show great promises as an electrolyte in solid‐state electrochemical devices operated at intermediate temperatures.  相似文献   

13.
Rational design and massive production of bifunctional catalysts with superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are essential for developing metal–air batteries and fuel cells. Herein, controllable large‐scale synthesis of sulfur‐doped CaMnO3 nanotubes is demonstrated via an electrospinning technique followed by calcination and sulfurization treatment. The sulfur doping can not only replace oxygen atoms to increase intrinsic electrical conductivity but also introduce abundant oxygen vacancies to provide enough catalytically active sites, which is further demonstrated by density functional theory calculation. The resulting sulfur‐modified CaMnO3 (CMO/S) exhibits better electrocatalytic activity for ORR and OER in alkaline solution with higher stability performance than the pristine CMO. These results highlight the importance of sulfur treatment as a facile yet effective strategy to improve the ORR and OER catalytic activity of the pristine CaMnO3. As a proof‐of‐concept, a rechargeable Zn–air battery using the bifunctional catalyst exhibits a small charge–discharge voltage polarization, and long cycling life. Furthermore, a solid‐state flexible and rechargeable Zn–air battery gives superior discharge–charge performance and remarkable stability. Therefore, the CMO/S nanotubes might be a promising replacement to the Pt‐based electrocatalysts for metal–air batteries and fuel cells.  相似文献   

14.
Thawing permafrost and the resulting mineralization of previously frozen organic carbon (C) is considered an important future feedback from terrestrial ecosystems to the atmosphere. Here, we use a dynamic process oriented permafrost model, the CoupModel, to link surface and subsurface temperatures from a moist permafrost soil in High‐Arctic Greenland with observed heat production and carbon dioxide (CO2) release rates from decomposition of previously frozen organic matter. Observations show that the maximum thickness of the active layer at the end of the summer has increased 1 cm yr?1 since 1996. The model is successfully adjusted and applied for the study area and shown to be able to simulate active layer dynamics. Subsequently, the model is used to predict the active layer thickness under future warming scenarios. The model predicts an increase of maximum active layer thickness from today 70 to 80–105 cm as a result of a 2–6 °C warming. An additional increase in the maximum active layer thickness of a few centimetres may be expected due to heat production from decomposition of organic matter. Simulated future soil temperatures and water contents are subsequently used with measured basal soil respiration rates in a respiration model to predict the corresponding depth‐integrated CO2 production from permafrost layers between 0.7 and 2 m below the surface. Results show an increase from present values of <40 g C m?2 yr?1 to between 120 and 213 g C m?2 yr?1 depending on the magnitude of predicted warming. These rates are more than 50% of the present soil CO2 efflux measured at the soil surface. Future modelling accounting for snow, vegetation and internal biological heat feedbacks are of interest in order to test the robustness of the above predictions and to describe the entire ecosystem response.  相似文献   

15.
Electrochemical reduction of CO2 provides an opportunity to reach a carbon‐neutral energy recycling regime, in which CO2 emissions from fuel use are collected and converted back to fuels. The reduction of CO2 to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for CO2 conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO2 reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The CO2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N4) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.  相似文献   

16.
The increasing demand for portable and wearable electronics requires lightweight, thin, and highly flexible power sources, for example, flexible zinc‐air batteries (ZABs). The so‐far reported flexible ZAB devices mostly remain bulky, with a design consisting of two relatively thick substrates (e.g., carbon cloths and/or metal foams) and a gel electrolyte‐coated separator in between. Herein, an ultrathin (≈0.2 mm) solid‐state ZAB with high flexibility and performance is introduced by directly forming self‐standing active layers on each surface of an alkaline polymer membrane through an ink‐casting/hot‐pressing approach. A Fe/N‐doped 3D carbon with hierarchic pores and an interconnected network structure is used as cathode electrocatalyst, so that the backing gas‐diffusion layer (e.g., carbon cloth) can be abandoned. What is further, a microstructure‐modulating method to significantly increase the FeN4 active sites for oxygen reduction reaction is developed, thus significantly boosting the performance of the ZAB. The assembled solid‐state ZAB manifests remarkable peak power density of 250 mW cm?3 and high capacity of 150.4 mAh cm?3 at 8.3 mA cm?3, as well as excellent flexibility. The new design should provide valuable opportunity to the portable and wearable electronics.  相似文献   

17.
In addition to a good perovskite light absorbing layer, the hole and electron transport layers play a crucial role in achieving high‐efficiency perovskite solar cells. Here, a simple, one‐step, solution‐based method is introduced for fabricating high quality indium‐doped titanium oxide electron transport layers. It is shown that indium‐doping improves both the conductivity of the transport layer and the band alignment at the ETL/perovskite interface compared to pure TiO2, boosting the fill‐factor and voltage of perovskite cells. Using the optimized transport layers, a high steady‐state efficiency of 17.9% for CH3NH3PbI3‐based cells and 19.3% for Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3‐based cells is demonstrated, corresponding to absolute efficiency gains of 4.4% and 1.2% respectively compared to TiO2‐based control cells. In addition, a steady‐state efficiency of 16.6% for a semi‐transparent cell is reported and it is used to achieve a four‐terminal perovskite‐silicon tandem cell with a steady‐state efficiency of 24.5%.  相似文献   

18.
Efficient vacuum‐deposited tandem organic photovoltaic cells (TOPVs) composed of pristine fullerenes as the acceptors and two complementary absorbing donors, 2‐((2‐(5‐(4‐(diphenylamino)phenyl)thieno[3,2‐b]thiophen‐2‐yl)thiazol‐5‐yl)methylene)malononitrile for the visible absorption and 2‐((7‐(5‐(dip‐tolylamino)thiophen‐2‐yl)benzo[c]‐[1,2,5]thiadiazol‐4‐yl)methylene)malononitrile for the near‐infrared absorption, are reported. Two subcells are connected by the interconnection unit (ICU) composed of electron‐transporting layer/metal/p‐doped hole‐transporting layer. The p‐doped layer in the ICU enables increasing the short‐circuit current density (J SC) of TOPVs by tuning the relative position of subcells in the tandem devices to have the maximum optical field distribution response, which is well matched with theoretical calculation. Moreover, the introduction of the doped layer benefits to the higher fill factor (FF) of the consisting subcells without losing open‐circuit voltage (V OC) even with the thick active layers. As a result, power conversion efficiency of 9.2% is achieved with higher FF of 0.62 than that of single‐junction subcells (0.54, 0.57), J SC of 8.7 mA cm?2, and V OC of 1.71 V using 80 nm thick active layers in both subcells.  相似文献   

19.
Currently, it is unknown what role tropical forest soils will play in the future global carbon cycle under higher temperatures. Many tropical forests grow on deeply weathered soils and although it is generally accepted that soil carbon decomposition increases with higher temperatures, it is not known whether subsurface carbon pools are particularly responsive to increasing soil temperatures. Carbon dioxide (CO2) diffusing out of soils is an important flux in the global carbon. Although soil CO2 efflux has been the subject of many studies in recent years, it remains difficult to deduct controls of this flux because of the different sources that produce CO2 and because potential environmental controls like soil temperature and soil moisture often covary. Here, we report results of a 5‐year study in which we measured soil CO2 production on two deeply weathered soil types at different depths in an old‐growth tropical wet forest in Costa Rica. Three sites were developed on old river terraces (old alluvium) and the other three were developed on old lava flows (residual). Annual soil CO2 efflux varied between 2.8–3.6 μmol CO2‐C m?2 s?1 (old alluvium) and 3.4–3.9 μmol CO2‐C m?2 s?1 (residual). More than 75% of the CO2 was produced in the upper 0.5 m (including litter layer) and less than 7% originated from the soil below 1 m depth. This low contribution was explained by the lack of water stress in this tropical wet forest which has resulted in very low root biomass below 2 m depth. In the top 0.5 m CO2 production was positively correlated with both temperature and soil moisture; between 0.6 and 2 m depth CO2 production correlated negatively with soil moisture in one soil and positively with photosynthetically active radiation in the other soil type. Below 2 m soil CO2 production strongly increased with increasing temperature. In combination with reduced tree growth that has been shown for this ecosystem, this would be a strong positive feedback to ecosystem warming.  相似文献   

20.
Efficient and selective earth‐abundant catalysts are highly desirable to drive the electrochemical conversion of CO2 into value‐added chemicals. In this work, a low‐cost Sn modified N‐doped carbon nanofiber hybrid catalyst is developed for switchable CO2 electroreduction in aqueous medium via a straightforward electrospinning technique coupled with a pyrolysis process. The electrocatalytic performance can be tuned by the structure of Sn species on the N‐doped carbon nanofibers. Sn nanoparticles drive efficient formate formation with a high current density of 11 mA cm?2 and a faradaic efficiency of 62% at a moderate overpotential of 690 mV. Atomically dispersed Sn species promote conversion of CO2 to CO with a high faradaic efficiency of 91% at a low overpotential of 490 mV. The interaction between Sn species and pyridinic‐N may play an important role in tuning the catalytic activity and selectivity of these two materials.  相似文献   

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