RESUMEN
Designing a high-performance cathode is essential for the development of proton-conducting solid oxide fuel cells (H-SOFCs), and nanocomposite cathodes have proven to be an effective means of achieving this. However, the mechanism behind the nanocomposite cathodes' remarkable performance remains unknown. Doping the Co element into BaZrO3 can result in the development of BaCoO3 and BaZr0.7Co0.3O3 nanocomposites when the doping concentration exceeds 30%, according to the present study. The construction of the BaCoO3/BaZr0.7Co0.3O3 interface is essential for the enhancement of the cathode catalytic activity, as demonstrated by thin-film studies using pulsed laser deposition to simulate the interface of the BCO and BZCO individual particles and first-principles calculations to predict the oxygen reduction reaction steps. Eventually, the H-SOFC with a BaZr0.4Co0.6O3 cathode produces a record-breaking power density of 2253 mW cm-2 at 700°C.
RESUMEN
Biological proton channels have perfect selectivity in aqueous environment against almost all ions and molecules, a property that differs itself from other biological channels and a feature that remains challenging to realize for bulk artificial materials. The biological perfect selectivity originates from the fact that the channel has almost no free space for ion or water transport but generates a hydrogen bonded wire in the presence of protons to allow the proton hopping. Inspired by this, we used the interlayer spacings of covalent organic framework materials consisting of hydrophilic functional groups as perfectly selective artificial proton channels. The interlayer spacings are so narrow that no atoms or molecules can diffuse through. However, protons exhibit a diffusivity in the same order of magnitude as that in bulk water. Density functional theory calculations show that water molecules and the COF material form hydrogen bonded wires, allowing the proton hopping. We further demonstrate that the proton transport rate can be tuned by adjusting the acidity of the functional groups.
RESUMEN
The pursuit of high-performance and long-lasting protonic ceramic electrochemical cells (PCECs) is impeded by the lack of efficient and enduring proton conductors. Conventional research approaches, predominantly based on a trial-and-error methodology, have proven to be demanding of resources and time-consuming. Here, this work reports the findings in harnessing high-throughput computational methods to expedite the discovery of optimal electrolytes for PCECs. This work methodically computes the oxygen vacancy formation energy (EV), hydration energy (EH), and the adsorption energies of H2O and CO2 for a set of 932 oxide candidates. Notably, these findings highlight BaSnxCe0.8-xYb0.2O3-δ (BSCYb) as a prospective game-changing contender, displaying superior proton conductivity and chemical resilience when compared to the well-regarded BaZrxCe0.8-xY0.1Yb0.1O3-δ (BZCYYb) series. Experimental validations substantiate the computational predictions; PCECs incorporating BSCYb as the electrolyte achieved extraordinary peak power densities in the fuel cell mode (0.52 and 1.57 W cm-2 at 450 and 600 °C, respectively), a current density of 2.62 A cm-2 at 1.3 V and 600 °C in the electrolysis mode while demonstrating exceptional durability for over 1000-h when exposed to 50% H2O. This research underscores the transformative potential of high-throughput computational techniques in advancing the field of proton-conducting oxides for sustainable power generation and hydrogen production.
RESUMEN
In this study, BaZr0.87Y0.1M0.03O3-δ perovskite electrolytes with sintering aids (M = Mn, Co, and Fe) were synthesized by a sustainable approach using spinach powder as a chelating agent and then compared with chemically synthesized BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) electrolytes for intermediate temperature SOFCs. This is the first example of such a sustainable synthesis of perovskite materials with sintering aids. Structural analysis revealed the presence of a cubic perovskite structure in BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) samples synthesized by both green and conventional chemical methods. No significant secondary phases were observed in the samples synthesized by a sustainable approach. The observed phenomena of plane shift were because of the disparities between ionic radii of the dopants, impurities, and host materials. The surface morphology analysis revealed a denser microstructure for the electrolytes synthesized via green routes due to metallic impurities in the organic chelating agent. The absence of significant impurities was also observed by compositional analysis, while functional groups were identified through Fourier-transform infrared spectroscopy. Conductivity measurements showed that BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) electrolytes synthesized by oxalic acid have higher conductivities compared to BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) electrolytes synthesized by the green approach. The button cells employing BaZr0.87Y0.1Co0.03O3-δ electrolytes synthesized by the chemical and green routes achieved peak power densities 344 and 271 mW·cm-2 respectively, suggesting that the novel green route can be applied to synthesize SOFC perovskite materials with minimal environmental impact and without significantly compromising cell performance.
RESUMEN
To reduce the risk of carbon monoxide (CO) poisoning, there is a strong need for small, compact gas sensors to detect and monitor CO at ppm concentrations. In this study, we focused on detecting CO with electrochemical sensors based on proton-conducting graphene oxide (GO) nanosheets at room temperature. We found that a Ce-doped GO nanosheet membrane fitted with the sensing electrode composed of Pt (10 wt %)-doped SnO2 nanocrystals exhibits an excellent sensor response to CO at 25 °C. Pt doping of SnO2 nanocrystals has made it possible to detect CO more selectively than H2 and ethanol. The CO detection mechanism is analyzed by operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Fourier transform infrared gas cell measurements, and comprehensive density functional theory-based calculations. The results revealed that adsorption of CO occurs predominantly on Pt sites, and the adsorbed CO is anodically oxidized at the interface between the sensing electrode and proton-conducting membrane, generating the selective sensor response. The strong adsorption of CO was realized with Pt (10 wt %)-doped SnO2 nanocrystals, as revealed by the DRIFTS analysis and temperature-programed desorption technique.
RESUMEN
Proton-conducting solid oxide fuel cells (H-SOFCs) have the potential to be a promising technology for energy conversion and storage. To achieve high chemical compatibility and catalytic activity, nickel-doped barium ferrate with triple conducting ability is developed as cathodes for H-SOFCs, presenting an impressive electrochemical performance at intermediate temperatures. The cell performance with the optimized BaCe0.26 Ni0.1 Fe0.64 O3 -δ (BCNF10) composite cathode reaches an outstanding performance of 1.04 W cm-2 at 600 °C. The high electrocatalytic capacity of the nickel-doped barium ferrate cathode can be attributed to its significant proton conductivity which is confirmed through hydrogen permeation experiments. Density functional theory (DFT) calculations are further conducted to reveal that the presence of nickel can enhance processes of hydration formation and proton migration, leading to improve proton conductivity and electro-catalytic activity.
RESUMEN
The use of ordered catalyst layers, based on micro-/nanostructured arrays such as the ordered Nafion array, has demonstrated great potential in reducing catalyst loading and improving fuel cell performance. However, the size (diameter) of the basic unit of the most existing ordered Nafion arrays, such as Nafion pillar or cone, is typically limited to micron or submicron sizes. Such small sizes only provide a limited number of proton transfer channels and a small specific area for catalyst loading. In this work, the ordered Nafion array with a pillar diameter of only 40 nm (D40) was successfully prepared through optimization of the Nafion solvent, thermal annealing temperature, and stripping mode from the anode alumina oxide (AAO) template. The density of D40 is 2.7 × 1010 pillars/cm2, providing an abundance of proton transfer channels. Additionally, D40 has a specific area of up to 51.5 cm2/cm2, which offers a large area for catalyst loading. This, in turn, results in the interface between the catalyst layer and gas diffusion layer becoming closer. Consequently, the peak power densities of the fuel cells are 1.47 (array as anode) and 1.29 W/cm2 (array as cathode), which are 3.3 and 2.9 times of that without array, respectively. The catalyst loading is significantly reduced to 17.6 (array as anode) and 61.0 µg/cm2 (array as cathode). Thus, the nanosized Nafion array has been proven to have high fuel cell performance with low Pt catalyst loading. Moreover, this study also provides guidance for the design of a catalyst layer for water electrolysis and electrosynthesis.
RESUMEN
Proton conducting acceptor-doped SrZrO3 has a history as long as that of BaZrO3 , but has attracted less interest. Inspired by its higher transport number of ionic conduction in wet oxygen revealed by our recent work, we here explore further aspects of doped SrZrO3 as electrolyte in proton ceramic electrochemical cells. In-situ high temperature XRD (HT-XRD) analysis of SrZr0.9 Y0.1 O3-δ (SZY10) indicated an anisotropic chemical expansion of hydration, stronger along the b than the a direction, and negative in the c direction. A systematic electromotive force (EMF) and impedance spectroscopy study as a function of p O 2 ${p_{{\rm{O}}_{\rm{2}} } }$ and p H 2 O ${p_{{\rm{H}}_{\rm{2}} {\rm{O}}} }$ allowed determination of partial conductivities of electron holes and ions (mainly protons) in bulk (grain interior) and grain boundaries. Enthalpies and preexponentials were determined and interpreted for bulk and grain boundary partial conductivities based on defect chemistry and a brick layer model. The hole conductivity in bulk is modest and ensures high ionic transport numbers in oxidizing atmospheres, while grain boundaries exhibit lower ionic transport numbers from a relatively higher hole conductivity attributed primarily to tunnelling past the deepest part of the space charge region. Y-doped SrZrO3 (SZY) materials exhibit lower proton conductivities but excel over Y-doped BaZrO3 (BZY) in terms of thermal expansion compatibility with electrode materials and higher ionic transport numbers in oxidizing atmospheres and may hence be candidates for functional layers between BZY-based electrolytes and positrodes in proton ceramic electrochemical cells.
RESUMEN
We have developed 12-membered silica-tetrahedra-ringed Na5YSi4O12-type sodium ion conducting glass-ceramics on the basis of the composition Na3+3x-yR1-xPySi3-yO9 (R: rare earth elements; denoted as Narpsio); especially, the material of Na4Y0.6P0.2Si2.8O9 with the combined parameters of (x, y) = (0.4, 0.2) gives rise to the maximum conductivity of 1 × 10-1 Scm-1 at 300 °C. Because glass-ceramics generally have the advantage of structural rigidity and chemical durability over sintered polycrystalline ceramics, the present study employed glass-ceramic Narpsio to perform chemically driven ion exchange of Na+ with protonated water molecules with an aim to produce a proton conductor. The ion exchange was carried out in a hydrochloric acid solution by changing immersion time, temperature, and acid concentration. The ion exchanged Na4Y0.6P0.2Si2.8O9-based glass-ceramics were analyzed by the complex impedance method, and the proton conductivity was found to exhibit 3 × 10-4 Scm-1 at 300 °C with the activation energy of 59 kJ/mol. The dependence of humidity-sensitive conductivity of the ion exchanged bulk glass-ceramics was also examined; the conductivity increased almost linearly from 0.6 × 10-4 Scm-1 in dry air to 1.5 × 10-4 Scm-1 in 75% humid ambience at 300 °C. Thus, the ion exchanged glass-ceramics can be considered to be high temperature proton conductors as well as humidity sensors.
RESUMEN
In this work, a class of ionic conductor (La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ (M=Ca, Sr, and Ba) with a cubic pyrochlore structure was reported. Two strategies were adopted to increase the concentration of oxygen vacancies favoring the hydration reaction to introduce protons. One was increasing the cation ratio between Yb and Nb over unity, the other was doping divalent alkaline earth elements to replace trivalent La. Proton conduction was evidenced by confirming the proton incorporation and H/D isotope effect in electrical conductivity. Doping Ca, Sr, and Ba further promoted the proton conduction. The results of crystal structure refinement indicated that the extrinsically introduced oxygen vacancies by the two strategies were accommodated in the tetrahedra (48 f) containing two La and two Yb/Nb cations, while the tetrahedra containing four La cations (8a) were fully occupied by oxide ions. A discussion was thereby performed, leading to the suggestion that not all the tetrahedra in the cubic pyrochlore structure of (La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ helped in incorporating and conducting protons, and only the oxygen vacancies surrounded by four Y cations (48 f site) or two La and two Y cations (8b site) were hydratable. It is thereby suggested that to enhance the proton conduction in pyrochlore oxides, an effective strategy might be tuning the ability of hydration or protonation of the tetrahedra to increase the proton concentration and expand the route for proton conduction.
RESUMEN
Catalytic dehydrogenation coupling of methane (DCM) represents an effective way to convert natural gas to more useful C2 products (C2H6, C2H4). In this work, BaCe0.85Tb0.05Co0.1O3-δ (BCTCo) perovskite hollow fiber membranes were fabricated by the combined phase inversion and sintering method. SrCe0.95Yb0.05O3-δ (SCYb) perovskite oxide was loaded as a catalyst onto the inner hollow fiber membrane surface, which promoted the CH4 conversion and the C2 hydrocarbon selectivity during the DCM reaction. The introduction of steam into the methane feed gas mixture elevated the C2 selectivity and yield due to the alleviation of coke deposition. Switching N2 to air as the sweep gas further increased the C2 selectivity and yield. However, the conversion of methane was limited by both the low permeability of the membrane and the insufficient catalytic activity of the catalyst, leading to low C2 yield.
RESUMEN
Y-doped BaZrO3 , BaCeO3 and BaZr1-x Cex O3 show high proton conductivity at intermediate temperature and are promising electrolyte candidates in electrochemical devices. However, in most cases, the present cell fabrication process seems to be unavailable to avoid the addition of NiO, which is either added to improve the sinterability of these electrolyte or diffuses from the electrode substrate during co-sintering. In this work, a systematic investigation was performed to study the effect of NiO on BaZr0.8-x Cex Y0.2 O3-δ (BZCY20) covering the full Ce range from 0 to 0.8. The results revealed that regardless of the composition of BZCY20, both the dehydration temperature and proton concentration decreased by adding NiO, which further greatly decreased the ionic conductivity and the transport number. And it is found that the redox cycles in Ce-rich samples containing Ni makes the grain boundary conductivity worse and the electrolyte brittle. The conclusion is that NiO is detrimental to the performance of the electrochemical cells using these materials as the electrolyte, although compromise might be achieved in certain degree by tuning the Ce content. However, it should be noted that to further improve the cell performance, a new sintering additive or new processing for cell fabrication is essential.
RESUMEN
Polyvinyl alcohol (PVA) based proton-conducting solid polymer electrolyte was prepared with a high salt concentration of ammonium nitrate (NH4NO3) by the technique of solvent casting. From the X-ray diffraction studies, the semicrystalline nature of PVA with the inclusion of NH4NO3 was studied. XRD analysis indicates that the highest ion conductive sample exhibits the minimum crystalline nature. The decreasing trend of Jonscher-exponent with temperature rise reveals that the present system is insured by the correlated barrier hopping (CBH) model. The maximum room temperature conductivity was found to be 5.17 × 10-5 S/cm for PVA loaded 30 wt.% of NH4NO3. The ionic transport of the proton-conducting solid polymer electrolyte was studied at the temperature range of 303-353 K. The conductivity-temperature relationship of the systems was analyzed using both the Arrhenius and Vogel-Tammann-Fulcher (VTF) models to explain the ionic hopping mechanism for the system.
RESUMEN
Iontronics are effective in modulating electrical properties through the electric double layers (EDLs) assisted with ionic migration/arrangement, which are highly promising for unconventional electronics, ionic sensory devices, and flexible interactive interface. Proton conductors with the smallest and most abundant protons (H+) can realize a faster migration/polarization under electric field to form the EDL with higher capacitance. Here, a versatile triboiontronic MoS2 transistor via proton conductor by sophisticated combination of triboelectric modulation and protons migration has been demonstrated. This device utilizes triboelectric potential originated from mechanical displacement to modulate the electrical properties of transistors via protons migration/accumulation. It shows superior electrical properties, including high current on/off ratio over 106, low cutoff current (â¼0.04 pA), and steep switching properties (89 µm/dec). Pioneering noise tests are conducted to the tribotronic devices to exclude the possible noise interference introduced by mechanical displacement. The versatile triboiontronic MoS2 transistor via proton conductor has been utilized for mechanical behavior derived logic devices and an artificial sensory neuron system. This work represents the reliable and effective triboelectric potential modulation on electronic transportation through protonic dielectrics, which is highly desired for theoretical study of tribotronic gating, active mechanosensation, self-powered electronic skin, artificial intelligence, etc.
RESUMEN
Developing novel proton conductors is crucial to the electrochemical technology for energy conversion and storage. Metal-organic frameworks (MOFs), with a highly ordered and controllable structure, have been widely explored to prepare high-performance proton conductors. Albeit the prominent merits and great potential of the MOF-based materials such as MOF pellets or composite polymer electrolytes, constructing well-defined proton-transfer channels with much lower grain boundary resistance and more homogeneous distribution deserves extensive explorations. Herein, a kind of nanostructured metal-organic gel (MOG) with a three-dimensional (3D) interconnected proton-conductive network is prepared by a facile sol-gel method using Cr3+ and sulfonated terephthalic as the metal source and organic ligand, respectively. During the gelation process, the primary metal-organic nanoparticles are cross-linked through mismatched growth and aggregate into the 3D well-percolated gel network. The resultant MOG features in the tunable hierarchical structure and long-range continuous proton-transfer channels, leading to remarkably reduced energy barrier for proton conduction. Attributed to the sulfonated ligand and well-interconnected proton-conductive pathways, MOG exhibits intrinsic proton conductivity that is about one order of magnitude higher than that of MIL-101-SO3H pellet (MIL, Matérial Institut Lavoisier). The method in this study can be extended to construct long-range continuous ionic channels for a number of solid electrolytes.
RESUMEN
BaZr0.9Y0.1O3-δ (BZY10), a promising proton conducting material, exhibits p-type conduction under oxidative conditions. Holes in BZY10 are of the small polaron type. However, there is no clear understanding at which places in the lattice they are localized. The main objectives of this work were, therefore, to discuss the nature of electronic defects in BZY10 on the basis of the combined measurements of the thermo-EMF and conductivity. Total electrical conductivity and Seebeck coefficient of BZY10 were simultaneously studied depending on partial pressures of oxygen (pO2), water (pH2O) and temperature (T). The model equation for total conductivity and Seebeck coefficient derived on the basis of the proposed defect chemical approach was successfully fitted to the experimental data. Transference numbers of all the charge carriers in BZY10 were calculated. The heat of transport of oxide ions was found to be about one half the activation energy of their mobility, while that of protons was almost equal to the activation energy of their mobility. The results of the Seebeck coefficient modeling indicate that cation impurities, rather than oxygen sites, should be considered as a place of hole localization.
RESUMEN
BaZr0.8Y0.2O3-δ (BZY20) is promising to be applied as an electrolyte in fuel cells, electrolysis cells, etc. However, when a half cell composed of a BZY20 electrolyte layer and a BZY20-NiO composite anode substrate is co-sintered (1400-1600 °C), Ni diffuses from the anode substrate into the electrolyte layer. Y content in the electrolyte layer decreases dramatically, since BZY20 cannot be equilibrated with NiO at such high temperature. Such Ni diffusion and Y loss are detrimental to the electrochemical performance of the electrolyte layer. In this work, we added MgO-NiO solid solution into the anode substrate to adjust the NiO activity (aNiO) during the co-sintering process, and used three different co-sintering methods to control the BaO activity (aBaO). The results revealed that by decreasing aNiO in the system, the as-co-sintered electrolyte layer had the composition shifting towards the direction of high Y and low Ni cation ratios. A clear correlation between the intra-grain concentration of Ni and Y was confirmed. In other words, to prepare the electrolyte with the same Y cation ratio, the Ni diffusion into the electrolyte layer can be suppressed by using the MgO-NiO solid solution with a high MgO ratio and a low Ni ratio. Moreover, by increasing aBaO, we found that the Y cation ratio increased and approached the nominal value of the pristine BZY20, when Mg1-xNixO (x = 0.3 and 0.5) was used. In summary, both aNiO and aBaO play important roles in governing the composition of the electrolyte layer prepared by the co-sintering process. To evaluate the quality of the electrolyte layer, both the intra-grain Y and Ni concentrations should be carefully checked.
RESUMEN
CsH2PO4 is a proton conductor pertaining to the acid salts group and shows a phase transition from monoclinic to cubic phase at 232 ± 2 °C under high-steam atmospheres (>30%). This cubic phase gives rise to the so-called superprotonic conductivity. In this work, the influence of the partial substitution of Cs by Ba and Rb, as well as the partial substitution of P by W, Mo, and S in CsH2PO4 on the phase transition temperature and electrochemical properties is studied. Among the tested materials, the partial substitution by Rb led to the highest conductivity at high temperature. Furthermore, Ba and S-substituted salts exhibited the highest conductivity at low temperatures. CsH2PO4 was used as electrolyte in a fully-assembled fuel cell demonstrating the applicability of the material at high pressures and the possibility to use other materials (Cu and ZnO) instead of Pt as electrode electrocatalyst. Finally, an electrolyzer cell composed of CsH2PO4 as electrolyte, Cu and ZnO as cathode and Pt and Ag as anode was evaluated, obtaining a stable production of H2 at 250 °C.
RESUMEN
Metal-organic frameworks (MOFs), as newly emerging materials, show compelling intrinsic structural features, e.g., the highly crystalline nature and designable and tunable porosity, as well as tailorable functionality, rendering them suitable for proton-conducting materials. The proton conduction of MOF is significantly improved using the postsynthesis or encapsulation strategy. In this work, the MOF-based proton-conducting material Im@MOF-808 has been prepared by incorporating the imidazole molecules into the pores of proton-conducting MOF-808. Compared with MOF-808, Im@MOF-808 not only possesses higher proton conductivity of 3.45 × 10-2 S cm-1 at 338 K and 99% RH, superior to that of any imidazole-encapsulated proton-conducting materials reported to date, but also good durable and stable proton conduction. Moreover, the thermal stability of H-bond networks is much improved owing to the water molecules partially replaced by higher boiling point imidazole molecules. Additionally, it is further discussed for the possible mechanism of imidazole encapsulation into the pores of MOF-808 to enhance proton conduction.
RESUMEN
Y-doped BaZrO3 (BZY) has high proton conductivity and is a promising electrolyte candidate for fuel cells and electrolytic cells at an intermediate temperature range. However, the conductivity of BZY has a large discrepancy in the literature. In particular, for BaZr0.9Y0.1O3-δ (BZY10), the reported bulk conductivity varies in the range of more than 2 orders of magnitude. With the aim of revealing the reason, in this work, we conducted synchrotron radiation X-ray diffraction analysis on a BZY10. The X-ray was adjusted to 17.027 keV to approach the Y-K absorption edge (17.037 keV), and the anomalous dispersion effect was thereby activated for a precise distinction between Zr and Y. High-resolution scanning transmission electron microscopy observation and electrochemical measurements were also performed. Assisted by these experimental results, Rietveld refinement with greatly improved quality was thereby available to generate precise information on both the phase behavior and crystal structure. The results revealed that the BZY10 samples after sintering at 1600 °C for 8 to 200 h have a bimodal microstructure. They were not single phases, but mixtures of two perovskite phases differing slightly in Y contents. The Y contents in the two phases after sintering for 8 h were about 12.3 and 8.7 mol %, respectively, and finally became 10.6 and 9.2 mol %, respectively, after sintering for 200 h. In addition, the partition of Y over both the Ba and Zr sites was not suggested, although small Ba-deficiency around 0.05 formed in the sample sintered for 40 h or longer. But notably, the formation of the Ba vacancies is reasonably believed as the possible reason for the decrease in bulk and also grain boundary conductivities.