NOVEL CHEMICALLY STABLE Ba3Ca1.18Nb1.82-xYxO9-bPROTON CONDUCTOR:IMPROVED PROTON CONDUCTIVITY THROUGH TAILORED CATION ORDERING
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Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers
Herein, we report the synthesis of proton-conducting sulfonated poly(ionic liquid) block copolymers (S-PILBCPs) containing one block with sulfonic acid (sulfonated styrene, SS) and the other with an IL moiety (vinylbenzylmethylimidazolium bis(trifluoromethylsulfonyl)imide, VBMIm-TFSI) using reversible addition–fragmentation chain-transfer (RAFT) polymerization and post-polymerization modifications (i.e., functionalization, anion exchange reactions, and sulfonation). The S-PILBCPs uniquely conjoin the SS block with mobile protons (H + ) and the PIL block with mobile anions (TFSI – ), where multiple highly desired properties, including high proton conductivity (from the SS block), and high IL-philicity and oxygen solubility (from the PIL block) can exist compartmentally within a microphase separated morphology (evidenced by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS)). High ion conductivity of 79.7 mS/cm at a PIL block composition of 21.6 mol % was observed at 80 °C and 90% relative humidity (RH) (comparable to the benchmark Nafion ionomer). This work successfully demonstrates the design of S-PILBCPs as a new material platform and showcases its promise as an ionomer for proton exchange membrane fuel cells (PEMFCs) as they simultaneously and compartmentally combine proton conductivity and oxygen solubility. Furthermore, these benefits have recently been leveraged to achieve substantial improvement in oxygen reduction reaction (ORR) activity and subsequently fuel cell performance.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Improving Proton Conductivity by Navigating Proton Trapping in High Scandium-Doped Barium Zirconate Electrolytes
Proton-conducting oxides are used in intermediate-temperature (300 °C < T < 700 °C) applications of fuel cells, electrolyzers, membrane reactors, hydrogen pumps, and sensors. The proton conductivity of doped ABO 3 perovskites is partly dependent on the proton concentration and hence on the level of material hydration. However, how the material hydration ability is affected by differences in doping is not fully understood. Here, we show the prospect of proton trapping and detrapping that influences material hydration and dehydration. The proton-trapping influence is significant for Sc-doped BaZrO 3 compared to Y-doped BaZrO 3 . Here, our work offers a perspective to understand how defect interaction/associations influence the hydration ability of proton-conducting oxides. Furthermore, positron annihilation lifetime spectroscopy was revealed to be a valuable technique for studying the proton-trapping phenomena and the defect chemistry of dense proton conductors. Density functional theory calculations also showed that a high hydration level in Sc-doped BaZrO 3 boosts proton migration. In contrast, the effect of boosting the proton migration due to increased hydration is limited for Y-doped BaZrO 3 . This effect, in turn, might explain the trend of conductivity with dopant concentration in doped BaZrO 3 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering Ionomer–Substrate Interface to Improve Thin-Film Proton Conductivity in Proton Exchange Membrane Fuel Cells
Not provided.
Materials Science↗
Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity
The proton conductivity of a dense coordination polymer (CP) was investigated under high-pressure conditions. Impedance measurements under high pressures revealed that the proton conductivity of the CP decreased more than 1000-fold at pressures of 3–7 GPa and that the activation energy for proton conduction almost doubled compared with that at ambient pressure. A synchrotron X-ray study under high pressure identified the amorphization process of the CP during compression, which rationally explains the decrease in conductivity and increase in activation energy. This phenomenon is categorized as reversible pressure-induced amorphization of a dense CP and is regarded as a demonstration of the coupling of the mechanical and electrical properties of a CP.
36 MATERIALS SCIENCE↗
In Situ Nanoscale Dynamics Imaging in a Proton‐Conducting Solid Oxide for Protonic Ceramic Fuel Cells
Abstract Hydrogen fuel cells and electrolyzers operating below 600 °C, ideally below 400 °C, are essential components in the clean energy transition. Yttrium‐doped barium zirconate BaZr 0.8 Y 0.2 O 3‐d (BZY) has attracted a lot of attention as a proton‐conducting solid oxide for electrochemical devices due to its high chemical stability and proton conductivity in the desired temperature range. Grain interfaces and topological defects modulate bulk proton conductivity and hydration, especially at low temperatures. Therefore, understanding the nanoscale crystal structure dynamics in situ is crucial to achieving high proton transport, material stability, and extending the operating range of proton‐conducting solid oxides. Here, Bragg coherent X‐ray diffractive imaging is applied to investigate in situ and in 3D nanoscale dynamics in BZY during hydration over 40 h at 200 °C, in the low‐temperature range. An unexpected activity of topological defects and subsequent cracking is found on a nanoscale covered by the macroscale stability. The rearrangements in structure correlate with emergent regions of different lattice constants, suggesting heterogeneous hydration. The results highlight the extent and impact of nanoscale processes in proton‐conducting solid oxides, informing future development of low‐temperature protonic ceramic electrochemical cells.
25 ENERGY STORAGE↗
Impact of the Sintering Additive Al{sub 2}O{sub 3} on the Electrical Conductivity of Proton-Conducting Electrolyte CaZr{sub 0.95}Sc{sub 0.05}O{sub 3 – δ}
The impact of sintering additive Al{sub 2}O{sub 3} on the electrical conductivity of calcium zirconate-based polycrystalline proton-conducting electrolyte CaZr{sub 0.95}Sc{sub 0.05}O{sub 3 – δ} (CZS) is studied. With the sintering additive Al{sub 2}O{sub 3}, ceramic samples synthesized by a combustion technique are denser, and relatively low synthesis temperatures can be used (1470°C). Adding 0.1–0.5 wt % Al{sub 2}O{sub 3} leads to an increase in the grain size from 100 nm to 1–2 μm. Increasing the Al{sub 2}O{sub 3} content up to 0.3 wt % favors a growth in the electrolyte conductivity. For samples containing Al{sub 2}O{sub 3}, calcium aluminates are detected at grain boundaries. In samples exposed to humid air, charge transfer both in the grain bulk and at intergrain boundaries is found to be mediated by protons.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Influence of Nonstoichiometry on Proton Conductivity in Thin-Film Yttrium-Doped Barium Zirconate
Proton-conducting perovskites have been widely studied because of their potential application as solid electrolytes in intermediate temperature solid oxide fuel cells. Structural and chemical heterogeneities can develop during synthesis, device fabrication, or service, which can profoundly affect proton transport. Here, we use time-resolved Kelvin probe force microscopy, scanning transmission electron microscopy, atom probe tomography, and density functional theory calculations to intentionally introduce Ba-deficient planar and spherical defects and link the resultant atomic structure with proton transport behavior in both stoichiometric and nonstoichiometric epitaxial, yttrium-doped barium zirconate thin films. The defects were intentionally induced through high-temperature annealing treatment, while maintaining the epitaxial single crystalline structure of the films, with an overall relaxation in the atomic structure. As a result, the annealed samples showed smaller magnitudes of local lattice distortions because of the formation of proton polarons, thereby leading to decreased proton-trapping effect. This resulted in a decrease in the activation energy for proton transport, leading to faster proton transport.
36 MATERIALS SCIENCE↗
Enhanced proton conductivity and dimensional stability of proton exchange membrane based on sulfonated poly(arylene ether sulfone) and graphene oxide
Highlights: • Proton conductivity of SPAES-GO-x membranes enhanced with increasing GO content. • Incorporating GO into SPAES matrix restrained SPAES-GO-x membranes swelling. • GO promoted the sulfonic acid groups of SPAES molecular chain aggregation (big ionic clusters) to enhance proton transport. - Abstract: A series composited membranes of sulfonated poly(arylene ether sulfone) and graphene oxide (SPAES-GO-x) have been exploited as proton exchange membrane. The properties of SPAES-GO-x membranes were evaluated including proton conductivity, water uptake, swelling ratio, oxide and thermal stability. Incorporating GO into SPAES matrix restrained the composite membranes swelling and enhanced their proton conductivity. The SPAES-GO-3% membrane showed a conductivity value of 0.183 S cm{sup −1} at 120 °C and relative humidity 100%. Compared with the pristine SPAES membrane, the swelling ratio of SPAES-GO-2% membrane was reduced by 55.7% at 90 °C. Small-Angle X-ray Scattering (SAXS) revealed GO promoted SPAES molecular chain movement to form bigger ionic clusters in favor of enhancing proton transport. X-Ray Diffraction and Field Emission Scanning Electron Microscope (XRD and FE-SEM) analysis further demonstrated GO was exfoliated and distributed throughout the SPAES matrix. These results indicated GO was an effective filler to trade off proton conductivity and swelling of composite membrane.
36 MATERIALS SCIENCE↗
Anhydrous Proton-Conducting Membranes for Fuel Cells
Polymeric electrolyte membranes that do not depend on water for conduction of protons are undergoing development for use in fuel cells. Prior polymeric electrolyte fuel-cell membranes (e.g., those that contain perfluorosulfonic acid) depend on water and must be limited to operation below a temperature of 125 C because they retain water poorly at higher temperatures. In contrast, the present developmental anhydrous membranes are expected to function well at temperatures up to 200 C. The developmental membranes exploit a hopping-and-reorganization proton- conduction process that can occur in the solid state in organic amine salts and is similar to a proton-conduction process in a liquid. This process was studied during the 1970s, but until now, there has been no report of exploiting organic amine salts for proton conduction in fuel cells.
Narayanan, Sekharipuram↗
Structural and proton conductivity studies of fibrous π-Ti 2 O(PO 4 ) 2 ·2H 2 O: application in chitosan-based composite membranes
The structure of π-Ti 2 O(PO 4 ) 2 ·2H 2 O was determined by the SR-PXRD method. The proton conductivity of chitosan/π-TiP membranes reached 4.5 × 10 −3 S cm −1 at 95%-RH.
Babaryk, Artem A.↗
Structure and proton conduction in sulfonated poly(ether ether ketone) semi-permeable membranes: a multi-scale computational approach.
The design of polymeric membranes for proton or ionic exchange highly depends on the fundamental understanding of the physical and molecular mechanisms that control the formation of the conduction channels. There is an inherent relation between the dynamical structure of the polymeric membrane and the electrostatic forces that drive membrane segregation and proton transport. Here, we used a multi-scale computational approach to analyze the morphology of sulfonated poly(ether ether ketone) membranes at the mesoscale. A self-consistent description of the electrostatic phenomenon was adopted, where discrete polymer chains and a continuum proton field were embedded in a continuum fluid. Brownian dynamics was used for the evolution of the suspended polymer molecules, while a convection-diffusion transport equation, including the Nernst-Planck diffusion mechanism, accounted for the dynamics of the proton concentration field. We varied the polymer concentration, the degree of sulfonation and the level of confinement to find relationships between membrane structure and proton conduction. Our results indicate that the reduced mobility of polymer chains, at concentrations above overlap, and a moderate degree of sulfonation -i.e., 30% - are essential elements for membrane segregation and proton domain connectivity. These conditions also ensure that the membrane structure is not affected by size or by potential gradients. Importantly, our analysis shows that membrane conductivity and current are linearly dependent on polymer concentration and quadratically dependent on the degree of sulfonation. We found that the optimal polymeric membrane design requires a polymer concentration above overlap and a degree of sulfonation around 50%. These conditions promote a dynamical membrane morphology with a constant density of proton channels. Our results and measurements agree with previous experimental works, thereby validating our model and observations.
Molina, Jarol↗
High performing triple-conductive Pr 2 NiO 4+δ anode for proton-conducting steam solid oxide electrolysis cell
The development of proton-conducting solid oxide electrolysis cells for the intermediate-temperature range application is largely hindered by the limited choice of adequate anode materials. In this study, the popular solid oxide fuel cell cathode material Pr 2 NiO 4+δ (PNO) is investigated as the anode for the electrolysis cell, considering its proton-conducting ability. The introduction of protons into the PNO lattice is confirmed through insertion-induced conductivity variation measurements. Good chemical compatibility is verified between PNO and BaZr 0.2 Ce 0.6 Y 0.2 O 3–δ (BZCY) proton-conducting electrolyte. Excellent catalytic activity towards water splitting is observed for the PNO–BZCY composite anode, 0.52 Ω cm 2 for 550 °C, 0.057 Ω cm 2 for 700 °C. The water-splitting process is disclosed by impedance spectroscopy measured under different conditions. Due to proton conduction in PNO, the PNO surface is activated for electrochemical reactions. The non-charge transfer processes account little to the electrode resistance. The performance of the PNO–BZCY anode is determined by two charge transfer processes whose kinetics are governed the electrolyzing potential. This charge transfer-limiting nature is relatively benign since the electrode resistance has been found to exponentially reduce with increasing overpotential. Cathode-supported Ni–BZCY//BZCY//PNO–BZCY thin film electrolyte single cells are fabricated and characterized. ~95% current efficiency is confirmed. At 700 °C, a current density of 977 mA cm –2 is achieved at a 1.3 V electrolyzing potential, e.g. 0.37 V overpotential, which is one of the best performances of proton-conducting steam electrolysis cells so far. The PNO–BZCY anode accounts only for 16% of the overall polarization resistance at 700 °C. Furthermore, these findings prove that the triple-conductive PNO is a promising anode material for proton-based steam electrolysis cells.
25 ENERGY STORAGE↗
Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity
Owing to their inherent pore structure, porous metal–organic frameworks (MOFs) can undergo postsynthetic modification, such as loading extra-framework proton carriers. However, strategies for improving the proton conductivity for nonporous MOFs are largely lacking, although increasing numbers of nonporous MOFs exhibit promising proton conductivities. Often, high humidity is required for nonporous MOFs to achieve high conductivities, but to date no clear mechanisms have been experimentally identified. Here we describe the new materials MFM-550(M), [M(HL 1 )], (H 4 L 1 = biphenyl-4,4'-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), MFM-550(Ba), [Ba(H 2 L 1 )], and MFM-555(M), [M(HL 2 )], (H 4 L 2 = benzene-1,4-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), and report enhanced proton conductivities in these nonporous materials by (i) replacing the metal ion to one with a lower oxidation state, (ii) reducing the length of the organic ligand, and (iii) introducing additional acidic protons on the MOF surface. Increased framework proton density in these materials can lead to an enhancement in proton conductivity of up to 4 orders of magnitude. Additionally, we report a comprehensive investigation using in situ 2H NMR and neutron spectroscopy, coupled with molecular dynamic modeling, to elucidate the role of humidity in assembling interconnected networks for proton hopping. This study constructs a relationship between framework proton density and the corresponding proton conductivity in nonporous MOFs, and directly explains the role of both surface protons and external water in assembling the proton conduction pathways.
36 MATERIALS SCIENCE↗
Oxygen Affinity: The Missing Link Enabling Prediction of Proton Conductivities in Doped Barium Zirconates
Proton-conducting oxides, specifically doped barium zirconates, have garnered much attention as electrolytes for solid-state electrochemical devices operable at intermediate temperatures (400–600 °C). In chemical terms, hydration energy, E hyd , and proton–dopant association energy, E as , are two key parameters that determine whether an oxide exhibits fast proton conduction, but to date ab initio studies have for the most part studied each parameter separately, with no clear correlation with proton conductivity identified in either case. Here, we demonstrate that the oxygen affinity, E O.dopant , defined as the energy released when an oxide ion enters an oxygen vacancy close to a dopant atom, is the missing link between these two parameters and correlates well with experimental proton conductivities in doped barium zirconates. Ab initio calculations of point defects and their complexes in Sc-, In-, Lu-, Er-, Y-, Gd-, and Eu-doped barium zirconates are used to determine E hyd , E as , E O.dopant , and the hydrogen affinity, E H.host , of each system. These four energy terms are related by E hyd = E O.dopant + 2E H.host + 2E as . Complementary impedance spectroscopy measurements reveal that the stronger the calculated oxygen affinity of a system, the higher the proton conductivity at 350 °C. Although the proton trapping site is also an important factor, the results show that oxygen affinity is an excellent predictor of proton conductivity in these materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A mini-review on proton conduction of BaZrO 3 -based perovskite electrolytes
Abstract Proton conducting ceramics show promise in fuel cells, electrolyzers, permeation membranes, sensor applications, and membrane reactors. Among several types of materials that exhibit proton conduction, perovskite oxides show high proton conductivity at intermediate temperatures, presenting potential benefits for long-term use and lower costs for energy applications. Doped barium zirconate, BaZrO 3 , is a material that has shown high proton conductivity with encouraging chemical stability. Therefore, it is considered a promising material especially for proton-conducting solid oxide electrochemical cells. Although the proton conduction of doped BaZrO 3 has been extensively characterized, the specific phenomena behind its proton conduction are not fully understood. Only recently have specialized techniques and computational tools begun to elucidate the phenomena that determine the conduction properties of the material. In this mini review, an evaluation of the factors affecting the proton conductivity of doped BaZrO 3 perovskites and the phenomena governing variations in proton concentration and mobility are presented. Special attention is given to proton interactions with dopants and their resulting effect on hydration and transport properties. Technical strategies are provided to give some guidance on the development of protonic ceramics in energy conversion applications.
08 HYDROGEN↗
Proton-conducting oxides for energy conversion and storage
Proton-conducting oxides are a class of solid-state ion-conducting ceramic materials that demonstrate significant hydrogen ion (proton) conductivity at intermediate temperatures (e.g., 300–700 °C). They are garnering significant attention due to several unique characteristics that distinguish them from both higher temperature oxygen ion conducting oxides and lower temperature proton-conducting polymers. By enabling proton-mediated electrochemistry under both dry and wet environments at moderate temperatures, protonic ceramics provide unique opportunities to enhance or synergize a diverse range of complementary electrochemical and thermochemical processes. Because of this potential, significant efforts have been devoted to advancing numerous energy-related applications using these materials. This review aims to comprehensively summarize these applications and analyze the most up-to-date and future developments of proton-conducting oxides. We aim to bring together this diverse subject matter by integrating the fundamentals of proton-conducting oxides with application-oriented insights. We begin with a historical roadmap, followed by a basic overview of the materials, theories and fundamentals, and fabrication and processing technologies underlying the field. The central section of our review summarizes major applications and developments of proton-conducting ceramics, ranging from maturing applications approaching commercialization to embryonic technologies just now emerging from the lab. These include protonic ceramic fuel cells, protonic ceramic electrolysis cells, reversible protonic ceramic electrochemical cells, protonic ceramic membrane reactors, and protonic ceramic electrochemical reactors. For each application, we analyze both the prospects and challenges and offer recommendations for future research directions so that tomorrow's researchers can continue to advance the development and commercialization of these fascinating materials.
Duan, Chuancheng (ORCID:0000000218261415)↗
Non-Contact Eddy Current Method for Assessing Proton Conductivity in Nafion Membranes
Accurate measurement of proton conductivity in Proton Exchange Membranes (PEMs) is vital for fuel cell performance and durability. This study explores eddy current testing as a non-destructive, non-contact and high-rate quality control (QC) method for measuring Nafion membrane proton conductivity, with potential for high-volume manufacturing applications.
33 ADVANCED PROPULSION SYSTEMS↗