Vanadium-Based Cathodes for Aqueous Zinc-Ion Batteries: Mechanisms, Challenges, and Strategies.

ConspectusZinc-ion batteries (ZIBs) are highly promising for large-scale energy storage because of their safety, high energy/power density, low cost, and eco-friendliness. Vanadium-based compounds are attractive cathodes because of their versatile structures and multielectron redox processes (+5 to +3), leading to high capacity. Layered structures or 3-dimensional open tunnel frameworks allow easy movement of zinc-ions without breaking the structure apart, offering superior rate-performance. However, challenges such as dissolution and phase transformation hinder the long-term stability of vanadium-based cathodes in ZIBs. Although significant research has been dedicated to understanding the mechanisms and developing high-performance vanadium-based cathodes, uncertainties still exist regarding the critical mechanisms of energy storage and dissolution, the actual active phase and the specific optimization strategy. For example, it is unclear whether materials such as α-V2O5, VO2, and V2O3 serve as the active phase or undergo phase transformations during cycling. Additionally, the root cause of V-dissolution and the role of byproducts such as Zn3(OH)2V2O7·2H2O in ZIBs are debated.In this account, we aim to outline a clear and comprehensive roadmap for V-based cathodes in ZIBs. On the basis of our studies, we analyzed intrinsic crystal structures and their correlation with performance to guide the design of V-based materials with high-capacity and high-stability for ZIBs. Then, we revealed the underlying mechanisms of energy storage and instability, enabling more effective design and optimization of V-based cathodes. After identifying the key challenges, we proposed effective design principles to achieve high cycling performance of V-based cathodes and outlined future development directions toward their practical application. Vanadium-based compounds include [VO4] tetrahedrons, [VO5] square pyramids, and [VO6] octahedra, which are connected through a cocorner, coedge and coplane. The [VO4] tetrahedron is inactive, and the [VO5] square pyramid is unstable in aqueous solutions because water attacks the exposed vanadium, whereas stable [VO6] octahedra are desirable because of their ability to reduce from +5 to +3 with minimal structural distortion. Therefore, high-performance vanadium-based oxides in ZIBs should maintain intact [VO6] octahedra while avoiding [VO4] tetrahedra or [VO5] square pyramids. The energy storage mechanism involves H2O/H+/Zn2+ coinsertion. The existence of interlayer water in V-based cathodes significantly improves the rate and cycling performance by expanding galleries, screening Zn2+ electrostatically via solvation, reducing ion diffusion energy barriers, and increasing layer flexibility. The insertion of H+/Zn2+ and the instability of V-based cathodes lead to the formation of byproducts such as basic zinc salts (i.e., Zn4SO4(OH)6·nH2O) and dead vanadium (Zn3(OH)2V2O7·2H2O), whose reversibility strongly affects long-term stability. To increase the cycling stability of vanadium-based cathodes, strategies such as electrolyte modulation and coating have been proposed to decrease water attack on the surface of V-oxides, thereby affecting the formation of byproducts. Additionally, in situ electrochemical transformation, ion preintercalation, and ion exchange were explored to prepare intrinsically stable V-based cathodes with enhanced performance. Furthermore, future research should focus on revealing atomic-scale mechanisms through advanced in situ characterization and theoretical calculations, enhancing rate-performance by facilitating ion/electron diffusion, promoting cycling stability by developing highly stable cathodes and refining interface engineering, and scaling up vanadium-based cathodes for practical ZIB applications.

Phosphorous and Nitrogen Dual-Doped Carbon as a Highly Efficient Electrocatalyst for Sodium-Oxygen Batteries.

Sodium-oxygen batteries have been regarded as promising energy storage devices due to their low overpotential and high energy density. Its applications, however, still face formidable challenges due to the lack of understanding about the influence of electrocatalysts on the discharge products. Here, a phosphorous and nitrogen dual-doped carbon (PNDC) based cathode is synthesized to increase the electrocatalytic activity and to stabilize the NaO2 superoxide nanoparticle discharge products, leading to enhanced cycling stability when compared to the nitrogen-doped carbon (NDC). The PNDC air cathode exhibits a low overpotential (0.36 V) and long cycling stability (120 cycles). The reversible formation/decomposition and stabilization of the NaO2 discharge products are clearly proven by in-situ synchrotron X-ray diffraction and ex-situ X-ray diffraction. Based on the density functional theory calculation, the PNDC has much stronger adsorption energy (-2.85 eV) for NaO2 than that of NDC (-1.80 eV), which could efficiently stabilize the NaO2 discharge products.

Multidimensional Building Blocks for Molecular Sieve Membranes.

Chemical separations aiming for high-purity commodities are critical to modern society. Compared to distillation, chemical absorption, and adsorption, membrane separation is attractive for its energy efficiency, ease of operation, and compact footprint. Molecular sieve membranes (MSMs) are broadly defined as membranes that are constructed from intrinsically and artificially porous materials. On the basis of our recent studies, this Account will first summarize the evolution of MSMs from the viewpoint of dimensionality of building blocks, which fundamentally determines the stacking architectures, intercrystalline gaps, and mass transfer channels of MSMs. Intergrowth of three-dimensional (3D) crystals as primary building blocks gives rise to classical MSMs. However, the poor connection between crystals inherent to those membranes results in intercrystalline gaps that are catastrophic for separation selectivity. We adopted a variety of strategies to close the crystal boundary gaps, including microwave synthesis, electrochemical-ionothermal synthesis, and modular integration. These efforts make us better understand the structure-performance relationship in membranes and create solutions for industrial processes. Excitingly, we first scaled-up the microwave synthesis of a Linde type A (LTA) zeolite membrane and built the world's largest ethanol dehydration membrane unit with an annual capacity of 100,000 tons. MSMs can also be made of two-dimensional (2D) nanosheets as primary building blocks. Those strike a balance between permeation rate and selectivity because the nanometer thickness ensures the minimization of the mass-transfer resistance of the membrane and the layer-by-layer stacking mode can significantly reduce the intercrystalline gaps. By publishing our first report on metal-organic framework (MOF) nanosheet membranes in Science, we committed to establishing top-down and bottom-up methods for assembly of laminae. Once the stacking, orientation, and connection between the layers are meticulously controlled, nanosheet building blocks with diversity open the door for ultrapermeable and selective MSMs. We recently proposed a supramolecule array membrane (SAM) with zero-dimensional (0D) molecules as primary building blocks, which has great potential to absolutely eliminate intercrystalline gaps in membranes. In contrast to the classical transport through nanopores of membranes, selective transport through the intermolecular spacing of supramolecules is creatively realized within the SAM, which marks a new breakthrough in ultraprecise sieving of molecules with tiny differences in size and revolutionizes MSMs in regard to stacking modes, intercrystalline gaps, and transport channels. MSMs have proven to be successful in diverse applications and have triggered wide interest. A unique perspective on the dimensionality evolution of building blocks will accelerate the progress of MSMs. The synergy of multidimensional MSMs will be a positive response to fundamental bottlenecks and industrial questions of membranes and will unlock the potential of membranes to displace the existing separation technologies in the future.

Critical Issues of Vanadium-Based Cathodes Towards Practical Aqueous Zn-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) are gaining significant attention for their numerous advantages, including high safety, high energy density, affordability, and environmental friendliness. However, the development of ZIBs has been hampered by the lack of suitable cathode materials that can store Zn2+ with high capacity and reversibility. Currently, vanadium-based materials with tunnel or layered structures are widely researched owing to their high theoretical capacity and diversified structures. However, their long-term cycling stability is unsatisfactory because of material dissolution, phase transformation, and restrictive kinetics in aqueous electrolytes, which limits their practical applications. Different from previous reviews on ZIBs, this review specifically addresses the critical issues faced by vanadium-based cathodes for practical aqueous ZIBs and proposes potential solutions. Focusing on vanadium-based cathodes, their ion storage mechanisms, the critical parameters affecting their performance, and the progress made in addressing the aforementioned problems are also summarized. Finally, future directions for the development of practical aqueous ZIB are suggested.

A LDH Template Triggers the Formation of a Highly Compact MIL-53 Metal-Organic Framework Membrane for Acid Upgrading.

Highly compact metal-organic framework (MOF) membranes offer hope for the ambition to cope with challenging separation scenarios with industrial implications. A continuous layer of layered double hydroxide (LDH) nanoflakes on an alumina support as a template triggered a chemical self-conversion to a MIL-53 membrane, with approximately 8 hexagonal lattices (LDH) traded for 1 orthorhombic lattice (MIL-53). With the sacrifice of the template, the availability of Al nutrients from the alumina support was dynamically regulated, which resulted in synergy for producing membranes with highly compact architecture. The membrane can realize nearly complete dewatering from formic acid and acetic acid solutions, respectively, and maintain stability in a continuous pervaporation over 200 h. This is the first success in directly applying a pure MOF membrane to such a corrosive chemical environment (lowest pH value of 0.81). The energy consumption is saved by up to 77 % when compared with the traditional distillation.

Modular Customization and Regulation of Metal-Organic Frameworks for Efficient Membrane Separations.

Metal-organic frameworks (MOFs) are considered ideal membrane candidates for energy-efficient separations. However, the MOF membrane amount to date is only a drop in the bucket compared to the material collections. The fabrication of an arbitrary MOF membrane exhibiting inherent separation capacity of the material remains a long-standing challenge. Herein, we report a MOF modular customization strategy by employing four MOFs with diverse structures and physicochemical properties and achieving innovative defect-free membranes for efficient separation validation. Each membrane fully displays the separation potential according to the MOF pore/channel microenvironment, and consequently, an intriguing H2 /CO2 separation performance sequence is achieved (separation factor of 1656-5.4, H2 permeance of 964-2745 gas permeation unit). Taking advantage of this strategy, separation performance can be manipulated by a non-destructive modification separately towards the MOF module. This work establishes a universal full-chain demonstration for membrane fabrication-separation validation-microstructure modification and opens an avenue for exclusive customization of membranes for important separations.

Hewettite ZnV6 O16 ⋠8H2 O with Remarkably Stable Layers and Ultralarge Interlayer Spacing for High-Performance Aqueous Zn-Ion Batteries.

Aqueous Zn-ion batteries (ZIBs) are promising candidates for grid-scale energy storage because of their intrinsic safety, low-cost and high energy-intensity. Vanadium-based materials are widely used as the cathode of ZIBs, especially A2 V6 O16 ⋅ nH2 O (AVO, A=NH4 + , Na, K). However, AVO suffers from serious dissolution, phase transformation and narrow gallery spacing (∼3 Å), leading to poor cycling stability and rate capability. Herein, we unveiled the root cause of the performance degradation in the AVO cathode and therefore developed a new high-performance cathode of ZnV6 O16 ⋅ 8H2 O (ZVO) for ZIB. Through a method of ion exchange induced phase transformation, AVO was converted to hewettite ZVO with larger gallery spacing (∼6 Å) and more stable V6 O16 layers. ZVO cathode thus constructed delivers a high capacity of 365 and 170 mAh g-1 at 0.5 and 15 A g-1 , while 86 % and 70 % of its capacity are retained at 0.5 A g-1 after 300 cycles and at 15 A g-1 after 10000 cycles, substantially better than conventional AVO.

Enhancing Energy Conversion Efficiency and Durability of Alkaline Nickel-Zinc Batteries with Air-Breathing Cathode.

Despite their high output voltage and safety advantages, rechargeable alkaline nickel-zinc batteries face significant challenges associated with the cathodic side reaction of oxygen evolution, which results in low energy efficiency (EE) and poor stability. Herein, we propose to leverage the side oxygen evolution reaction (OER) in nickel-zinc batteries by coupling electrocatalysts for oxygen reduction reactions (ORR) in the cathode, thus constructing an air breathing cathode. Such a novel battery (Ni-ZnAB), designed in a pouch-type cell with a lean electrolyte, exhibits an outstanding EE of 85 % and a long cycle life of 100 cycles at 2 mA cm-2 , which are significantly superior to those of traditional Ni-Zn batteries (54 %, 50 cycles). Compared to Ni-Zn, the enhanced EE of Ni-ZnAB is attributed to the contribution from ORR, while the improved cycling stability is because the stability of the anode, cathode and electrolyte are also enhanced in Ni-ZnAB. Furthermore, an ultrahigh stability of 500 cycles with an average EE of 84 % at 2 mA cm-2 was achieved using a mold cell with rich electrolyte, demonstrating the strong application potential of Ni-ZnAB.

Structure Regulation of MOF Nanosheet Membrane for Accurate H2 /CO2 Separation.

High-purity H2 production accompanied with a precise decarbonization opens an avenue to approach a carbon-neutral society. Metal-organic framework nanosheet membranes provide great opportunities for an accurate and fast H2 /CO2 separation, CO2 leakage through the membrane interlayer galleries decided the ultimate separation accuracy. Here we introduce low dose amino side groups into the Zn2 (benzimidazolate)4 conformation. Physisorbed CO2 served as interlayer linkers, gently regulated and stabilized the interlayer spacing. These evoked a synergistic effect of CO2 adsorption-assisted molecular sieving and steric hinderance, whilst exquisitely preserving apertures for high-speed H2 transport. The optimized amino membranes set a new record for ultrathin nanosheet membranes in H2 /CO2 separation (mixture separation factor: 1158, H2 permeance: 1417 gas permeation unit). This strategy provides an effective way to customize ultrathin nanosheet membranes with desirable molecular sieving ability.

Reversibly Phase-Transformative Zeolitic Imidazolate Framework-108 and the Membrane Separation Utility.

Reversible phase transformations (RPTs) of metal-organic frameworks not only create material diversity but also promise a self-restoration of crystals in a controllable manner. However, there are only limited examples because seeking for a convenient and effective trigger for RPTs, especially for RPTs with respect to spatiotemporal harmony in cleavage and reconstruction of metal-linker chemical bonds, is challenging. In this work, we found that zeolitic imidazolate framework (ZIF)-108 with Zn-N coordination bonds showing moderate strength was an ideal platform. We reported three crystal phases of ZIF-108, namely, sodalite (SOD), diamondoid (DIA), and large pore_sodalite (lp_SOD) topologies, and identified RPTs between phases: (1) when exposed to water or water vapor, the SOD structure could transform to a compact DIA version as a result of the decomposition of four-membered rings and synchronous reorganization of six-membered rings. Then, the DIA structure could also return back to SOD when soaked in dimethylformamide (DMF) or DMF vapor. (2) High-temperature treatment of SOD gives rise to lp_SOD, which then reverts to SOD by DMF. (3) lp_SOD could also be compressed into the DIA phase by water or water vapor and can then be restored via a two-step treatment, namely, soaking in DMF (DIA → SOD) right before a high-temperature therapy (SOD → lp_SOD). From the perspective of the separation utility, we found that the lp_SOD version of ZIF-108, relative to SOD-structured ZIF-108, can produce mixed matrix membranes having an interesting interfacial structure with the polymer chains, though both share the same chemical composition. We verified that the large pore of lp_SOD can allow being penetrated by polymer chains, which contributed to not only reinforcing the bi-phase interface but also sharpening the molecule sieve properties of fillers toward CO2 and CH4.

In situ Dispersed Nano-Au on Zr-Suboxides as Active Cathode for Direct CO2 Electroreduction in Solid Oxide Electrolysis Cells.

CO2 electrochemical reduction in solid oxide electrolysis cells is an effective way to combine CO2 conversion and renewable electricity storage. A Au layer is often used as a current collector, whereas Au nanoparticles are rarely used as a cathode because it is difficult to keep nanosized Au at high temperatures. Here we dispersed a Au layer into Au nanoparticles (down to 2 nm) at 800 °C by applying high voltages. A 75-fold decrease in the polarization resistance was observed, accompanied by a 38-fold improvement in the cell current density. Combining electronic microscopy, in situ near-ambient pressure X-ray photoelectron spectroscopy, and theoretical calculations, we found that the interface between the Au layer and the electrolyte (yttria-stabilized zirconia (YSZ)) was reconstructed into nano-Au/Zr-suboxide interfaces, which are active sites that show a much lower reaction activation energy than that of the Au/YSZ interface. The formation of Zr-suboxides promotes Au dispersion and Au nanoparticle stabilization due to the strong interaction between Au and Zr-suboxides.

Flexible Soft-Solid Metal-Organic Framework Composite Membranes for H2 /CO2 Separation.

The development of a facile strategy to construct defect-free and flexible metal-organic framework (MOF)-based membranes with high selectivity and good scalability holds great appeal. Here we report the fabrication of soft-solid MOF composite membranes on polyvinylidene fluoride substrates. A representative membrane comprised of quasi-vertically grown lamellar Zn2 (Bim)4 (Bim=benzimidazolate) and lateral ultrathin polyamide film adhering to the MOF side facets. The straight interlayer galleries within unwrapped Zn2 (Bim)4 acted as predominant pathways, while the polyamide served the function of defect elimination, synergistically inducing an unprecedented H2 /CO2 selectivity of 1084 which set a new record for MOF-based membranes. Separation performance was held constant after membrane rolling up into a tube with a diameter of 3 mm or folding and unfolding at 90° for 50 times. ZIF-67 and ZIF-8 composite membranes based on this strategy also realized extremely high H2 /CO2 separation accuracies. These results, which demonstrate the intrinsic molecular sieving capability of MOFs, will promote the development of MOF-based membranes in practical separation applications.

Hetero-Lattice Intergrown and Robust MOF Membranes for Polyol Upgrading.

Metal-organic framework membranes are frequently used in gas separations, but rare in pervaporation for liquid chemical upgrading, especially for separating water from polyols, due to lack of highly compact and robust micro-architecture. Here, we report hetero-lattice intergrown membranes in which amino-MIL-101 (Cr) particles embedded into the micro-gaps of MIL-53 (Al) rod arrays after secondary growth. By means of high-resolution TEM and two-dimensional topologic simulation, the connection between these two distinct MOF lattices at the molecular-level and their crystallographic geometry harmony is identified, which leads to a close-knit structure at the crystal boundaries of membranes. Typically, the membrane shows a separation factor as high as 13 000 for a 90/10 ethanediol/water solution in pervaporation, yields polymer-grade ethanediol, and saves ca. 32 % of energy consumption vs. vacuum distillation. It has a highly robust micro-architecture, with great tolerance to high pressure, durability against ultrasonic therapy and long-term separation stability over 600 h.

Ball Milling Solid-State Synthesis of Highly Crystalline Prussian Blue Analogue Na2-x MnFe(CN)6 Cathodes for All-Climate Sodium-Ion Batteries.

With a series of merits, Prussian blue analogs (PBAs) have been considered as superior cathode materials for sodium-ion batteries (SIBs). Their commercialization, however, still suffers from inferior stability, considerable [Fe(CN)6 ] defects and interstitial water in the framework, which are related to the rapid crystal growth. Herein, a "water-in-salt" nanoreactor is proposed to synthesize highly crystallized PBAs with decreased defects and water, which show both superior specific capacity and rate capability in SIBs. The air-stability, all-climate, and full-cell properties of our PBA have also been evaluated, and it exhibits enhanced electrochemical performance and higher volume yield than its counterpart synthesized via the water-based co-precipitation method. Furthermore, their highly reversible sodium-ion storage behavior has been measured and identified via multiple in situ techniques. This work could pave the way for the PBA-based SIBs in grid-scale energy-storage systems.

A Highly Selective Supramolecule Array Membrane Made of Zero-Dimensional Molecules for Gas Separation.

We orderly assembled zero-dimensional 2-methylimidazole (mim) molecules into unprecedented supramolecule array membranes (SAMs) through solvent-free vapor processing, realizing the intermolecular spacing of mim at ca. 0.30 nm available as size-sieving channels for distinguishing the tiny difference between H2 (kinetic diameter: 0.289 nm) and CO2 (kinetic diameter: 0.33 nm). The highly oriented and dense membranes yield a separation factor above 3600 for equimolar H2 /CO2 mixtures, which is one order of magnitude higher than those of the state-of-the-art membranes defining 2017's upper bound for H2 /CO2 separation. These SAMs define a new benchmark for molecular sieve membranes and are of paramount importance to precombustion carbon capture. Given the range of supramolecules, we anticipate SAMs with variable intermolecular channels could be applied in diversified separations that are prevalent in chemical processes.

Single-Phase Covalent Organic Framework Staggered Stacking Nanosheet Membrane for CO2 -Selective Separation.

Two-dimensional covalent organic frameworks (2D COFs) are considered as potential candidates for gas separation membranes, benefiting from permanent porosity, light-weight skeletons, excellent stability and facilely-tailored functionalities. However, their pore sizes are generally larger than the kinetic diameters of common gas molecules. One great challenge is the fabrication of single-phase COF membranes to realize precise gas separations. Herein, three kinds of high-quality ß-ketoenamine-type COF nanosheets with different pore sizes were developed and aggregated to ultrathin nanosheet membranes with distinctive staggered stacking patterns. The narrowed pore sizes derived from the micro-structures and selective adsorption capacities synergistically endowed the COF membranes with intriguing CO2 -philic separation performances, among which TpPa-2 with medium pore size exhibited an optimal CO2 /H2 separation factor of 22 and a CO2 permeance of 328 gas permeation units at 298 K. This membrane performance reached the target with commercial feasibility for syngas separations.

Tuning of Delicate Host-Guest Interactions in Hydrated MIL-53 and Functional Variants for Furfural Capture from Aqueous Solution.

Capture of high-boiling-point furfural from diluted aqueous solution is a critical but challenging step in sustainable bio-refinery processes, but conventional separation methods such as distillation and liquid-liquid extraction requires prohibitive energy consumption. We report control over the microenvironment of hydrated MIL-53 and isoreticular variants with diversified functional terephthalic acid linkers for the purpose of preferential binding of furfural through delicate host-guest interactions. Methyl-bounded MIL-53 with improved binding energy in the hydrated form results in highly efficient capture ratio (ca. 98 %) in the extremely low concentration of furfural solution (0.5-3 wt %) and 100 % furfural specificity over xylose. The distinct hydrogen bonding sites and multiple Van de Wall interactions for furfural adsorption was testified by computational modeling. Furthermore, the recovery ratio of furfural reaches ca. 93 % in desorption.

Application of In Situ Techniques for the Characterization of NiFe-Based Oxygen Evolution Reaction (OER) Electrocatalysts.

Developing high-efficiency and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a crucial bottleneck on the way to the practical applications of rechargeable energy storage technologies and water splitting for producing clean fuel (H2 ). In recent years, NiFe-based materials have proven to be excellent electrocatalysts for OER. Understanding the characteristics that affect OER activity and determining the OER mechanism are of vital importance for the development of OER electrocatalysts. Therefore, in situ characterization techniques performed under OER conditions are urgently needed to monitor the key intermediates together with identifying the OER active centers and phases. In this Minireview, recent advances regarding in situ techniques for the characterization of NiFe-based electrocatalysts are thoroughly summarized, including Raman spectroscopy, X-ray absorption spectroscopy, ambient pressure X-ray photoelectron spectroscopy, Mössbauer spectroscopy, Ultraviolet-visible spectroscopy, differential electrochemical mass spectrometry, and surface interrogation scanning electrochemical microscopy. The results from these in situ measurements not only reveal the structural transformation and the progressive oxidation of the catalytic species under OER conditions, but also disclose the crucial role of Ni and Fe during the OER. Finally, the need for developing new in situ techniques and theoretical investigations is discussed to better understand the OER mechanism and design promising OER electrocatalysts.

Two-Dimensional Metal-Organic Framework Nanosheets for Membrane-Based Gas Separation.

Metal-organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass-transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet-based membranes remain as great challenges. A modified soft-physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub-10 nm-thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H2 /CO2 separation performance, with a separation factor of up to 166 and H2 permeance of up to 8×10-7  mol m-2 s-1 Pa-1 at elevated testing temperatures owing to a well-defined size-exclusion effect. This nanosheet-based membrane holds great promise as the next generation of ultrapermeable gas separation membrane.

Nanoparticles at Grain Boundaries Inhibit the Phase Transformation of Perovskite Membrane.

The high-energy nature of grain boundaries makes them a common source of undesirable phase transformations in polycrystalline materials. In both metals and ceramics, such grain-boundary-induced phase transformation can be a frequent cause of performance degradation. Here, we identify a new stabilization mechanism that involves inhibiting phase transformations of perovskite materials by deliberately introducing nanoparticles at the grain boundaries. The nanoparticles act as "roadblocks" that limit the diffusion of metal ions along the grain boundaries and inhibit heterogeneous nucleation and new phase formation. Ba0.5Sr0.5Co0.8Fe0.2O3-δ, a high-performance oxygen permeation and fuel cell cathode material whose commercial application has so far been impeded by phase instability, is used as an example to illustrate the inhibition action of nanoparticles toward the phase transformation. We obtain stable oxygen permeation flux at 600 °C with an unprecedented 10-1000 times increase in performance compared to previous investigations. This grain boundary stabilization method could potentially be extended to other systems that suffer from performance degradation due to a grain-boundary-initiated heterogeneous nucleation phase transformations.