A Cobalt-Free Multi-Phase Nanocomposite as Near-Ideal Cathode of Intermediate-Temperature Solid Oxide Fuel Cells Developed by Smart Self-Assembly

An ideal solid oxide fuel cell (SOFC) cathode should meet multiple requirements, i.e., high activity for oxygen reduction reaction (ORR), good conductivity, favorable stability, and sound thermo-mechanical/chemical compatibility with electrolyte, while it is very challenging to achieve all these requirements based on a single-phase material. Herein, a cost-effective multi-phase nanocomposite, facilely synthesized through smart self-assembly at high temperature, is developed as a near-ideal cathode of intermediate-temperature SOFCs, showing high ORR activity (an area-specific resistance of ≈0.028 Ω cm² and a power output of 1208 mW cm⁻² at 650 °C), affordable conductivity (21.5 S cm⁻¹ at 650 °C), favorable stability (560 h operation in single cell), excellent chemical compatibility with Sm_0.2Ce_0.8O_1.9 electrolyte, and reduced thermal expansion coefficient (≈16.8 × 10⁻⁶ K⁻¹). Such a nanocomposite (Sr_0.9Ce_0.1Fe_0.8Ni_0.2O_3–δ) is composed of a single perovskite main phase (77.2 wt%), a Ruddlesden–Popper (RP) second phase (13.3 wt%), and surface-decorated NiO (5.8 wt%) and CeO₂ (3.7 wt%) minor phases. The RP phase promotes the oxygen bulk diffusion while NiO and CeO₂ nanoparticles facilitate the oxygen surface process and O²⁻ migration from the surface to the main phase, respectively. The strong interaction between four phases in nanodomain creates a synergistic effect, leading to the superior ORR activity.     

Structure, conductivity and redox stability of solid solution Ce1?xCaxVO4 (0?≤?x?≤?0.4125)

A-site-substituted cerium orthovanadates, Ce_1−x Ca _x VO₄, were synthesised by solid-state reactions. At room temperature, the solid solution limit in Ce_1−x Ca _x VO₄ series is at x = 0.4125. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I4₁/amd with a = 7.4004 (1) and c = 6.4983 (6) ? for CeVO₄. The UV–Visible absorption spectra indicated that the compounds have band gaps at room temperature in the range of 4.2–4.5 eV. Conductivity measurements were performed for the first time up to the calcium solid solution limit in both air and dry 5% H₂/Ar with conductivity values at 600 °C ranging from 0.3 to 20 mS cm⁻¹ in air to 3 to 30 mS cm⁻¹ in reducing atmosphere. In general, the conductivity of Ca-doped CeVO₄ is higher in air but lower in a reducing atmosphere comparing to pure CeVO₄. The H₂/air electrochemical cell measurement indicates that the conduction of sample Ce_0.7Ca_0.3VO₄ is electronic dominant. Samples Ce_0.9Ca_0.1VO₄ and Ce_0.8Ca_0.2VO₄ are redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.     

Near-infrared quantum cutting platform in transparent oxyfluoride glass–ceramics for solar sells

This study investigated the photoluminescent properties of Er³⁺/Yb³⁺ and Ce³⁺/Er³⁺/Yb³⁺ -doped oxyfluoride glass–ceramics. The transparent oxyfluoride glass–ceramics were prepared by high temperature melting method and subsequent heat treatment. Effect of heat treatment schedules on crystallization behavior and microstructure were analyzed by differential scanning caborimetry, X-ray diffraction, infrared spectrum and scanning electron microscopy. The structure of fluoride nanocrystals indicates that the main phase in the oxyfluoride glass ceramics is CaF₂ nanocrystal sized at 25 nm at the optimal crystallization temperature 600 °C for 8 h. The Ce³⁺/Er³⁺/Yb³⁺ tri-doped oxyfluoride glass–ceramics shows wider absorption bands comparing with Er³⁺/Yb³⁺ co-doped oxyfluoride glass–ceramics. The effective energy transfer processes from Ce³⁺ to Yb³⁺, Er³⁺ to Yb³⁺ and Ce³⁺ to Er³⁺ all can take place simultaneously. The idea of using Ce³⁺ together with Er³⁺ and Yb³⁺ ions could enhance the ultraviolet visible light absorption and the 960–1040 nm near infrared emission. Results of this study demonstrate that the tri-activator Ce³⁺/Er³⁺/Yb³⁺ materials are promising for practical application to enhance the energy efficiency of crystalline Si solar cells via spectrum modification.     

Sintering and electrical properties of Ce<Subscript>0.8</Subscript>Sm<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> film prepared by spray pyrolysis and tape casting

Ce_0.8Sm_0.2O_1.9 (SDC) powder was synthesized by spray pyrolysis at 650 °C. XRD results showed that phase-pure SDC powder with an average crystallite size of 11 nm was synthesized. SDC electrolyte film was prepared by tape casting and sintered at different temperatures of 1,300, 1,400 and 1,500 °C for 2 h, respectively. The SDC electrolyte film was relatively denser and showed finer microstructure at relatively lower temperature of 1,400 °C, which might be due to the high sintering activity of the spray pyrolysis SDC powder. The ionic conductivity of the SDC electrolyte film sintered at 1,400 °C reached a maximum value of 9.5 × 10⁻³ S cm⁻¹ (tested at 600 °C) with an activation energy for conduction of 0.90 eV.     

Fe-Regulated Amorphous-Crystal Ni(Fe)P2 Nanosheets Coupled with Ru Powerfully Drive Seawater Splitting at Large Current Density

Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P₂ nanosheet bifunctional catalyst (Ru-Ni(Fe)P₂/NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P₂, and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P₂/NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm⁻² for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO₂/NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm⁻² and 600 mA cm⁻² for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting.     

The rock salt oxide Li2MgTiO4: Type I dielectric and ionic conductor

The exploration of the Li–Ti–Mg–O system, using both sol–gel technique and solid state reaction method, allowed a new phase, Li₂MgTiO₄, with disordered rock salt structure (a = 4.159 Å) to be synthesized. The latter is shown to be a good type I dielectric material, with a relative constant of 15 at high frequency and low dielectric loss (tanδ < 10⁻³) over the temperature range −60 to 160 °C. It is also observed that the sintering temperature of this phase is strongly lowered by adopting the sol–gel technique compared to solid state reaction (1150 °C instead of 1300 °C). Finally we show that this phase exhibits cationic conductivity above 400 °C (σ_600 °C = 9 × 10⁻⁵ S cm⁻¹).     

Synthesis and properties of Ce1−xGdxO2−x/2 solid solution prepared by flame spray pyrolysis

Flame spray pyrolysis, which produces ultrafine particles, was applied to the synthesis of Ce_1−xGd_xO_2−x/2 solid solutions by substituting Gd from a mole fraction of 0–0.40. The solubility limit of Gd in the Ce_1−xGd_xO_2−x/2 solid solution produced by flame spray pyrolysis was between 0.25 and 0.30, which is consistent with the reported value. The as-prepared Ce_1−xGd_xO_2−x/2 particles had a square morphology and a nanometer range in the equivalent diameter. The small particle size made it possible to reduce the sintering temperature of the Ce_1−xGd_xO_2−x/2 solid solution from 1650 °C to 1400 °C for the ceria-based solid electrolytes produced by the solid state preparation. The maximum ionic conductivity was achieved when the mole fraction of Gd was 0.25. The mole fraction for the highest ionic conductivity was the same as the particles produced by hydrothermal synthesis. However, the ionic conductivity of the Ce_1−xGd_xO_2−x/2 prepared by the flame spray pyrolysis (1.01 × 10⁻² S/cm at 600 °C) was higher than that prepared by the hydrothermal synthesis (7.53 × 10⁻³ S/cm at 600 °C).     

Constructing the high-areal-capacity,solid-state Li polymer battery via the multiscale ion transport pathway design

The parasitic Li dendrite formation and retarded ion diffusion dynamics inhibit the deployment of solid-state batteries (SSBs) at high areal capacity loadings. Here, we present the modular design of the Li⁺ percolating network by grafting the ionic-conductive polyether amine (PEA) at the multiple scales: the PEA modified zinc hydroxystannate (PEA@ZHS) (flame retardant units) and polyamide 6 (mechanical rigid units) are coherently introduced to optimize the PEO-based solid electrolyte (PX-PEA@ZHS) with the Young's modulus (3.41 GPa), ionic conductivity (4.29 × 10⁻⁴ S cm⁻¹ at 55 °C) and flame retardancy (22% reduction of heat release rate); on the other hand, PEA molecules are grafted onto the acetylene black additive to establish the dual conductive network, endowing two orders of magnitude increase of ionic conductivity for the high-compaction cathodes. The as-integrated symmetric cell exhibits a critical current density up to 0.8 mA cm⁻² and cycling endurance for 1000 h at 0.2 mA cm⁻²; upon the SSBs assembly with the record high loading of LiFePO₄ (12.4 mg cm⁻²), the high-areal-capacity, cycling stability as well as the extreme temperature endurance till 110 °C are simultaneously realized, which inspire the rational design of commercially feasible, energy-dense, flame-resistance energy storage prototype.     

Sandwich-Structured Quasi-Solid Polymer Electrolyte Enables High-Capacity,Long-Cycling,and Dendrite-Free Lithium Metal Battery at Room Temperature

The insufficient ionic conductivity, limited lithium-ion transference number (t_Li+), and high interfacial impedance severely hinder the practical application of quasi-solid polymer electrolytes (QSPEs). Here, a sandwich-structured polyacrylonitrile (PAN) based QSPE is constructedin which MXene-SiO₂ nanosheets act as a functional filler to facilitate the rapid transfer of lithium-ion in the QSPE, and a polymer and plastic crystalline electrolyte (PPCE) interface modification layer is coated on the surface of the PAN-based QSPE of 3 wt.% MXene-SiO₂ (SS-PPCE/PAN-3%) to reduce interfacial impedance. Consequently, the synthesized SS-PPCE/PAN-3% QSPE delivers a promising ionic conductivity of ≈1.7 mS cm⁻¹ at 30 °C, a satisfactory t_Li+ of 0.51, and a low interfacial impedance. As expected, the assembled Li symmetric battery with SS-PPCE/PAN-3% QSPE can stably cycle more than 1550 h at 0.2 mA cm⁻². The Li||LiFePO₄ quasi-solid-state lithium metal battery (QSSLMB) of this QSPE exhibits a high capacity retention of 81.5% after 300 cycles at 1.0 C and at RT. Even under the high-loading cathode (LiFePO₄ ≈ 10.0 mg cm⁻²) and RT, the QSSLMB achieves a superior area capacity and good cycling performance. Besides, the assembled high voltage Li||NMC811(loading ≈ 7.1 mg cm⁻²) QSSLMB has potential applications in high-energy fields.     

Investigation of La3 + Doped Yb2Sn2O7 as new thermal barrier materials

Low thermal conductivity is one of the key requirements for thermal barrier coating materials. From the consideration of crystal structure and ion radius, La^3 + Doped Yb₂Sn₂O₇ ceramics with pyrochlore crystal structures were synthesized by sol–gel method as candidates of thermal barrier materials in aero-engines. As La^3 + and Yb^3 + ions have the largest radius difference in lanthanoid group, La^3 + ions were expected to produce significant disorders by replacing Yb^3 + ions in cation layers of Yb₂Sn₂O₇. Both experimental and computational phase analyses were carried out, and good agreement had been obtained. The lattice constants of solid solution (La_xYb_1 − x)₂Sn₂O₇ (x = 0.3, 0.5, 0.7) increased linearly when the content of La^3 + was increased. The thermal properties (thermal conductivity and coefficients of thermal expansion) of the synthesized materials had been compared with traditional 8 wt.% yttria stabilized zirconia (8YSZ) and La₂Zr₂O₇ (LZ). It was found that La^3 + Doped Yb₂Sn₂O₇ exhibited lower thermal conductivities than un-doped stannates. Amongst all compositions studied, (La_0.5Yb_0.5)₂Sn₂O₇ exhibited the lowest thermal conductivity (0.851 W·m^− 1·K^− 1 at room temperature), which was much lower than that of 8YSZ (1.353 W·m^− 1·K^− 1), and possessed a high coefficient of thermal expansion (CTE), 13.530 × 10^− 6 K^− 1 at 950 °C.     

MOF-Based Solid-State Proton Conductors Obtained by Intertwining Protic Ionic Liquid Polymers with MIL-101

Solid-state proton conductors based on the use of metal–organic framework (MOF) materials as proton exchange membranes are being investigated as alternatives to the current state of the art. This study reports a new family of proton conductors based on MIL-101 and protic ionic liquid polymers (PILPs) containing different anions. By first installing protic ionic liquid (PIL) monomers inside the hierarchical pores of a highly stable MOF, MIL-101, then carrying out polymerization in situ, a series of PILP@MIL-101 composites was synthesized. The resulting PILP@MIL-101 composites not only maintain the nanoporous cavities and water stability of MIL-101, but the intertwined PILPs provide a number of opportunities for much-improved proton transport compared to MIL-101. The PILP@MIL-101 composite with HSO₄⁻ anions shows superprotonic conductivity (6.3 × 10⁻² S cm⁻¹) at 85 °C and 98% relative humidity. The mechanism of proton conduction is proposed. In addition, the structures of the PIL monomers were determined by single crystal X-ray analysis, which reveals many strong hydrogen bonding interactions with O/N H···O distances below 2.6 Å.     

Synthesis and dc conductivity of Nd2/3TiO2.988

The A-site deficient perovskite Nd_2/3TiO_3 − δ was synthesized under an H₂–CO₂ gas mixture. The sample was found to have slight oxygen deficiency of δ∼0.012. The crystal structure was assigned to a double perovskite structure with orthorhombic space group Pmmm, as in the case of La_2/3TiO_3 − δ. Electrical conductivity measurement has also been performed. The temperature dependence of conductivity shows that electronic transport in Nd_2/3TiO_2.988 is well described by Emin–Holstein adiabatic small polaron model. The polaron density extracted from the conductivity measurement is ∼1.96 × 10²⁰ cm^− 3. This result agrees well with nominal polaron density for Nd_2/3TiO_2.988, ∼2.1 × 10²⁰cm^− 3. We have also derived important quantities for transport in Nd_2/3TiO_2.988.     

Novel dual-phase symmetrical electrode materials for protonic ceramic fuel cells

Protonic ceramic fuel cells (PCFCs) can use hydrogen and hydrocarbon fuels to generate electricity with good performance and anti-cooking resistance. Herein, a novel dual-phase perovskite oxide BaCe_0.5Fe_0.4Ni_0.1O_3-δ (BCFN) with BaCe_0.5Fe_0.5O_3-δ (BCF) as one reference was synthesized, characterized and then evaluated as the symmetrical electrodes for PCFCs. Both BCF and BCFN can be self-assembled into an orthorhombic cerium-rich oxide phase and a cubic iron-rich oxide phase after calcined at 1000 °C and show good redox stability. BCFN shows much better electrical conductivity and lower area specific resistance than BCF. Applying BCF and BCFN as symmetrical electrodes for PCFCs with the BaZr_0.1Ce_0.7Y_0.2O_3-δ (BZCY) electrolyte supporting, the cell performance with BCFN symmetrical electrode is almost twice (141 mW·cm² at 700 °C) than those with BCF symmetrical electrode, and the electrode polarization resistances are also reduced from 0.7 to 0.5 Ω·cm² using humidified H₂. The preliminary experimental results can demonstrate that dual-phase perovskite oxides with nanoparticle in situ precipitation are very promising symmetrical electrodes for protonic ceramic fuel cells.

     

Construction of Inorganic/Organic Hybrid Layer for Stable Na Metal Anode Operated under Wide Temperatures

Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/C F/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm⁻²/1 mA cm⁻² in carbonate electrolyte. The assembled full battery of IOHL-Na||Na₃V₂(PO₄)₃ delivers a high discharge capacity of 85 mAh g⁻¹ at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na₃V₂(PO₄)₃ cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of −40 °C, the full cell achieves 40 mAh g⁻¹ at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.     

Boosting the Thermoelectric Performance of the Doped DPP-EDOT Conjugated Polymer by Incorporating an Ionic Additive

The thermoelectric (TE) performance of organic materials is limited by the coupling of Seebeck coefficient and electrical conductivity. Herein a new strategy is reported to boost the Seebeck coefficient of conjugated polymer without significantly reducing the electrical conductivity by incorporation of an ionic additive DPPNMe₃Br . The doped polymer PDPP - EDOT thin film exhibits high electrical conductivity up to 1377 ± 109 S cm⁻¹ but low Seebeck coefficient below 30 µV K⁻¹ and a maximum power factor of 59 ± 10 µW m⁻¹ K⁻². Interestingly, incorporation of small amount (at a molar ratio of 1:30) of DPPNMe₃Br into PDPP - EDOT results in the significant enhancement of Seebeck coefficient along with the slight decrease of electrical conductivity after doping. Consequently, the power factor (PF) is boosted to 571 ± 38 µW m⁻¹ K⁻² and ZT reaches 0.28 ± 0.02 at 130 °C, which is among the highest for the reported organic TE materials. Based on the theoretical calculation, it is assumed that the enhancement of TE performance for the doped PDPP - EDOT by DPPNMe₃Br is mainly attributed to the increase of energetic disorder for PDPP - EDOT .     

Facile Proton Transport in Ammonium Borosulfate—An Unhumidified Solid Acid Polyelectrolyte for Intermediate Temperatures

High proton conductivity is reported for unhumidified ammonium borosulfate, NH₄[B(SO₄)₂], a solid acid coordination polymer that contains 1D, hydrogen-bonded NH₄⁺···¹_∞[B(SO₄)_4/2]⁻ chains. NH₄[B(SO₄)₂] is thermally stable to 320 °C and is amenable to sintering into monolithic, polycrystalline discs at 200 °C and about 300 MPa of uniaxial pressure. Impedance spectroscopy measurements reveal ionic conductivities for sintered ammonium borosulfate of 0.1 mS cm⁻¹ at 25 °C and up to 10 mS cm⁻¹ at 180 °C in ambient air. No superprotonic transition is observed in the temperature range of 25–180 °C. Ab initio molecular dynamics simulations show these high conductivities are aided by free rotation of the NH₄⁺ units and significant gyrational mobility of the SO₄ tetrahedra, which, in turn, provide facile pathways for proton locomotion. High conductivities, a wide operational temperature window, and tolerance to both ambient and anhydrous conditions make NH₄[B(SO₄)]₂ an attractive candidate electrolyte for intermediate-temperature hydrogen fuel cells that may enable operation at temperatures as high as 300 °C without active humidification.     

Oxide-ion conductivity in CuxCe1−xO2−δ (0 ≤ x ≤ 0.10)

Up to 10 at.% of copper readily substitutes for cerium in ceria. It is found that at oxygen partial pressures between 0.21 atm and 10⁻⁵ atm, Cu_xCe_1−xO_2−δ (0 ≤ x ≤ 0.10) solid solution behave as an oxide-ion electrolyte. Interestingly, Cu_0.10Ce_0.90O_2−δ exhibits the oxide-ion conductivity of ca. 10⁻⁴ Ω⁻¹ cm⁻¹ at 600 °C at an oxygen partial pressure of 10⁻⁵ atm.     

High-Performance Bifunctional Porous Iron-Rich Phosphide/Nickel Nitride Heterostructures for Alkaline Seawater Splitting

Seawater is the most abundant natural water resource in the world, which is an inexhaustible and low-cost feedstock for hydrogen production by alkaline water electrolysis. It is appearling to develop robust and stable electrocatalysts for alkaline seawater electrolysis. However, the development of seawater electrolysis is seriously impeded by anodic chloride corrosion and chlorine evolution reaction, and few non-noble electrocatalysts show prominent catalytic performance and excellent durability. Here, a heterogeneous electrocatalyst constructed by in situ growing highly dispersed iron-rich bimetallic phosphide nanoparticles on metallic Ni₃N (Fe_2−2xCo_2xP/Ni₃N), which exhibits outstanding bifunctional catalytic activities for alkaline seawater splitting, is reported. The optimal (Fe_0.74Co_0.26)₂P/Ni₃N and Fe₂P/Ni₃N electrocatalysts demand only 113 and 212 mV to afford 100 mA cm⁻² for hydrogen and oxygen evolution reactions (HER and OER) in 1 m KOH, respectively, thus substantially expediting overall water/seawater electrolysis at 100 mA cm⁻² with 1.592/1.645 V. Particularly, Fe₂P/Ni₃N displays an unprecedented overpotential of 302 mV at 500 mA cm⁻², which represents the best alkaline seawater oxygen evolution activity among the ever-reported non-noble electrocatalysts; and thus substantially expedites overall water/seawater splitting at 500 mA cm⁻² with 1.701/1.768 V, surpassing most of the reported non-noble lectrocatalysts. This work provides a new approach for developing high-performance electrocatalysts for seawater splitting.     

Synthesis and characterization of Gd3+ and Nd3+ co-doped ceria by using citric acid–nitrate combustion method

A series of Ce_0.8Gd_0.2?xNd_xO_2?δ (x = 0–0.20) compositions have been synthesized by citric acid–nitrate combustion method. XRD measurements indicate that all the obtained materials crystallized in cubic fluorite-type structure. Lattice parameters were calculated by Rietveld method and the parameter a values in Ce_0.8Gd_0.2?xNd_xO_2?δ system obey Vegard's law, a (Å) = 5.4224 + 0.1208x. The obtained powders have good sinterability and the relative density could reach above 95% after being sintered at 1400 °C. Impedance spectroscopy measurements indicated that the conductivity of Ce_0.8Gd_0.2?xNd_xO_2?δ first increased and then decreased with Nd dopant content x. The maximum conductivity, σ_700 °C = 6.26 × 10^?2 S/cm, was found in Ce_0.8Gd_0.12Nd_0.08O_1.9 when sintered at 1300 °C. The corresponding activation energies of conduction had a minimum value E_a = 0.676 eV. The results tested experimentally the validity of the effective atomic number concept of recent density functional theory, which had suggested that co-dopant with effective atomic number between 61 (Pm) and 62 (Sm) was the ideal dopant exhibiting high ionic conductivity and low activation energy.     

Super Proton Conductivity Through Control of Hydrogen-Bonding Networks in Flexible Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have received much attention as a solid-state electrolyte in proton exchange membrane fuel cells. The introduction of proton carriers and functional groups into MOFs can improve the proton conductivity attributed to the formation of hydrogen-bonding networks, while the underlying synergistic mechanism is still unclear. Here, a series of flexible MOFs (MIL-88B, [Fe₃O(OH)(H₂O)₂(O₂C-C₆H₄-CO₂)₃] with imidazole) is designed to modify the hydrogen-bonding networks and investigate the resulting proton-conducting characteristics by controlling the breathing behaviors. The breathing behavior is tuned by varying the amount of adsorbed imidazole into pore (small breathing (SB) and large breathing (LB)) and introducing functional groups onto ligands (-NH₂, -SO₃H), resulting in four kinds of imidazole-loaded MOFs−Im@MIL-88B-SB, Im@MIL-88B-LB, Im@MIL-88B-NH₂, and Im@MIL-88B-SO₃H. Im@MIL-88B-LB without functional groups exhibits the highest proton conductivity of 8.93 × 10⁻² S cm⁻¹ at 60 °C and 95% relative humidity among imidazole-loaded proton conductors despite the mild condition, indicating that functional groups may not be always required to enhance proton conductivity. The elaborately controlled pore size and host–guest interaction in flexible MOFs through imidazole-dependent structural transformation are translated into the high proton concentration without the limitation of proton mobility, contributing to the formation of effective hydrogen-bonding networks in imidazole conducting media.