Interdispersed Amorphous MnOx–Carbon Nanocomposites with Superior Electrochemical Performance as Lithium‐Storage Material

The realization of manganese oxide anode materials for lithium‐ion batteries is hindered by inferior cycle stability, rate capability, and high overpotential induced by the agglomeration of manganese metal grains, low conductivity of manganese oxide, and the high stress/strain in the crystalline manganese oxide structure during the repeated lithiation/delithiation process. To overcome these challenges, unique amorphous MnO_x–C nanocomposite particles with interdispersed carbon are synthesized using aerosol spray pyrolysis. The carbon filled in the pores of amorphous MnO_x blocks the penetration of liquid electrolyte to the inside of MnO_x, thus reducing the formation of a solid electrolyte interphase and lowering the irreversible capacity. The high electronic and lithium‐ion conductivity of carbon also enhances the rate capability. Moreover, the interdispersed carbon functions as a barrier structure to prevent manganese grain agglomeration. The amorphous structure of MnO_x brings additional benefits by reducing the stress/strain of the conversion reaction, thus lowering lithiation/delithiation overpotential. As the result, the amorphous MnO_x‐C particles demonstrated the best performance as an anode material for lithium‐ion batteries to date.     

High Proton Conductivity in β-Ba2ScAlO5 Enabled by Octahedral and Intrinsically Oxygen-Deficient Layers

Proton conductors are promising materials for clean energy, but most available materials exhibit sufficient conductivity only when chemically substituted to create oxygen vacancies, which often leads to difficulty in sample preparation and chemical instability. Recently, proton conductors based on hexagonal perovskite-related oxides have been attracting attention as they exhibit high proton conductivity even without the chemical substitutions. However, their conduction mechanism has been elusive so far. Herein, taking three types of oxides with different stacking patterns of oxygen-deficient layers (β-Ba₂ScAlO₅, α-Ba₂Sc_0.83Al_1.17O₅, and BaAl₂O₄) as examples, the roles of close-packed double-octahedral layers and oxygen-deficient layers in proton conduction are shown. It is found that “undoped” β-Ba₂ScAlO₅, which adopts a structure having alternating double-octahedral layer and double-tetrahedral layer with intrinsically oxygen-deficient hexagonal BaO (h') layer, shows high proton conductivity (≈10⁻³ S cm⁻¹ above 300 °C), comparable to representative proton conductors. In contrast, the structurally related oxides α-Ba₂Sc_0.83Al_1.17O₅ and BaAl₂O₄ exhibit lower conductivity. Ab initio molecular dynamics simulations revealed that protons in β-Ba₂ScAlO₅ migrate through the double-octahedral layer, while the h′ layer plays the role of a “proton reservoir” that supplies proton carriers to the proton-conducting double-octahedral layers. The distinct roles of the two layers in proton conduction provide a strategy for developing high-performance proton conductors.     

Hybrid Proton and Electron Transport in Peptide Fibrils

Protons and electrons are being exploited in different natural charge transfer processes. Both types of charge carriers could be, therefore, responsible for charge transport in biomimetic self‐assembled peptide nanostructures. The relative contribution of each type of charge carrier is studied in the present work for fibrils self‐assembled from amyloid‐β derived peptide molecules, in which two non‐natural thiophene‐based amino acids are included. It is shown that under low humidity conditions both electrons and protons contribute to the conduction, with current ratio of 1:2 respectively, while at higher relative humidity proton transport dominates the conductance. This hybrid conduction behavior leads to a bimodal exponential dependence of the conductance on the relative humidity. Furthermore, in both cases the conductance is shown to be affected by the peptide folding state under the entire relative humidity range. This unique hybrid conductivity behavior makes self‐assembled peptide nanostructures powerful building blocks for the construction of electric devices that could use either or both types of charge carriers for their function.     

Pristine Titanium Carbide MXene Films with Environmentally Stable Conductivity and Superior Mechanical Strength

2D titanium carbide (Ti₃C₂T_x MXene) has potential application in flexible/transparent conductors because of its metallic conductivity and solution processability. However, solution‐processed Ti₃C₂T_x films suffer from poor hydration stability and mechanical performance that stem from the presence of intercalants, which are unavoidably introduced during the preparation of Ti₃C₂T_x suspension. A proton acid colloidal processing approach is developed to remove the extrinsic intercalants in Ti₃C₂T_x film materials, producing pristine Ti₃C₂T_x films with significantly enhanced conductivity, mechanical strength, and environmental stability. Typically, pristine Ti₃C₂T_x films show more than twofold higher conductivity (10 400 S cm^?1 vs 4620 S cm^?1) and up to 11‐ and 32‐times higher strength and strain energy at failure (112 MPa, 1,480 kJ m^?3, vs 10 MPa, 45 kJ m^?3) than films prepared without proton acid processing. Simultaneously, the conductivity and mechanical integrity of pristine films are also largely retained during the long‐term storage in H₂O/O₂ environment. The improvement in mechanical performance and conductivity is originated from the intrinsic strong interaction between Ti₃C₂T_x layers, and the absence of extrinsic intercalants makes pristine Ti₃C₂T_x films stable in humidity by blocking the intercalation of H₂O/O₂. This method makes the material more competitive for real‐world applications such as electromagnetic interference shielding.     

Versatile and Highly Efficient Controls of Reversible Topotactic Metal–Insulator Transitions through Proton Intercalation

The ability to tailor a new crystalline structure and associated functionalities with a variety of stimuli is one of the key issues in material design. Developing synthetic routes to functional materials with partially absorbed nonmetallic elements (i.e., hydrogen and nitrogen) can open up more possibilities for preparing novel families of electronically active oxide compounds. Fast and reversible uptake and release of hydrogen in epitaxial ABO₃ manganite films through an adapted low‐frequency inductively coupled plasma technology is introduced. Compared with traditional dopants of metallic cations, the plasma‐assisted hydrogen implantations not only produce reversibly structural transformations from pristine perovskite (PV) phase to a newly found protonation‐driven brownmillerite one but also regulate remarkably different electronic properties driving the material from a ferromagnetic metal to a weakly ferromagnetic insulator for a range of manganite (La_1?xSr_xMnO₃) thin films. Moreover, a reversible perovskite‐brownmillerite‐perovskite transition is achieved at a relatively low temperature (T ≤ 350 °C), enabling multifunctional modulations for integrated electronic systems. The fast, low‐temperature control of structural and electronic properties by the facile hydrogenation/dehydrogenation treatment substantially widens the space for exploring new possibilities of novel properties in proton‐based multifunctional materials.     

Facile Synthesis of Blocky SiOx/C with Graphite‐Like Structure for High‐Performance Lithium‐Ion Battery Anodes

SiO_x‐containing graphite composites have aroused great interests as the most promising alternatives for practical application in high‐performance lithium‐ion batteries. However, limited loading amount of SiO_x on the surface of graphite and some inherent disadvantages of SiO_x such as huge volume variation and poor electronic conductivity result in unsatisfactory electrochemical performance. Herein, a novel and facile fabrication approach is developed to synthesize high‐performance SiO_x/C composites with graphite‐like structure in which SiO_x particles are dispersed and anchored in the carbon materials by restoring original structure of artificial graphite. The multicomponent carbon materials are favorable for addressing the disadvantages of SiO_x‐based anodes, especially for the formation of stable solid electrolyte interphase, maintaining structural integrity of electrode materials and improving electrical conductivity of electrode. The resultant SiO_x/C anodes demonstrate high reversible capacities (645 mA h g^?1), excellent cycling stability (≈90% capacity retention for 500 cycles), and superior rate capabilities. Even at high pressing density (1.3 g cm^?3), SiO_x/C anodes still present superior cycling performance due to the high tap density and structural integrity of electrode materials. The proposed synthetic method can also be developed to address other anode materials with inferior electronic conductivity and huge volume variation.     

Manganese‐Based Functional Nanoplatforms: Nanosynthetic Construction,Physiochemical Property,and Theranostic Applicability

Transition metal‐based nanoparticles have shown their broad applications in versatile biomedical applications. Although traditional iron‐based nanoparticles have been extensively explored in biomedicine, transition metal manganese (Mn)‐based nanoparticulate systems have emerged as a multifunctional nanoplatform with their intrinsic physiochemical property and biological effect for satisfying the strict biomedical requirements. This comprehensive review focuses on recent progress of Mn‐based functional nanoplatforms in biomedicine with the particular discussion on their elaborate construction, physiochemical property, and theranostic applicability. Several Mn‐based nanosystems are discussed in detail, including solid/hollow MnO_x nanoparticles, 2D MnO_x nanosheets, MnO_x‐silica/mesoporous silica nanoparticles, MnO_x‐Fe₃O₄ nanoparticles, MnO_x‐Au, MnO_x‐fluorescent nanoparticles, Mn‐based organic composite nanosystem, and some specific/unique Mn‐based nanocomposites. Their versatile biomedical applications include pH/reducing‐responsive T₁‐weighted positive magnetic resonance imaging, controlled drug loading/delivery/release, protection of neurological disorder, photothermal hyperthermia, photodynamic therapy, chemodynamic therapy, alleviation of tumor hypoxia, immunotherapy, and some specific synergistic therapies, which are based on their disintegration behavior under the mildly acidic/reducing condition, multiple enzyme‐mimicking activity, catalytic‐triggering Fenton reaction, etc. The biological effects and biocompatibility of these Mn‐based nanosystems are also discussed, accompanied with a discussion on challenges/critical issues and an outlook on the future developments and clinical‐translation potentials of these intriguing Mn‐based functional nanoplatforms.     

An Easily Sintered,Chemically Stable,Barium Zirconate‐Based Proton Conductor for High‐Performance Proton‐Conducting Solid Oxide Fuel Cells

Yttrium and indium co‐doped barium zirconate is investigated to develop a chemically stable and sintering active proton conductor for solid oxide fuel cells (SOFCs). BaZr_0.8Y_0.2‐xIn_xO_{3‐ δ} possesses a pure cubic perovskite structure. The sintering activity of BaZr_0.8Y_0.2‐xIn_xO_{3‐ δ} increases significantly with In concentration. BaZr_0.8Y_0.15In_0.05O_{3‐ δ} (BZYI5) exhibits the highest total electrical conductivity among the sintered oxides. BZYI5 also retains high chemical stability against CO₂, vapor, and reduction of H₂. The good sintering activity, high conductivity, and chemical stability of BZYI5 facilitate the fabrication of durable SOFCs based on a highly conductive BZYI5 electrolyte film by cost‐effective ceramic processes. Fully dense BZYI5 electrolyte film is successfully prepared on the anode substrate by a facile drop‐coating technique followed by co‐firing at 1400 °C for 5 h in air. The BZYI5 film exhibits one of the highest conductivity among the BaZrO₃‐based electrolyte films with various sintering aids. BZYI5‐based single cells output very encouraging and by far the highest peak power density for BaZrO₃‐based proton‐conducting SOFCs, reaching as high as 379 mW cm^?2 at 700 °C. The results demonstrate that Y and In co‐doping is an effective strategy for exploring sintering active and chemically stable BaZrO₃‐based proton conductors for high performance proton‐conducting SOFCs.     

Spatially Separated CdS Shells Exposed with Reduction Surfaces for Enhancing Photocatalytic Hydrogen Evolution

To the photocatalytic H₂ evolution, the exposure of a reduction surface over a catalyst plays an important role for the reduction of hydrogen protons. Here, this study demonstrates the design of a noble‐metal‐free spatially separated photocatalytic system exposed with reduction surfaces (MnO_x @CdS/CoP) for highly solar‐light‐driven H₂ evolution activity. CoP and MnO_x nanoparticles are employed as the electron and hole collectors, which are selectively anchored on the outer and inner surface of CdS shells, respectively. Under solar light irradiation, the photogenerated holes and electrons can directionally move to the MnO_x and CoP, respectively, leading to the exposure of a reduction surface. As a result, the H₂ evolution increases from 32.0 to 238.4 µmol h^?1, which is even higher than the activity of platinum‐loaded photocatalyst (MnO_x @CdS/Pt). Compared to the pure CdS with serious photocorrosion, the MnO_x @CdS/CoP maintains a changeless activity for the H₂ evolution and rhodamine B degradation, even after four cycles. The research provides a new strategy for the preparation of spatially separated photocatalysts with a selective reduction surface.     

Li‐Doped Cr2MnO4: A New p‐Type Transparent Conducting Oxide by Computational Materials Design

To accelerate the design and discovery of novel functional materials, here, p‐type transparent conducting oxides, an inverse design approach is formulated, integrating three steps: i) articulating the target properties and selecting an initial pool of candidates based on “design principles”, ii) screening this initial pool by calculating the “selection metrics” for each member, and iii) laboratory realization and more‐detailed theoretical validation of the remaining “best‐of‐class” materials. Following a design principle that suggests using d5⁵ cations for good p‐type conductivity in oxides, the Inverse Design approach is applied to the class of ternary Mn(II) oxides, which are usually considered to be insulating materials. As a result, Cr₂MnO₄ is identified as an oxide closely following “selection metrics” of thermodynamic stability, wide‐gap, p‐type dopability, and band‐conduction mechanism for holes (no hole self‐trapping). Lacking an intrinsic hole‐producing acceptor defect, Li is further identified as a suitable dopant. Bulk synthesis of Li‐doped Cr₂MnO₄ exhibits at least five orders of magnitude enhancement of the hole conductivity compared to undoped samples. This novel approach of stating functionality first, then theoretically searching for candidates that merits synthesis and characterization, promises to replace the more traditional non‐systematic approach for the discovery of advanced functional materials.     

Polyoxometalate‐Modified Sponge‐Like Graphene Oxide Monolith with High Proton‐Conducting Performance

Graphene oxide (GO) contains abundant oxygen‐containing functional groups acting as hydrogen bond acceptors for proton conduction on its basal plane. However, the dilemma in realizing bulk in‐plane conduction and the metastability at room temperature of GO films both obstruct its application. Polyoxometalate‐modified sponge‐like GO monolith (PEGO) with 3D cross‐linking inner structure, which exhibits unique “shrink‐expand” effect to polar solvent, are synthesized. Owing to the introduction of polyoxometalates and the replacement of unstable epoxy groups by ethylenediamine, PEGO exhibits hitherto the highest proton conductivity under low relative humidity (1.02 × 10^?2 S cm^?1 at 60% relative humidity) and excellent long‐term stability (more than 1 month). The outstanding conductivity originates from 3D transporting pathways, high‐density hopping sites, and eliminated grain boundary resistance. This study provides a practical way to design GO‐based proton‐conducting material dominated by in‐plane diffusion.     

A New Family of Proton‐Conducting Electrolytes for Reversible Solid Oxide Cells: BaHfxCe0.8−xY0.1Yb0.1O3−δ

Reversible solid oxide cells based on ceramic proton conductors have potential to be the most efficient system for large‐scale energy storage. The performance and long‐term durability of these systems, however, are often limited by the ionic conductivity or stability of the proton‐conducting electrolyte. Here new family of solid oxide electrolytes, BaHf_xCe_0.8?xY_0.1Yb_0.1O_3?δ (BHCYYb), which demonstrate a superior ionic conductivity to stability trade‐off than the state‐of‐the‐art proton conductors, BaZr_xCe_0.8?xY_0.1Yb_0.1O_3?δ (BZCYYb), at similar Zr/Hf concentrations, as confirmed by thermogravimetric analysis, Raman, and X‐ray diffraction analysis of samples over 500 h of testing are reported. The increase in performance is revealed through thermodynamic arguments and first‐principle calculations. In addition, lab scale full cells are fabricated, demonstrating high peak power densities of 1.1, 1.4, and 1.6 W cm^?2 at 600, 650, and 700 °C, respectively. Round‐trip efficiencies for steam electrolysis at 1 A cm^?2 are 78%, 72%, and 62% at 700, 650, and 600 °C, respectively. Finally, CO₂? H₂O electrolysis is carried out for over 700 h with no degradation.     

Protein‐Directed Metal Oxide Nanoflakes with Tandem Enzyme‐Like Characteristics: Colorimetric Glucose Sensing Based on One‐Pot Enzyme‐Free Cascade Catalysis

It is difficult and significant to realize the aim of “one‐pot” and “nonenzyme” for traditional colorimetric detection of blood glucose. The synthesis of nanomaterials with 2D morphology is also a challenge for the bovine serum albumin (BSA)‐directed method. Here, the BSA‐directed synthesis avenue for metal oxide with 2D nanomorphology is developed. MnO₂ nanoflakes (NFs) with controllable morphology can be obtained by changing the synthesis conditions. Fortunately, not only is the glucose oxidase (GOx)‐like nanozyme (MnO₂ NFs) discovered, but MnO₂ NFs also show dual enzyme activities (GOx‐like activity and peroxidase‐like activity) in similar pH range. That is to say, a “tandem nanozyme” (nanomaterial with tandem enzyme‐like characteristics) is presented here. Further, the one‐pot nonenzymatic strategy is proposed for the colorimetric detection of glucose, where the oxidation of glucose and the colorimetric detection of H₂O₂ are simultaneously conducted under the catalysis of the single nanozyme (MnO₂ NFs). The method shows high sensitivity, low limit of detection, and short detection time, due to the proximity effect and in situ reaction. The as‐synthesized 2D tandem nanozyme expands the species of nanozymes, and the proposed strategy breaks traditional colorimetric detection process, accomplishing the purposes of “one‐pot” and “nonenzyme” in the true sense.     

Significantly Enhanced Thermoelectric Performance in n‐type Heterogeneous BiAgSeS Composites

High performance n‐type bulk BiAgSeS is successfully synthesized to construct heterogeneous composites which consist of mesoscale grains of both pristine BiAgSeS and doped BiAgSeS_1‐xCl_x ( x = 0.03 or 0.05). Without perceptibly deteriorating the Seebeck coefficient, a significant enhancement on electrical conductivity is obtained due to an anomalous increase of both carrier mobility and concentration; the enhanced carrier mobility is proven to be a direct result of modulation doping which relates to the band alignments, while the increased carrier concentration is attributed to the possible charge transfer from Cl rich nanoscale precipitates at the heterogeneous BiAgSeS/BiAgSeS_1‐xCl_x grain boundaries. Eventually, an enhanced figure of merit ZT ≈ 1.23 at 773 K in the composite (BiAgSeS)_0.5(BiAgSeS_0.97Cl_0.03)_0.5 is achieved, indicating that heterogeneous composites ultilizing the mechanism of modulation doping shall be a promising means of boosting the performance of thermoelectric materials. This strategy should be very likely applicable to other thermoelectrics.     

Magnetism and Phase Formation in the Candidate Dilute Magnetic Semiconductor System In2 − xCrxO3: Bulk Materials are Dilute Paramagnets

Well‐characterized bulk materials in the candidate dilute magnetic semiconductor system In_{2 − x}Cr_xO₃ are prepared for 0 ≤ x < 0.15, with cation site preferences in the bixbyite structure identified by diffraction methods. Small ferromagnetic moments are observed; their size (<10⁻² µ_B/dopant ion) is not consistent with bulk ferromagnetism. The resulting bulk materials display dilute paramagnetic behaviour, with all of the moment expected per Cr³⁺ cation dopant being involved in this paramagnetic response.     

Employing Interfaces with Metavalently Bonded Materials for Phonon Scattering and Control of the Thermal Conductivity in TAGS‐x Thermoelectric Materials

The thermoelectric compound (GeTe)_x(AgSbTe₂)_1?x, in short (TAGS‐x), is investigated with a focus on two stoichiometries, i.e., TAGS‐50 and TAGS‐85. TAGS‐85 is currently one of the most studied thermoelectric materials with great potential for thermoelectric applications. Yet, surprisingly, the lowest thermal conductivity is measured for TAGS‐50, instead of TAGS‐85. To explain this unexpected observation, atom probe tomography (APT) measurements are conducted on both samples, revealing clusters of various compositions and sizes. The most important role is attributed to Ag₂Te nanoprecipitates (NPs) found in TAGS‐50. In contrast to the Ag₂Te NPs, the matrix reveals an unconventional bond breaking mechanism. More specifically, a high probability of multiple events (PME) of ≈60% is observed for the matrix by APT. Surprisingly, the PME value decreases abruptly to ≈20–30% for the Ag₂Te NPs. These differences can be attributed to differences in chemical bonding. The precipitates' PME value is indicative of normal bonding, i.e., covalent bonding with normal optical modes, while materials with this unconventional bond breaking found in the matrix are characterized by metavalent bonding. This implies that the interface between the metavalently bonded matrix and covalently bonded Ag₂Te NP is partly responsible for the reduced thermal conductivity in TAGS‐50.     

Exploring the Energy Storage Mechanism of High Performance MnO2 Electrochemical Capacitor Electrodes: An In Situ Atomic Force Microscopy Study in Aqueous Electrolyte

The basic microstructure‐dependent charge storage mechanisms of nanostructured MnO₂ are investigated via dynamic observation of the growth and in situ probing the mechanical properties by using in situ AFM in conjunction with in situ nanoindentation. The progressive nucleation followed by three‐dimensional growth yields pulsed current deposited porous nanostructured γ‐MnO₂, which exhibits a high specific capacitance of 437 F/g and a remarkable cycling performance with >96% capacitance retention after 10 000 cycles. The proton intercalation induced expansion of MnO₂ can be self‐accommodated by the localized compression and reduction of the porosity. More coincidentally, the proton intercalation induced softening is favorable for the elastic deformation of MnO₂. This self‐adaptive capability of nanostructured MnO₂ could generate high structural reliability during cycling. These discoveries offer important mechanistic insights for the design of advanced electrochemical capacitors.     

Network Structure Modification‐Enabled Hybrid Polymer Dielectric Film with Zirconia for the Stretchable Transistor Applications

Stretchable electronic devices should be enabled by the smart design of materials and architectures because their commercialization is limited by the tradeoff between stretchability and electrical performance limits. In this study, thin‐film transistors are fabricated using strategies that combine the unit process of a novel hybrid gate insulator and low‐temperature indium gallium tin oxide (IGTO) channel layer and a stress‐relief substrate structure. Novel hybrid dielectric films are synthesized and their molecular structural configurations are analyzed. These films consist of a polymer [poly(4‐vinylphenol‐co‐methylmethacrylate)], cross‐linkers having different binding structures [1,6‐bis(trimethoxysilyl)hexane (BTMSH), dodecyltrimethoxysilane, and poly(melamine‐co‐formaldehyde)], and an inorganic zirconia component (ZrO_x). The hybrid film with BTMSH cross‐linker and 0.2 M ZrO_x exhibits excellent insulating properties as well as mechanical stretchability. IGTO transistors fabricated on polyimide‐coated glass substrates are transferred to the rubber substrate to offer stretchability of the transistor pixelated thin‐film transistors. IGTO transistors fabricated on stretchable substrates using these strategies show promising electrical performance and mechanical durability. After 200 stretchability test cycles under uniaxial elongation of approximately 300%, the IGTO transistor still retains a high carrier mobility of 21.7 cm² V^?1 s^?1, a low sub‐threshold gate swing of 0.68 V decade^?1 and a high I_ON/OFF ratio of 2.0 × 10⁷.     

The Formation of Performance Enhancing Pseudo‐Composites in the Highly Active La1–xCaxFe0.8Ni0.2O3 System for IT‐SOFC Application

The La_1–xCa_xFe_0.8Ni_0.2O_3–δ (0 ≤ x ≤ 0.9) system is investigated for potential application as a cathode material for intermediate temperature solid oxide fuel cells (IT‐SOFCs). A broad range of experimental techniques have been utilized in order to elucidate the characteristics of the entire compositional range. Low A‐site Ca content compositions (x ≤ 0.4) feature a single perovskite solid solution. Compositions with 40% Ca content (x = 0.4) exhibit the highest electrical and ionic conductivities of these single phase materials (250 and 1.9 × 10^?3 S cm^?1 at 800 °C, respectively), a level competitive with state‐of‐the‐art (La,Sr)(Fe,Co)O₃. Between 40 and 50% Ca content (0.4 > x > 0.5) a solubility limit is reached and a secondary, brownmillerite‐type phase appears for all higher Ca content compositions (0.5 ≤ x ≤ 0.9). While typically seen as detrimental to electrochemical performance in cathode materials, this phase brings with it ionic conductivity at operational temperatures. This gives rise to the effective formation of pseudo‐composite materials which feature significantly enhanced performance characteristics, while also providing the closest match in thermal expansion behavior to typical electrolyte materials. This all comes with the advantage of being produced through a simple, single‐step, low‐cost production route without the issues associated with typical composite materials. The highest performing pseudo‐composite material (x = 0.5) exhibits electronic conductivity of 300–350 S cm^?1 in the 600–800 °C temperature range while the best polarisation resistance (R_p) values of approximately 0.2 Ω cm² are found in the 0.5 ≤ x ≤ 0.7 range.     

Microstructural Engineering of Hydroxyapatite Membranes to Enhance Proton Conductivity

A new approach to enhancing proton conductivity of ceramics is demonstrated by aligning proton conductive pathways and eliminating resistive grain boundaries. Hydroxyapatite (HAP) membranes are synthesized by multistage crystallization onto palladium. The synthesis involves three steps: electrochemical deposition of HAP seeds, secondary hydrothermal crystallization onto the seed layer to promote c‐axis growth normal to the substrate, and tertiary hydrothermal crystallization to promote a‐axis growth to fill the gaps between the aligned crystals. The c‐axis alignment with crystal domains spanning the membrane thickness significantly enhances proton conduction since protons are primarily transported along the c‐axes of HAP crystals. The novel HAP membranes display proton conductivity almost four orders of magnitude higher than traditional sintered HAP ceramics. The HAP membranes on palladium hydrogen membrane substrates hold promise for use in intermediate‐temperature fuel cells, chemical sensors, and other devices. The synthesis approach presented may also be applied to other ion‐conducting membrane materials to enhance transport properties.