ABSTRACT Reducing iridium (Ir) loading while maintaining high activity and durability remains a critical challenge for proton exchange membrane water electrolysis. While oxide‐supported catalysts offer a pathway for Ir reduction, their intrinsic low electronic conductivity and inefficient charge transfer at catalyst‐support interfaces remain imperative bottlenecks. Herein, we report a synergistic interfacial engineering strategy of catalyst‐support based on partial ex‐solution of Bi from a Bi 3 TaO 7 support. Ex‐solved Bi forms highly active Ir─Bi alloy domains while generating a Bi‐deficient support and markedly improving the conductivity of the support. Moreover, this coupled reconstruction lowers the work function of the Ir‐based catalyst while increasing the work function of the support, shifting the catalyst‐support contact from rectifying to ohmic, thereby facilitating efficient electron transport. The resulting IrBi/Bi 3‐x TaO 7 exhibits enhanced half‐cell oxygen evolution reaction activity (248 mV at 10 mA/cm 2 ), mass activity (1077 mA/mg Ir at 1.55 V), and durability (15.8 h). Furthermore, single‐cell measurements achieve outstanding performance of 1.824 V at 2 A/cm 2 with a low Ir loading of 0.38 mg/cm 2 and negligible voltage degradation over 100 h. This work highlights a generalizable strategy for simultaneous electronic integration of catalyst and support, offering new insights into the design of efficient and durable electrocatalysts for PEMWE.
ABSTRACT Sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs) have emerged as significant contenders for large‐scale energy storage technology due to their substantial resource reserves and cost effectiveness. However, their large‐scale development is hindered by several key challenges, including the structural degradation of electrode materials during cycling, slow kinetics, and instability at the electrode–electrolyte interface. Entropy‐regulation strategies, particularly medium‐to‐high‐entropy designs, represent an emerging paradigm in materials design. The integration of multiple components, with the aim of leveraging their synergistic effects, presents a novel approach to address the aforementioned challenges in a systematic manner. It has been demonstrated that, owing to its elevated configurational entropy, this strategy accomplishes two objectives: first, it provides thermodynamic stabilization of the crystal structure, and second, it suppresses undesirable phase transitions. Additionally, it induces kinetic effects that result in slow diffusion, thereby effectively delaying element migration and side reactions. Concurrently, entropy regulation fosters the establishment of a stable interfacial film at the electrode‐electrolyte interface, thereby enhancing interfacial ionic transport efficiency and chemical stability. This paper systematically reviews the mechanistic insights and research progress of entropy‐regulation strategies in cathode materials, anode materials, and interface engineering for SIBs and PIBs, and outlines future directions for this field.
ABSTRACT Composite polymer electrolytes (CPEs) exhibit considerable potential for solid−state lithium−metal batteries (SLBs). However, incompatibilities between the various components in the electrolyte continue to hinder the full realization of its performance and practical applications. In this work, a multifunctional ceria interfacial layer is proposed to achieve uniform dispersion of ceramic fillers and facilitated interfacial transport of lithium ions in CPEs. At the same time, the physical barrier provided by this multifunctional interface layer prevents direct contact between the ceramic filler and the lithium metal, thereby avoiding potentially harmful side reactions that could further lead to a performance deterioration in battery cycling. Owing to the introduction of this multifunctional interface layer, the CPE exhibits high ionic conductivity (0.772 mS cm −1 ) and Li–ion transference number (0.626), with a wide electrochemical window (5.03 V). Furthermore, the Li|CPE|Li symmetric cell exhibits a lithium deposition/stripping capacity exceeding 1500 h at room temperature, indicating the CPE's excellent ability to suppress interfacial side reactions. Li|CPE|NCM811 cells retained a capacity of 77% after 350 cycles, whilst pouch cells retained 76% after 300 stable cycles at room temperature and 0.5 C. The method of optimizing ceramic fillers offers new insights into the design of novel composite solid–state electrolytes for SLBs.
ABSTRACT Anode‐free sodium metal batteries (AFSMBs) promise ultrahigh energy density (>350 Wh kg −1 ) and low cost, yet their operation under low‐temperature and fast‐charging conditions is critically hindered by limited sodium inventory and sluggish interfacial kinetics. This conflict creates a “stability paradox”: the pursuit of high energy density amplifies interfacial instability, leading to inhomogeneous sodium deposition and rapid capacity decay. This review systematically analyzes AFSMB failure mechanisms under extreme conditions and demonstrates that overcoming these bottlenecks requires integrated co‐design across four synergistic domains: (1) engineering electrolyte solvation structures (weakly solvating, high‐concentration, and high‐entropy designs) to lower the desolvation barrier and stabilize the solid–electrolyte interphase; (2) tailoring current collector interfaces with sodiophilic coatings or three‐dimensional architectures to guide uniform sodium deposition; (3) incorporating rational pre‐sodiation strategies to compensate irreversible sodium loss; and (4) leveraging artificial intelligence and molecular simulations for data‐driven electrolyte screening. We critically assess the trade‐offs of each strategy and provide a forward‐looking perspective on reversible sodium compensation, multi‐scale AI platforms, and full‐cell integration. This review offers a roadmap for developing practical, wide‐temperature‐range, high‐energy‐density AFSMBs, with recent pouch cells already demonstrating >200 Wh kg −1 and stable cycling from −40°C to 60°C.
ABSTRACT Sulfide‐based all‐solid‐state lithium batteries (ASSLBs) with high‐loading cathodes are currently hindered by sluggish Li + /electron kinetics and poor interfacial compatibility. Conventional carbon additives, despite their high conductivity, often trigger detrimental side reactions with sulfide electrolytes. To mitigate these issues, we introduce a multifunctional nanoscale In 2 O 3 conductive agent, integrated via a facile one‐step ball milling process. This nano‐In 2 O 3 effectively mediates interactions between large Li 5.5 PS 4.5 Cl 1.5 (LPSC) and LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) particles, enhancing mixing homogeneity and collision efficiency. The resulting composite cathode features a low‐tortuosity Li + transport network and establishes rapid “NCM‐nano In 2 O 3 ‐NCM” electronic pathways within particle gaps. Crucially, In 2 O 3 improves interfacial compatibility between the LPSC and conductive additives, suppressing interfacial degradation. Consequently, a high‐loading cathode (18.34 mg cm −2 ) demonstrates a specific capacity of 131 mAh g −1 at 3C and exhibits excellent cyclability, retaining 97.6% capacity after 500 cycles in NCM811||Li cells. This strategy highlights the potential of nanoscale metal oxide additives for achieving high‐energy‐density ASSLBs through optimized interfacial and transport kinetics.
ABSTRACT Gas evolution during water electrolysis forms bubble layers that block active sites and increase transport and ohmic losses. Decoupling bubble‐mediated mass transport from intrinsic hydrogen evolution reaction (HER) kinetics remains challenging because surface modifications affect both activity and bubble dynamics. Here, a surface‐strained NiMo cathode ( s ‐NiMo) enables kinetics‐decoupled hydrogen bubble management in a near‐neutral electrolyte. In 0.5 m potassium phosphate buffer (pH 7.0), NiMo and s ‐NiMo exhibit nearly identical intrinsic HER kinetics, consistent with similar H* adsorption energetics. Under bubble‐regulated operation, s ‐NiMo shows a 63 mV lower steady‐state overpotential at −20 mA cm −2 . High‐speed imaging reveals smaller, faster‐departing H 2 bubbles, reducing the mean residence time from 0.5 s to 0.2 s. Interfacial analyses indicate enhanced hydrophilicity and more negative surface‐charge‐related characteristics. Ensemble calculations based on the Universal Model for Atoms show that the surface‐associated *H 2 state is 0.52 eV higher in the s ‐NiMo‐representative environment, while electrochemical fluorescence lifetime imaging microscopy reveals a 1.5‐fold higher nanobubble event density. In a single‐cell electrolyzer at 300 mA cm −2 , s‐NiMo maintains a 280 mV lower cell voltage over 100 h. These findings establish bubble management as an independent design axis for stable near‐neutral water electrolysis.
ABSTRACT Strain engineering has emerged as an effective strategy for tailoring the electronic structure and catalytic behavior of materials at the atomic scale. For electrochemical water splitting, the sluggish kinetics of the hydrogen evolution reaction and oxygen evolution reaction are largely limited by scaling relationships and nonoptimized adsorption energetics of key intermediates. High‐entropy materials, featuring multiprincipal‐element compositions and pronounced lattice distortion, offer a unique platform for strain‐mediated catalytic regulation. Their intrinsic microstrain fields, derived from atomic size mismatch together with sluggish diffusion and cocktail effects, enable tunable electronic structures and abundant metastable active sites. This review summarizes recent advances in strain engineering of high‐entropy materials for water splitting. Fundamental concepts of strain and its influence on d‐band centers, adsorption energetics, and reaction kinetics are first introduced. This is followed by a discussion of strain modulation strategies, including doping, solid solution alloying, and defect engineering. Special emphasis is placed on the distinct behavior of high‐entropy materials compared with conventional alloys, particularly their nonlinear electronic hybridization and multisite synergy. Finally, key challenges involving strain quantification, operando evolution, and strain‐entropy coupling are highlighted, providing guidance for the rational design of next‐generation water‐splitting catalysts.
ABSTRACT Benefiting from the anionic redox activity, lithium‐rich layered oxide cathodes exhibit high specific capacity, but the migration of transition metal (TM) can exacerbate vacancy clustering, resulting in domino‐like structural degradation. To stabilize the structure, the electrostatic pinning effect is precisely incorporated into the Li layer to mitigate the TM migration via strong electrostatic repulsion. Concurrently, this configuration effectively modulates the electronic distribution around the oxygen ligands, thereby stabilizing the oxygen redox. Furthermore, robust electrostatic interactions endow the material with the capability to adaptively adjust its interlayer spacing, thereby buffering the structural evolution of the layered framework during (de)lithiation processes. The modified cathode achieves an 89.1% capacity retention over 400 cycles in half‐cells and an impressive 96.2% over 1000 cycles in full cells. To further decouple the capacity‐stability trade‐off while concurrently enhancing both bulk and interfacial stability, we engineered a gradient shielding architecture. This design not only attains 219.8 mAh g −1 at 0.5C and delivers capacity retention of 90.8% after 400 cycles but also promotes the formation of a compact CEI at the near‐surface region, markedly improving interfacial stability under harsh conditions. This progressive structural engineering paradigm offers fresh insights into overcoming the intrinsic structural challenges of lithium‐rich cathode materials.
ABSTRACT Two‐dimensional covalent organic frameworks (2D‐COFs) with tunable structures offer a promising platform for photocatalytic overall water splitting (OWS) under visible‐light. However, it is challenging to quickly find photocatalytic OWS materials from the massive amounts of 2D‐COFs and then achieve precise synthesis. In this work, we constructed 11 934 hcb‐type 2D‐COFs by assembling 28 building blocks and 9 linkages. The machine learning (ML) and high‐throughput computation (HTC) were integrated to predict feasible photocatalytic OWS hcb‐type 2D‐COFs. Through training 10 initial algorithms and optimizing the hyperparameters of top 4 algorithms in terms of performance, the ETR model for predicting the band‐edge levels with R 2 of 0.97 and 0.99 was developed, and the KNR and RFR models were built for predicting Δ G *H and Δ G *OH with R 2 of 0.99 and 0.83, respectively. 2581 2D‑COFs (21.63% of dataset) are screened to be potential structures for visible‑light‑driven water splitting. After applying the optimal ML models on all assembled 2D‐COFs, a list of high‐frequency building blocks and linkages is suggested as a set of suitable candidates for the first time. Then TBTZ_FBN0_Imine (TBTZ‐FBN0‐COF) was assembled and experimentally synthesized. Its OWS activity verified our ML‐HTC paradigm, which provides the researchers recommendation to construct photocatalytic OWS 2D‐COFs.
ABSTRACT Balancing high catalytic activity with long‐term electrochemical durability remains a significant challenge for practical green hydrogen production, especially under the harsh operating conditions of water electrolysis. Here, we report a robust three‐dimensional core‐shell nanoporous electrocatalyst with a noble metal (NM) skin, synthesized via a two‐step dealloying strategy that exploits the atomic enthalpy difference between noble and transition metals. The resulting core‐shell nanoporous catalyst (NP‐IrNi@Ir) exhibits ultra‐low overpotentials of 102.4, 154.6, and 209.5 mV for the hydrogen evolution reaction (HER) in acidic, alkaline, and alkaline seawater electrolytes, respectively, at an industry‐level current density of 1 A cm −2 . Serving as a bifunctional catalyst for both HER and oxygen evolution reaction (OER), NP‐IrNi@Ir presents overall water splitting voltages of 1.45, 1.50, and 1.46 V in acidic, neutral, and alkaline electrolytes at 10 mA cm −2 . When coupled with a monolithic perovskite‐silicon tandem solar cell, the integrated device attains a remarkable solar‐to‐hydrogen conversion efficiency of 22.4% in alkaline seawater electrolysis, among the highest values reported to date. Notably, NP‐IrNi@Ir exhibits exceptional stability over 2000 h of continuous operation in alkaline natural seawater, with negligible performance degradation, underscoring the outstanding durability of its three‐dimensional core‐shell nanoarchitecture under high‐voltage conditions.
ABSTRACT Employing organic semiconductors (OSs) for photoelectrochemical (PEC) solar‐driven water splitting represents a promising route for sustainable hydrogen production; however, OS‐based photoanodes remain limited by poor stability for the PEC oxygen evolution reaction. Here, a bilayer heterojunction (BiHJ) architecture, obtained through orthogonal solution processing of two separate OS layers, is developed to enhance both charge transfer and operational durability compared to conventional bulk heterojunction (BHJ) structures. The BiHJ photoanode achieves a remarkable photocurrent onset near 0 V RHE and retains 62% of its initial activity after 22 h under sacrificial conditions, whereas the BHJ counterpart fails within 6 h. Electrochemical impedance spectroscopy reveals reduced interfacial resistance and charge accumulation at the BiHJ/electrolyte interface, and grazing incidence wide‐angle X‐ray scattering and Fourier‐transform infrared spectrocopy analyses confirm that the enhanced structural order and chemical robustness mitigate O 2 ‐induced degradation. When integrated with a poly(triarylamine) hole‐transport layer and Li‐IrO x catalyst, the BiHJ photoanode performs water oxidation for >15 h with significantly improved stability compared to the BHJ device under high applied bias at pH 9. This work establishes a viable device‐engineering approach toward achieving efficient and durable organic photoanodes for integrated Z‐scheme PEC water splitting.
ABSTRACT The development of efficient and durable platinum‐free electrocatalysts for the hydrogen evolution reaction (HER) is crucial for advancing anion exchange membrane water electrolyzer (AEMWE) powered by intermittent renewable energy. Herein, we report ultra‐stable sub‐1 nm Ru‐based high‐entropy clusters embedded on oxyphilic cerium oxide for alkaline HER, which achieves low overpotentials of 25 and 66 mV at 10 and 100 mA cm −2 , with mass activity (4543 mA mg −1 Ru ) and turnover frequency (2.38 H 2 s −1 ) exceeding Pt/C by 16.5 and 8.5 times. When integrated into an AEMWE, it attains 1.0 and 2.0 A cm −2 at 1.75 and 1.95 V with negligible degradation over 1300 h. Experimental and theoretical results reveal that the strong electron metal‐support interaction (EMSI) mediated by Ru─O─Ce bonds not only activates an efficient dual interfacial Ce‐Ru water dissociation site, accelerating the rate‐limiting Volmer step, but also optimizes the electronic structure of Ru sites, yielding a near‐ideal hydrogen adsorption free energy and enhancing resistance to hydroxyl species poisoning. Most importantly, the combined high‐entropy effect and EMSI‐induced confinement provide dual thermodynamic and kinetic stabilization of the clusters, suppressing the degradation under intermittent operating conditions. This study offers a new design principle for developing robust electrocatalysts suited for dynamic renewable energy systems.
ABSTRACT The deployment of silicon anodes in high‐energy lithium‐ion batteries is restricted by substantial volume expansion during cycling. Herein, we report a scalable synthetic strategy for a silicon‐confined porous carbon composite anode to mitigate this limitation. Through an industrial‐scale process, we achieved the atomic‐level confinement of silicon, chemically anchoring single atoms and nanoclusters (below 1.0 nm) within the microporous architecture of a robust carbon host. This engineered structure utilizes pre‐reserved internal void space to accommodate lithiation‐induced expansion, significantly mitigating macroscopic electrode swelling relative to conventional materials. When integrated into 2 Ah P‐Si/C‐Gr||NCM811 pouch cells, the resulting cells deliver a high capacity retention of 81.2% after 1000 cycles with only 11.5% cell swelling. Furthermore, industrial production analysis confirms high consistency and cost‐competitiveness, establishing a viable pathway linking fundamental atomic‐level materials design with commercial requirements (100 kg/batch) for high‐performance silicon anodes.
ABSTRACT Alluaudite–type sodium iron sulfates are attractive low–cost, high–voltage cathodes for sodium–ion batteries (SIBs), as the strong inductive effect of SO 4 2− lifts the Fe 2+ /Fe 3+ redox couple to ∼3.8 V. However, poor intrinsic framework stability hinders their practical deployment, causing Fe–Fe Coulombic repulsion–induced antisite defects, sluggish Na + diffusion, and moisture–triggered surface hydration. Herein, a cation–substitution strategy is developed to concurrently regulate the bulk and surface framework stability of Na 2+2x Fe 2−x (SO 4 ) 3 via partial Cu–for–Fe occupation. X–ray absorption spectroscopy, in situ X–ray diffraction, and density functional theory calculations reveal that Cu incorporation enlarges Fe–Fe separation, widens Na + migration channels, narrows the band gap from 3.27 to 2.23 eV, and suppresses surface H 2 O affinity. The optimized Na 2.6 Fe 1.6 Cu 0.1 (SO 4 ) 3 /C (NFCS/C) cathode delivers a reversible capacity of 109.6 mAh g −1 at 0.1C, retains 78.3% capacity over 10 000 cycles at 5C, sustains operation from −20°C to 80°C, and preserves its electrochemistry after 168 h ambient air exposure. The assembled HC//NFCS/C full cell with 5.1 mg cm −2 cathode loading achieves 89.6% capacity retention after 1300 cycles at 1C. This work establishes cation substitution as an effective handle for concurrent bulk–surface stabilization of alluaudite sulfates, advancing a viable route toward high–voltage, long–life SIBs.
ABSTRACT Double‐sided fully‐textured (3–5 µm) perovskite/silicon tandem solar cells (PS‐TSCs) emerge as a promising pathway for tandem photovoltaics due to their excellent optical management and low manufacturing costs. However, their commercialization is hindered by operational instability, largely attributable to ion migration within the wide‐bandgap perovskite top cell. Here, we report a B‐site cation alloying strategy employing strontium (Sr 2+ ) to enhance the stability of wide‐bandgap perovskites through local lattice engineering. Owing to its lower electronegativity and polarizability relative to lead (Pb 2+ ), Sr 2+ incorporation strengthens the metal‐halide bonding network, thereby forming a more rigid and ordered octahedral framework with weakened electron‐phonon coupling. The Sr/Pb alloyed perovskite films exhibit significantly enhanced stability under illumination and/or thermal stress. Fully‐textured PS‐TSCs incorporating this strategy achieve a power conversion efficiency of 31.66%. Importantly, encapsulated devices show less than 7% performance loss after more than 1391 h at maximum power point tracking, corresponding to a projected T 80 lifetime of approximately 6785 h under continuous 1‐sun illumination. Under thermal aging at 65°C, devices further demonstrate a T 90 lifetime exceeding 1100 h.
ABSTRACT Halide solid‐state electrolytes (SSEs) are promising for all‐solid‐state batteries (ASSBs) but are often limited by the challenge of simultaneously achieving sufficient ionic conductivity and cost‐effectiveness. Herein, we demonstrate that weakening ion transport anisotropy is an effective route to achieve superionic conduction in low‐cost Li 2 ZrCl 6 through an anion‐cation co‐doping strategy using InF 3 . Mechanistic analysis reveals that moderate co‐doping reduces the intrinsic anisotropy of Li‐ion transport, thereby facilitating faster long‐range diffusion, whereas excessive doping introduces localized migration bottlenecks in the monoclinic lattice, leading to diminished ionic conductivity. The optimized Li 2.1 Zr 0.9 In 0.1 Cl 5.7 F 0.3 exhibits a high ionic conductivity of 1.03 × 10 −3 S cm −1 with a low activation energy of 0.357 eV. As a result, the ASSBs using this optimized halide SSE deliver high reversible capacity, excellent rate capability, and long‐term stability, retaining 92.5% capacity after 500 cycles at 1 C and operating stably over 2500 cycles at 4 C. Moreover, the enhanced ionic conductivity enables stable operation at a high cathode loading of 31.2 mg cm −2 . This work highlights weakening ionic transport anisotropy as an effective strategy for designing high‐performance halide SSEs.
ABSTRACT Electrocaloric (EC) cooling technology offers advantages such as miniaturization, low energy consumption, and solid‐state operation. However, the temperature span (Δ T span ) of EC devices remains limited and must be enhanced. Here, we construct a six‐layer cascade electrocaloric cooling device (SCECD) that achieves a large Δ T span . The synergy of electrostatic actuation and self‐actuation ensures that electrostatic force and deformation force always act in the same direction on the EC stack, enhancing heat transfer efficiency in the SCECD. The copper (Cu) as the electrode is evaporated onto the EC stack to increase its stiffness and raise the critical voltage for instability, which typically manifests as localized wrinkling or dimpling. This enhancement improves the resistance of the EC stack to instability, thus ensuring uniform deformation under actuation conditions. As a result, the SCECD, which combines electrostatic actuation and self‐actuation, achieves a Δ T span of 13.07 K and a cooling temperature change (Δ T cooling ) of 6.45 K. The SCECD not only achieves an outstanding cooling performance within the field of polymer‐based EC devices, but also contributes to ongoing efforts in developing practical solid‐state cooling technologies.
ABSTRACT The efficiency of the alkaline hydrogen evolution reaction (HER) is fundamentally constrained by the scaling relationship between water dissociation and hydrogen adsorption/desorption steps. To achieve differentiated optimization of the reaction pathway, a Ni‐Ga‐Pt ternary catalyst with function‐partitioned active sites was constructed in this work by introducing Ga. Through Ga mediation, a site‐specific d ‐band center upshift at Ni sites enhanced hydroxyl (OH) adsorption, thereby accelerating water dissociation. Meanwhile, a downshifted d ‐band center by 0.22 eV at Pt sites optimized the hydrogen adsorption energy (ΔG H* ) to a near‐thermoneutral value of −0.08 eV. This synergistic mechanism reduced the water dissociation energy barrier by 24.5%, enabling the catalyst to achieve an ultralow overpotential of 26 mV at 10 mA cm −2 . When integrated into an anion exchange membrane (AEM) electrolyzer using simulated seawater, the Ni‐Ga‐Pt‐based cathode exhibits long‐term stability by maintaining continuous operation at 500 mA cm −2 for over 600 h, while significantly outperforming the Pt/C || NiFeO x ‐based benchmark device—thus highlighting its significant potential for industrial‐scale seawater electrolysis. This study elucidates a d ‐band partitioning strategy from the perspective of orbital hybridization, providing a generalizable approach to the design of efficient and durable multi‐step electrocatalysts.
ABSTRACT Smart windows based on all‐thin‐film electrochromic devices (ECDs) with coordinated visible (VIS) and infrared (IR) modulation offer promising solutions for energy‐efficient buildings. However, conventional single‐layer ECDs often suffer from limited IR modulation, sluggish kinetics, poor durability, and restricted spectral control. Here, we develop a separated‐function electrochromic device (SF‐ECD) that decouples VIS and IR regulation into independent functional layers. ENZ‐ITO enables electrically driven IR modulation through carrier‐mediated localized surface plasmon resonance (LSPR), while NiO x provides VIS modulation via polaron‐based electrochromism. This architecture achieves synergistic multi‐band optical control, delivering average emissivity modulations of 0.76, 0.68, 0.75, and 0.68 across the 3–5, 8–14, 16–25, and 2.5–25 µm bands, respectively, with a maximum visible transmittance modulation of 52.1% and emissivity modulation of 0.83. The SF‐ECD exhibits rapid IR switching (<5.0 s), excellent cycling stability (>5 × 10 4 cycles), and sustained performance after 1‐year storage. Outdoor tests demonstrate a temperature reduction of 5°C–6°C under solar irradiation, highlighting its potential for advanced thermal management in intelligent buildings.
ABSTRACT Developing piezoelectric materials with a high figure‐of‐merit (FOM = d 33 × g 33 /tan δ ) is crucial for advanced energy‐harvesting technologies. Here, a high FOM is achieved in [001]‐oriented Pb(Mg 1/3 Nb 2/3 )O 3 ‐PbZrO 3 ‐PbTiO 3 (PMN‐PZT) textured ceramics by synergistically integrating grain orientation, defect engineering, and morphotropic phase boundary (MPB) design. The textured ceramic exhibits exceptional properties (piezoelectric charge coefficient d 33 = 1120 pC·N −1 , piezoelectric voltage coefficient g 33 = 62 × 10 −3 V·m·N −1 , and an ultralow dielectric loss tan δ = 0.23%). Atomic‐scale analysis reveals that the [001] intrinsic anisotropy and mixed rhombohedral‐tetragonal domains facilitate polarization rotation to boost d 33 and g 33 , while Mn doping‐induced defect dipoles suppress dielectric loss. Consequently, an ultrahigh FOM of 30,180 × 10 −12 m 2 ·N −1 is realized. Furthermore, a cantilever energy harvester utilizing this textured ceramic delivers an outstanding power density of 0.72 µW·mm −3 , which is 78 times higher than that of commercial soft PZT. This work provides an effective strategy for designing high‐FOM piezoelectric materials for high performance energy harvesting applications.
