The rational design of high-performance bifunctional electrocatalysts for oxygen reduction reaction (ORR) and ethanol oxidation reaction (EOR) remains pivotal for advancing direct ethanol fuel cells (DEFCs). Herein, we report Mo-doped core-shell PdAu@Pd nanocrystals (Mo-PdAu@Pd) with intrinsic tensile strain as an exceptional bifunctional catalyst. The synergistic integration of Mo dopants and a PdAu@Pd core-shell architecture optimizes electronic configurations via d-band center downshifting, while oxophilic Mo and lattice strain engineering enhance intermediate adsorption and reaction kinetics. In alkaline media, Mo-PdAu@Pd delivers a record mass activity of 0.992 A mgPd -1 at 0.9 V for ORR, surpassing commercial Pt/C and Pd/C by 8.07- and 9.92-fold, respectively, with only 4.7% activity loss after 10,000 cycles. For EOR, it achieves 5.95 A mgPd -1, outperforming Pt/C and Pd/C by 5.13- and 5.41-fold, alongside superior durability. In situ Raman spectroscopy and density functional theory (DFT) calculations reveal that the incorporation of oxophilic Mo species acts as auxiliary active sites, promoting O2 adsorption and *OOH formation, while together with the intrinsic tensile strain, the surface electronic state is optimized, which leads to higher ORR activity of Mo-PdAu@Pd. This work provides a universal strategy for engineering strain-modulated, dopant-enhanced catalysts, offering a guideline for the rational design of exceptional bifunctional catalysts.

The practical implementation of silicon anodes is hindered by interfacial instability and limited cycling durability, primarily due to significant volume changes and associated mechanical stresses during operation. To address these challenges, we present a stress-dissipating binder (PAA/C beta-CD@TA) that utilizes the reversible boat-chair conformational transitions of carbonyl-beta-cyclodextrin (C beta-CD) to effectively dissipate stress and reduce intensity. The host-guest interactions between tannic acid (TA) and poly(acrylic acid) (PAA) form mechanically interlocked networks, enhancing stability. Notably, the recognition between the pyrogallol groups of TA and the C beta-CD cavity facilitates the conversion of localized stress into reversible elastic deformation, significantly suppressing damage accumulation. This structure endows the binder with unprecedented mechanical properties, exhibiting 38.26 fold higher toughness than linear PAA, a 480 MPa reduction in Young's modulus, and 2.29 fold enhanced adhesion strength. As a result, it demonstrates exceptional electrochemical performance, retaining 73.32% capacity after 300 cycles at 4.0 A g-1, with an initial Coulombic efficiency of 88.99% for pure silicon anodes. For commercial silicon/carbon systems, it achieves 82.25% and 75.27% capacity retention over 500 cycles at 1.0 and 2.0 C, respectively. This study provides fundamental insights into the conformational transitions of binders for stress dissipation and establishes a new paradigm for designing next-generation silicon-based anodes.

Pr2O3/RuO2 heterostructures achieve record-low acidic OER activity (162 mV) and high mass activity (246.5 A gRu-1), surpassing commercial RuO2. The interfacial effect optimizes intermediate adsorption and stability, reducing energy barriers.

Li2NiO2 (LNO) as a prelithiation additive faces critical challenges including poor rate capability (≤0.1C), limited capacity, and gas evolution during cycling. Here, we report a metal-dopant lattice engineering strategy that simultaneously addresses these challenges through three synergistic mechanisms: (i) particle size reduction from 30 μm to 500nm, shortening Li+ diffusion pathways; (ii) b-axis lattice expansion (Δb/b ≈ 0.29%) and bandgap narrowing (from 1.2eV to 0.6eV), enhancing both ionic and electronic transport; and (iii) strengthened oxygen anchoring via short Cu–O bonds (1.885Å), suppressing superoxide-related side reactions. Critically, this synthesis employs a one-step solid-state heat treatment using only conventional furnace equipment, directly compatible with existing production lines. The doped LNO (Li2Ni0.9Cu0.1O2, designated as LCNO) delivers an exceptional capacity of 492.1 mAh g⁻1 at 0.5C (vs. 282.0 mAh g⁻1 for pristine LNO). When integrated into manufacturing-relevant NCM-811‖Si/C pouch cells activated under fast-formation protocols (2h), LCNO delivers 87% capacity retention (vs. 80% for pristine LNO) after 250 cycles with suppressed gas evolution. Notably, this scalable doping strategy enables industrial manufacturing, bridging the gap from laboratory innovation to commercial production for high-performance prelithiation additives.

Abstract Developing Pt-based catalysts with maximized atomic utilization and optimized electronic structures remains crucial for accelerating the cathodic hydrogen evolution reaction (HER). Herein, we develop a MOF-on-MOF-derived confinement strategy to construct a defect-mediated nanoconfined Pt microenvironment within hierarchically nanoporous carbon microspheres (NCMS), yielding the final catalyst denoted as Pt@NCMS. Specifically, the pre-fabricated Zn/Cu-BTC precursor undergoes pyrolysis and selective etching to generate an interconnected porous carbon enriched with defect sites, enabling confinement of platinum nanocrystals with enhanced metal-support electronic coupling. Structural characterizations reveal that the nanoconfined architecture effectively suppresses Pt aggregation, enhances carbonaceous graphitization, and exposes abundant active sites. XPS and X-ray absorption spectroscopy demonstrate interfacial charge redistribution between Pt species and the defect-rich carbon matrix, which indicates modulation of the Pt electronic structure. Density functional theory calculations further confirm that the nanoconfined Pt microenvironment shifts the Pt d-band center to a lower energy level, thereby optimizing hydrogen adsorption and reducing the rate-determining energy barrier for HER. Benefiting from hierarchical porosity, nanoscale confinement, and electronic modulation, Pt@NCMS exhibits outstanding HER activity with low overpotentials of 19.0 mV in 0.5 M H2SO4 and 51.0 mV in 1.0 M KOH at 10 mA cm–2, together with excellent long-term stability over 100 h. This work demonstrates a feasible strategy for engineering nanoconfined Pt electronic microenvironments for high-performance electrocatalysis.

The substantial irreversible capacity loss during initial cycling, primarily caused by solid electrolyte interface (SEI) formation, leads to significant consumption of active lithium in lithium-ion batteries (LIBs), thereby constraining their energy density and long-term cycling stability. This work presents a Li2CO3/LiCoO2 heterostructure as an efficient cathode prelithiation agent to address this issue. Through the integrated recrystallization and thermal treatment, an in-situ Li2CO3/LiCoO2 heterojunction was formed, which with only 3 wt% LiCoO2, yields a refined morphology and a notably reduced decomposition potential of ∼4.0 V. When incorporated into LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes, the additive not only compensates for the lithium loss but also enhances interfacial kinetics, as evidenced by a reduction in charge-transfer resistance and improved Li⁺ diffusion. Furthermore, it promotes the formation of stable, inorganic-rich interphases on both cathode and anode electrodes, effectively suppressing electrolyte decomposition. In NCM811‖Si/C@Gr full cells, the additive delivers a high initial reversible capacity of 209.17 mAh/g, compared to only 166.24 mAh/g for the baseline. Consequently, the full cell achieves an initial energy density of 520.72 Wh/kg, representing a 20.53 % increase over the baseline. This work demonstrates an effective interface-engineering strategy to mitigate initial lithium loss and advance high-energy-density LIBs.

The local coordination structure plays a critical role in determining the catalytic behavior of platinum (Pt)-based alloy nanomaterials, yet its influence on bifunctional electrocatalysis remains insufficiently understood. Herein, PtNi nanocrystals with a locally asymmetric, Pt-dominant coordination structure were developed as efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and the ethylene glycol oxidation reaction (EGOR). Synchrotron X-ray absorption spectroscopy reveals unequal Pt-Ni/Ni-Pt coordination numbers together with reconstructed local bond distances, demonstrating that the PtNi nanocrystals deviate from a random alloy structure and possess pronounced heteronuclear coupling. Benefiting from this unique local coordination environment, the PtNi nanocrystals exhibit mass activity (MA) of 0.74 and 3.13 A mgPt -1 for ORR and EGOR, respectively, corresponding to 6.73- and 3.86-fold enhancements over commercial Pt/C, together with excellent durability. Combining with density functional theory (DFT) calculations and in situ electrochemical infrared spectroscopy results confirms that unique PtNi nanocrystals show an upshifted d-band center (-2.03 eV), leading to stronger adsorption of O2 and EG on PtNi than on monometallic Pt, thus promoting activation of reactant and formation of key oxygenated intermediates during both ORR and EGOR. This work provides mechanistic insight into the role of local coordination engineering in regulating bifunctional electrocatalysis for the design of advanced Pt-based alloy catalysts.

Electrocatalytic reduction of NO3- to ammonia (NO3RR) provides a sustainable method for utilizing NO3--containing wastewater. However, in real aquatic environments with NO3- concentrations typically below 500 ppm, mass-transfer limitations and intensified hydrogen evolution reactions hinder NO3RR efficiency and selectivity. To address these challenges, we propose a capacitive deionization (CDI)-electrocatalytic coupling strategy that regulates the local reaction environment through NO3- enrichment. Under an applied electric field, NO3- are directionally driven and accumulated within the internal cavities of a three-dimensional mesoporous electrode, constructing a localized NO3--rich microenvironment. After the enrichment step, the same electrode is directly employed as the cathode for electrocatalytic NO3RR, ensuring sustained high substrate availability at the active sites. This strategy achieves an NH3 yield of 617.8 mu g h-1 cm-2, with a Faradaic efficiency (FE) of 76.4% and a NO3--to-NH3 conversion rate of 58% at -0.4 V vs. RHE, even at an ultralow NO3- concentration of 34 ppm. Increasing the NO3- concentration to 68 ppm boosts the NH3 yield to 1287.62 mu g h-1 cm-2, FE to 92.5%, and conversion rate to 73.9%. This work establishes a feasible electrochemical strategy for efficient NO3RR under NO3--deficient conditions, providing a promising foundation for wastewater purification and green ammonia synthesis.

Developing high-capacity cathode prelithiation agents remains challenging due to severe kinetic limitations, high operational voltages, or insufficient stability in conventional materials. To address this, we report a cobalt-decorated lithium fluoride composite (S-LiF/Co, with a Co content of 15.76 wt% by ICP-OES) synthesized via a scalable solid-state route. The in situ formed LiF/Co heterointerface serves as a catalytic center, which, as evidenced by theoretical calculations, effectively weakens LiF bonds and significantly lowers the energy barriers for both Li+ migration and LiF decomposition. This enables S-LiF/Co to deliver a high initial charge capacity of 886.23 mAh g-1. When incorporated into NCM811 cathodes, it substantially promotes a stable, LiF-rich cathode electrolyte interphase (CEI). In NCM811||Si/C full cells, this additive effectively compensates for irreversible lithium loss, yielding a high initial energy density of 483.84 Wh kg-1 and superior cycling stability with 80.42% capacity retention after 170 cycles. This work provides an effective interface-engineering strategy to overcome the intrinsic barriers of LiF-based materials, offering a promising prelithiation solution for next-generation high-energy-density batteries.

Industrial water electrolysis requires oxygen evolution anodes that maintain high activity and exceptional durability at current densities exceeding 500 mA cm- 2, a benchmark that remains challenging for non-preciousmetal catalysts. Herein, we report a monolithic OER anode fabricated via an innovative strategy combining metallurgy and the space-holder method. This electrode delivers exceptional performance in alkaline media, achieving a low overpotential of 137 mV at 10 mA cm- 2 and sustaining operation for 500 h at 1000 mA cm- 2 with negligible degradation, performance that significantly surpasses that of all other comparative anodes. Furthermore, it demonstrates a superior performance to Ni foam as an anode in overall water splitting electrolyzer under realistic conditions (30 wt% KOH solution at 85 degrees C). Experimental and theoretical analyses reveal that its superior activity and stability originate from the synergistic effects of a highly accessible active surface area, an optimized electronic structure, and a unique permeable architecture that facilitates rapid bubble release. These attributes make our electrode a highly promising candidate for practical industrial applications.

Precise control of the interfacial electronic structure is crucial for designing high-performance metal carbide catalysts. Herein, we report an N-doped carbon-encapsulated Fe3C catalyst (Fe3C@NC), in which the intrinsic curvature of the carbon shell induces significant interfacial electronic modulation. Structural characterization and density functional theory (DFT) calculations reveal that curvature-driven electron redistribution optimizes Fe 3d states and enhances oxygen adsorption and conversion to *OOH at the active sites. This electronic regulation promotes the dissociative oxygen reduction pathway under alkaline conditions, leading to a high onset potential (Eonset: 1.03 V vs RHE) and half-wave potential (E1/2: 0.90 V vs RHE) with excellent durability. When tested in a Zn-air battery, Fe3C@NC achieves a high peak power density of 187.5 mA cm-2, demonstrating the practical relevance of the catalyst. These results highlight interfacial curvature as an important structural parameter for tuning the electronic properties of metal carbides and provide new insights into the rational design of advanced inorganic electrocatalysts.

Lithium||sulfur batteries promise high energy density but are plagued by sluggish polysulfide conversion under lean-electrolyte conditions. Here we show the formation of chiral LiPS-LiTFSI dimers, fundamentally reshaping the intrinsic chemistry of polysulfides. Building on this finding, we design biomimetic MOF catalysts (MOF-L-His-Cu) in which L-histidine-Cu centers selectively recognize the chiral dimers, accelerating sulfur redox via enzyme-like kinetics. Such MOF-L-His-Cu catalyst achieves 1.84-fold higher activity than its D-enantiomer, enabling lithium||sulfur pouch cells with specific energy of 408 Wh kg-1 (based on the mass of the whole pouch cell deducting the package) at high sulfur loading (12 mg cm-2) and low electrolyte/sulfur ratio (3 μL mg-1). Our findings suggest that chiral coordination could be a previously overlooked factor in lithium||sulfur chemistry. This insight may inform the design of selective electrocatalysts for next-generation energy storage, representing a potential step forward in the field.

Designing tailored multifunctional catalysts that enhance lean-electrolyte sulfur redox kinetics is crucial for achieving high-energy-density lithium-sulfur batteries; however, it still remains challenge. Motivated by the structural protection of active sites in natural enzymes, we implant natural glutathione (GSH) within the metal-organic framework MIL-47 (V) cavity for GSH@MIL-47 (V) biomimetic catalysts, thereby stabilizing and activating its thiol functionality. Quantification using 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) as a probe confirmed successful GSH incorporation, revealing that GSH@MIL-47 (V) enables a continuous and stable catalytic reaction cycle. Moreover, in-situ and ex-situ spectroscopies indicate thiol-driven S-S bond breakage that lowers the reaction energy barrier and concurrently promotes lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) decomposition. As a result, GSH@MIL-47 (V) cells, at 6 C rate, deliver a discharge capacity of 733.1 mAhg-1 and maintain 573.0 mAhg-1 after 750 cycles. Even under an electrolyte-to-sulfur ratio of 5.5 mu Lmg-1, it maintains 867.2 mAhg-1 at a high-rate of 0.5 C. This strategy highlights the potential of enzyme-inspired catalysts for enhancing lithium-sulfur batteries.

The synergistic integration of two-electron oxygen reduction reaction (2e-ORR) and water oxidation reaction (2e-WOR) enables efficient overall electrosynthesis of hydrogen peroxide (H2O2). However, the rational development of effective bifunctional electrocatalysts remains challenging. Herein, a nitrogen-bridged Ni-Sn dual-atom catalyst embedded within a conductive metal-organic framework (NiSn-HITP) is developed, which enables efficient overall electrosynthesis of H2O2 through site-specific synergistic catalysis in the separated half-reactions. Atomically dispersed Ni and Sn sites endow the catalyst with outstanding individual performance, achieving a Faradaic efficiency for H2O2 (FEH2O2) of up to 98.8 % in ORR and 66.9 % in WOR. Notably, when employed as a bifunctional catalyst in a single electrolytic cell, NiSn-HITP delivers an impressive overall FEH2O2 of 171.5 % with a maximum H2O2 yield rate of 9.1 mol gcat-1 h-1. Theoretical calculations reveal that Ni and Sn act as the primary active sites for the 2e-WOR and 2e-ORR, respectively, thus enabling complementary dual-site catalysis. More importantly, the tailored electronic structure, modulated by orbital coupling, promotes both the efficiency and selectivity of H2O2 electrosynthesis. In-situ Fourier-transform infrared spectroscopy further elucidates the reaction pathways. This work offers a new design strategy for bifunctional electrocatalysts, paving the way for practical applications of green H2O2 electrosynthesis.

The pursuit of high-voltage Ni-rich LiNi0.8Mn0.1Co0.1O2 (NCM811) has been constrained by severe interfacial instability. Herein, we demonstrate a preemptive interface engineering strategy enabled by a MoS2-catalyzed Li2CO3 (MCL) additive. Benefiting from the synergistic effect of biphasic MoS2 catalyst and the intrinsic potential difference between MCL and delithiated NCM811, the effective decomposition voltage of Li2CO3 is reduced from >4.7 V to 3.9 V. Such low-potential activation enables the in situ formation of a thin, uniform, and inorganic-rich (Li2O/Li2CO3) cathode-electrolyte interphase (CEI) prior to both native CEI buildup and the detrimental H2/H3 phase transitions in NCM811. Meanwhile, Li+ released from Li2CO3 compensate irreversible lithium loss during cycling, while Li2CO3 decomposition products promote the formation of a robust solid electrolyte interphase (SEI). This dual interfacial regulation on both electrodes synergistically reinforces the interfacial integrity of the battery system. As a result, a 2.5 Ah-NCM811||Si/C cylindrical cell incorporating MCL delivers a capacity retention of 85.0% after 600 cycles at 4.2 V and 68.7% after 200 cycles at 4.5 V, substantially outperforming the corresponding blank cells (78.6% and 51.8%, respectively). This work overcomes the intrinsic ultrahigh-voltage decomposition limitation of Li2CO3 and establishes a general preemptive strategy for developing durable Ni-rich cathodes under aggressive high-voltage operation.

The commercial application of silicon-carbon microparticles (Si/C) as anode materials in advanced high-energy-density lithium-ion batteries (LIBs) has been hindered by suboptimal interfacial stability and insufficient cycling durability, which are primarily attributed to the detrimental stress generated during the lithiation and delithiation processes. In this study, a polymeric binder (PTR) was developed for Si/C anodes in lithium-ion batteries. The PTR binder was fabricated by integrating rigid poly(acrylic acid) (PAA) with flexible carboxylated styrene-butadiene rubber (XSBR) through cross-linking with tannic acid (TA), thereby forming a stable molecular architecture. Additionally, carboxylated single-wall carbon nanotubes (SWCNTs) were incorporated to construct a dual cross-linking conductive network. This unique design effectively alleviates the stress induced by silicon expansion, suppresses chain slippage, and maintains the structural integrity of the electrode. Electrochemical tests demonstrated that Si/C anodes employing the PTR binder exhibited significantly enhanced capacity retention and rate performance in comparison to those utilizing traditional binders. This research offers a promising strategy for improving the structural stability and electrochemical performance of Si/C anodes, thereby facilitating the advancement of high-energy-density LIBs.

Sulfurized polyacrylonitrile (SPAN) restricts the polysulfides shuttle and offers long cycle life in comparison to the conventional cyclooctasulfur cathodes. However, SPAN cathode is currently hindered by the low sulfur content (∼40 wt%) that limits the energy density of SPAN-based lithium‑sulfur (LiS) batteries, and the redox mechanism still remains elusive. Here, we report a strategy to synthesize high sulfur content SPAN (51.7 wt%) via sulfuration condition optimization. This SPAN cathode exhibits high reversible capacity, exceptional cycle life, and minimal self-discharge. Impressively, Ah-level pouch cells demonstrate typical voltage profiles of SPAN and stable cycling over 30 cycles. In-situ and ex-situ characterizations and theoretical calculations are conducted to elucidate the molecular structure and electrochemical reaction mechanism. During the initial discharge, cleavage of SS and CS bonds forms Li2S, while partial scission of CC and CN bonds generate LiCCLi and LiCNLi species, contributing to additional specific capacity. Subsequent charging reforms SS and CS bonds from Li2S oxidation, stabilizing the electrode. We demonstrate that although the lithium ions incorporated into the carbon backbone are largely irreversible, which accounts for the capacity loss in the first cycle, these residual lithium ions enhance polymer conductivity, significantly reducing electrode impedance and voltage polarization, thereby improving performance. This work provides deep insights into the redox mechanism of SPAN cathodes and contributes to the rational design of high-performance LiS batteries.

Lithium-sulfur (Li-S) batteries, despite their high energy density, suffer from sluggish sulfur redox kinetics and lithium dendrite growth. Here, we introduce bis(chloromethyl)benzene (BzCl2) as a potent organic electrolyte additive. Through a systematic investigation of the steric configuration of BzCl2, we uncover that 1,4-BzCl2 exhibits superior reactivity compared to its 1,2-and 1,3-isomers, stemming from its unique spatial arrangement, which enhances electronic interactions and minimizes steric hindrance, enabling effective engagement with polysulfide molecules. Consequently, 1,4-BzCl2 forms a LiBzMe center dot radical that reacts with polysulfides, facilitating the formation of a LiBzMe-S-MeBzLi intermediate, which promotes Li2S formation and improves the sulfur utilization. Moreover, 1,4-BzCl2 significantly contributes to the formation of a robust solid electrolyte interphase (SEI) enriched with LiCl and LiF on the lithium anode, effectively amplifying ion conductivity and protecting against solvent and polysulfide decomposition. Consequently, Li-S batteries fortified with 1,4-BzCl2 as an additive demonstrate remarkable cycling stability, retaining a high capacity of 592 mAh g-1 even after 894 cycles at a rate of 0.5 C, with minimal capacity fade (0.051 % per cycle). This study presents a novel approach to enhancing the electrochemical performance of both cathode and anode, offering valuable insights into electrolyte design for the development of high-performance Li-S batteries.

Silicon carbon (SiC) has emerged as a promising alternative to conventional graphite anodes for high-energy lithium-ion batteries (LIBs) by virtue of their higher specific capacity, high safety and abundant resources. However, the practical implementation of SiC1000 (SiC with a specific capacity of 1000mAh/g) electrodes remains challenging due to the disintegration and interfacial instability of the internal Si particles. Herein, a novel double-layer-binder designing strategy was proposed to address these issues. The inner "hard" layer comprises lithiated polyacrylic acid (LiPAA) filled with single-walled carbon nanotubes (SWCNTs), providing high modulus and dual electronic and ionic conductivity. The outer "soft" layer, inspired by a fishnet structure, consists of a low-modulus and self-healing three-dimensional polyurethane (3D-s-PU) network. This outer 3D-s-PU layer serves as a buffer, mitigating residual stress and preventing structural damage to the rigid LiPAA layer. This gradient binder design, transitioning from hard to soft, demonstrates excellent cycle stability and rate performance of SiC anodes, presenting a new strategy for polymer binder design and advancing high-performance LIBs development.

Sulfurized polyacrylonitrile (SPAN) represents a highly promising cathode material for lithium–sulfur (Li–S) batteries, leveraging a solid‐solid sulfur conversion mechanism. However, persistent interfacial side reactions and sluggish redox kinetics in SPAN cathodes compromise the electrochemical performance. Here, quaternized chitosan (QCS) is employed as a functional agent to stabilize the SPAN cathode electrolyte interphase (CEI). The positively charged quaternary ammonium groups selectively adsorb PF 6 – anions, modifying the Helmholtz layer structure and facilitating the formation of an anion‐derived CEI enriched with LiF. Consequently, the SPAN@QCS‐1.0% cathode delivers a high discharge capacity of 1499 mAh g −1 at 0.2 C, an outstanding rate capability of 902 mAh g −1 at 10 C, and a prolonged cycle life exceeding 1500 cycles at 1 C. Under practical conditions of high sulfur loading (12.0 mg cm −2 ) and lean electrolyte (E/S ratio = 5 µL mg −1 ), the SPAN cell achieves a high areal capacity of 17.1 mAh cm −2 , surpassing that of conventional lithium–ion batteries (≈4 mAh cm −2 ) by more than fourfold. Furthermore, a 0.9 Ah pouch‐cell prototype demonstrates stable cycling for over 30 cycles. The interface strategy provides a facile and effective approach to developing high‐performance SPAN‐based Li–S batteries.