Science China Materials最新文献

Lithium metal anodes (LMAs) are among the most promising candidates for next-generation batteries with high energy density. However, their practical application is hindered by persistent challenges such as dendritic lithium growth, unstable solid electrolyte interphases (SEI), and poor Coulombic efficiency. Surface coating has emerged as a viable solution to address these limitations. In particular, atomic and molecular layer deposition (ALD/MLD) techniques offer unparalleled control over the fabrication of ultrathin, conformal coatings, making them especially suitable for stabilizing LMAs interfaces. This review comprehensively summarizes recent progress in applying ALD and MLD methodologies to construct durable artificial interphases on LMAs. We discuss the underlying mechanisms through which these coatings inhibit dendrite formation, improve interfacial integrity, and facilitate uniform lithium-ion transport. The roles of inorganic ALD coatings, organic MLD coatings, and their organic–inorganic hybrids are systematically examined, with a focus on their chemical composition, deposition behavior, and electrochemical characteristics. Moreover, we highlight the enhanced performance achieved through the integration of ALD/MLD-engineered interfaces in full-cell systems. The review concludes with a discussion of current challenges and potential research avenues aimed at advancing the rational development of effective LMAs protection strategies. Overall, this work offers valuable insights into the role of interfacial engineering via ALD and MLD in enabling the practical deployment of lithium metal batteries.

Designing photosensitizers with efficient intersystem crossing (ISC) and long-lived triplet excited state is critically essential for photodynamic therapy in biomedical applications. To achieve this goal, exploring new molecule design principles to enhance photosensitization remains an urgent need. Herein, we propose a facile and rational strategy to design a series of guanidinium-modified photosensitizers that exhibit prolonged triplet excited state lifetimes and considerable reactive oxygen species (ROS) production, in contrast to unmodified fluorophores which show intense fluorescence and negligible ROS production. The design strategy is not limited to specific molecular structures, thus demonstrating its generality. Through electron paramagnetic resonance spectroscopy and high-resolution mass spectrometry, we identify stable radicals on guanidinium substitutes that play a pivotal role in converting the intrinsically non-photosensitive fluorophores into effective ROS-generating photosensitizers. Mechanistic studies suggest that the nitrogen-centered radical cation could be stabilized by the p-π conjugation effect of guanidinium, which favors enhanced ISC and prolonged triplet excited state. In vitro and in vivo experiments demonstrate that the guanidinium-modified photosensitizers can elicit anti-tumor immunity by inducing immunogenic cell death, thereby achieving potent anti-tumor effects. Overall, this work provides a new perspective as a universal and facile strategy for designing organic photosensitizers through the introduction of stable radical cation-containing building blocks.

Existing robotic end-effector gripping technologies often encounter challenges such as poor adaptability to environmental changes, incomplete deformation sensing, and insufficient adhesion stability, which can compromise operational safety and reliability. Here, we present the bio-inspired self-sensing suction cup, in which the core self-sensing capability is achieved by combining high-performance, laser-induced graphene/Ag NWs flexible sensors with a Wheatstone bridge design. The flexible sensors provide high sensitivity, while the Wheatstone bridge circuit enables accurate and stable detection of deformation during the gripping process. Integrated into the octopus-inspired suction cup, this system allows for real-time monitoring of deformation and adsorption stability. The self-sensing suction cup demonstrates good performance across a 0–25 kPa negative pressure range, with outstanding linearity (R² = 0.993) and high sensitivity (GF = 10.436 kPa⁻¹). Experimental results confirm that the suction cup can achieve stable adsorption under varying loads and enable real-time monitoring of the suction cup status during the gripping process. This design provides a promising solution for intelligent gripping systems, logistics, and object recognition in challenging environments.

The solution aggregation structures of conjugated polymers are pivotal in determining their film morphology and optoelectronic properties, yet the relationship between solution aggregation and device performance remains elusive in organic photodiode (OPD) systems. Herein, we introduce the first examination of solution aggregation structures of all-polymer OPD blends, with a focus on how molecular entanglement modulates aggregation behavior and subsequent photodiode performance of low-cost poly(3-pentylthiophene). Using small-angle neutron scattering and freeze-dried imaging, we provide a comprehensive analysis of the solution-state aggregation behavior of poly(3-pentylthiophene) and its evolution in the blend, revealing profound impacts on film morphology and device performance. With finely optimized aggregation, the resulting all-polymer OPD achieves a record-high specific detectivity of ∼4×10¹³ Jones at zero bias, outperforming all bulk heterojunction (BHJ)-type self-powered OPDs reported to date. This device also demonstrates remarkable thermal stability, with negligible performance degradation after over 800 h of thermal annealing at 85 °C. Furthermore, the self-powered OPD exhibits excellent performance across a broad spectral range, enabling its application in both water quality monitoring and biosensing. This work offers new insights into the solution aggregation behavior of conjugated polymers in OPDs and highlights the importance of resolving solution aggregation in optimizing device function.

Metal single-atoms with optimized coordination structure on highly accessible substrate can maximize the metal utilization efficiency along with enhancing catalytic activities. Herein, axial nitrogen-coordinated Fe-N₅ sites on N-doped carbon (denoted as FeN₅@N-C) hollow microplates are fabricated via a unique Fe³⁺-chelated polydopamine assisted hollowing strategy using ZIF-L microplates as multifunctional templates. Due to the powerful chelating and adhesive ability of polydopamine, this hollow-carbon strategy can be extended to fabricate single-atom Fe-N-C hollow structures with different shapes and encapsulate other transition-metal single atoms (Ni, Co, Mn, and Cu) into the N-doped carbon hollow microplates. The FeN₅@N-C hollow microplates exhibit outstanding oxygen reduction reaction (ORR) capability with an impressive half-wave potential of 0.93 V vs. reversible hydrogen electrode and high stability, which can serve as air-cathode catalysts for high-performance Zn-air batteries with high peak power density of 225.3 mW cm⁻² and stable cyclability of up to 400 h. Comprehensive analysis and theoretical calculations elucidate that axial nitrogen coordination in Fe-N₅ catalytic sites, unlike the planar Fe-N₄ configuration, can compete well with the bonding of OH* through additional 3d-2p orbital hybridization, thereby giving moderate bonding strength to enhance the ORR activity.

Idiopathic pulmonary fibrosis (IPF) is a chronic interstitial lung disease with a high mortality rate and limited therapeutic options. Dysregulated macrophage polarization as a driver of fibroblast activation and epithelial-mesenchymal transition (EMT) is the key to IPF evolution, but lacks an effective management approach. Herein, we develop a novel inhalable methane nanocapsule (MNC) which is able to spatiotemporally control methane release in the lung to locally remodel fibrogenic microenvironment in IPF. MNC is formulated through self-assembly of biodegradable poly(lactic-co-glycolic acid)-polyethylene glycol (PLGA-PEG) copolymer and a new acid-responsive methane prodrug Fe(BPY)₂(CH₃)₂ to enhance the efficacy of pulmonary methane delivery by facilitating mucosal penetration and sustained methane release in response to the acidic inflammatory niche. In a bleomycin (BLM)-induced pulmonary fibrosis model, MNC inhalation achieves efficient MNC deposition and sustained methane release in the lung, significantly reducing inflammation progression, ameliorating fibrosis formation, and improving lung function without systemic side effects. Mechanistically, MNC not only rebalances macrophage polarization by inhibiting M2 phenotype overexpression but also downregulates the ratio of MMP9/TIMP-1 to suppress myofibroblast proliferation and EMT, synergistically suspending the fibrotic progression of IPF. The developed inhalable methane nanocapsule offers a promising strategy to remodel pulmonary fibrogenic microenvironment for safe and effective treatment of IPF.

The development of substitutable meniscus implants that can effectively protect articular cartilage remains a great challenge. Herein, a polyurethane with chemical crosslinking and sulfobetaine extenders containing hydrophobic chains (PU-CL-hSB) is developed, which could improve comprehensive properties and long-term stability simultaneously. By regulating the mole ratio of functional groups, PU-CL-hSB with appropriate mechanical properties, excellent tribological properties, and good fatigue resistance is used to prepare substitutable meniscus implant by hot-pressing. Due to the synergistic effect of functional groups, PU-CL-hSB meniscus implant presents comparable or even superior properties to native meniscus. It withstands a maximum force of 26.08 N versus 25.14 N for native meniscus, an energy dissipation from 45.93 to 39.17 N mm compared to 28.83 to 19.11 N mm for native meniscus over 300 cycles, and a friction coefficient from 0.08 to 0.19 compared to 0.11 to 0.26 for native meniscus. This PU-CL-hSB meniscus implant is further implanted into live rabbit knee joints for 8 and 25 weeks by a new approach, and in vivo data indicate that PU-CL-hSB meniscus implant not only protects articular cartilage from severe damage without eliciting inflammatory responses, but also can maintain normal physiological activities in the native state. Our findings present a substitutable meniscus implant that could be applied in vivo and propose evaluation methodologies for meniscus implants.

Layered transition metal oxide cathode materials have garnered increasing attention for sodium-ion batteries (SIBs). However, they are plagued by the Jahn–Teller distortion of MnO₆, Na⁺/vacancy ordering, and irreversible lattice oxygen loss, which collectively lead to capacity fading and voltage decay. Herein, we report a P2-type material, Na_0.67Ni_0.3Mn_0.6Li_0.09Sn_0.01O₂ (NNMO-Li0.09Sn0.01), modified with two closed-shell dopants (i.e., Li⁺ and Sn⁴⁺). Benefiting from the unique electronic configurations of closed-shell ions, NNMO-Li0.09Sn0.01 exhibits enhanced structural and electrochemical stability. Specifically, the incorporation of Li⁺ increases the Mn⁴⁺/Mn³⁺ ratio, thereby mitigating Jahn–Teller distortion during (de)sodiation process. In addition, Li⁺ disrupts the Ni/Mn ordering in the transition metal layer, suppressing Na⁺/vacancy ordering. Meanwhile, the introduction of Sn⁴⁺ forms stronger Sn–O bonds (548 kJ mol⁻¹), thereby enhancing the bonding strength between neighboring transition metal ions and surrounding oxygen atoms, effectively reducing oxygen loss during cycling. NNMO-Li0.09Sn0.01 exhibits significantly improved cycling stability, delivering a specific capacity of 90.3 mAh g⁻¹ with 62.9% capacity retention after 50 cycles at 0.1 C (1 C = 200 mA g⁻¹), along with 90.3% voltage retention. This substitution strategy based on closed-shell ions offers a viable approach for enhancing the structural stability of wide-voltage layered oxide cathodes.

Lead halide perovskites have emerged as promising scintillators for X-ray imaging owing to their high X-ray absorption efficiency, excellent luminescence properties, and facile synthesis. However, their intrinsic ionic nature poses a fundamental challenge in simultaneously achieving high photoluminescence efficiency and environmental robustness. Here, we introduce a multilevel encapsulation strategy by sequentially coating CsPbBr₃ quantum dots (QDs) with Cs₄PbBr₆, SiO₂, and polydimethylsiloxane (PDMS), thereby synergistically enhancing both optical performance and stability. Cs₄PbBr₆ effectively passivates surface defects of CsPbBr₃ QDs, while the SiO₂ and PDMS layers serve as protective barriers against moisture, heat, and radiation. The resulting CsPbBr₃@Cs₄PbBr₆/SiO₂/PDMS flexible films exhibit a high photoluminescence quantum yield of 85%, outstanding mechanical flexibility, and remarkable durability under stretching, bending, and compressing. Moreover, the films retain excellent emission stability under elevated temperatures, prolonged X-ray irradiation, and extended water immersion. X-ray imaging evaluations further demonstrate a spatial resolution of 12 lp/mm, enabling distortion-free imaging of curved objects, while their superior water resistance allows for long-term underwater X-ray imaging. This work highlights the critical role of hierarchical encapsulation in balancing luminescence efficiency and environmental stability, offering a viable pathway toward practical high-performance flexible perovskite scintillators.

Layered chalcogenide compounds have attracted much attention for optoelectronic applications owing to their rich structural diversity and unique physical properties, such as high carrier mobility, ferromagnetism, ferroelectricity, and outstanding optoelectronic and thermoelectric performance. In particular, their tunable bandgaps and strong light absorption make them highly suitable for next-generation photodetectors. However, the environmental instability of many 2D chalcogenides poses a critical challenge for practical applications. In this work, we report a high-performance, polarization-sensitive photodetector based on an air-stable ternary chalcogenide FeIn₂Se₄. Angle-resolved polarized Raman spectroscopy reveals that the four characteristic Raman modes exhibit a 60° periodic variation in intensity, highlighting the material’s pronounced in-plane anisotropy. Benefiting from its strong absorption over a broad spectral range (510–1028 nm), the FeIn₂Se₄-based device demonstrates reliable photoresponse under multiple excitation wavelengths (405, 473, 515, and 638 nm), showcasing its wideband detection capabilities. Furthermore, XPS measurements after prolonged air exposure confirm the enhanced chemical stability of FeIn₂Se₄ compared to binary chalcogenides. These findings demonstrate 2D ternary FeIn₂Se₄ is an excellent candidate for advanced anisotropic optoelectronic devices as it offers broadband photodetection, robust polarization sensitivity, and excellent environmental resilience.