Halide solid-state electrolytes (HSSEs) combine high ionic conductivity with wide electrochemical stability windows, making them promising candidates for all-solid-state lithium batteries (ASSLBs). However, their poor humid-air stability demands ultra-dry processing environments, severely limiting industrial scalability. Here, we report a water-assisted synthesis strategy to construct a zirconium-based core-shell structured HSSE, Li2Zr1.5OCl6@Li2CO3 (LZOC-H), under industrially viable dry-room conditions (dew point <-40 °C). By exploiting trace ambient H2O and CO2 during synthesis, a self-derived Li2CO3-rich layer is formed in situ, significantly enhancing air stability. The resulting LZOC-H electrolyte achieves a relatively high room-temperature ionic conductivity of 1.12 mS cm-1 and excellent moisture resistance. Full cell (Ni89|LZOC-H|LPSC|Li-In) shows an initial capacity of 200.4 mAh g-1 and retains 93.5% capacity over 1000 cycles at 1 C. Moreover, a pouch cell with a silicon anode fabricated in a dry room demonstrates stable cycling (85.1% retention over 300 cycles). This work offers a scalable and rare-earth-metal-free pathway for producing moisture-resistant HSSEs, addressing key challenges in ASSLBs' commercialization.
All-solid-state lithium-sulfur batteries (ASSLSBs) couple the high theoretical energy density of sulfur (2600 Wh kg-1) with the safety and polysulfide-shuttle suppression advantages of solid electrolytes (SEs). In practice, however, sluggish solid-state conversion kinetics, chemo-mechanical degradation in composite cathodes, and large solid-solid interfacial resistance remain the principal barriers to practical implementation. This review systematically examines recent progress across the three key components of ASSLSBs: cathodes, solid electrolytes, and interfaces. For cathodes, S/C composite design strategies and alternative active materials-including Li2S, metal sulfides, and organosulfur compounds-are discussed. For solid electrolytes, inorganic (sulfide, oxide, halide, and hydride), polymer, and hybrid composite systems are compared. For interfaces, physical strategies (stack pressure, compliant interlayers, three-dimensional cathode architectures) and chemical strategies (cathode-SE and Li metal-SE interphase engineering, in situ stabilization) are evaluated. Outstanding challenges and design guidelines for next-generation ASSLSBs are discussed.
The correlation between the electrochemical performance and the electronic structure and chemical composition of the cathode/electrolyte- and anode/electrolyte interfaces in all-solid-state batteries (ASSB) is systematically studied. ASSBs are composed of LiCoPO4 (LCP) or LiCoO2 (redox potential ∼4.8 V and ∼3.8 V vs Li+/Li, respectively) thin-film cathode materials, Li1+xAlxTi2-x(PO4)3 (LATP) as the solid-state electrolyte, and lithium metal as the anode. X-ray photoelectron spectroscopy (XPS) interface experiments on LCP thin-film deposition on the LATP surface reveal a partial reduction of Ti4+ ions attributed to electronic charge transfer from LCP to LATP without the involvement of the PO4 polyanion in the process. Electrochemical activity of the ASSBs is primarily limited by the anode/electrolyte interface rather than the cathode/electrolyte interface. Postcycling XPS analysis of the Li|LATP interface indicates lateral and in-depth chemical inhomogeneity with a strong change in PO4 polyanionic chemical environment and Li+ accumulation at the areas with a better electrolyte/anode contact. Engineering the Li|LATP interface via coating of the LATP surface with lithium oxynitride (LiPON) or a LiTFSI-PEO polymer electrolyte, or by wetting the LATP with the liquid electrolytes, significantly improves battery cycling stability even without artificial interface modification at the cathode side. The optimized Li|LiTFSI-PEO|LATP|LCP cells showed excellent cycling performance between 3.0 and 5.0 V at a charging time of 12 min (≈ 5C rate). Stable cycling was sustained over 10 cycles, followed by 30 and 50 additional cycles at reduced charging rates (≈ 4C and 1C, respectively). Good electrochemical cyclability was further demonstrated with an upper cutoff voltage of 5.3 V vs Li+/Li.
Achieving in situ and time-resolved monitoring of microbial metabolites without disrupting the microbial growth environment remains a key challenge in electrochemical biosensing. Herein, we propose a self-healing bilayer hydrogel-based solid-state electrochemical sensing platform for the in situ, time-resolved analysis of purine metabolites produced by Escherichia coli (E. coli). This platform integrates an upper Agar culture module and a lower borax-crosslinked poly(vinyl alcohol) (PVA) detection module, forming a contiguous structure that allows metabolites (e.g., guanine, xanthine, hypoxanthine) to migrate across the solid-solid interface for sensitive electrochemical detection. The detection layer exhibits excellent ionic conductivity; when coupled with its robust structural self-healing capacity, the platform achieved a detection limit of 0.05 µM for guanine. For E. coli detection, a linear response range of 1.1 × 106 to 9.5 × 106 CFU·mL-1 (R2 = 0.9974) was obtained, and relative standard deviations (RSDs) of less than 2.34% even after two weeks of storage. Leveraging this integrated design, the platform enables continuous, label-free tracking of bacterial metabolic dynamics throughout all growth phases. Notably, it detects metabolic transition points earlier than traditional plate counting methods and accurately evaluates antibiotic inhibition trends, with results consistent with colony-forming unit (CFU) analysis. This integrated culture-detection architecture thus provides a versatile strategy for functional microbial analysis and rapid antimicrobial susceptibility testing.
Dipolar recoupling techniques play a fundamental role in solid-state NMR spectroscopy, enabling precise structural characterization of solid materials under magic-angle spinning (MAS). Among these, the supercycled R41 2 (SR4) stands out for its efficiency and stability in recoupling heteronuclear dipolar interactions under fast MAS conditions (≥40 kHz). However, its performance significantly degrades at slow-to-moderate MAS rates (<35 kHz), which restricts its wide applications. To overcome this limitation, herein we introduce a practical modification of SR4 through the strategic incorporation of adjustable window delays between the recoupling π pulses, dubbed windowed SR4 (wSR4). This design introduces the variability of pulse duration and rf amplitude, which simplifies the recoupling optimization procedure, while enabling enhanced recoupling performance and improved tolerance to experimental imperfections. Theoretical analysis and NMR experiments collectively confirm that wSR4 substantially boosts heteronuclear dipolar recoupling efficiency while effectively suppressing undesired spin interactions, particularly under slow MAS conditions. The practical utility of wSR4 is further validated in in situ NMR experiments on SAPO zeolite, where the markedly improved 2D correlation spectroscopy provides deeper insights into local structures. This approach enables precise dipolar measurement, efficient polarization transfer, and the establishment of high-fidelity heteronuclear correlations, all of which are critical for structural elucidation in complex solid systems. Moreover, the windowed SR4 design strategy introduced here is expected to provide a generalizable framework for optimizing symmetry-based recoupling sequences across a wide range of MAS conditions.
This work presents the production of fungal conidia from the thermotolerant and entomopathogenic fungi Metarhizium robertsii, by means of solid-state fermentation (SSF) in packed-bed bioreactors (PBR) up to a pilot scale of 100 L. The M. robertsii strain used (EAMa 01/158-su) presents both thermotolerant and entomopathogenic properties. Its thermotolerance is an unusual trait as entomopathogenic strain, and can help to surpass heat accumulation, the main limitation when increasing scale in SSF. Using a mixture of beer spent grains (BSG) and wood chips as substrates, work is performed at 3 different scales: laboratory (0.5 L), bench (22 L) and pilot (100 L). Air-filled porosity (AFP), specific airflow (sAF) and superficial velocity (VZ) were chosen as parameters to compare across scales. At 0.5 L, production time was optimised at 5 days. At 22 L, successful batch operation yielded homogeneous production throughout the packed bed. At pilot scale of 100 L, conidia production (conidia g-1BSG) and yield achieved were not significantly different from values achieved at 0.5 L, confirming the robustness of the process across reactor volumes. The results highlight the relevance of AFP, sAF and VZ as critical parameters for SSF reactor design and process evaluation and provide a basis for future industrial implementation of fungal SSF in PBR. This work validates thermotolerant entomopathogenic fungi as a viable strategy for industrial-scale SSF in packed-bed bioreactors, demonstrating the potential of thermotolerant entomopathogenic strains in fungal PBR conidia production by reaching pilot scale of 100 L.
All-solid-state lithium-ion batteries are promising next-generation energy-storage systems, but interfacial instability between cathodes and solid electrolytes remains a major barrier to long-term durability. Interfacial coatings can mitigate these reactions, yet coating selection is limited by the vast chemical design space and incomplete database coverage. In this study, coating discovery is formulated as a prediction-and-design problem in which interfacial reaction energies define a composition-to-reactivity map that generalizes to unseen compounds. Reaction energies are calculated for 809 phase-stable Li-containing compounds from the Materials Project against 10 oxide cathodes and 7 sulfide solid electrolytes. Unsupervised clustering identifies distinct reactivity groups, and composition-based analysis reveals signatures, including polyanion tolerance and fixed-valence cations, that define a low-reactivity design envelope. Using composition-derived physicochemical descriptors, an ensemble regressor predicts pair-averaged reaction energies for newly enumerated compositions. Within this envelope, charge-balanced Li─M─O and Li─M─A─O compositions (A = B, P, Si) are enumerated, pre-screened, and validated by phase-diagram analysis. This workflow enables interpretable machine-learning-guided expansion beyond existing databases for scalable coating discovery.
The Mo-O-Ni anchoring bonds for hydrogen spillover are constructed by room temperature solid-state reduction. The optimized 12%-PMA@Ni with well-balanced Mo-O-Ni anchoring bonds achieves complete naphthalene hydrogenation to decalin within 2 h at 180 °C under 1 MPa H2. DFT reveals a reduced H2 activation barrier (0.31 eV) and strong naphthalene adsorption (-1.75 eV), enabling efficient hydrogen migration.
Antimicrobial peptides (AMPs) are promising alternatives to conventional antibiotics due to their broad-spectrum activity and low tendency to induce resistance. Based on their modes of action, AMPs are generally classified as membrane-active or intracellular-targeting peptides. Rational design of next-generation AMPs with enhanced efficacy and reduced cytotoxicity requires a detailed understanding of their antimicrobial mechanisms. Solid-state nuclear magnetic resonance (ssNMR) has emerged as a powerful tool for probing AMP-target interactions, providing high-resolution structural and dynamic information under native-like membrane conditions. This review summarizes recent advances in ssNMR methodologies applicable in model membranes and intact cells and highlights their contributions to elucidating AMP antimicrobial mechanisms. Representative investigations reveal that the membrane-active peptide protegrin-1 disrupts lipid bilayers via a toroidal pore mechanism, whereas lipid II-targeting AMPs inhibit cell wall biosynthesis by immobilizing lipid II through supramolecular assembly.
Zirconium (Zr) is a strategic metal resource whose performance is significantly degraded by high oxygen content. The external gettering process is an effective approach for in-depth deoxidation of Zr. In this study, the deoxidation behavior of Zr in the Ca-Y-CaCl2 external gettering system was investigated by adjusting the chlorine potential through YCl3 addition. The change of oxygen potential and its synergistic control mechanism during the variation of chlorine potential were systematically examined. The results demonstrated that with increasing chlorine potential, the system undergoes a sequence of reactions: chlorination of Ca, formation of metallic Y, formation of YOCl, dissolution of Y2O3, and formation of YCl3, ultimately reaching a three-phase equilibrium of Y-YOCl-YCl3. During this process, the oxygen content of Zr fluctuates notably, which is primarily attributed to the shift in the oxygen-transfer medium from Ca to Y. This transition changes the oxygen potential control mechanism from indirect Y-Ca control to direct Y control. After reaching equilibrium at 1173 K for 72 h, the equilibrium oxygen content of Zr initially remains stable with increasing chlorine potential, then gradually decreases, eventually reaching 20 ppmw. This trend is consistent with the mutual interaction of oxygen potential and chlorine potential. The findings provide important theoretical insights into the interaction between oxygen and chlorine potentials in deoxidation systems, elucidate the multi-element synergistic mechanism for oxygen control, and contribute to the design of efficient deoxidation systems.
A series of 4-cyanoazobenzene containing monomers and their corresponding side-chain polymers with different polymer backbones and alkoxy spacer lengths were analyzed to investigate the influence of polymer backbones on the thermotropic liquid crystalline behavior. The solid-state features of the monomers were elucidated by single crystal X-ray diffraction, revealing the presence of C─H···X (X = O/N/F), C─X···π (X = H/O) and π···π interactions. Hirshfeld surface and energy framework analysis further demonstrated that dispersion interactions are the dominant contributor to the overall crystal packing. Thermal analysis of the acrylate and 2-fluoroacrylate based monomer indicated the presence of nematic mesophase over a narrow temperature window (1°C-2°C), whereas the methacrylate-terminated monomers did not display liquid crystalline behavior. In contrast, polymerization resulted in a significantly broadened nematic mesophase range exceeding 70°C, highlighting the critical role of the polymer backbone in mesophase stabilization. Further, the monomers displayed photoinduced nematic-isotropic phase transition upon irradiation with 365 nm UV light. Additionally, the monomers and polymers exhibited reversible trans ↔ $ \leftrightarrow $ cis isomerization in solution under 365 nm UV and 510 nm visible light irradiation, achieving up to 90% conversion efficiency. These findings underscore the role of the polymer backbone in promoting liquid crystallinity and photoresponse toward the development of stimuli-responsive materials.
Resveratrol (RSV) is a poorly water-soluble polyphenolic compound with various potential health benefits, but its pharmaceutical application is limited by low aqueous solubility and poor oral bioavailability. Additive manufacturing (AM), particularly fused deposition modeling (FDM) 3D printing, offers a flexible approach for fabricating oral dosage forms with customized geometry and internal architecture. In this study, hot-melt extrusion (HME) combined with fused deposition modeling (FDM) 3D printing was used to prepare RSV-loaded tablets with different infill patterns. Hydroxypropyl methylcellulose acetate succinate and hydroxypropyl cellulose were selected as polymeric carriers to prepare RSV-loaded filaments suitable for FDM printing. The effects of infill pattern on the solid-state characteristics, dimensional accuracy, mechanical properties, floating behavior, and in vitro drug release of the printed tablets were systematically investigated. Differential scanning calorimetry, powder X-ray diffraction, and polarized light microscopy indicated that RSV was mainly converted into an amorphous or molecularly dispersed state after HME and FDM processing. All designed tablets were successfully printed and showed acceptable shape fidelity, while different infill patterns resulted in variations in tablet weight, mechanical strength, floating duration, and release behavior. In vitro dissolution studies showed that the RSV release profiles were dependent on the internal infill architecture. Tablets with more complex infill patterns generally exhibited slower drug release, which may be related to differences in internal pore structure, medium penetration pathways, matrix hydration, and diffusion distance. Release kinetic analysis further suggested that RSV release from the printed tablets involved a combination of diffusion and polymer relaxation processes. These results demonstrate that infill pattern is an important structural parameter for modulating the mechanical performance and drug release behavior of FDM 3D-printed RSV tablets. This study provides useful guidance for the design of 3D-printed oral dosage forms with tunable release characteristics.
Undoped, silver (Ag) and samarium (Sm) doped, and Ag-Sm co-doped Li2B4O7 glassy systems were synthesized using the solid-state method, and a comprehensive structural, optical, and thermoluminescence (TL) characterization was carried out. The highest TL intensity was found in the co-doped Li2B4O7:1% Ag:2% Sm composition, which exhibits a significant enhancement in TL performance with an increase of approximately 200% in peak intensity compared to the undoped matrix. The material also demonstrates a highly linear dose response relationship (R ≈ 1) over the 1-500 Gy range, along with excellent repeatability (<1% variation), thereby fulfilling key criteria for reliable dosimetry applications. These results provide clear experimental evidence that Ag-Sm3+ co-doping is an effective strategy for enhancing the TL efficiency of Li2B4O7 under beta irradiation. Consequently, this material emerges as a promising candidate for radiation dosimetry, underscoring the critical role of multi-dopant synergy in optimizing luminescent detectors systems.
Additive friction stir deposition (AFSD) is a solid-state additive manufacturing process that enables the fabrication of fully dense metallic components without common fusion-related defects. Inconel 718, widely used in aerospace and energy sectors, requires high structural reliability; therefore, evaluating its response to AFSD is essential for advanced applications. This study investigates the effects of AFSD on IN718 by comparing the mechanical properties and microstructure of the as-deposited material with the feedstock condition. Tensile testing showed that the ultimate tensile strength (UTS) increased by 5% along the traverse direction, whereas elongation was reduced compared to the feedstock. In contrast, build-direction tensile specimens exhibited lower UTS and substantially reduced elongation, revealing mechanical anisotropy. Microhardness increased by 20%, consistent with substantial grain refinement from 11 µm to 3 µm due to dynamic recrystallization during deposition. X-ray diffraction (XRD) revealed no clearly detectable secondary phase formation after AFSD within the resolution limits of conventional XRD, suggesting that the increased hardness and traverse-direction strength can be partly explained by grain refinement. Elemental mapping detected oxygen-enriched Al/Ti regions at interlayer boundaries, which may contribute to the reduced build-direction ductility. Overall, AFSD refined the microstructure, enhanced hardness, and improved traverse-direction strength, while build-direction tensile testing revealed anisotropic mechanical behavior.
The recovery of valuable metals from spent lithium-ion batteries (LIBs) has attracted increasing attention in recent years. However, conventional recycling processes typically rely heavily on chemical reagents, leading to significant secondary pollution. To address this issue, this study proposes a mechanochemical reaction (MR) induced synergistic strategy for the recycling of spent LiNixCoyMnzO2 and LiFePO4. In this process, the MR process was coupled with the intrinsic redox properties of the cathode materials, utilizing Fe2(SO4)3 as an inducer. As a result, valuable metals can be efficiently and selectively leached under acid-free conditions without the need for additional oxidants or reductants. The results indicate that the MR process induced structural activation and solid-state redox reactions in the mixed powder, thereby markedly enhancing the reactivity of the system. Under optimized conditions, the leaching efficiencies of Li, Ni, Co and Mn all exceeded 99.0%, while the dissolution of Fe and P was limited to 2.5% and 0.5%, respectively. Compared to systems without MR process, the MR process reduced the Fe2(SO4)3 dosage by 66.7% while improving the leaching efficiency and selectivity of valuable metals. Kinetics analysis further revealed that the rate-limiting step shifted from surface chemical control to solid product layer diffusion control, significantly decreasing the apparent activation energy. This strategy minimizes chemical reagents consumption, simplifies subsequent separation and purification steps, and provides a novel route for the efficient and sustainable recycling of spent LIBs.
A spontaneous absolute asymmetric synthesis of cyanohydrins has been developed without any external chiral source through the combination of conglomerate formation and solution-phase racemization. This method integrates HCN addition reaction to an aldehyde with subsequent Viedma ripening; consequently, spontaneous deracemization and enantioselective reactive crystallization of cyanohydrins are achieved for the first time. Importantly, the hydrolysis products of the cyanohydrin-namely, the corresponding α-hydroxy acid and hydroxyamide-serve as chiral inducers that direct the handedness of solid-state asymmetric amplification, leading to highly enantioenriched cyanohydrins with matching chirality. This feedback between product formation and asymmetric amplification establishes a reaction network in which chirality is propagated and reinforced across molecular transformations. In combination with cyanohydrin hydrolysis, this system constitutes a chemically coupled process that approaches the replication of chiral α-hydroxy acids and hydroxyamides, key products in abiotic Strecker-type synthesis, and is therefore relevant to the origin of biological homochirality.
The integration of efficient proton transport and reversible redox activity in a single material is highly desirable for advanced electrochemical devices, yet remains challenging. Herein, two novel crystalline pyridine-decorated polyoxometalates, namely H10{CuII0.5[MoV6O12(OH)3(HPO4)4]2}2·8HPy·24H2O (1) and H8CdII[MoV6O12(OH)3(HPO4)4]2·2Cl·2HPy·2Me2NH (2), are designed and synthesized via a hydrothermal route. The pyridine molecules endow the materials with remarkable proton conductivity, reaching 9.63 × 10-3 S cm-1 (1) and 2.21 × 10-3 S cm-1 (2) at 85 °C and 95% RH. The excellent proton conduction stems from the ordered hydrogen-bonding networks facilitated by both the pyridine N sites and the terminal/surface oxygen atoms of the {P4MoV6O31} anions. Furthermore, the title complexes as electrochemically active materials are loaded onto the surface of carbon paper to assemble solid-state proton energy storage devices; the 1-CP@PANI-SC devices can achieve an outstanding specific capacitance of 330.12 F g-1 and cycling stability of 94.2% after 1000 cycles. Crucially, electrochemical analysis coupled with proton conduction studies indicates that the pre-established proton-conducting pathways significantly facilitate the transport of charge-compensating protons (H+) during the rapid redox reactions of molybdenum centers, thereby enhancing the pseudo-capacitive kinetics and overall electrochemical efficiency. This work not only presents high-performance multifunctional electroactive materials but also establishes a material design principle that links proton conduction with charge storage dynamics for next-generation energy storage systems.
Two-dimensional van der Waals magnetic semiconductor CrSBr offers an ideal platform to achieve exciton-polaritons correlated with magnetic order for developing solid-state quantum, spintronic, and photonic devices. However, for the exciton-polaritons formed by lower-energy excitons (XL ≈ 1.37 eV), the coupling strength and nonlinear optical response are almost inert to the external magnetic field. Here, we demonstrate robust strong coupling between higher-energy excitons (XH ≈ 1.8 eV) and photons that persists up to room temperature, along with giant magnetic-field tunability. The Rabi splitting energy is tuned up to 100 meV within a moderate 0.45 T in-plane magnetic field due to changes in excitonic states during the spin transitions. Besides, we observe significantly enhanced polariton nonlinearity in the intermediate magnetic phase, which exhibits a distinct mode-number dependence and originates from magnon-assisted long-range attractive interactions and coupling strength reduction. These results advance the development of on-demand polariton platforms for spin-correlated quantum optoelectronics.
As promising cathode materials for sodium-ion batteries (SIBs), Prussian blue analogues (PBAs) have gained significant attention due to their facile synthesis and high theoretical capacity. However, the low practical capacity limits PBAs for battery applications. In this work, we propose a Fe vacancy-type PBA and systematically investigate its electrochemical activities, kinetics, and sodium storage mechanism. We demonstrate that although the capacity is enhanced as the vacancy content increases, an excessive concentration of vacancies leads to a deterioration of the cycling performance. Moreover, we show an enhancement of the Na+ diffusion kinetics due to Fe vacancies through multiscan rate cyclic voltammetry, electrochemical impedance spectroscopy, and molecular simulations. Furthermore, operando X-ray diffraction, ex situ solid-state nuclear magnetic resonance, and Raman reveal the sodium intercalation behavior, confirming the high structural reversibility of vacancy-type PBAs. This study not only proposes a novel vacancy-mediated strategy in PBAs but also highlights the significance of defect engineering in boosting the sodium storage for SIBs.
Focused-ion-beam scanning electron microscopy (FIB-SEM) provides site-specific access to buried interfaces, particle interiors, porous electrode architectures, and localized degradation regions in energy materials. This capability is particularly valuable for rechargeable batteries, solid-state ion conductors, alkali-metal electrodes, and reactive solid-liquid interfaces, where the structures governing transport and failure are rarely exposed at a free surface. However, the preparation and imaging steps that reveal these regions may also alter them. Ion milling, environmental transfer, vacuum exposure, scanning electron microscopy (SEM), cryogenic handling, transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), electron energy-loss spectroscopy (EELS), and atom probe tomography (APT) can each modify local morphology, chemistry, or phase state. These effects are especially important when the intended evidence involves light elements, metastable phases, nanoscale coatings, reactive interphases, volatile species, or ion-conducting materials. This perspective develops a claim-specific framework for evaluating such results. Preparation- and imaging-induced changes are related to the material feature being interpreted and to the minimum control needed to distinguish the two origins. For porous electrodes, the relevant outputs include pore volume, connectivity, tortuosity, crack geometry, phase fraction, and active surface area. For reactive interfaces and solid electrolytes, the critical questions concern alkali-metal redistribution, surface amorphization, light-element contrast, implanted-species chemistry, and beam-induced phase formation. The discussion further compares conventional Ga-FIB, cryogenic FIB, Xe plasma FIB, low-energy Ar+ polishing, broad-ion-beam preparation, ultramicrotomy, and repeated particle-oriented FIB workflows. Reliable interpretation requires the preparation route, transfer conditions, imaging dose, analytical acquisition, and claim-specific controls to be reported together with the final microscopy result.