Journal of Colloid and Interface Science最新文献

Solvent coordination structures, including contact ion pairs (CIPs), aggregates (AGGs) and solvent-separated ion pairs (SSIPs) in solid polymer electrolytes (SPEs) are considered to profoundly affect the ionic conductivity and formation of stable solid electrolyte interphase (SEI). The significance of individual effect of SSIPs has been neglected although numerous studies have focused on investigating their collaborative impact on the SEI by regulating the proportion of solvent coordination structures. Here, this work intends to study the unique effect of SSIPs by tailoring the concentration of SSIPs from 0 % to 2.8 % through introducing vinylene carbonate (VC). The comprehensive analysis based on experiments and theoretical calculations indicates that the SSIPs induced by strong competitive coordination effect is beneficial to promote fast Li⁺ ion transport and facilitate the formation of an organic/inorganic composite SEI. Moreover, a highly stable electrochemical interface is achieved by constructing a uniformly distributed lithium fluoride (LiF) SEI. Specifically, stable cycling of Li||Li symmetric cells for 1200 h is demonstrated at a current density of 0.1 mA cm^-2. Additionally, Li||LFP cells exhibit 550 stable cycles at 0.5C, with an average coulombic efficiency exceeding 99.9 % and a capacity retention of 96.5 %. This strategy independently investigates the role of SSIPs in SPEs and offers a new approach for further research on advanced lithium metal batteries.

Lack of double-high (high energy density and power density) anode materials is the key bottleneck for the application of Aqueous alkaline batteries (AABs). Although the emergence of Bismuth-based materials provides an opportunity to solve this issue, due to their high theoretical capacity via a three-electron redox reaction and suitable operating potential, their restricted ion diffusion kinetics via closed-packed atomic arrangement limit their application performance. Herein, the bismuth oxyfluoride hollow nanorods (BiOF-HNs) with intrinsic layer atom configuration have been constructed by the crystallization optimization and morphology engineering synergistic strategy during MOF etching process. Bi³⁺ hydrolysis is the key points to achieve the co-precipitating and repining reactions of BiOF at the surface of Bi MOF for hollow nanorods morphology. The BiOF-HNs deliver dramatically increased electron conductivity and ion transport ratio with the work function of 6.42 eV and OH^- diffusion value of 2.11 × 10^-13 cm² s^-1. Therefore, the optimized BiOF-HNs electrode delivers a remarkable specific capacity of 342.2 mAh g^-1 (1232 F g^-1) at 1 A g^-1 and maintains 86% capacity retention at 20 A g^-1. Furthermore, the assembled BCNP (basic cobalt/nickel phosphate)//BiOF-HNs AABs achieve a high energy density of 157.81 Wh kg^-1 at 1.28 kW kg^-1 and outstanding cycling stability (81% after 9000 cycles). The exploration of BiOF materials with morphology and crystalline optimization in AABs application, may offer new insights of design high performance aqueous anode materials.

Mass transfer limitations directly govern the utilization efficiency of active sites in gas-involving reactions, thereby hindering intrinsically active sites from functioning effectively at high current densities. Consequently, designing porous structures to improve the transport efficiency of both reactants and products constitutes a central challenge for realizing efficient and stable electrocatalytic processes. To address this challenge, a nickel‑cobalt (NiCo) alloy was fabricated via digital light processing (DLP) technology, and cobalt-nanocarbon (Co NC) active material was incorporated in situ to establish a robust catalytic system. Furthermore, the deliberate structural design promoted bubble mass-transfer kinetics, thereby further improving its performance across multiple catalytic reactions. The electrolysis water device composed of it can operate stably for over 500 h at a current density of 500 mA cm^-2 and a voltage of 1.78 V. The assembled zinc-air battery shows a peak power density of 73.5 mW cm^-2 and outstanding cyclic durability, lasting for over 300 h. More importantly, the assembled integrated device generates an equivalent amount of hydrogen during both day and night. This innovative strategy offers a reliable reference for the practical implementation of three-dimensional electrodes in highly efficient mass transfer reactions.

Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) emerges as a cost-effective structurally stable and environmentally benign cathode material, exhibiting significant potential in the energy storage of sodium-ion batteries. However, inherent low ionic mobility and electronic conductivity of NFPP have affected its power performance. In this study, high-valence transition metal cations (Mo⁶⁺, Ta⁵⁺, Nb⁵⁺, and W⁶⁺) are doped within the NFPP lattice, which induces internal electronic rearrangement and average valence state decrease of Fe cations through distortion of locally corner-sharing FeO polyhedra. The increased FeO bond lengths within Mo-doped NFPP crystals and altered electronic cloud distribution further validates this ionic charge compensation mechanism. High-valence metal-doping can also decrease the bandgap, enhance average electronic conductivity, as well as lower Na⁺ migration barrier, thus increasing Na⁺ diffusion coefficient by three orders of magnitude. Therefore, the optimized Na₄Fe_2.91Mo_0.09(PO₄)₂P₂O₇ cathode material demonstrates excellent rate performance and outstanding cycling stability (retaining 85.86% capacity after 1300 cycles at 1C). In addition, the universal effectiveness of the high-valence transition metal doping strategy is verified by investigation of Ta⁵⁺, Nb⁵⁺, and W⁶⁺ doping based on experimental characterizations and theoretical calculations. These findings provide a new perspective to modulate electronic structure and ionic transport pathway of NFPP, and shedding light on great application prospects of iron-based mixed polyanion cathode materials.

Lithium metal batteries demand electrolytes that combine high ionic conductivity with mechanical robustness and interfacial stability. This study presents a novel composite gel polymer electrolyte (GPE) engineered by integrating a cyano-functionalized polysiloxane (PCMS) frameworks, diethylene glycol dimethyl ether (DEGDME) plasticizers, and electrospun polyacrylonitrile (PAN) nanofiber scaffolds. The optimized GPE system achieves an exceptional combination of properties: high ionic conductivity (3.3 × 10^-3 S cm^-1 at 30 °C), outstanding Li⁺ transference number (0.79), and remarkable mechanical strength (3.9 MPa). Theoretical calculations and experimental analyses collectively confirm that the -CN groups competitively coordinate with Li⁺, restructuring the solvation environment to favor TFSI^- anion participation, thereby facilitating the formation of a robust solid electrolyte interphase (SEI) enriched with LiF and Li₃N. As a result, the GPE demonstrates a wide electrochemical stability window (5.3 V vs. Li⁺/Li) and stable lithium plating/stripping for 1000 h at 0.1 mA cm^-2. Additionally, LiFePO₄/GPE/Li full cells achieve 94.9% capacity retention after 500 cycles at 0.5C, while NCM811/GPE/Li cells deliver a high discharge capacity of 153.8 mAh g^-1 with 86.5% retention after 150 cycles. This work establishes a scalable and promising strategy for the development of high-performance lithium metal batteries.

Hydrogen-bonded organic frameworks (HOFs) are considered as potential choice for future energy storage systems due to their adjustable chemistry, environmental benignity, and cost-effectiveness. However, the electrochemical reaction mechanisms of the HOFs remain elusive. Herein, we demonstrate the site-selective electrochemical storage of alkaline metal ions (Li⁺, Na⁺, and K⁺) in porphyrin-based hydrogen-bonded organic framework (PFC-72-Co). Through systematic experimental and theoretical investigations, three active sites are identified, namely, carbonyl site (site 1), porphyrin site (site 2), and interstitial site (site 3). The carbonyl functional group can accommodate all alkaline metal ions (Li⁺, Na⁺, K⁺), whereas the porphyrin and interstitial sites are selective only for Li⁺ ions. As a result, the monomer Co-TCPP, with its abundant active sites, is a promising anode material for potassium-ion batteries, hosting 7 K⁺ ions and delivering a reversible capacity of 247.6 mAh g^-1. In contrast, the PFC-72-Co framework, owing to its low solubility in the electrolyte, serves as a stable anode for lithium-ion batteries, exhibiting ultrahigh cycling stability of over 10,000 cycles. This work provides new understanding of the electrochemical reaction mechanisms of organic materials for alkaline metal-ion batteries.

Low-temperature CO₂ methanation efficiently enables efficient conversion of CO₂ into methane under mild conditions, presenting substantial potential for enhanced energy efficiency and economic feasibility. However, achieving highly efficient low-temperature CO₂ activation remains a critical challenge due to inherent kinetic constraints. In this study, the inverse-supported Ce/Ni catalyst (11 mol% Ce/Ni) was synthesized, which achieved 82% CO₂ conversion and nearly 100% CH₄ selectivity under photothermal synergy at 220 °C (300 W xenon lamp, 300-2500 nm, 1.5 W·cm^-2), outperforming most conventional nickel-based catalysts. Moreover, the catalyst exhibited outstanding long-term stability, with only an 8% activity loss after 100 h of continuous operation. This superior performance was attributed to its CeO₂-Ni interfacial configurations and abundant oxygen vacancies. In situ diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that the CO₂ methanation over this catalyst proceeds via a dual-intermediate pathway involving CO* and HCOO*, with photothermal synergy significantly accelerating the intermediate conversion without altering the intrinsic reaction pathway. This study establishes an innovative strategy for designing low-temperature and high-performance CO₂ methanation catalysts via the integration of an inverse Ce/Ni configuration with photothermal synergy.

Hydrovoltaic power generation technology, which converts the chemical energy from ubiquitous moisture into electrical energy, represents a promising emerging green energy harvesting strategy. The incorporation of renewable biomass materials further enhances the appeal of this approach. In this study, an all wood-based hydrovoltaic electricity generator (WHEG) based on water migration is developed through simple chemical treatment of poplar wood. The removal of lignin releases micro- and nano-scale pores, while maleic anhydride (MAH)-mediated chemical modification enhances surface charge density, collectively improving the electrical output performance of the MAH modified delignified wood (MDW). The WHEG device achieves an open-circuit voltage (V_OC) exceeding 0.3 V during water infiltration and evaporation. Remarkably, the HEG device utilizing ZnC electrodes demonstrates a significantly higher V_OC of about 1.3 V and a power density of 6.2 μW/cm². WHEGs in series can power commercial electronics and self-powered systems. Integrated WHEG units enable customizable power outputs for direct energy storage or supply. Beyond electricity generation, the multifunctional MDW exhibits real-time responsiveness to water droplet movement, offering potential applications in leakage detection and rainfall monitoring. This work provides a novel pathway for designing efficient generators using sustainable materials, thereby expanding the application scope of hydrovoltaic technology.

The serious shuttle effect involving lithium polysulfides (LiPSs) stands as a critical obstacle impeding the advancement of lithium‑sulfur batteries (LSBs). In this paper, flexible NbSe₂/carbon nanofibers (CNF) film was fabricated through electrospinning and calcination processes. The NbSe₂/CNF film possesses efficient conductive network and strong chemical-capturing capabilities for LiPSs. Owing to the synergistic combination, the NbSe₂/CNF composite can remarkably alleviate the shuttling behavior of LiPSs. Consequently, the battery integrated NbSe₂/CNFs interlayer achieves a reversible capacity of 762 mAh g^-1 following 300 cycles at 0.5C. Furthermore, it shows superior rate performance, reaching a capacity of 475 mAh g^-1 when subjected to the high rate of 4C. This study offers a reasonable approach for manufacturing flexible interlayers with optimized structures to boost the electrochemical behavior of LSBs.