Organic-inorganic Interface Research Articles

Hollow glass microsphere/polybutadiene composites with low dielectric constant and ultralow dielectric loss in high‐frequency

AbstractHigh‐frequency dielectric materials have been widely and rapidly applied in areas such as automotive radar, Internet of Things, artificial intelligence, and quantum computing. Currently, the challenge in high‐frequency dielectric materials lies in reducing the dielectric constant (Dk) and dielectric loss (Df) without sacrificing its mechanical properties. This study addresses this challenge by introducing air, as the most common “low dielectric factor,” into the polymer matrix in the form of hollow glass microspheres. Meanwhile, the reactive vinyl groups were also introduced onto the surface of the hollow glass microspheres, enabling an interfacial chemical reaction between the side vinyl groups of polybutadiene and its surface so that the organic–inorganic interface compatibility and interface peel strength are simultaneously improved. Consequently, the minimum Dk of 1.29 and Df of 0.0012 in 3–18 GHz are achieved, and the interface peel strength also reaches 0.65 N/mm. Molecular dynamics simulations, analysis of dielectric properties, and interface peel strength reveal the influence of hollow glass microspheres' morphology and chemical structure on their high‐frequency dielectric performance and adhesive strength. This paper provides effective strategies for the structural design and preparation of high‐frequency, low‐dielectric composites, contributing to the further development of next‐generation microwave communication devices towards higher frequencies and faster information transmission.

Enhanced thermoelectric performance of silicon powder arrays by remotely doping

We report improved thermoelectric (TE) properties of mesostructured silicon powder arrays simply prepared by die-pressing without sintering. In contrast to bromoethane's modest effect, the symmetric dibromoethane molecule coupling could significantly increase the conductivity of Si powder array TE device, from 12.7 S cm−1 of a silicon powder array to 62.3 S cm−1, which is possibly caused by the high electronic transmission probability of symmetric organic molecule–Si crystal coupling, and additionally enhanced by Si bandgap narrowing and defect states of an organic–inorganic interface identified by UV–vis absorption spectra and photoluminescence spectroscopy. Boosted by the very low thermal conductivity (0.58 W m−1 K−1), the dimensionless figure of merit, the ZT value of an Si powder array remotely doped by dibromoethane, ∼0.173, was obtained at 385 K, which is about 17 times higher than that of the bulk Si. An Si–organic hybrid TE device shows potentials to approach the threshold of practical applications with moderate ZT performance and low cost.

The preparation and construction of biomimetic mineralization compatible interface of wood fiber/foamed magnesium oxychloride lightweight composites

The purpose of this study is to improve the application performance of foamed magnesium oxychloride cement (FMOC) and solve the problem of poor interfacial compatibility between the organic-inorganic interface of traditional inorganic composite materials. Inspired by the adhesion mechanism of barnacles to inorganic substrates through amyloid nanofibers and phosphoprotein, a simple green method was proposed to improve the strength and water resistance of the system. The FMOC composites (30×30×30 mm) were prepared by adding wood flour (WF) and phytic acid (PA) to the mixture of magnesium oxide and magnesium chloride. The influences of WF and PA on the compressive strength, composition, microstructure, pore structure, water resistance and flame retardant properties of FMOC were investigated. WF was used as a skeleton structure to induce cement particle aggregation, the PA molecule was used as a connecting bridge to activate the fiber skeleton to increase the active sites, and promote crystal nucleation and aggregation through hydrogen and ionic bond interactions to construct the biomimetic mineralized structure. The results show that the introduction of PA improves the compressive strength and water resistance of the FMOC/WF/PA composite system. When the PA addition amount is 0.8 %, the compressive strength of FMOC/WF/PA-0.8 % composites reached 6.64 MPa, which was 3 times compared to the FMOC composites. The softening coefficient and water absorption of the obtained FMOC/WF/PA-0.8 % composites were 0.81 and 13.84 %, respectively, which were superior to FMOC composites and presented better behavior in water resistance. Meanwhile, the modified composites have more stable pore structure and flame retardant properties, thus these green FMOC/WF/PA composites displayed potential application value in building energy conservation, aerospace and other fields.

Flexible Hybrid Membrane with Synergistic Exciton Dynamics for Excessive 280 h of Durably Piezo-Photocatalytic H2O-to-H2 Conversion.

Solar-driven H2O-to-H2 conversion is a feasible artificial photoconversion technology for clean energy production. However, low photon utilization efficiency has become a major obstacle limiting the practical application of this technology. Herein, a metal atomic replacement (Sb→Ni) is conducted to disintegrate bulk Sb2S3 nanorods and synchronously grow the NiS nanolayers, and a flower-like Sb2S3-NiS nanocomposite with high BET specific surface area and synergistic exciton dynamics is constructed for simulated solar (SSL)-driven H2O-to-H2 conversion. The optimal Sb2S3-NiS nanocomposite is compounded with polyvinylidene fluoride (PVDF) to prepare a flexible PVDF/Sb2S3-NiS (PSN) hybrid membrane with stable structure and excellent recyclability via an electrospinning method. Due to the synergistically interacted organic-inorganic interface and high porosity, it is conducive to the exposure of effective active sites, exciton conduction and mass transfer and exchange, thereby an outstanding alkaline (Ph=13.0) H2O-to-H2 conversion activity with a 0.06% of solar-to-hydrogen efficiency and over 280 h (70 cycles) of durable recycling is achieved under the collaborative drives of SSL and weak ultrasound (40 Hz). This study raises a state-of-the-art membrane material for solar-driven panel reaction technology.

Atomic-Level Structure of the Organic-Inorganic Interface of Colloidal ZnO Nanoplatelets from Dynamic Nuclear Polarization-Enhanced NMR.

Colloidal semiconductor nanoplatelets (NPLs) have emerged as a new class of nanomaterials that can exhibit substantially distinct optical properties compared to those of isotropic quantum dots, which makes them prime candidates for new-generation optoelectronic devices. Insights into the structure and anisotropic growth of NPLs can offer a blueprint for their controlled fabrication. Here, we present an atomic-level investigation of the organic-inorganic interface structure in ultrathin and stable benzamidine (bza)-supported ZnO NPLs prepared by the modified one-pot self-supporting organometallic approach. High-resolution transmission electron microscopy analysis showed a well-faceted hexagonal shape of ZnO NPLs with lateral surfaces terminated by nonpolar (101̅0) facets. The basal surfaces are flat and well-formed on one side and corrugated on the other side, which indicates that the layer-by-layer growth in the thickness of the NPLs likely occurs only in one direction via the expansion of 2D islands on the surface. The ligand coordination modes were elucidated using state-of-the-art dynamic nuclear polarization (DNP)-enhanced solid-state NMR spectroscopy supported by density functional theory chemical shift calculations. Specifically, it was found that (101̅0) nonpolar facets are stabilized by neutral L-type bza-H ligands with hydrogen bond-supported η1-coordination mode, while polar (0001) and (0001̅) facets are covered by μ2-coordinated X-type anionic bza ligands with different conformations of aromatic rings. Moreover, the ligand packing on (101̅0) lateral facets was determined using 13C natural abundance (∼1.1%) homonuclear dipolar correlation experiments. Overall, an in-depth understanding of the growth mechanism and the unique bimodal X-type/L-type ligand coordination shell of ZnO NPLs is provided, which will facilitate further design of anisotropic nano-objects.

Advanced Organic–Inorganic Hybrid Materials for Optoelectronic Applications

AbstractResearch on organic–inorganic hybrid materials (OIHMs) has experienced explosive growth in the past decades. The diversity of organic components allows for the introduction of various spatial scales, functional groups, and polarities, while inorganic components provide higher hardness, heat resistance, and stability, their flexible combination facilitates the formation of diverse structures. Furthermore, simple and cost‐effective synthesis methods, such as room temperature solution processes and mechanochemical techniques, enable precise control over the materials' properties at different scales, thus achieving adjustable structure–performance relationships. This review will discuss the recent research progress of OIHMs within the field of optoelectronics and related optoelectronic device applications. According to the dimension of inorganic components and the nature of organic–inorganic interface, this review divides OIHMs into four structural categories. The ongoing research has revealed diverse applications for OIHMs in the fields of solar cells, light‐emitting devices, detectors, and memristors. As an outlook, the potential of perovskite and 0D metal halide materials, which are currently the most studied, for enhancing optoelectronic performance and stability is discussed.

Tailoring MnO2 Cathode Interface via Organic–Inorganic Hybridization Engineering for Ultra‐Stable Aqueous Zinc‐Ion Batteries

AbstractManganese (Mn)‐based aqueous zinc ion batteries show great promise for large‐scale energy storage due to their high capacity, environmental friendliness, and low cost. However, they suffer from the severe capacity decay associated with the dissolution of Mn from the cathode/electrolyte interface. In this study, theoretical modeling inspires that the amino acid molecule, isoleucine (Ile), can be an ideal surface coating material for α‐MnO2 to stabilize the surface Mn lattice and mitigate Mn dissolution, thereby enhancing cycling stability. Furthermore, the coated Ile molecular layers can accumulate Zn2+ ions from the electrolyte and promote those ions’ transport to the α‐MnO2 cathode while prohibiting H2O from accessing the α‐MnO2 surface, reducing the surface erosion. The compact organic–inorganic interface is experimentally synthesized for α‐MnO2 utilizing Ile that shows homogeneous distribution on the well‐defined Ile‐α‐MnO2 nanorod electrodes. The fabricated aqueous zinc‐ion battery exhibits a high specific capacity (332.8 mAh g−1 at 0.1 A g−1) and excellent cycling stability (85% after 2000 cycles at 1 A g−1) as well as good inhibition toward Mn2+ dissolution, surpassing most reported cathode materials. This organic–inorganic hybrid interface design provides a new, simple avenue for developing high‐performance and low‐cost Mn‐based aqueous zinc ion batteries (AZIBs).

Organic-Inorganic Interfacial Dipole Induced by Energy Level Alignment for Efficient Photocatalytic Sterilization.

Photocatalytic molecules are considered to be one of the most promising substitutions of antibiotics against multidrug-resistant bacterial infections. However, the strong excitonic effect greatly restricts their efficiency in antibacterial performance. Inspired by the interfacial dipole effect, a Ti3C2 MXene modified photocatalytic molecule (MTTTPyB) is designed and synthesized to enhance the yield of photogenerated carriers under light irradiation. The alignment of the energy level between Ti3C2 and MTTTPyB results in the formation of an interfacial dipole, which can provide an impetus for the separation of carriers. Under the role of a dipole electric field, these photogenerated electrons can rapidly migrate to the side of Ti3C2 for improving the separation efficiency of photogenerated electrons and holes. Thus, more electrons can be utilized to produce reactive oxygen species (ROS) under light irradiation. As a result, over 97.04% killing efficiency can be reached for Staphylococcus aureus (S. aureus) when the concentration of MTTTPyB/Ti3C2 was 50 ppm under 660 nm irradiation for 15 min. A microneedle (MN) patch made from MTTTPyB/Ti3C2 was used to treat the subcutaneous bacterial infection. This design of an organic-inorganic interface provides an effective method to minimize the excitonic effect of molecules, further expanding the platform of inorganic/organic hybrid materials for efficient phototherapy.

Noncovalent Interactions-Driven Self-Assembly of Polyanionic Additive for Long Anti-Calendar Aging and High-Rate Zinc Metal Batteries.

Zinc anodes of zinc metal batteries suffer from unsatisfactory plating/striping reversibility due to interfacial parasitic reactions and poor Zn2+ mass transfer kinetics. Herein, methoxy polyethylene glycol-phosphate (mPEG-P) is introduced as an electrolyte additive to achieve long anti-calendar aging and high-rate capabilities. The polyanionic of mPEG-P self-assembles via noncovalent-interactions on electrode surface to form polyether-based cation channels and in situ organic-inorganic hybrid solid electrolyte interface layer, which ensure rapid Zn2+ mass transfer and suppresses interfacial parasitic reactions, realizing outstanding cycling/calendar aging stability. As a result, the Zn//Zn symmetric cells with mPEG-P present long lifespans over 9000 and 2500 cycles at ultrahigh current densities of 120 and 200mA cm-2, respectively. Besides, the coulombic efficiency (CE) of the Zn//Cu cell with mPEG-P additive (88.21%) is much higher than that of the cell (36.4%) at the initial cycle after the 15-day calendar aging treatment, presenting excellent anti-static corrosion performance. Furthermore, after 20-day aging, the Zn//MnO2 cell exhibits a superior capacity retention of 89% compared with that of the cell without mPEG-P (28%) after 150 cycles. This study provides a promising avenue for boosting the development of high efficiency and durable metallic zinc based stationary energy storage system.

All-in-One: Plasmonic Janus Heterostructures for Efficient Cooperative Photoredox Catalysis.

Janus heterostructures consisting of multiple jointed components with distinct properties have gained growing interest in the photoredox catalytic field. Herein, we have developed a facile low-temperature method to gain anisotropic one-dimensional Au-tipped CdS (Au-CdS) nanorods (NRs), followed by assembling Ru molecular co-catalyst (RuN5) onto the surface of the NRs. The CdS NRs decorated with plasmonic Au nanoparticles and RuN5 complex harness the virtues of metal-semiconductor and inorganic-organic interface, giving directional charge transfer channels, spatially separated reaction sites, and enhanced local electric field distribution. As a result, the Au-CdS-RuN5 can act as an efficient dual-function photocatalyst for simultaneous H2 evolution and valorization of biomass-derived alcohols. Benefiting from the interfacial charge decoupling and selective chemical bond activation, the optimal all-in-one Au-CdS-RuN5 heterostructure shows greatly enhanced photoactivity and selectivity as compared to bare CdS NRs, along with a remarkable apparent quantum yield of 40.2 % at 400 nm. The structural evolution and working mechanism of the heterostructures are systematically analyzed based on experimental and computational results.

(Invited) Photon Upconversion: Getting Molecules and Nanocrystals to Talk Triplets

Photon upconversion offers the prospect of combining low energy near-infrared radiation to make high energy photons in the visible wavelengths to improve photovoltaics and introduce new bioimaging techniques. In order to harness the intrinsic ability of colloidal semiconductor nanocrystals to couple strongly with light, it is important to efficiently outcouple energy from photoexcited quantum dots (QDs), much like how nature uses molecular antennas to direct light during photosynthesis. This talk focuses on the organic-inorganic interface for triplet-fusion based photon upconversion, where orbital overlap between the QD donor and molecular acceptor is critical for efficient energy transduction. In the past 8 years, we have learnt a great deal about how the electronic interactions between chalcogenide nanocrystals and acene conjugated molecules affect the photon upconversion quantum yield. We apply the lessons learnt to extending photon upconversion to silicon nanocrystal light absorbers, addressing synthetic challenges with invaluable insight from time-resolved spectroscopy.

High-voltage electrosynthesis of organic-inorganic hybrid with ultrahigh fluorine content toward fast Li-ion transport.

Hybrid materials with a rational organic-inorganic configuration can offer multifunctionality and superior properties. This principle is crucial but challenging to be applied in designing the solid electrolyte interphase (SEI) on lithium metal anodes (LMAs), as it substantially affects Li+ transport from the electrolyte to the anode. Here, an artificial SEI with an ultrahigh fluorine content (as high as 70.12 wt %) can be successfully constructed on the LMA using a high-voltage electrosynthesis strategy. This SEI consists of ultrafine lithium fluoride nanocrystals embedded in a fluorinated organic matrix, exhibiting excellent passivation and mechanical strength. Notably, the organic-inorganic interface demonstrates a high dielectric constant that enables fast Li+ transport throughout the SEI. Consequently, LMA coated with this SEI substantially enhances the cyclability of both half-cells and full cells, even under rigorous conditions. This work demonstrates the potential of rationally designed hybrid materials via a unique electrosynthetic approach for advanced electrochemical systems.

Interlayer expansion and conductive networking of MoS2 nanoroses mediated by bio-derived carbon for enhanced potassium-ion storage

Potassium-ion batteries (PIBs) represent a promising battery technology for energy storage applications. Nevertheless, the progress of PIBs is still hindered by the lack of electrode materials that allow rapid and repeatable accommodation of the large K+ ions. Herein, a composite anode material containing interlayered-expanded MoS2 (55.6% larger) nanoroses in carbon nanonets (MoS2/C@CNs) is designed with the assistance of biomass bagasse, of which the dual carbon sources convert into interlayer and skeleton carbon, respectively. The unique structure facilitates electron/ion transport in the entire electrode and offers excellent structural stability, leading to much improved electrochemical performance compared to simple MoS2/C composite and pure MoS2. Furthermore, the role of electrolyte salts (potassium hexafluorophosphate and potassium bis(fluorosulfonyl)imide) and the electrolyte concentration on the interfacial properties in PIBs have been explored. The results indicate that the low-concentration potassium bis(fluorosulfonyl)imide electrolyte helps to produce optimized organic-inorganic solid electrolyte interface films, contributing to a capacity retention of 90% after 1,000 cycles at 2 A g-1.

Ultra-wide temperature range aqueous electrolyte through local aggregation anchoring active water towards practical aqueous zinc metal battery

The key to realizing the application of aqueous electrolytes to extreme environments lies in rational constraints on active water. Herein, a strategy for local aggregation electrolyte (LA-Zn(OTf)2) with dynamic anchoring of active H2O is proposed and achieved by precisely regulating the molecular weight and addition amount of organic long chains enriched with hydrogen-bond acceptors. The results show that the saturated vapor pressure of LA-Zn(OTf)2 is reduced by 16 % at 90 °C and it does not freeze at -30 °C, achieving a wide operating temperature range of 120 °C. In LA-Zn(OTf)2, the local aggregation of Zn2+, solvent water, and ether bonding groups form a contact ion pair (CIP) structure, which enables rapid and stable deposition of Zn metal. Moreover, a stable organic-inorganic solid electrolyte interface (SEI) is formed to suppress corrosion and hydrogen evolution. At room temperature, the Zn|LA-Zn(OTf)2|Zn symmetric cell is stably cycled for over 4000 h at 1 mA cm-2. At the extreme temperatures of 90 and -30 °C, the Zn|LA-Zn(OTf)2|NVO full cells achieve stable cycling more than 1400 and 2000 cycles at 0.5 A g-1, respectively, and the capacity retention rates are 70.1 % and 80.5 %, respectively.

Protonation-triggered self-assembly of chiral copper nanoclusters: Chirality transfer and circularly polarized luminescence generation

Complex biological processes are inseparable from the transmission of chiral information, and the realization of chiral transfer in the process of designing and manufacturing chiral functional materials is conducive to explore sophisticated nature activities. The construction of chiral nanomaterials using self-assembly strategy can effectively constitute asymmetric molecular stacking pattern and occur hierarchical chirality transfer, but there are few studies on the chirality modulation or amplification of metal nanoclusters in self-assembled systems. Herein, we select a chiral glutathione-stabilized copper nanocluster (R-GSH-Cu NCs) as the chiral donor and introduced achiral cationic polymer poly (allylamine hydrochloride) (PAH) to self assembly to form R-GSH-Cu NCs/PAH nanoaggregates. Through thesynergistic effectof hydrogen bonding and electrostatic interaction. Through the synergistic effect of hydrogen bonding and electrostatic interaction, the optical properties of nanoaggregates were greatly regulated, especially in the supramolecular chirality and circularly polarized luminescence (CPL). Meanwhile, the addition of external proton source (hydrochloric acid, HCl) into the R-GSH-Cu NCs/PAH complexes increased the protonation degree of PAH, resulting in chiral inversion and CPL amplification. Regulating chiral properties of chiral metal NCs provides a nanoscale platform for understanding chiral transfer at organic–inorganic interface, which provided candidate in 3D display, biological probes, encrypted information transmission.

Isomeric dichloropyrazine of dual-function additives: Synergistic enhancement of lithium anode protection and sulfur redox kinetics in lithium–sulfur batteries

Lithium-sulfur batteries (LSBs) currently face challenges such as low sulfur utilization, inadequate cycling stability, and unstable lithium anode interfaces. In this study, dichloropyrazines (DCPs) are introduced as dual-functional additives into electrolyte and 2,5-DCP exhibits the most promising performance enhancement. This superiority can be attributed to its strong redox activity, lower molecular orbital energy gap, and more negative relative binding energy compared to the other DCP isomers. Specifically, DCPs demonstrate their dual functionality by promoting the formation of a stable organic-inorganic hybrid solid electrolyte interface (SEI) rich in LiCl on lithium anodes. This ensures uniform lithium deposition and suppresses dendrite growth. At sulfur cathodes, density functional theory (DFT) calculations confirm that DCPs facilitate lithium polysulfides (LiPSs) conversion kinetics through Li–N bond formation. LSBs with 2,5-DCP exhibit excellent stability at a 1C rate and retain 86.6 % capacity after 800 cycles. This study demonstrates DCPs' potential as effective dual-functional electrolyte additives in designing high-performance LSBs.

Improved thermoelectric performance in polypyrrole/Cu2SnS3 composites

Polypyrrole (PPy) is a promising thermoelectric organic material due to low thermal conductivity, higher electrical conductivity, easy preparation and stability. However, its thermoelectric performance is limited by the intrinsic low Seebeck coefficient. In this paper, PPy/xCu2SnS3 (x = 0–5 wt%) composites with enhanced thermoelectric properties were prepared through chemical oxidation method using iron chloride (FeCl3) as oxidant and methyl orange (MO) as soft template. The obtained composites were investigated by X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Raman spectroscopy. The Cu2SnS3 increased the carrier density and electrical conductivity, meanwhile, thanks to the energy filtering effect and phonon scattering at the organic-inorganic interface of PPy and Cu2SnS3, the Seebeck coefficient increased and thermal conductivity decreased for PPy/ xCu2SnS3 (x > 0) composites. The highest electrical conductivity (74.571 S/cm) and Seebeck coefficient (11.165 μV/K) at 300 K were obtained from PPy/xCu2SnS3 (x = 1 wt%), resulting in a maximum figure of merit (ZT) of 1.646×10−3, which is 8.5 times higher than that of pure PPy.

Interface Visualization of Bio-material Interaction Via Cryo-AEM Using the Biosynthesis of Iron-Based Nanoparticles as a Model.

Although interaction between organisms and nonorganisms is vital in environmental processes, it is difficult to characterize at nanoscale resolution. Biosynthesis incorporates intracellular and extracellular processes involving crucial interfacial functions and electron and substance transfer processes, especially on the inorganic-organic interface. This work chooses the biosynthesis of iron-based nanoparticles (nFe) as a model for biomaterial interaction and employs Cryo-AEM (i.e., S/TEM, EELS, and EDS analysis based on sample preparation with cryo-transfer holder system), combined with CV, Raman, XPS, and FTIR to reveal the inorganic-organic interface process. The inorganic-organic interactions in the biosynthesis of iron-based nanoparticles by Shewanella oneidensis MR-1 (M-nFe) were characterized by changes in electron cloud density, and the corresponding chemical shifts of Fe and C EELS edges confirm that M-nFe acquires electrons from MR-1 on the interface. Capturing intact filamentous-like, slightly curved, and bundled structure provides solid evidence of a "circuit channel" for electron transfer between organic and inorganic interface. CV results also confirm that adding M-nFe can enhance electron transfer from MR-1 to ferric ions. A mechanism for the synthesis of M-nFe with MR-1 based on intracellular and extracellular conditions under facultative anaerobic was visualized, providing a protocol for investigating the organic-inorganic interface.

Bulk Photovoltaic Effect Induced by Non-Covalent Interactions in Bilayered Hybrid Perovskite for Efficient Passive X-Ray Detection.

Hydrogen bonding as a multifunctional tool has always influenced the structure of hybrid perovskites. Compared with the research on hydrogen bonding, the study of halogen-halogen interactions on the structure and properties of hybrid perovskites is still in its early stages. Herein, a polar bilayered hybrid perovskite (IEA)2FAPb2I7 (IEA+ is 2-iodoethyl-1-ammonium, FA is formamidinium) with iodine-substituted spacer is successfully constructed by changing the configuration of interlayer cations and regulating non-covalent interactions at the organic-inorganic interface, which shows a shorter interlayer spacing and higher density (ρ = 3.862gcm-3). The generation of structure polarity in (IEA)2FAPb2I7 is caused by the synergistic effect of hydrogen bonding and halogen-halogen interactions. Especially, as the length of the carbon chain in organic cations decreases, the I---I interaction in the system gradually strengthens, which may be the main reason for the symmetry-breaking. Polarity-induced bulk photovoltaics (Voc = 1.0V) and higher density endow the device based on (I-EA)2FAPb2I7 exhibit a high sensitivity of 175.6µCGy-1cm-2 and an ultralow detection limit of 60.4nGys-1 at 0V bias under X-ray irradiation. The results present a facile approach for designing polar multifunctional hybrid perovskites, also providing useful assistance for future research on halogen-halogen interactions.

A novel composite solid electrolyte based on chemical bonding and physical reinforcing for all-solid-state lithium metal batteries

Sulfide electrolytes are a highly promising type of electrolyte due to their intrinsically soft properties and ultrahigh ionic conductivity. However, compatibility issues at the lithium interface have hindered their development in all-solid-state lithium metal batteries. Composite polymer electrolytes can indeed address interface issues, enhancing battery safety. Nonetheless, the incompatibility at the inorganic-organic interface within composite electrolytes can lead to reduced conductivity and diminished mechanical performance. Herein, we demonstrate a composite polymer electrolyte (CPE) composed of the Li6PS5Cl and polyethylene oxide (PEO) by the chemical bridging effect of (3-chloropropyl) trimethoxysilane (CTMS) on the 3D PET nonwoven framework to resolving the incompatibility between the inorganic and organic components, thereby reinforcing the chemical and mechanical performance of the electrolyte. The CPE shows superior characteristics, including elevated ionic conductivity (7.5 × 10−4 S cm−1), an extended electrochemical stability window (5.3 V versus Li/Li+), an expanded lithium transference number (t(Li+) = 0.52), and higher mechanical strength (9.35 MPa). The assembly of a Li/Li symmetric cell, operating steadily for 400 h at a current density of 0.3 mA cm−2 while maintaining a stable and relatively low polarization voltage (70 mV), demonstrates exceptional stability with respect to the lithium electrode. Moreover, the LiFePO4/Li cell initially exhibits a discharge-specific capacity of 163.6 mAh g−1 with a coulombic efficiency approaching 100 % after 100 cycles at 0.1C. This endeavor offers a robust, attainable, and scalable methodology for crafting composite electrolytes, thereby paving the path for the practical implementation of all-solid-state lithium metal batteries.