RESUMEN

With the depletion of petroleum resources, the development of sustainable alternatives for plastic substitutes has grown in importance. It is urgently desirable yet challenging to design high-performance polyesters with extensive mechanical and prominent gas barrier properties. This work uses bio-based PBF polyester as a matrix, "leaf-shaped" carbon nanotube@boron nitride nano-sheet (CNT@BNNS) covalent hetero-junctions as functional fillers, to fabricate CNT@BNNS/PBF (denoted as CBNP) composite films through an "in-situ polymerizing and hot-pressing" strategy. The covalent CNT "stem" suppresses the re-stacking of BNNS "leaf", endowing hetero-structured CNT@BNNS illustrates superior stress transfer and physical barrier effect. The covalently hetero structure and high orientation degree of CNT@BNNS greatly improve the comprehensive performance of the CBNP composites, including excellent mechanical (strength of 76 MPa, modulus of 2.3 GPa, toughness of 85 MJ m-3, elongation at break of 193%) and gas barrier (O2 of 0.015 barrer, and H2O of 1.1 × 10-14 g cm cm-2 s-1 Pa-1) properties that are much higher than for pure PBF or other-type polyesters, and most engineering plastics. Moreover, the CBNP composites also boast easy recyclability, overcoming the tradeoff between high performance and easy recycling of traditional plastics, which makes the polyester composite competitive as a plastic substitute.

RESUMEN

Solid-state lithium-metal batteries (SSLMBs) have attracted great attention due to their outstanding advantages in safety, electrochemical stability and interfacial compatibility. However, the low ionic conductivity and narrow electrochemical window restrict their practical application. Herein, in-situ polymerization electrolytes (IPEs) crosslinked by acrylonitrile (AN) and ethylene glycol dimethacrylate (EGDMA) exhibit the superior ionic conductivity of 1.77×10-3 S cm-1 at 25 °C, the ultrahigh lithium transference number (tLi+) of 0.784 and the wider electrochemical stable window (ESW) of 5.65 V. The IPEs make the symmetrical Li||Li cells achieve the highly stable lithium stripping/plating cycling for over 3000 h at 0.1 mA cm-2. Meanwhile, IPE endows the solid-state LiFePO4||Li batteries with an excellent long-cycle performance over 700 cycles at 2.5 C with a capacity retention ratio over 95 %, as well as 1000 cycles at 1 C and superior capacity retention of 85 %. More importantly, the in-situ polymerized electrolytes containing polyacrylonitrile (PAN) open up a new frontier to promote the practical application of solid-state batteries with high safety and high energy density via in-situ solidification technology.

RESUMEN

The all-inorganic CsPbBr3 perovskite solar cells exhibit excellent stability against humidity and thermal conditions as well as relatively low production cost, rendering them a gradually emerging research hot spot in the field of photovoltaics. However, the absence of a hole transport layer (HTL) in its common structure and the substantial energy level difference of up to 0.6 eV between the highest occupied molecular orbital (HOMO) level of CsPbBr3 and the work function of the carbon electrode have emerged as the primary factor limiting the improvement of its power conversion efficiency (PCE). In this work, the monomer 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) is spin-coated onto the surface of the CsPbBr3 film directly and then subjected to annealing; DBEDOT undergoes in situ polymerization to form poly(3,4-ethylenedioxythiophene) (PEDOT), which aims to ameliorate the issue of excessive energy level difference between CsPbBr3 and the carbon electrode, and to facilitate the extraction and transport efficiency of holes between the CsPbBr3 perovskite and the carbon electrode. Compared to the pristine device, the PCE of the device based on in situ polymerization is enhanced and achieves a maximum efficiency of 9.81%. Furthermore, the unencapsulated devices based on in situ polymerization maintain 95.9% of their original efficiency after 40 days of stability testing.

RESUMEN

Lithium-ion batteries using quasi-solid gel electrolytes (QSEs) have gained increasing interest due to their enhanced safety features. However, their commercial viability is hindered by low ionic conductivity and poor solid-solid contact interfaces. In this study, a QSE synthesized by in situ polymerizing methyl methacrylate (MMA) in 1,2-dimethoxyethane (DME)-based electrolyte is introduced, which exhibits remarkable performance in high-loading graphite||LiNi0.8Co0.1Mn0.1O2 (NCM811) pouch cells. Owing to the unique solvent-lacking solvation structure, the graphite exfoliation caused by the well-known solvent co-intercalation is prohibited, and this unprecedented phenomenon is found to be universal for other graphite-unfriendly solvents. The high ionic conductivity and great interfacial contact provided by DME enable the quasi-solid graphite||NCM811 pouch cell to demonstrate superior C-rate capability even at a high cathode mass loading (17.5 mg cm-2), surpassing liquid carbonate electrolyte cells. Meanwhile, the optimized QSE based on carbonates exhibits excellent cycle life (92.4% capacity retention after 1700 cycles at 0.5C/0.5C) and reliable safety under harsh conditions. It also outperforms liquid electrolytes in other high-energy-density batteries with larger volume change. These findings elucidate the polymer's pivotal role in QSEs, offering new insights for advancing quasi-solid-state battery commercialization.

RESUMEN

Carbonate-based electrolytes show distinct advantages in high-voltage cathodes but generate nonuniform and mechanically fragile solid-electrolyte interphase (SEI) in lithium (Li) metal batteries. Herein, we propose a LiF-rich SEI incorporating an in situ polymerized poly(hexamethylene diisocyanate)-based gel polymer electrolyte (GPE) to improve the homogeneity and mechanical stability of SEI. Fluoroethylene carbonate (FEC) as a fluorine-based additive for building LiF-rich SEI on Li metal electrodes. With this strategy, the assembled Li symmetric batteries cycled stably for 700 h, and the formation of byproducts on the Li electrode surface was significantly inhibited. The Li/LiFePO4 battery delivered significant capacity retention (91% retention after 800 cycles) at 1 C. With high-voltage LiNi0.8Co0.1Mn0.1O2 (NCM811) as cathode, the Li/GPE-FEC/NCM811 cell delivered a discharge capacity of 168.9 mAh g-1 with a capacity retention of 82% after 300 cycles at 0.5 C. From the above, the work could assist the rapid development of high-energy-density rechargeable Li metal batteries toward remarkable performance.

RESUMEN

Luminescent wood materials are an emerging class of biomass hybrid host materials owing to the hierarchical porous structure and functionalization versatility. The fluorescence properties are largely dependent on exogenous fluorophores, which are, however, often plagued by notorious aggregation effects. In this work, an efficient strategy for the preparation of luminescent transparent wood materials is developed by incorporating tetraphenylethylene-derived aggregation-induced emission (AIE)-active fluorophores during a delignification-backfill transparency process. These wood hybrids showed unexpected luminescence enhancement that significantly increased the fluorescence quantum yield of the fluorophores up to 99%, much higher than that of the fluorophores in other states such as crystalline solids or doped in a polymer substrate. Mechanistic investigations reveal that in situ polymerization of prepolymerized methyl methacrylate in delignified microporous wood frames produces high molecular weight ordered PMMA polymers, resulting in a rigid molecular environment that improves the luminescence efficiency of TPE-based fluorophores at the interfaces of PMMA polymer and cell walls. By confocal laser scanning microscopy (CLSM), this excellent fluorescence staining capability was furthermore utilized to visualize the intrinsic porous network of wood in three dimensions over a large volume with submicrometer resolution, thus providing an alternative approach to the study of structure-function relationships in such wood hybrids.

RESUMEN

Solid polymer electrolytes (SPEs) represent a pivotal advance toward high-energy solid-state lithium metal batteries. However, inadequate interfacial contact remains a significant bottleneck, impeding scalability and application. Inadequate interfacial contact remains a significant bottleneck, impeding scalability and application. Recent efforts have focused on transforming liquid/solid interfaces into solid/solid ones through in situ polymerization, which shows potential especially in reducing interface impedance. Here, we designed high-voltage SSLMBs with dual-reinforced stable interfaces by combining interface modification with an in situ polymerization technology inspired by targeted effects in medicine. Theoretical calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis demonstrate that tetramethylene sulfone (TMS) and bis(2,2,2-trifluoromethyl) carbonate (TFEC) exhibit selective adsorption at the interface of the LiNi0.8Co0.1Mn0.1O2 (NCM) cathode and Li anode, respectively. These compounds further decompose to form a stable cathode-electrolyte interface (CEI) film and a solid electrolyte interface (SEI) film, thereby simultaneously achieving a superior interface between the SPE and both the Li anode and NCM cathode. The developed Li||SPE||Li cell sustained cycling for more than 1000 h at 0.3 mA cm-2, and the NCM||SPE||Li cell also demonstrated an excellent capacity retention of 86.8% after 1000 cycles at 1 °C. This work will provide valuable insights for the rational design of high-voltage SSLMBs with stable interfaces, leveraging in situ polymerization as a cornerstone technology.

RESUMEN

Electromagnetic interference (EMI) shielding materials play a vital role in human society, especially in light of the rapid development of electronic communication equipment. Therefore, it is urgent to develop green, high-efficiency EMI shielding materials. Wood, as a renewable raw material, possesses significant structural advantages in studying EMI materials due to its unique 3D pore structure. Herein, we report magnetoelectric lignocellulosic matrix composites derived from the delignified wood for efficient EMI shielding. The composite was fabricated by in-situ polymerization of PEDOT conductive coating and magnetic Fe3O4 in delignified wood. The conductive 3D pore structure of Fe3O4/PEDOT@wood could effectively cause dielectric loss and multiple internal reflections. Combined with the magnetic loss of Fe3O4, the material exhibited excellent EMI shielding effectiveness (SE), which could be attributed to the synergistic effect of dielectric and magnetic losses. The Fe3O4/PEDOT@wood showed excellent conductivity (103 S/m), good magnetism (26.7 emu/g), the EMI SE up to 59.8 dB, and high SEA/SET ratios of∼84.2 % to 95.7 % at 2 mm in X -band. Moreover, the material exhibited a high compressive strength and tensile strength of 100.8 MPa and 18.1 MPa, respectively. Therefore, this work provided a reference for the preparation of high-efficiency EMI shielding materials.

Asunto(s)

RESUMEN

Due to the advantages of low energy consumption, no air and water pollutions, the reactive polyurethane films (RPUFs) are replacing the solvated and waterborne PUFs nowadays, which significantly promotes the green and low-carbon production of PU films. However, the microstructure evolution and in situ film-formation mechanism of RPUFs in solvent-free media are still unclear. Herein, according to time-temperature equivalence principle, the in situ polyaddition and film-formation processes of RPUFs generated by the typical polyaddition of diisocyanate terminated prepolymer (component B) and polyether glycol (component A) are thoroughly investigated at 25 °C. According to the temporal change of viscosity, the RPUFs gradually transfer from liquid to gel and finally to solid state. Further characterizing the molecular weight, hydrogen bonds, crystallinity, gel content, and phase images, the polyaddition and film-formation processes can be divided into three stages as 1) chain extension and microcrystallization; 2) gelation and demicrocrystallization; 3) microphase separation and film-formation. This work promotes the understanding of the microstructure evolution and film-formation mechanism of RPUFs, which can be used as the theoretical guidance for the controllable preparation of high-performance products based on RPUFs.

RESUMEN

Silicon-based anodes are becoming promising materials due to their high specific capacity. However, the intrinsically large volume change brought about by the alloying reaction results in the crushing of the active particles and destruction of the electrode structure, which severely limits its practical application. Various structured and modified silica-based anodes exhibit improved cycling stability and the demonstrated ability to mitigate their volume changes through interfacial and binder strategies. However, the issue of large volume changes in silicon-based anodes remains. Herein, we report a gel polymer electrolyte (GPE) prepared through an in situ thermal polymerization process that is suitable for SiOx anode materials and achieving long-term cycling stability. GPE-based cells essentially mitigate the volume change of SiOx anodes by guiding the unique lithiation/delithiation mechanism that tends to favor the formation and delithiation of amorphous-LixSi (a-LixSi) with smaller volume change, thereby mitigating electrode damage and cracking, and achieving the significant improvement in cycling performance. The prepared GPE-SiOx cells retained 693.80 mAh g-1 reversible capacity after 450 cycles at 500 mA g-1. In addition, the prelithiation process was incorporated to mitigate capacity fluctuations and improve the Initial Coulombic Efficiency (ICE), and a reversible capacity of 641.90 mAh g-1 was retained after 480 cycles.

RESUMEN

Ni-rich cathodes have been intensively adopted in Li-ion batteries to pursuit high energy density, which still suffering irreversible degradation at high voltage. Some unstable lattice O2- species in Ni-rich cathodes would be oxidized to singlet oxygen 1O2 and released at high volt, which lead to irreversible phase transfer from the layered rhombohedral (R) phase to a spinel-like (S) phase. To overcome the issue, the amphiphilic copolymers (UMA-Fx) electrolyte were prepared by linking hydrophobic C-F side chains with hydrophilic subunits, which could self-assemble on Ni-rich cathode surface and convert to stable cathode-electrolyte interphase layer. Thereafter, the oxygen releasing of polymer coated cathode was obviously depressed and substituted by the Co oxidation (Co3+→Co4+) at high volt (>4.2 V), which could suppressed irreversible phase transfer and improve cycling stability. Moreover, the amphiphilic polymer electrolyte was also stable with Li anode and had high ion conductivity. Therefore, the NCM811//UMA-F6//Li pouch cell exhibited outstanding energy density (362.97 Wh/kg) and durability (cycled 200 times at 4.7 V), which could be stalely cycled even at 120°C without short circuits or explosions.

RESUMEN

Amidst the growing challenge of meeting global energy demands with conventional sources, self-powered devices offer promising solution. Flexible and stretchable electronics are pivotal in wearable technology, enhancing the scope and functionality of these devices. This study employs potassium sodium niobite-lithium antimonate (K0.5Na0.5NbO3-LiSbO3) nanoparticles as fillers in polyvinylidene fluoride (PVDF) to fabricate piezoelectric thin films. These films are integrated with fabric-based electrodes to develop high-performance, flexible self-powered sensors. The sensor comprises a fabric-based electrode with polypyrrole (PPy) coated on plain nylon fabric, a 0.93KNN-0.07LS/PVDF composite piezoelectric thin film, and a protective PET layer. Results demonstrate that the 0.93KNN-0.07LS/PVDF-PPy/nylon composite sensors exhibit a stable piezoelectric output. Under 6 Hz and 10 N excitation, the piezoelectric output reaches approximately 6.1 V upon pressing. Additionally, the device shows good linear sensitivity in the 2-20 N pressure range and produces clear, regular output waveforms under cyclic pressures of varying frequencies and amplitudes, indicating excellent response repeatability. Even after extensive bending, twisting, and 5000 pressing cycles, the sensors maintain considerable cyclic stability, demonstrating high durability. These tests collectively indicate that the developed sensors possess high sensitivity, flexibility, durability, stability, and significant self-powered potential. This research provides a reference for the next generation of textile-based electrodes and offers potential strategies for flexible, wearable applications.

RESUMEN

Sn-based perovskite solar cells (Sn-PSCs) have received increasing attention due to their nontoxicity and potentially high efficiency. However, the poor stability of Sn2+ ions remains a major problem in achieving stable and efficient Sn-PSCs. Herein, an in situ polymerization strategy using allyl thiourea and ethylene glycol dimethacrylate as cross-linking agents in the Sn-based perovskite precursor is proposed to improve the device performance of Sn-PSCs. The C═S and N-H bonds of the cross-linkers are able to coordinate with SnI2 and inhibit the oxidation of Sn2+, thereby reducing defect density and improving the stability of Sn-based perovskite films. The high quality of the perovskite film induced by the in situ polymerization strategy delivers an improved power conversion efficiency (PCE) from 7.50 to 9.22%. More importantly, the unpackaged device with cross-linkers maintained more than 70% of the initial PCE after 150 h of AM 1.5G light soaking in a nitrogen atmosphere and 80% of the initial PCE after 1800 h in dark conditions. This work demonstrates that the in situ polymerization strategy is an effective method to enhance the stability of Sn-based perovskite films and devices.

RESUMEN

Recently, open tubular capillary electrochromatography (OT-CEC) has captured considerable interest; its efficient separation capability hinges on the interactions between analytes and polymer coatings. However, in situ growth of stimuli-responsive polymers as coatings has been rarely studied and is crucial for expanding the OT-CEC technique and its application. Herein, following poly(styrene-maleicanhydride) (PSM) chemically bonded onto the inner surface of the capillary, a dual pH/temperature stimuli-responsive block copolymer, P(SMN-COOH), was prepared by in situ polymerizing poly(N-isopropylacrylamide) carboxylic acid terminated [P(N-COOH)] in PSM. An OT-CEC protocol was first explored using the coated capillary for epimedins separation. As a proof of concept, the developed OT-CEC system facilitated hydrogen bonding and tuning the hydrophilic/hydrophobic interactions between the test analytes and the P(SMN-COOH) coating by varying buffer pH and environmental temperature. Four epimedins with similar chemical structures were baseline separated under 40 °C at pH 10.0, exhibiting dramatical improvement in separation efficiency in comparison to its performance under 25 °C at pH 4.0. In addition, the coated capillary showed good repeatability and reusability with relative standard deviations for migration time and peak area between 0.7 and 1.7% and between 2.9 and 4.6%, respectively, and no significant changes after six runs. This work introduces a paradigm for efficient OT-CEC separation of herbal medicines through adjusting the interactions between analytes and smart polymer coatings, addressing polymer coating design and OT-CEC challenges.

RESUMEN

Lithium metal batteries (LMBs) with high-voltage nickel-rich cathodes show great potential as energy storage devices due to their exceptional capacity and power density. However, the detrimental parasitic side reactions at the cathode electrolyte interface result in rapid capacity decay. Herein, a polymerizable electrolyte additive, pyrrole-1-propionic acid (PA), which can be in situ electrochemically polymerized on the cathode surface and involved in forming cathode electrolyte interphase (CEI) film during cycling is proposed. The formed CEI film prevents the formation of microcracks in LiNi0.8Co0.1Mn0.1O2 (NCM811) secondary particles and mitigates parasitic reactions. Additionally, the COO- anions of PA promote the acceleration of Li+ transport from cathode particles and increase charging rates. The Li||NCM811 batteries with PA in the electrolyte exhibit a high capacity retention of 83.83% after 200 cycles at 4.3 V, and maintain 80.88% capacity after 150 cycles at 4.6 V. This work provides an effective strategy for enhancing interface stability of high-voltage nickel-rich cathodes by forming stable CEI film.

RESUMEN

In the area of energy storage and conversion, Metal-Organic Frameworks (MOFs) are receiving more and more attention. They combine organic nature with long-range order and low thermal conductivity, giving them qualities to be potentially attractive for thermoelectric applications. To make the framework electrically conductive so far, thermoelectricity in this class of materials requires infiltration by outside conductive guest molecules. In this study, an in-situ polymerization of conductive polyaniline inside the porous structure of MOF-801 was conducted to synthesize PANi@MOF-801 nanocomposites for thermoelectrical applications. The growth of polyaniline chains of different loadings inside the host MOF matrix generally enhanced bulk electrical conductivity by about 6 orders of magnitude, leading to Seebeck coefficient value of -141 µVK-1 and improved thermal stability. The unusual increase in electrical conductivity was attributed to the formation of highly oriented conductive PANi chains inside the MOF pores, besides host-guest physical interaction, while the Seebeck coefficient enhancement was because of the energy filtering effect of the developed structure. Modulating the composition of PANi@MOF-801 composites by varying the aniline: MOF-801 ratio in the synthesis bath from 2:1 and 1:1 to 1:2 leads to a change in the semiconductor properties from p-type semiconductor to n-type. Among the examined composites with n-type semiconducting properties exhibited the highest ZT value, 0.015, and lowest thermal conductivity, 0.24 Wm-1 K-1. The synthesized composites have better performance than those recently reported for a similar category of thermoelectric materials related to MOF-based composites.

RESUMEN

This work highlights the development of a superior cathode|electrolyte interface for the quasi solid-state rechargeable zinc metal battery (QSS-RZMB) by a novel hydrogel polymer electrolyte using an ultraviolet (UV) light-assisted in situ polymerization strategy. By integrating the cathode with a thin layer of the hydrogel polymer electrolyte, this technique produces an integrated interface that ensures quick Zn2+ ion conduction. The coexistence of nanowires for direct electron routes and the enhanced electrolyte ion infiltration and diffusion by the 3D porous flower structure with a wide open surface of the Zn-MnO electrode complements the interface formation during the in situ polymerization process. The QSS-RZMB configured with an integrated cathode (i-Zn-MnO) and the hydrogel polymer electrolyte (PHPZ-30) as the separator yields a comparable specific energy density of 214.14 Wh kg-1 with that of its liquid counterpart (240.38 Wh kg-1, 0.5 M Zn(CF3SO3)2 aqueous electrolyte). Other noteworthy features of the presented QSS-RZMB system include its superior cycle life of over 1000 charge-discharge cycles and 85% capacity retention with 99% coulombic efficiency at the current density of 1.0 A g-1, compared to only 60% capacity retention over 500 charge-discharge cycles displayed by the liquid-state system under the same operating conditions.

RESUMEN

Lithium-sulfur (Li-S) batteries are expected to be the next-generation energy storage system due to the ultrahigh theoretical energy density and low cost. However, the notorious shuttle effect of higher-order polysulfides and the uncontrollable lithium dendrite growth are the two biggest challenges for commercially viable Li-S batteries. Herein, these two main challenges are solved by in situ polymerization of bi-functional gel polymer electrolyte (GPE). The initiator (SiCl4) not only drives the polymerization of 1,3-dioxolane (DOL) but also induces the construction of a hybrid solid electrolyte interphase (SEI) with inorganic-rich compositions on the Li anode. In addition, diatomaceous earth (DE) is added and anchored in the GPE to obtain PDOL-SiCl4-DE electrolyte through in situ polymerization. Combined with density functional theory (DFT) calculations, the hybrid SEI provides abundant adsorption sites for the deposition of Li+, inhibiting the growth of lithium dendrites. Meanwhile, the shuttle effect is greatly alleviated due to the strong adsorption capacity of DE toward lithium polysulfides. Therefore, the Li/Li symmetric cell and Li-S full cell assembled with PDOL-SiCl4-DE exhibit excellent cycling stability. This study offers a valuable reference for the development of high performance and safe Li-S batteries.

RESUMEN

The development of wearable thermoelectric generators (wTEG) represents a promising strategy to replace batteries and supercapacitors required to supply electrical energy for portable electronic devices. However, the main drawback of wTEGs is that the thermal gradient between the skin and the ambient is minimal, reducing the power output produced by the generator. Therefore, it is necessary to improve the thermal management of wTEG in order to increase its efficiency. This work deals with the preparation of a thermoelectric generator that harnesses the plasmonic heating effect to enhance the thermal gradient of the final device. The thermoelectric layer is created through the in situ polymerization of terthiophene (3T) within a polyurethane matrix, utilizing silver (Ag) (I) and copper (II) perchlorate as oxidants. The plasmonic film, composed of Ag-NP (nanoparticles), is formed via photocatalytic reduction of silver nitrate in the presence of titanium oxide. These layers are then meticulously assembled to yield the hybrid plasmonic/thermoelectric generator.

RESUMEN

Silicon (Si) stands out as a promising high-capacity anode material for high-energy Li-ion batteries. However, a drastic volume change of Si during cycling leads to the electrode structure collapse and interfacial stability degradation. Herein, a multifunctional quasisolid gel polymer electrolyte (QSGPE) is designed, which is synthesized through the in situ polymerization of methylene bis(acrylamide) with silica-nanoresin composed of nanosilica and a trifunctional cross-linker in cells, leading to the creation of a "breathing" three-dimensional elastic Li-ion conducting framework that seamlessly integrates an electrode, a binder, and an electrolyte. The silicon particles within the anode are encapsulated by buffering the QSGPE after cross-linking polymerization, which synergistically interacts with the existing PAA binder to reinforce the electrode structure and stabilize the interface. In addition, the formation of the LiF- and Li3N-rich SEI layer further improves the interfacial property. The QSGPE demonstrates a wide electrochemical window until 5.5 V, good flame retardancy, high ionic conductivity (1.13 × 10-3 S cm-1), and a Li+ transference number of 0.649. The advanced QSGPE and cell design endow both nano- and submicrosized silicon (smSi) anodes with high initial Coulombic efficiencies over 88.0% and impressive cycling stability up to 600 cycles at 1 A g-1. Furthermore, the NCM811//Si cell achieves capacity retention of ca. 82% after 100 cycles at 0.5 A g-1. This work provides an effective strategy for extending the cycling life of the Si anode and constructing an integrated cell structure by in situ polymerization of the quasisolid gel polymer electrolyte.