Advancements and Challenges in Organic–Inorganic Composite Solid Electrolytes for All‑Solid‑State Lithium Batteries

To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.

Functional inorganic additives in composite solid-state electrolytes for flexible lithium metal batteries

Flexible lithium metal batteries with high capacity and power density have been regarded as the core power resources of wearable electronics.However,the main challenge lies in the limited electrochemical performance of solid-state polymer electrolytes,which hinders further practical applications.Incorporating functional inorganic additives is an effective approach to improve the performance,including increasing ionic conductivity,achieving dendrite inhibiting capability,and improving safety and stability.Herein,this review summarizes the latest developments of functional inorganic additives in composite solid-state electrolytes for flexible metal batteries with special emphasis on their mechanisms,strategies,and cutting-edge applications,in particular,the relationship between them is discussed in detail.Finally,the perspective on future research directions and the key challenges on this topic are outlooked.

Preparation of inorganic molten salt composite phase change materials and study on their electrothermal conversion properties

Due to their limitations in conductivity and shape stability,molten salt phase change materials have encountered obstacles to effectively integrating into electric heating conversion technologies,which are crucial in energy storage and conversion fields.In this study,we synthesized an inorganic molten salt composite phase change material(CPCM)with enhanced conductivity and shape stability using a gasphase silica adsorption method.Our findings revealed the regularities in thermal properties modulation by expanded graphite(EG)within CPCM and delved into its characteristics of electric heating conversion.The study elucidated that a conductive network is essentially formed when the EG content exceeds 3 wt%.Following the fabrication of CPCM into electric heating conversion modules,we observed a correlation between the uniformity of module temperature and the quantity of EG,as well as the distribution of electrode resistance and external voltage magnitude.Building upon this observation,we proposed a strategy to adjust the module temperature field with an electric field.Comparing the proposed direct electrical heating energy storage method with traditional indirect electrical heating methods,the energy storage rate increases by 93.8%,with an improved temperature uniformity.This research offers valuable insights for the application of molten salt electric heating conversion CPCMs.

Tailoring Practically Accessible Polymer/Inorganic Composite Electrolytes for All-Solid-State Lithium Metal Batteries:A Review

Solid-state electrolytes(SSEs)are widely considered the essential components for upcoming rechargeable lithium-ion batteries owing to the potential for great safety and energy density.Among them,polymer solid-state electrolytes(PSEs)are competitive candidates for replacing commercial liquid electrolytes due to their flexibility,shape versatility and easy machinability.Despite the rapid development of PSEs,their practical application still faces obstacles including poor ionic conductivity,narrow electrochemical stable window and inferior mechanical strength.Polymer/inorganic composite electrolytes(PIEs)formed by adding ceramic fillers in PSEs merge the benefits of PSEs and inorganic solid-state electrolytes(ISEs),exhibiting appreciable comprehensive properties due to the abundant interfaces with unique characteristics.Some PIEs are highly compatible with high-voltage cathode and lithium metal anode,which offer desirable access to obtaining lithium metal batteries with high energy density.This review elucidates the current issues and recent advances in PIEs.The performance of PIEs was remarkably influenced by the characteristics of the fillers including type,content,morphology,arrangement and surface groups.We focus on the molecular interaction between different components in the composite environment for designing high-performance PIEs.Finally,the obstacles and opportunities for creating high-performance PIEs are outlined.This review aims to provide some theoretical guidance and direction for the development of PIEs.

Thixotropic composite hydrogels based on agarose and inorganic hybrid gellants

Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becoming liquid when use.Stable and thixotropic hydrogel has good potential as water-retaining material and oxidant of metal-based propellant.In this study,we prepared organic/inorganic composite hydrogels by combining inorganic gellants hectorite and fumed silica with organic gellant agarose,respectively.The total content of the gellants can be reduced to less than 2%by adding agarose.The influence of agarose on water content,phase transition temperature,centrifugal stability and other basic physical properties of composite hydrogels were discussed.The results show that the composite hydrogels have better thixotropy and stability than pure inorganic hydrogels,and the gel-sol transformation can be realized by applying shear force or heating to the phase transition temperature.The composite hydrogels have good shear thinning ability and improved mechanical stability.Fumed silica/agarose hydrogels have better physical stability,while the thixotropy and shear thinning ability of hectorite/agarose hydrogels are better.

Ameliorating the interfacial issues of all-solid-state lithium metal batteries by constructing polymer/inorganic composite electrolyte

Lithium metal is one of the most promising anodes for next-generation batteries due to its high capacity and low reduction potential.However,the notorious Li dendrites can cause the short life span and safety issues,hindering the extensive application of lithium batteries.Herein,Li_(7)La_(3)Zr_(2)O_(12)(LLZO)ceramics are integrated into polyethylene oxide(PEO)to construct a facile polymer/inorganic composite solid-state electrolyte(CSSE)to inhibit the growth of Li dendrites and widen the electrochemical stability window.Given the feasibility of our strategy,the designed PEO-LLZO-LiTFSI composite solid-state electrolyte(PLLCSSE)exhibits an outstanding cycling property of 134.2 mAh g^(-1) after 500 cycles and the Coulombic efficiency of 99.1%after 1000 cycles at 1 C in LiFePO_(4)-Li cell.When cooperated with LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)cathode,the PLL-CSSE renders a capacity retention of 82.4%after 200 cycles at 0.2 C.More importantly,the uniform dispersion of LLZO in PEO matrix is tentative tested via Raman and FT-IR spectra and should be responsible for the improved electrochemical performance.The same conclusion can be drawn from the interface investigation after cycling.This work presents an intriguing solid-state electrolyte with high electrochemical performance,which will boost the development of all-solid-state lithium batteries with high energy density.

Thermal transport in organic/inorganic composites

Composite materials, which consist of organic and inorganic components, are widely used in various fields because of their excellent mechanical properties, resistance to corrosion, low-cost fabrication, etc. Thermal properties of organic/inorganic composites play a crucial role in some applications such as thermal interface materials for micro-electronic packaging, nano-porous materials for sensor development, thermal insulators for aerospace, and high-performance thermoelectric materials for power generation and refrigeration. In the past few years, many studies have been conducted to reveal the physical mechanism of thermal transport in organic/ inorganic composite materials in order to stimulate their practical applications. In this paper, the theoretical and experimental progresses in this field are reviewed. Besides, main factors affecting the thermal conductivity of organic/ inorganic compositcs are discussed, including the intrinsic properties of organic matrix and inorganic fillers, topolo- gical structure of composites, loading volume fraction, and the interfacial thermal resistance between fillers and organic matrix.

The critical role of inorganic nanofillers in solid polymer composite electrolyte for Li+transportation

Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cycle life;therefore,ASSLBs have been identified as promising candidates for next-generation safe and stable high-energy-storage devices.The design and fabrication of solid-state electrolytes(SSEs)are vital for the future commercialization of ASSLBs.Among various SSEs,solid polymer composite electrolytes(SPCEs)consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs.The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE.In this review,the mechanisms of Li+transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail.On the basis of the recent progress,the respective contributions of polymer chains,passive ceramic nanofillers,and active ceramic nanofillers in affecting the Li+transport process of SPCE are reviewed systematically.The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed.Finally,the challenges and future perspectives for developing high-performance SPCE are put forward.This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler-reinforced SPCE and highlight their inspiration for future research directions.

Organic/inorganic nanocomposite polymer electrolyte

The organic/inorganic nanocomposites polymer electrolytes were designed and synthesized. The organic/inorganic nanocomposites membrane materials and their lithium salt complexes have been found thermally stable below 200 °C. The conductivity of the organic/inorganic nanocomposites polymer electrolytes prepared at room temperature was at magnitude range of 10(?6) S/cm.

Flame Retardancy Enhancement of Hybrid Composite Material by Using Inorganic Retardants

This study aims to investigate the possibility of improving the flame Retardancy for the hybrid composite material consisting araldite resin (CY223). The hybrid composite was reinforced by hybrid fibers from carbon and Kevlar fibers on woven roving form (45o -0o), by using a surface layer of 4mm thick of Zinc Borate flame retardant. Afterward, the structure was exposed directly to gas flame of 2000oC due to 10 mm and 20mm exposure interval. The retardant layer thermal resistance and protection capability were determined. The study was continued to improve the performance of Zinc Borate layer mixed by 10%, 20% and 30% of Antimony Trioxide. To determine the heat transfer of the composite material the opposite surface temperature method was used. Zinc Borate with (30%) Antimony Trioxide gives the optimized result of the experiment.

Synthesis and characterization of luminescent organic-inorganic hybrid nanocomposite from polyhedral oligomeric silsesquioxane

A novel polyhedral oligomeric silsesquioxane(POSS)-based organic-inorganic hybrid nanocomposite(EF-POSS) was prepared by Pt-catalyzed hydrosilylation reaction of octahydridosilsesquioxane(T_8H_8,POSS) with a luminescent substituted acetylene(2- ethynyl-7-(4-(4-methylstyryl)styryl)-9,9-dioctyl-9H-fluorene(EF)) in high yield.The hybrid nanocomposite was soluble in common solvents such as CH_2Cl_2,CHCl_3,THF and 1,4-dioxane.Its structure and property were characterized by FTIR, NMR,TGA,UV and PL,respectively.The results show that the hybrid nanocomposite with high thermal stability emits stable blue light as a result of photo excitation and possesses high photoluminescence quantum efficiency(φ_(FL)).

Organic-inorganic Hybrids Towards the Preparation of Nanoporous Composite Thin Films for Microelectronic Application

Silicon containing materials have traditionally been used in microelectronic fabrication. Semiconductor devices often have one or more arrays of patterned interconnect levels that serve to electrically couple the individual circuit elements forming an integrated circuit. These interconnect levels are typically separated by an insulating or dielectric film. Previously, a silicon oxide film was the most commonly used material for such dielectric films having dielectric constants( k ) near 4 0. However, as the feature size is continuously scaling down, the relatively high k of such silicon oxide films became inadequate to provide efficient electrical insulation. As such, there has been an increasing market demand for materials with even lower dielectric constant for Interlayer Dielectric(ILD) applications, yet retaining thermal and mechanical integrity. We wish to report here our investigations on the preparation of ultra low k ILD materials using a sacrificial approach whereby organic groups are burnt out to generate low k porous ORMOSIL films. We have been able to prepare a variety of organically modified silicone resins leading to highly microporous thin films, exhibiting ultra low k from 1 80 to 2 87, and good to high modulus, 1 5 to 5 5 GPa. Structure property influences on porosity, dielectric constant and modulus will be discussed.

Effects of long-term partial substitution of inorganic fertilizer with pig manure and/or straw on nitrogen fractions and microbiological properties in greenhouse vegetable soils

Partial substitution of inorganic fertilizers with organic amendments is an important agricultural management practice.An 11-year field experiment(22 cropping periods)was carried out to analyze the impacts of different partial substitution treatments on crop yields and the transformation of nitrogen fractions in greenhouse vegetable soil.Four treatments with equal N,P_(2)O_(5),and K_(2)O inputs were selected,including complete inorganic fertilizer N(CN),50%inorganic fertilizer N plus 50%pig manure N(CPN),50%inorganic fertilizer N plus 25%pig manure N and 25%corn straw N(CPSN),and 50%inorganic fertilizer N plus 50%corn straw N(CSN).Organic substitution treatments tended to increase crop yields since the 6th cropping period compared to the CN treatment.From the 8th to the 22nd cropping periods,the highest yields were observed in the CPSN treatment where yields were 7.5-11.1%greater than in CN treatment.After 11-year fertilization,compared to CN,organic substitution treatments significantly increased the concentrations of NO_(3)^(-)-N,NH_(4)^(+)-N,acid hydrolysis ammonium-N(AHAN),amino acid-N(AAN),amino sugar-N(ASN),and acid hydrolysis unknown-N(AHUN)in soil by 45.0-69.4,32.8-58.1,49.3-66.6,62.0-69.5,34.5-100.3,and 109.2-172.9%,respectively.Redundancy analysis indicated that soil C/N and OC concentration significantly affected the distribution of N fractions.The highest concentrations of NO_(3)^(-)-N,AHAN,AAN,AHUN were found in the CPSN treatment.Organic substitution treatments increased the activities ofβ-glucosidase,β-cellobiosidase,N-acetyl-glucosamidase,L-aminopeptidase,and phosphatase in the soil.Organic substitution treatments reduced vector length and increased vector angle,indicating alleviation of constraints of C and N on soil microorganisms.Organic substitution treatments increased the total concentrations of phospholipid fatty acids(PLFAs)in the soil by 109.9-205.3%,and increased the relative abundance of G^(+)bacteria and fungi taxa,but decreased the relative abundance of G-bacteria,total bacteria,and actinomycetes.Overall,long-term organic substitution management increased soil OC concentration,C/N,and the microbial population,the latter in turn positively influenced soil enzyme activity.Enhanced microorganism numbers and enzyme activity enhanced soil N sequestration by transforming inorganic N to acid hydrolysis-N(AHN),and enhanced soil N supply capacity by activating non-acid hydrolysis-N(NAHN)to AHN,thus improving vegetable yield.Application of inorganic fertilizer,manure,and straw was a more effective fertilization model for achieving sustainable greenhouse vegetable production than application of inorganic fertilizer alone.

Preparation of Polymer-Mineral Nanocomposites Based on Vinyl Monomers and Dispersed Inorganic Oxides

The polymer-mineral composites were synthesized using vinyl monomers styrene, methyl acrylate, and butyl acrylate with nano dispersed oxides Fe2O3, Cr2O3, V2O5 and SiO2 in the presence of benzoyl peroxide and other peroxide initiators. Benzoyl peroxide adsorption on Fe2O3, Cr2O3, and V2O5 surfaces was studied. The adsorption parameters were found: adsorption-desorption equilibrium constants, maximum adsorption, and the area occupied by the molecule benzoyl peroxide on the surface of the adsorbent. The molecular weights of the polymers in the composites and the degree of grafting of the macromolecules of the polymer to the surface of oxides were studied. It has been found that the surface of the dispersed oxides influences the rate of thermal decomposition of the peroxide initiators and the polymerization parameters of the vinyl monomers.

Semitransparent organic photovoltaics enabled by transparent p-type inorganic semiconductor and near-infrared acceptor

Semitransparent organic photovoltaics(STOPVs)have gained wide attention owing to their promising applications in building-integrated photovoltaics,agrivoltaics,and floating photovoltaics.Organic semiconductors with high charge carrier mobility usually have planar and conjugated structures,thereby showing strong absorption in visible region.In this work,a new concept of incorporating transparent inorganic semiconductors is proposed for high-performance STOPVs.Copper(I)thiocyanate(CuSCN)is a visible-transparent inorganic semiconductor with an ionization potential of 5.45 eV and high hole mobility.The transparency of CuSCN benefits high average visible transmittance(AVT)of STOPVs.The energy levels of CuSCN as donor match those of near-infrared small molecule acceptor BTP-eC9,and the formed heterojunction exhibits an ability of exciton dissociation.High mobility of CuSCN contributes to a more favorable charge transport channel and suppresses charge recombination.The control STOPVs based on PM6/BTP-eC9 exhibit an AVT of 19.0%with a power conversion efficiency(PCE)of 12.7%.Partial replacement of PM6 with CuSCN leads to a 63%increase in transmittance,resulting in a higher AVT of 30.9%and a comparable PCE of 10.8%.

Covalent organic frameworks/carbon nanotubes composite with cobalt(II)pyrimidine sites for bifunctional oxygen electrocatalysis

With characteristics and advantages of functional composite materials,they are commendably adopted in numerous fields especially in oxygen electrocatalysis,which is due to the significant synergies between various components.Herein,a novel bifunctional oxygen electrocatalyst(Co-CNT@COF-Pyr)has been synthesized through in-situ growth of covalent organic frameworks(COFs)layers on the outer surface of highly conductive carbon nanotubes(CNTs)followed by coordination with Co(Ⅱ).For electrocatalytic OER,Co-CNT@COF-Pyr reveals a low overpotential(438 mV)in alkaline electrolyte(1.0 M aqueous solution of KOH)with a current density of 10 mA cm^(-2),which is comparable to most discovered COF-based catalysts.For electrocatalytic ORR,CoCNT@COF-Pyr exhibits a low H_(2)O_(2) yield range(9.0%-10.1%)and a reaction pathway close to 4e^(-)(n=3.82-3.80)in alkaline electrolyte(0.1 M aqueous solution of KOH)within the test potential range of 0.1-0.6 V vs.RHE,which is superior to most reported COF-based catalysts.Hence,this research could not only offer an innovative insight into the construction of composites,but also facilitate the practical application of renewable fuel cells,closed water cycle,and rechargeable metal-air batteries.

Removal of ammonia nitrogen from inorganic wastewater by AgBr/C_(3)N_(5)heterojunction under visible light irradiation

AgBr/C_(3)N_(5)composite was prepared by in-situ precipitation of AgBr on the surface of nitrogen-rich carbon nitride(C_(3)N_(5)).The crystal phase,chemical composition,elemental composition,spectral absorption and photoelectron-hole separation of the composite were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-vis DRS)and photoluminescence spectroscopy(PL).The construction of AgBr and C_(3)N_(5)heterojunction could broaden the spectral response range,realize the efficient separation of photoelectrons and holes,and thus improve the photocatalytic performance.The photocatalytic performance of the composite material was studied by simulating inorganic ammonia nitrogen wastewater with NH_(4)Cl solution.The dosage of the composite material was 0.10 g,the initial mass concentration of NH_(4)Cl solution was 100 mg/L,and the initial pH was 10.0.The removal rate of ammonia nitrogen by the composite material reached 90.27%after 60 min of simulated visible light irradiation.After 5 cycles,the removal rate of ammonia nitrogen only declined by 0.12%.The composite material showed good photocatalytic performance and stability.The Z-scheme mechanism effectively retained the reduction and oxidation activities of photoelectrons and holes,which could change O_(2)and H2O to active groups such as superoxide radicals(·O_(2)-)and hydroxyl radicals(·OH),respectively,achieving efficient removal of inorganic ammonia nitrogen.

Ag nanoparticles anchored organic/inorganic Z‐scheme 3DOMM‐TiO_(2‒x)‐based heterojunction for efficient photocatalytic and photoelectrochemical water splitting

Narrow spectral response,low charge separation efficiency and slow water oxidation kinetics of TiO_(2)limit its application in photoelectrochemical and photocatalytic water splitting.Herein,a promising organic/inorganic composite catalyst Ag/PANI/3DOMM‐TiO_(2–x)with a three‐dimensional ordered macro‐and meso‐porous(3DO MM)structure,oxygen vacancy and Ti^(3+)defects,heterojunction formation and noble metal Ag was designed based on the Z‐scheme mechanism and successfully prepared.The Ag/PANI/3DOMM‐TiO_(2–x)ternary catalyst exhibited enhanced hydrogen production activity in both photocatalytic and photoelectrochemical water splitting.The photocatalytic hydrogen production rate is 420.90μmol g^(–1)h^(–1),which are 19.80 times and 2.06 times higher than the commercial P25 and 3DOMM‐TiO_(2),respectively.In the photoelectrochemical tests,the Ag/PANI/3DOMM‐TiO_(2–x)photoelectrode shows enhanced separation and transfer of carriers with a high current density of 1.55 mA cm^(–2)at equilibrium potential of 1.23 V under simulated AM 1.5 G illumination,which is approximately 5 times greater than the 3DOMM‐TiO_(2).The present work has demonstrated the promising potential of organic/inorganic Z‐scheme photocatalyst in driving water splitting for hydrogen production.

Factors controlling the phytoplankton crops,taxonomic composition,and particulate organic carbon stocks in the Cosmonaut Sea,East Antarctica

The ecosystems in Southern Ocean(SO)are undergoing significant changes in the context of climate change.To identify environment-phytoplankton feedbacks in SO,seawater samples were collected in the Cosmonaut Sea(CS)during the 37 th China Antarctic Research Expedition(Jan.2021)(CHINARE-37)and subjected to analysis of particulate organic carbon(POC)and phytoplankton pigments.The remote sensing data,CHEMTAX community compositional modeling analysis,and physicochemical measurements were combined to explore the spatial variation of phytoplankton crops,taxonomic composition,and their environmental drivers.Historical phytoplankton community data from the area were also compared against those of this study to investigate inter-annual community differences and their potential causes.The column-integrated POC and chlorophyll-a(Chl-a)concentrations were 12.0±4.9 g/m^(2) and 73.8±50.5 mg/m^(2),respectively.The two most dominant taxa were haptophyte that are adapted to high Fe availability(Hapt-HiFe,mainly Phaeocystis antarctica)and Diatoms-A(Phaeodactylum tricornutum)that contributed to 33%±25%and 24%±14%to the total phytoplankton crops,respectively.Through cluster analysis,the study area was divided into two regions dominated by Hapt-HiFe and Diatoms-A,respectively.Spatially,Hapt-HiFe was mainly concentrated in the southwest coastal area that featured low temperatures,low salinity,and shallow euphotic zones.The coastal region southwest of the southern boundary of the Antarctic circumpolar current was experiencing a bloom of Hapt-HiFe during the study period that significantly contributed to the POC pool and Chl-a concentrations(R=0.46,P<0.01;R=0.42,P<0.01).Besides,the dominance of Hapt-HiFe in the CS suggests a high biological availability of dissolved Fe that is primarily associated with inputs from sea ice melt and upwellings.