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.

12.6μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries

Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

Ultraviolet‑Irradiated All‑Organic Nanocomposites with Polymer Dots for High‑Temperature Capacitive Energy Storage

Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.

Construction of a High‑Performance Composite Solid Electrolyte Through In‑Situ Polymerization within a Self‑Supported Porous Garnet Framework

Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs.To overcome these challenges,we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZT)to produce the CSE.The synergy of the continuous conductive LLZT network,well-organized polymer,and their interface can enhance the ionic conductivity of the CSE at room temperature.Furthermore,the in-situ polymerization process can also con-struct the integration and compatibility of the solid electrolyte–solid electrode interface.The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm^(-1),a significant lithium transference number of 0.627,and exhibited electrochemical stability up to 5.06 V vs.Li/Li+at 30℃.Moreover,the Li|CSE|LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cell delivered a discharge capacity of 105.1 mAh g^(-1) after 400 cycles at 0.5 C and 30℃,corresponding to a capacity retention of 61%.This methodology could be extended to a variety of ceramic,polymer electrolytes,or battery systems,thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs.

A"Concentrated lonogel-in-Ceramic"Silanization Composite Electrolyte with Superior Bulk Conductivity and Low Interfacial Resistance for Quasi-Solid-State Li Metal Batteries

The ideal composite electrolyte for the pursued safe and high-energy-density lithium metal batteries(LMBs)is expected to demonstrate peculiarity of superior bulk conductivity,low interfacial resistances,and good compatibility against both Li-metal anode and high-voltage cathode.There is no composite electrolyte to synchronously meet all these requirements yet,and the battery performance is inhibited by the absence of effective electrolyte design.Here we report a unique"concentrated ionogel-in-ceramic"silanization composite electrolyte(SCE)and validate an electrolyte design strategy based on the coupling of high-content silane-conditioning garnet and concentrated ionogel that builds well-percolated Li+transport pathways and tackles the interface issues to respond all the aforementioned requirements.It is revealed that the silane conditioning enables the uniform dispersion of garnet nanoparticles at high content(70 wt%)and forms mixed-lithiophobic-conductive LiF-Li3N solid electrolyte interphase.Notably,the yielding SCE delivers an ultrahigh ionic conductivity of 1.76 X 10^(-3)S cm^(-1)at 25℃,an extremely low Li-metal/electrolyte interfacial area-specific resistance of 13Ωcm^(2),and a distinctly excellent long-term 1200 cycling without any capacity decay in 4.3 V Li‖LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)quasi-solid-state LMB.This composite electrolyte design strategy can be extended to other quasi-/solid-state LMBs.

A Tri-Salt Composite Electrolyte with Temperature Switch Function for Intelligently Temperature-Controlled Lithium Batteries

The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requirements for battery systems.The high-energy lithium batteries are expected to respond or react under different environmental conditions.In this work,a tri-salt composite electrolyte is designed with a temperature switch function for intelligently temperature-controlled lithium batteries.Specifically,the halide Li_(3)YBr_(6)together with LiTFSI and LiNO_(3)works as active fillers in a low-melting-point polymer matrix(polyethyleneglycol dimethyl ether(PEGDME)and polyethylene oxide(PEO)),which is further filled into the pre-lithiated alumina fiber skeleton.Above 60°C,the composite electrolyte exists in the liquid state and fully contacts with the working electrodes on the liquid–solid interface,effectively minimizing the interfacial resistance and leading to high discharge capacity in the cell.The electrolyte is changed into a solid state below 30°C so that the ionic conductivity is significantly reduced and the interface resistance is increased dramatically on the solid–solid interface.Therefore,by simply adjusting the temperature,the cell can be turned“ON”or“OFF”intentionally.This novel function of the composite electrolyte has enlightening significance in developing intelligently temperature-controlled lithium batteries.

Influence of Mass Ratio of Resin and Stabilizer on Mechanical Properties of Mo Fiber-reinforced Granite Polymer Composite

Because inferior mechanical strength of granite polymer composite(GPC)has become the main drawback limiting its application and popularization,Mo fibers were added into(GPC)to improve its mechanical strength.Mechanical properties of matrix materials with different mass ratio of resin and stabilizer(MRRS)were investigated systematically.The influences of MRRS on interface bonding strength of Mo fiber-matrix,wettability and mechanical strength of GPC were discussed,respectively,and the theoretical calculation result of MRRS k was obtained,with the optimal value of k=4.When k=4,tensile strength,tensile strain and fracture stress of the cured resin achieve the maximum values.But for k=7,the corresponding values reach the minimum.With the increase of MRRS k,surface free energy of the cured resin first increases and then decreases,while contact angles between Mo sample and matrix have displayed the opposite trend.Wettability of resin to Mo fiber is the best at k=4.Pulling load of Mo fiber and interface bonding strength appear the maximum at k=4,followed by k=5,k=3 the third,and k=7 the minimum.When k=4,mechanical properties of Mo fiber-reinforced GPC are optimal,which is consistent with the result of theoretical calculation.This study is of great significance to get better component formulas of Mo fiber reinforced GPC and to improve its application in machine tools.

Sandwich-type composited solid polymer electrolytes to strengthen the interfacial ionic transportation and bulk conductivity for all-solid-state lithium batteries from room temperature to 120℃

The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.

Flexible piezoresistive pressure sensor based on a graphene-carbon nanotube-polydimethylsiloxane composite

Flexible sensors are used widely in wearable devices, specifically flexible piezoresistive sensors, which are common and easy to manipulate.However, fabricating such sensors is expensive and complex, so proposed here is a simple fabrication approach involving a sensor containing microstructures replicated from a sandpaper template onto which polydimethylsiloxane containing a mixture of graphene and carbon nanotubes is spin coated. The surface morphologies of three versions of the sensor made using different grades of sandpaper are observed, and the corresponding pressure sensitivities and linearity and hysteresis characteristics are assessed and analyzed. The results show that the sensor made using 80-mesh sandpaper has the best sensing performance. Its sensitivity is 0.341 kPa-1in the loading range of 0–1.6 kPa, it responds to small external loading of 100 Pa with a resistance change of 10%, its loading and unloading response times are 0.126 and 0.2 s, respectively,and its hysteresis characteristic is ~7%, indicating that the sensor has high sensitivity, fast response, and good stability. Thus, the presented piezoresistive sensor is promising for practical applications in flexible wearable electronics.

Supposition of graphene stacks to estimate the contact resistance and conductivity of nanocomposites

In this study,the effects of stacked nanosheets and the surrounding interphase zone on the resistance of the contact region between nanosheets and the tunneling conductivity of samples are evaluated with developed equations superior to those previously reported.The contact resistance and nanocomposite conductivity are modeled by several influencing factors,including stack properties,interphase depth,tunneling size,and contact diameter.The developed model's accuracy is verified through numerous experimental measurements.To further validate the models and establish correlations between parameters,the effects of all the variables on contact resistance and nanocomposite conductivity are analyzed.Notably,the contact resistance is primarily dependent on the polymer tunnel resistivity,contact area,and tunneling size.The dimensions of the graphene nanosheets significantly influence the conductivity,which ranges from 0 S/m to90 S/m.An increased number of nanosheets in stacks and a larger gap between them enhance the nanocomposite's conductivity.Furthermore,the thicker interphase and smaller tunneling size can lead to higher sample conductivity due to their optimistic effects on the percolation threshold and network efficacy.

Revealing the specific role of sulfide and nano-alumina in composite solid-state electrolytes for performance-reinforced ether-nitrile copolymers

Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combinations between polymers and fillers is vital,but blind attempts are often made due to a lack of understanding of the mechanisms involved in the interaction between polymers and fillers.Herein,we employ in-situ polymerization to prepare a polymer based on an ether-nitrile copolymer with high cathode stability as the foundation and discuss the performance enhancement mechanisms of argyrodite and nano-alumina.With 1%content of sulfide interacting with the polymer at the two-phase interface,the local enhancement of lithium-ion migration capability can be achieved,avoiding the reduction in capacity due to the low ion conductivity of the passivation layer during cycling.The capacity retention after 50cycles at 0.5 C increases from 83.5%to 94.4%.Nano-alumina,through anchoring the anions and interface inhibition functions,eventually poses an initial discharge capacity of 136.8 m A h g^(-1)at 0.5 C and extends the cycling time to 1000 h without short-circuiting in lithium metal batteries.Through the combined action of dual fillers on the composite solid-state electrolyte,promising insights are provided for future material design.

Novel sandwich structured glass fiber Cloth/Poly(ethylene oxide)-MXene composite electrolyte

Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.

Physical and Chemical Properties of Horns Sheaths Particles for the Manufacture of Composite Materials

Salvaged cow horns from slaughterhouses have been transformed into fine particles for a physical characterization that has led us to determine the humidity rate (2.34% ± 0.054%), the actual density situated between 0.586 g/cm3 and 0.732 g/cm3, the swelling rate (12%), and one chemical characterization that permitted us to determine the rate of dry matters (97.05%), of mineral matters (2.5%), of protein matters (94.52%). From these weak values, it can easily be seen that cow horn case doesn’t absorb much water and improve the mechanical characteristics of the composite;the high rate of protein shows that keratin which is the structural molecule favors its gripping as reinforcing element in the manufacturing of composite materials.

Research Progress on the Preparation of Inorganic/Natural Materials Composite Microspheres

Microspheres are a new type of drug carrier with great potential for development and application.Natural polymers have good biocompatibility,biodegradability,and are easily dispersed in living organisms,making them suitable for preparing microspheres.Inorganic materials(mainly inorganic minerals)have excellent mechanical properties and are inexpensive and easy to obtain.Through the coupling and hybridization of natural polymers and inorganic materials,they can complement each other's advantages and synergistically enhance efficiency,resulting in many excellent physical and chemical properties.Inorganic materials/natural polymer composite microspheres can be prepared by modifying natural polymers with inorganic materials through various methods such as emulsification crosslinking,solution mixing,in-situ synthesis,extrusion,etc.The application of inorganic materials/natural polymer composite microspheres in drug delivery systems has significant sustained-release effects,is safe and non-toxic,and the cost of carrier materials is relatively low,which has certain significance for the development of new drug carriers.This article reviews the recent research on the preparation,drug loading and release properties of inorganic material/natural polymer composite microspheres,analyzes the advantages and disadvantages of commonly used preparation methods,and looks forward to the development direction of composite microspheres.

A review on machinability of carbon fiber reinforced polymer(CFRP)and glass fiber reinforced polymer(GFRP)composite materials

Fiber reinforced polymer(FRP) composite materials are heterogeneous and anisotropic materials that do not exhibit plastic deformation. They have been used in a wide range of contemporary applications particularly in space and aviation,automotive,maritime and manufacturing of sports equipment. Carbon fiber reinforced polymer(CFRP) and glass fiber reinforced polymer(GFRP) composite materials,among other fiber reinforced materials,have been increasingly replacing conventional materials with their excellent strength and low specific weight properties. Their manufacturability in varying combinations with customized strength properties,also their high fatigue,toughness and high temperature wear and oxidation resistance capabilities render these materials an excellent choice in engineering applications.In the present review study,a literature survey was conducted on the machinability properties and related approaches for CFRP and GFRP composite materials. As in the machining of all anisotropic and heterogeneous materials,failure mechanisms were also reported in the machining of CFRP and GFRP materials with both conventional and modern manufacturing methods and the results of these studies were obtained by use of variance analysis(ANOVA),artificial neural networks(ANN) model,fuzzy inference system(FIS),harmony search(HS) algorithm,genetic algorithm(GA),Taguchi's optimization technique,multi-criteria optimization,analytical modeling,stress analysis,finite elements method(FEM),data analysis,and linear regression technique. Failure mechanisms and surface quality is discussed with the help of optical and scanning electron microscopy,and profilometry. ANOVA,GA,FEM,etc. are used to analyze and generate predictive models.

DEVELOPMENT OF POLYMER MINERAL COMPOSITE AND ITS DAMPING PROPERTY

The principle of production of polymer mineral composite was analyzed. Property parameters and the procedure for producing PMC components were also given. Damping property and principle of vibration absorption of polymer mineral composite were also investigated. Reduced experiment was conducted for two jigs which are similar in structure only different in material that one made of PMC the other made of casting iron to test their dynamic characteristic.

Lithium–matrix composite anode protected by a solid electrolyte layer for stable lithium metal batteries

Lithium (Li) metal with an ultrahigh specific theoretical capacity and the lowest reduction potential is strongly considered as a promising anode for high-energy-density batteries. However, uncontrolled lithium dendrites and infinite volume change during repeated plating/stripping cycles hinder its practical applications immensely. Herein, a house-like Li anode (housed Li) was designed to circumvent the above issues. The house matrix was composed of carbon fiber matrix and affords a stable structure to relieve the volume change. An artificial solid electrolyte layer was formed on composite Li metal, just like the roof of a house, which facilitates uniform Li ions diffusion and serves as a physical barrier against electrolyte corrosion. With the combination of solid electrolyte layer and matrix in the composite Li metal anode, both dendrite growth and volume expansion are remarkably inhibited. The housed Li|LiFePO4 batteries exhibited over 95% capacity retention after 500 cycles at 1.0 C in coin cell and 85% capacity retention after 80 cycles at 0.5 C in pouch cell. The rationally combination of solid electrolyte layer protection and housed framework in one Li metal anode sheds fresh insights on the design principle of a safe and long-lifespan Li metal anode for Li metal batteries.

Status and prospect of garnet/polymer solid composite electrolytes for all-solid-state lithium batteries

Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at ambient temperature. Inorganic solid electrolytes(ISEs), garnet-type Li7La3Zr2O12 and its derivatives(LLZO-based) in particular, possess high ionic conductivity at room temperature, wide electrochemical stability window, large Li+transference number as well as good stability against Li metal anode.Nevertheless, lithium dendrites growth, interfacial contact issue and brittle nature of LLZO-based ceramic electrolytes prevent their practical applications. In response to these shortcomings, LLZO-based/polymer solid composite electrolytes(SCEs), taking complementary advantages of two kinds of electrolytes, and thus simultaneously improving the electrode wettability, ionic conductivity and mechanical strength, have been made to develop high-performance SCEs in recent years. Herein, the intrinsic properties and research progress of LLZO-based/polymer SCEs, including LLZO-based/PEO SCEs(LLZO-based/PEO SCEs with uniform dispersion of LLZO-based fillers and LLZO-based/PEO layered SCEs) and LLZO-based/novel polymers SCEs, are summarized. Besides, comprehensive updates on their applications in solid-state batteries are also presented. Finally, challenges and perspectives of LLZO-based/polymer SCEs for advanced allsolid-state lithium batteries(ASSLBs) are suggested. This review paper aims to provide systematic research progress of LLZO-based/polymer SCEs, to allow for more efficient and target-oriented research on improving LLZO-based/polymer SCEs.

Thermal conductivity model of filled polymer composites

Theoretical and empirical models for predicting the thermal conductivity of polymer composites were summarized since the 1920s.The effects of particle shape,filler amount,dispersion state of fillers,and interfacial thermal barrier on the thermal conductivity of filled polymer composites were investigated,and the agreement of experimental data with theoretical models in literatures was discussed.Silica with high thermal conductivity was chosen to mix with polyvinyl-acetate （EVA） copolymer to prepare SiO2/EVA co-films.Experimental data of the co-films＇ thermal conductivity were compared with some classical theoretical and empirical models.The results show that Agari＇s model,the mixed model,and the percolation model can predict well the thermal conductivity of SiO2/EVA co-films.

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.