Rational Design of High-Performance PEO/Ceramic Composite Solid Electrolytes for Lithium Metal Batteries

Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.

Fabrication of Ceramic Composites by Directed Metal Oxidation

To explain the growth mechanism of Al 2O 3/Al Lanxide composites,the dynamics of the directed oxidation of Al-Mg-Si alloys are analyzed.The experimental methods to produce Lanxide composites by directed oxidation of metal melts at high temperatures are presented.The effect of the processing factors on the microstructures and properties of Al 2O 3/Al composites and enforced Al 2O 3/Al composites is also analyzed.Compared with sintering ceramic composites,the advantages of Lanxide process and Lanxide materials are as following:it is a near net shaped process;the process is very simple;the microstructures and properties of Lanxide materials can be adjusted;and this process can be used to infiltrate ceramic fiber or particle preforms.

Preparation of Fe-M Intermetallic/TiC-M_2O_3 Ceramic Composites from Ilmenite by SHS

Fe-Al intermetallic/TiC-Al2O3 ceramic composites were successfully prepared by selfpropagating high-temperature synthesis （SHS） from natural ilmenite, aluminium and carbon as the raw materials. The effects of carbon sources, preheating time and heat treatment temperature on synthesis process and products were investigated in detail, and the reaction process of the FeTiO3-Al-C system was also discussed. It is shown that the temperature and velocity of the combustion wave are higher when graphite is used as the carbon source, which can reflect the effect of the carbon source structure on the combustion synthesis; Prolonging the preheating time or heat treatment temperature is beneficial to the formation of the ordered intermetallics; The temperature and velocity of the combustion wave are improved, but the disordered alloys are difficult to eliminate with the preheating time prolonged. The compound powders mainly containing ordered Fe3Al intermetallic can be prepared through heat treatment at 750 ℃.

Identification of Growth Promoter to Fabrication SiCp/Al₂O₃Ceramic Matrix Composites Prepared by Directed Metal Oxidation of An Al Alloy

SiC particulates reinforced alumina matrix composites were fabricated using Directed Metal Oxidation (DIMOX) process. Continuous oxidation of an Al-Si-Mg-Zn alloy with different interlayers (dopents) as growth promoters, will encompasses the early heating of the alloy ingot, melting and continued heating to temperature in the narrow range of 950°C to 980°C in an atmosphere of oxygen. Varying interlayers (dopents) are incorporated to examine the growth conditions of the composite materials and to identification of suitable growth promoter. The process is extremely difficult because molten aluminum does not oxidize after prolonged duration at high temperatures due to the formation of a passivating oxide layer. It is known that the Lanxide Corporation had used a combination of dopents to cause the growth of alumina from molten metal. This growth was directed, i.e. the growth is allowed only in the required direction and restricted in the other directions. The react nature of the dopants was a trade secret. Though it is roughly known that Mg and Si in the Al melt can aid growth, additional dopents used, the temperatures at which the process was carried out, the experimental configurations that aided directed growth were not precisely known. In this paper we have evaluated the conditions in which composites can be grown in large enough sizes for evaluation application and have arrived at a procedure that enables the fabrication of large composite samples by determining the suitable growth promoter (dopant). Scanning electron microscopic, EDS analysis of the composite was found to contain a continuous network of Al2O3, which was predominantly free of grain-boundary phases, a continuous network of Al alloy. Fabrication of large enough samples was done only by the inventor company and the property measurements by the company were confirmed to those needed to enable immediate applications. Since there are a large number of variable affecting robust growth of the composite, fabrication large sized samples for measurements is a difficult task. In the present work, to identify a suitable window of parameters that enables robust growth of the composite has been attempted.

Laser‑Induced and MOF‑Derived Metal Oxide/Carbon Composite for Synergistically Improved Ethanol Sensing at Room temperature

Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.

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.

Evaluation of Dielectric Properties of CCTO-BT/Epoxy Composites for Electronic Applications

In the current study,the calcium copper titanate(CCTO)/epoxy,barium titanate(BT)/epoxy and CCTO-BT/epoxy composite samples with variable volume fractions of CCTO and BT are fabricated using hand lay-up and compression moulding process. The composite samples are characterized for the frequency dependence on dielectric properties,conductivity,impedance spectroscopy and electrical modulus.X-ray diffraction(XRD)representation of CCTO-BT/epoxy composite samples confirmed the presence of both CCTO and BT ceramic samples separately. The dielectric characteristics of hybrid CCTO-BT/epoxy composite samples with CCTO∶BT ratio of 40∶60, 60∶40,and 50∶50 was found relatively better than those of single ceramic filler reinforced epoxy composites. AC conductivity analysis shows improvement in the results of hybrid filler-filled CCTO-BT/epoxy composites in comparison with single filler-filled epoxy composite.50∶50 CCTO-BT/epoxy composite shows the best AC conductivity value of~ 2.2 ×10^(-5) ohm^(-1)·m^(-1) at a higher frequency of 1MHz. The impedance analysis confirms the higher insulating properties for hybrid 40∶60 and 60∶40 CCTO-BT/epoxy composites with respect to the single and other hybrid ceramic epoxy composites. The analysis suggests the hybrid CCTO-BT/epoxy composites to be adopted as a potential dielectric material for energy storage devices and other electronic applications.

Atomically bonding Na anodes with metallized ceramic electrolytes by ultrasound welding for high-energy/power solid-state sodium metal batteries

A solid-state sodium metal battery has cut a striking figure in next-generation large-scale energy storage technology on account of high safety,high energy density,and low cost.Nevertheless,the large interfacial resistance and sodium dendrite growth originating from the poor interface contact seriously hinder its practical application.Herein,a modified ultrasound welding was proposed to atomically bond Na anodes and Au-metalized Na_(3)Zr_(2)Si_(2)PO_(12) electrolytes associated with the in situ formation of Na–Au alloy interlayers.Thereupon,intimate Na_(3)Zr_(2)Si_(2)PO_(12)-Au/Na interfaces with a low interfacial resistance(~23Ωcm^(2))and a strong dendrite inhibition ability were constructed.The optimized Na symmetric battery can cycle steadily for more than 900 h at 0.3 mA cm^(-2) under a low overpotential(<50 mV)of Na electroplating/stripping and deliver a high critical current density of 0.8 mAcm^(-2) at room temperature.By incorporating the above interface into the solid-state Na metal battery,taking three-dimensional Na_(3)V_(2)(PO_(4))_(3) as the cathode,the full battery offers a high energy density of 291 Wh kg^(-1) at a high power density of 1860Wkg^(-1).A pouch-type solid-state sodium metal full battery based on a ceramic electrolyte was assembled for the first time,and it lit a 3 V LED lamp.Such a strategy of the ultrasound welding metalized solid-state electrolyte/Na interface by engineering the Na-Au interlayer would pave a new pathway to engineer a low-resistance and highly stable interface for high-energy/density solid-state sodium metal batteries.

Oxidation behavior of Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2)C-M_(x)C(M=Ti,Zr,Hf,Nb,Ta) composite ceramic at high temperature

Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2)C-M_(t)C composite ceramic was prepared by hot press sintering,with the Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2)C high-entropy carbide as the main phase.Secondary phase M_(x)C(M=Ti,Zr,Hf,Nb,Ta) was found to be distributed relatively uniform in the composite ceramic.The oxidation behavior of the ceramic was examined after exposure to 923 K and 1173 K.Morphology of the surface and cross sections of all oxidation samples were observed.The characteristics of the oxidation behavior of the high-entropy carbide and the secondary phase M_(x)C were compared and analyzed.The secondary phases(such as Ti-rich carbide or Hf-rich carbide) in the material were seriously oxidized at 923 K and 1173 K,which reflects the superior oxidation performance of the high-entropy carbide.The nano high-entropy oxides with Ti,Zr,Hf,Nb,Ta,and O elements were discovered by oxidation of the composite ceramic.This research will help deepen the understanding of the oxidation mechanism of high-entropy carbide and composite ceramic.

Development of 3D bicontinuous metal-intermetallic composites through subsequent alloying process after liquid metal dealloying

This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initially, porous Ti structures are produced using the LMD process, followed by immersion in a molten Mg-3Al(wt%) metal. Due to the higher thermodynamic miscibility of Al with Ti compared to Mg, the concentration of Al in the Ti matrix increases as the immersion time increases. This results in a sequential phase transition within the Ti matrix: α-Ti → Ti_(3)Al → Ti Al. The phase transition considerably affects the hardness and strength of the composite material,with the Mg-Ti_(3)Al-Ti Al composite exhibiting a maximum hardness nearly twice as high as that of the conventional Mg-Ti composite. This innovative process holds potential for the development of various bicontinuous metal-intermetallic composites.

Mechanical behavior of entangled metallic wire materials-polyurethane interpenetrating composites

Composite materials exhibit the impressive mechanical properties of high damping and stiffness,which cannot be attained by employing conventional single materials.Along these lines,a novel material architecture is presented in this work in order to fabricate composites with enhanced mechanical characteristics.More specifically,entangled metallic wire materials were used as the active matrix,whereas polyurethane was employed as the reinforcement elements.As a result,an entangled metallic wire material-polyurethane composite with high damping and stiffness was prepared by enforcing the vacuum infiltration method.On top of that,the mechanical properties(loss factor,energy consumption,and average stiffness)of the proposed composite materials were characterized by performing dynamic tests,and its fatigue characteristics were verified by the micro-interface bonding,as well as the macro-damage factor.The impact of the density,preloading spacing,loading amplitude,and exciting frequency on the mechanical properties of the composites were also thoroughly analyzed.The extracted results indicate that the mechanical properties of the composites were significantly enhanced than those of the pure materials due to the introduction of interface friction.Moreover,the average stiffness of the composites was about 10 times the respective value of the entangled metallic wire material.Interestingly,a rise in the loading period leads to some failure between the composite interfaces,which reduces the stiffness property but enhances the damping dissipation properties.Finally,a comprehensive dynamic mechanical model of the composites was established,while it was experimentally verified.The proposed composites possess higher damping features,i.e.,stiffness characteristics,and maintain better fatigue characteristics,which can broaden the application range of the composites.In addition,we provide a theoretical and experimental framework for the research and applications in the field of metal matrix composites.

Effects of Co_(2)O_(3)Addition on Microstructure and Properties of SiC Composite Ceramics for Solar Absorber and Storage

SiC composite ceramics for solar absorber and storage integration are new concentrating solar power materials.SiC composite ceramics for solar absorber and storage integration were fabricated using SiC,black corundum and kaolin as the raw materials,Co_(2)O_(3)as the additive via pressureless graphite-buried sintering method in this study.Influences of Co_(2)O_(3)on the microstructure and properties of SiC composite ceramics for solar absorber and storage integration were studied.The results indicate that sample D2(5wt%Co_(2)O_(3))sintered at 1480℃exhibits optimal performances for 119.91 MPa bending strength,93%solar absorption,981.5 kJ/kg(25-800℃)thermal storage density.The weight gain ratio is 12.58 mg/cm2after 100 h oxidation at 1000℃.The Co_(2)O_(3)can decrease the liquid phase formation temperature and reduce the viscosity of liquid phase during sintering.The liquid with low viscosity not only promotes the elimination of pores to achieve densification,but also increases bending strength,solar absorption,thermal storage density and oxidation resistance.A dense SiO_(2) layer was formed on the surface of SiC after 100 h oxidation at 1000℃,which protects the sample from further oxidation.However,excessive Co_(2)O_(3)will make the microstructure loose,which is disadvantageous to the performances of samples.

Development and Characterization of Aluminium-Based Metal Matrix Composites

Aluminum based metal matrix composites were fabricated using stir casting where silicon carbide and alumina were the reinforcements. Different types of properties (physical-density, mechanical-tensile, hardness, chemical-corrosion etc.) were measured and compared with base metals/alloys. The properties were significantly varied. The highest density was obtained for pure aluminium with 5% Al2O3 whereas the lowest was obtained for AA-4032 alloy. The highest hardness was obtained for AA-4032 with 5% Al2O3 whereas the lowest was obtained for pure Al with 5% Al2O3. The highest strength was obtained for AA-6061 with 5% coarse SiC whereas the lowest was obtained for pure Al. The highest impact strength was obtained for AA-4032 with 5% Al2O3 whereas the lowest was obtained for AA-6061. The corrosion resistance of all composites was lower than that of the base materials.

ELASTIC BEHAVIOR ANALYSIS OF 3D ANGLE-INTERLOCK WOVEN CERAMIC COMPOSITES

A micromechanical model for elastic behavior analysis of angle-interlock woven ceramic composites is proposed in this paper. This model takes into account the actual fabric structure by considering the fiber undulation and continuity in space, the cavities between adjacent yarns and the actual cross-section geometry of the yarn. Based on the laminate theory, the elastic properties of 3D angle-interlock woven ceramic composites are predicted. Different numbers of interlaced wefts have almost the same elastic moduli. The thickness of ceramic matrix has little effect on elastic moduli. When the undulation ratio increases longitudinal modulus decreases and the other Young＇s moduli increase. Good agreement between theoretical predictions and experimental results demonstrates the feasibility of the proposed model in analyzing the elastic properties of 3D angle-interlock woven ceramic composites. The results of this paper verify the fact that the method of analyzing polyester matrix composites is suitable for woven ceramic composites.

Lithiated Nafion-garnet ceramic composite electrolyte membrane for solid-state lithium metal battery

Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.

Mechanical Behaviors of ZrO_2-Al_2O_3 Ceramic Composites with Y_2O_3 as Stabilizer

The ZrO2-Al2O3 ceramic composites were prepared by appropriate techniques with commercial ZrO2 and Al2O3 powders as raw materials and Y2O3 as stabilizer. The results indicate that with the introduction of Al2O3 into the ZrO2 matrix where the quantity of additive Y2O3 is 3.5% (mole fraction), the growth of ZrO2 grains is efficiently inhibited, which helps the ZrO2 grains exist in a metastable tetragonal manner; thus higher strength and toughness are acquired. When the content of alumina is 20% (mass fraction), the bending strength and fracture toughness of the composites are 676.7 MPa and 10 MPa·m1/2 respectively, the mechanical behaviors are close to those prepared with ZrO2 and Al2O3 powders synthesized through wet chemical approach. The mechanical behaviors of the composites are well improved owing to the dispersion toughening of alumina grains and phase transformation toughening of zirconia grains.

FRACTURAL PROCESS AND TOUGHENING MECHANISM OF LAMINATED CERAMIC COMPOSITES

Based on the model of multi-layer beam and the assumption of micro-inhomogeneity of material, the 3D fractural characteristics of laminated ceramic composites have been studied with numerical simulation. Under three-point bending load, crack initiation, coalescence, propagation, tuning off in the weak interface and final rupture have been simulated. The spatial distribution and evolution process of acoustic emission are also presented in the paper. The simulation verifies the primary mechanism of the weak interface inducing the crack to expand along there and absorbing the fractural energy. The disciplinary significance of the effect of strength and properties of material on the toughness and strength of laminated ceramic composites is, therefore, discussed in this paper.

Vacuum brazing of Si/SiC ceramic composite and Invar alloy using TiSOCu-W filler metals

Si/SiC ceramic composite and lnvar alloy were successfidly joined by vacuum brazing using Ti5OCu-W filler metals into which W was added to release the thermal stress of the brazed joint. Microstructures of the brazed joints were irwestigated by scanning electron micrascope （SEM） and energy dispersive spectrometer （EDS）. The mechanical properties of the brazed joints were measured by shearing tests. The results showed that the brazed joints were composed of Ti-Cu phase, W phase and Ti-Si phase. W had no effect on the wettability and mobility of the .filler metals. The growth of Ti2 Cu phase was restrained, and the reaction between ceramic composite and filler metals was weakened. The specimen, brazed at 970°C for 5 rain, had the maximum shear strength of 108 MPa at room temperature.

Ceramic-Metal Composite Coating by Laser Cladding

Four kinds of ceramics (silicon carbide, boron carbide, aluminum oxide and tungsten carbide) were added into Ni base self-fluxing alloy as reinforcing materials in order to obtain metalceramic composite coating by means of laser cladding. A lot of experiments have been carried out to test the processability of the four kinds of ceramics with different sizes and contents. The microstructures of sintered tungsten carbide (S-WC) and cast tungsten carbide (C-WC) reinforced Ni base alloy coatings were analysed, the distortion regulation of laser clad specimens was revealed. The wear resistance of the composite coating has been tested.

Preparation and Mechanical Properties of Al_2O_3/Al Laminated Ceramic Matrix Composites

Three series of Al2O3/Al laminated ceramic matrix composites,named SPA,SPV and HP,were fabricated by different methods.SPA and SPV were prepared using Al2O3 slices and Al slurry via screen printing and subsequent heat treatment in air or vacuum.HP samples were made by hot pressing the layered stack of Al foils and Al2O3 slices.SEM and XRD were applied to analyze the microstructure and the interlayer crystal phase.The bending strength,fracture toughness and fracture work of the samples made by the three methods were measured and compared.The results show that the composites have much better toughness and higher fracture work than the Al2O3 slice.Among the samples made by the three methods,the samples made by hot pressing have the optimum mechanical performance.The displacement-load curves and fracture mechanism were analyzed.