Boosting thermoelectric efficiency of Ag_(2)Se through cold sintering process with Ag nano-precipitate formation

Silver selenide(Ag_(2)Se)stands out as a promising thermoelectric(TE)material,particularly for applications near room temper-atures.This research presents a novel approach for the fabrication of bulk Ag_(2)Se samples at a relatively low temperature(170℃)using the cold sintering process(CSP)with AgNO_(3)solution as a transient liquid agent.The effect of AgNO_(3)addition during CSP on the micro-structure and TE properties was investigated.The results from phase,composition and microstructure analyses showed that the introduc-tion of AgNO_(3)solution induced the formation of Ag nano-precipitates within the Ag_(2)Se matrix.Although the nano-precipitates do not af-fect the phase and crystal structure of orthorhombicβ-Ag_(2)Se,they suppressed crystal growth,leading to reduced crystallite sizes.The samples containing Ag nano-precipitates also exhibited high porosity and low bulk density.Consequently,these effects contributed to sig-nificantly enhanced electrical conductivity and a slight decrease in the Seebeck coefficient when small Ag concentrations were incorpor-ated.This resulted in an improved average power factor from~1540μW·m^(−1)·K^(−2)for pure Ag_(2)Se to~1670μW·m^(−1)·K^(−2)for Ag_(2)Se with additional Ag precipitates.However,excessive Ag addition had a detrimental effect on the power factor.Furthermore,thermal conductiv-ity was effectively suppressed in Ag_(2)Se fabricated using AgNO_(3)-assisted CSP,attributed to enhanced phonon scattering at crystal inter-faces,pores,and Ag nano-precipitates.The highest figure-of-merit(zT)of 0.92 at 300 K was achieved for the Ag_(2)Se with 0.5wt%Ag dur-ing CSP fabrication,equivalent to>20%improvement compared to the controlled Ag_(2)Se without extra Ag solution.Thus,the process outlined in this study presents an effective strategy to tailor the microstructure of bulk Ag_(2)Se and enhance its TE performance at room temperature.

Strong ferroelectric and luminescence properties of 0-3 type 0.8BaTiO_(3)-0.2CaTiO_(3):Pr^(3+)composite ceramics prepared by cold sintering process

0-3 type ferroelectric-phosphor composite ceramics cannot be prepared by the traditional solid-state sintering(SSS)method due to the strong chemical reaction between ferroelectrics and phosphors during high-temperature sintering.The cold sintering process(CSP)may solve this issue by densifying ceramics at ultralow sintering temperatures.In this work,dense 0-3 type 0.8BaTiO_(3)-0.2CaTiO_(3):Pr^(3+)(0.8BT-0.2CT:Pr^(3+))binary composite ceramics were fabricated at an ultralow temperature of 225℃via CSP with the Ba(OH)2·8H2O hydrated flux.The effects of the Ba(OH)_(2)·8H2O content,sintering temperature,and sintering time on the microstructure and densification of the ceramics were investigated.The density of the composite ceramics prepared by the optimized sintering parameters reaches 89%.Both energy-dispersive X-ray(EDX)spectroscopy and X-ray diffraction(XRD)confirm the existence of BT and CT:Pr^(3+)phases in the prepared ceramics.A strong ferroelectric performance is obtained,and the luminescent properties of CT:Pr^(3+)are preserved for the ceramics.Furthermore,the 0.8BT-0.2CT:Pr^(3+)composite ceramics prepared by CSP have stronger photoluminescence and photo-stimulated luminescence than their counterparts prepared by cold sintering assistance(CSA)and SSS methods.Therefore,CSP is a promising method for combining luminescent and ferroelectric properties into 0-3 type composite ceramics.

The role ofγ-C_(2)H_(5)NO_(2) as a new transient liquid phase in cold sintering process of BaTiO_(3) composites

Dielectric materials,such as barium titanate(BT)-based materials,have excellent dielectric properties but require high temperatures(above 1300℃)for ceramic fabrication,leading to high costs and energy loss.The cold sintering process(CSP)offers a solution to these issues and is gaining worldwide attention as an innovative fabrication route.In this work,we proposed an alternative organic ferroelectric phase,gamma-glycine(γ-GC),which acts as a transient liquid phase to fabricate high-density composites with barium titanate(BT)at low temperatures through CSP.Our findings show that the density of 15γ-GC/85BT reached 96.7%±1.6%when it was sintered at 120℃for 6 h under 10 MPa uniaxial pressure.Scanning electron microscopy‒energy dispersive X-ray spectroscopy(SEM‒EDS)mappings of the composite suggested thatγ-GC completely underwent the precipitation-dissolution process and,therefore,filled between BT particles.Moreover,X-ray diffraction(XRD)and Fourier-transform infrared spectroscopy(FTIR)confirmed the preservation ofγ-GC without undesired phase transformation.In addition,the ferroelectric and dielectric properties ofγ-GC/BT composites have been reported.The high dielectric constant(ε_(r))was 3600,and the low dielectric loss(tanδ)was 1.20 at 200℃and 100 kHz for the 15γ-GC/85BT composite.The hysteresis loop showed a remanent polarization(P_(r))of 0.55µC·cm^(−2)and a coercive field(E_(c))of 7.25 kV·cm^(−1).Our findings reaffirmed that an organic ferroelectric material(γ-GC)can act as a transient liquid phase in a CSP that can successfully and sustainably fabricateγ-GC/BT composites at low temperatures while delivering outstandingly high performance.

Fabrication of form stable NaCl-Al2O3 composite for thermal energy storage by cold sintering process

A form stable NaCl-Al2O3(50-50 wt-%)composite material for high temperature thermal energy storage was fabricated by cold sintering process,a process recently applied to the densification of ceramics at low temperature 300℃ under uniaxial pressure in the presence of small amount o f transient liquid.The fabricated composite achieved as high as 98.65% of the theoretical density.The NaCl-Al2O3 composite also retained the chloride salt without leakage after 30 heating-cooling cycles between 750℃-850℃ together with a holding period o f 24h at 850℃.X-ray diffraction measurements indicated congruent solubility o f the alumina in chloride salt,excellent compatibility o f NaCl with Al2O3,and chemical stability at high temperature.Structural analysis by scanning electron microscope also showed limited grain growth,high density,uniform NaCl distribution and clear faceted composite structure without inter-diffusion.The latent heat storage density o f 252.5J/g was obtained from simultaneous thermal analysis.Fracture strength test showed high sintered strength around 5 GPa after 50 min.The composite was found to have fair mass losses due to volatilization.Overall,cold sintering process has the potential to be an efficient,safe and cost-effective strategy for the fabrication of high temperature thermal energy storage materials.

Combining cold sintering and Bi_(2)O_(3)-Activated liquid-phase sintering to fabricate high-conductivity Mg-doped NASICON at reduced temperatures

The cold sintering process(CSP)and Bi_(2)O_(3)-activated liquid-phase sintering(LPS)are combined to densify Mg-doped NASICON(Na_(3.256)Mg_(0.128)Zr_(1.872)Si_(2)PO_(12))to achieve high densities and conductivities at reduced temperatures.As an example,a cold-sintered specimen with the addition of 1.1wt%Bi_(2)O_(3)sintering additive achieved a high conductivity of 0.91 mS/cm(with~96%relative density)after annealing at 1000℃;this conductivity is>70%higher than that of a cold-sintered specimen without adding the Bi_(2)O_(3)sintering additive,and it is>700%of the conductivity of a dry-pressed counterpart with the same amount of Bi_(2)O_(3)added,all of which are subjected to the same heating profile.The highest conductivity achieved in this study via combining CSP and Bi_(2)O_(3)-activated LSP is>1.5 mS/cm.This study suggests an opportunity to combine the new CSP with the traditional LPS to sinter solid electrolytes to achieve high densities and conductivities at reduced temperatures.This combined CSP-LPS approach can be extended to a broad range of other materials to fabricate the“thermally fragile”solid electrolytes or solid-state battery systems,where reducing the processing temperature is often desirable.

Current understanding and applications of the cold sintering process

In traditional ceramic processing techniques,high sintering temperature is necessary to achieve fully dense microstructures.But it can cause various problems including warpage,overfiring,element evaporation,and polymorphic transformation.To overcome these drawbacks,a novel processing technique called“tcold sintering process(CSP)”has been explored by Randall et al.CSP enables densification of ceramics at ultra-low temperature(<300℃)with the assistance o f transient aqueous solution and applied pressure.In CSP,the processing conditions including aqueous solution,pressure,temperature,and sintering duration play critical roles in the densification and properties of ceramics,which will be reviewed.The review will also include the applications of CSP in solid-state rechargeable batteries.Finally,the perspectives about CSP is proposed.

Realizing translucency in aluminosilicate glass at ultralow temperature via cold sintering process

Glass with high visible-light transparency is widely considered as the most important optical material,which typically requires a processing temperature higher than 1000℃.Here,we report a translucent aluminosilicate glass that can be prepared by cold sintering process(CSP)at merely 300℃.After eliminating structural pores in hexagonal faujasite(EMT)-type zeolite by heat treatment,the obtained highly active nanoparticles are consolidated to have nearly full density by adding NaOH solution as liquid aids.However,direct densification of EMT powder cannot remove the structural pores of zeolite completely,leading to an opaque compact after the CSP.It is proved that the chemical reaction between the NaOH-and zeolite-derived powders is highly beneficial to dissolution–precipitation process during sintering,leading to the ultra-low activation energy of 27.13 kJ/mol.Although the addition of 5 M NaOH solution greatly promotes the densification via the reaction with aluminosilicate powder,lower or higher concentration of solvent can deteriorate the transmittance of glass.Additionally,the CSP-prepared glass exhibits a Vickers hardness of 4.3 GPa,reaching 60%of the reported value for spark plasma sintering(SPS)-prepared sample.

Cold sintering process for fabrication of a superhydrophobic ZnO-polytetrafluoroethylene(PTFE)ceramic composite

Composite coatings or films with polytetrafluoroethylene(PTFE)are typically utilized to offer superhydrophobic surfaces.However,the superhydrophobic surfaces usually have limited durability and require complicated fabrication methods.Herein,we report the successful integration of PTFE with ZnO ceramics to achieve superhydrophobicity via a one-step sintering method,cold sintering process(CSP),at 300℃.(1–x)ZnO–x PTFE ceramic composites with x ranging from 0 to 70 vol%are densified with relative density of over 97%.Micro/nano-scale PTFE polymer is dispersed among ZnO grains forming polymer grain boundary phases,which modulate surface morphology and surface energy of the ZnO–PTFE ceramic composites.For the 60 vol%ZnO–40 vol%PTFE ceramic composite,superhydrophobic properties are optimized with static water contact angles(WCAs)and sliding angles(SAs)of 162°and 7°,respectively.After abrading into various thicknesses(2.52,2.26,and 1.99 mm)and contaminating with graphite powders on the surface,WCA and SA are still maintained with a high level of 157°–160°and 7°–9.3°,respectively.This work indicates that CSP provides a promising pathway to integrate polymers with ceramics to realize stable superhydrophobicity.

Cold Hydrostatic Sintering:From shaping to 3D printing

We developed a novel consolidation technique,Cold Hydrostatic Sintering(CHS),which allows near full densification of silica.The technique is inspired by biosilicification and geological formation of siliceous rocks.Unlike established cold sintering method which is based on uniaxial pressure,CHS employs an isostatic pressure to enable room temperature consolidation of bulks having a complex threedimensional shape.The resulting material is transparent(in line transmittance exceeding 70% in the visible range)and amorphous.After drying,the Vickers hardness was as high 1.4 GPa which half of materials consolidated at 1200℃ and it is the highest among all materials processed at room temperature.The CHS method,because of its simplicity,might be suitable for broad range of applications including 3D printing,mould forming and preparation of multi-layered devices.Because of the absence of the firing step,CHS could be directly integrated in the manufacturing of a wide range of hybrid(organic/inorganic)materials for functional and biological applications.

Cold sintered BaTiO_(3)–poly(ether imide)nanocomposites with superior comprehensive performances

With the rapid development of the electronics industry,the demand for dielectric materials with high permittivities,low losses,and excellent electrical breakdown strengths prepared via low-temperature fabrication techniques is increasing.Herein,we propose a one-step cold sintering process route to improve the comprehensive performance of BaTiO_(3)−based ceramics by integrating polyetherimide(PEI).Dense BaTiO_(3)–PEI nanocomposites can be prepared via a cold sintering process at 250℃ using Ba(OH)_(2∙8)H_(2)O and H_(2)TiO_(3) as the transient liquid phase.The grain growth of BaTiO_(3) is inhibited,and thin PEI layers less than 10 nm in size are located at the grain boundaries.The dissolution‒precipitation process triggered by the transient liquid phase and viscous flow assisted by PEI dominates the cold sintering mechanism of the(1−x)BaTiO_(3)–xPEI nanocomposites.The dielectric properties are stable over a broad temperature range up to 200℃.Compared with BaTiO_(3),80%BaTiO_(3)–20%PEI has superior performance,with a relative permittivity of 163 and a low dielectric loss of 0.014,and the electrical breakdown strength is increased by 80.65%compared with BaTiO_(3).Overall,the cold sintering process provides a potential way to develop dielectric nanocomposites with excellent comprehensive performance.

Cold sintering process:A green route to fabricate thermoelectrics

Cold sintering is a newly developed low-temperature sintering technique that has attracted extensive attention in the fabrication of functional materials and devices.Low sintering temperatures allow for a substantial reduction in energy consumption,and simple experimental equipment offers the possibility of large-scale fabrication.The cold sintering process(CSP)has been demonstrated to be a green and cost-effective route to fabricate thermoelectric(TE)materials where significant grain growth,secondary phase formation,and element volatilization,which are prone to occur during high-temperature sintering,can be well controlled.In this review,the historical development,understanding,and application of thermoelectric materials produced via cold sintering are highlighted.The latest attempts related to the cold sintering process for thermoelectric materials and devices are discussed and evaluated.Despite some current technical challenges,cold sintering provides a promising and sustainable route for the design of advanced high-performance thermoelectrics.

Room-temperature-densified H_(3)BO_(3) microwave dielectric ceramics with ultra-low permittivity and ultra-high Qf value

With the rapid development of mobile communication technology towards 5G and 6G,the microwave dielectric materials with ultra-low permittivity and ultra-high Qf value are urgently demanded.Here,the excellent microwave dielectric properties are reported in H3BO3 ceramics with the molecular crystal structure,whose permittivity(2.84)and density(1.46 g/cm^(3))are record-low among the low-loss ceramics.The ultra-high Qf value of 146,000 GHz(or the ultra-low dielectric loss of 1.03×10^(-4) at 15 GHz)is also distinguished.Besides,the H_(3)BO_(3) ceramics can be densified at room temperature by a simple cold sintering process in a short time of 10 min,and this brings many advantages for the integration with microwave circuits.The large molecule volume originating from the molecular crystal structure and the low dielectric polarizabilities of H^(+) and B^(3+) are responsible for the ultra-low permittivity of H_(3)BO_(3) ceramics,and more microwave dielectric materials with ultra-low permittivity and ultra-high Qf value are expected to be explored in the molecular crystals.