Deep eutectic solvent-based supramolecular gel polymer electrolytes for high-performance electrochemical double layer capacitors

Gel polymer electrolytes (GPEs) can avoid the electrolyte leakage risk of electrochemical double layer capacitors (EDLCs). But aqueous GPEs often suffer from narrow electrochemical windows. Herein, a series of deep eutectic solvent (DES)-based supramolecular GPEs are firstly developed for carbon-based EDLCs with wide voltage windows. The as-fabricated DES-based GPE shows an ionic conductivity of ~58 mS cm^?1, which makes the stable voltage window of a carbon-based EDLC reach 2.4 V. The carbon-based EDLC exhibits a specific capacitance of 32.1 F g^?1, an energy density of 24.6 Wh kg^?1 and a capacitance retention of ~90% after 15,000 charge-discharge cycles. Moreover, when quinhydrone is added into the DES-based GPE, the specific capacitance and energy density of the corresponding EDLC can be further expanded to 60 F g^?1 and 43.6 Wh kg^?1, respectively. Therefore, our work may present a universal strategy to prepare novel supramolecular GPEs for high-performance EDLCs with wide voltage windows.     

Competitive growth of Al2O3/YAG/ZrO2 eutectic ceramics during directional solidification: Effect of interfacial energy

The microstructure evolution and growth behavior of the Al₂O₃/Y₃Al₅O₁₂(YAG)/ZrO₂ ternary eutectic ceramics during directional solidification were well investigated. During directional solidification of the Al₂O₃/YAG/ZrO₂ ternary eutectic ceramics, {} Al₂O₃ paralleled with {001}ZrO₂ while they did not parallel with {001}YAG at the same time in the competitive growth stage. All of the interfaces parallel to each other finally. The area percentage of the Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are 40.4 ± 0.2% and 30.8 ± 0.1%, respectively, higher than that of the Al₂O₃/YAG (28.8 ± 0.2%). The content of Al₂O₃ and YAG phases are 39.9% and 41.1%, respectively, almost double of that of ZrO₂. The interfaces of Al₂O₃/ZrO₂ and YAG/ZrO₂ are shorter and more dispersed than that of the Al₂O₃/YAG. It was found that the interfacial energy of Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are lower than that of Al₂O₃/YAG. It can be concluded that interfacial energy plays a decisive role in affecting the crystallographic orientation and interfaces distribution in the Al₂O₃/YAG/ZrO₂ eutectic since the interfaces of Al₂O₃/ZrO₂ and YAG/ZrO₂ with lower interfacial energy can be formed more easily during directional solidification. Therefore, the contents of Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are higher. This study can provide theoretical guidance for interface design of multi-phase materials.     

Strain rate dependence of the contribution of surface diffusion to bulk sintering viscosity

Modeling of bulk sintering viscosity usually neglects the contribution of pore surface diffusion with respect to grain-boundary diffusion. This approximation is questionable at the high densification rates used today in advanced fast sintering techniques. A two-dimensional analysis of the problem shows that the influence of surface diffusion on bulk viscosity at high strain rate can be decomposed as the sum of two terms: a term linked to the change in pore surface curvature and a term linked to the change in grain-boundary size. The computational procedure relies on the partition of pore profile evolution into a transient component accounting for non-densifying phenomena and an asymptotic component accounting for strain-rate-controlled phenomena. The largest impact of surface diffusion is found to arise from the change in grain-boundary size. It follows a transition from Newtonian viscosity at low strain rate to non-Newtonian viscosity which, during densification, increases nearly linearly with strain rate. In some conditions, viscosity can then reach more than twice the value estimated when neglecting pore surface diffusion. Reversely, expansion is accompanied by a decrease in grain-boundary size which causes a decrease in viscosity and can lead to grain separation at high strain rate.     

A strategy for defects healing in 3D printed ceramic compact via cold isostatic pressing: Sintering kinetic window and microstructure evolution

In this study, we developed a unique defect healing method for 3D printed ceramic compact via cold isostatic pressing (CIP) after debinding, and typical features of interlayer interface defects of 3D-printed zirconia compact were characterized and found to be reduced significantly. The characteristic sintering kinetics window and microstructure evolution of the healed sintered bodies were systematically investigated, which was found to be quite different from conventional shaping methods. The three sintering stages are probed by their feature microstructure details such as the mechanically flattening surface at the early sintering stage, the heterogeneous microstructure and high porosity in the interlayer interface region at the middle stage, and the slightly ripple-like structural features combined with the healed interlayer defects at the final stage. The evolution of the pore structure of the healed 3D printed bodies were traced and the mechanical properties such as the Young's modulus, hardness, and fracture toughness were measured to understand the significance of the heal effect.     

Fabrication and optical properties of transparent LaErZr2O7 ceramic with high excess contents of La and Er

In this study, transparent LaErZr₂O₇ ceramic with high excess La and Er contents (nominally La_1.28Er_1.28Zr₂O_7.84) was successfully prepared by vacuum sintering at 1850?°C for 6?h using nanosized powder. The XRD, SEM, EDX and TEM results reveal that the single pyrochlore phase in the powder sample transforms to the coexistence of La-rich pyrochlore phase and Er-rich defect fluorite phase after high temperature sintering. The high excess amounts of La and Er favor the formation of pyrochlore structure. Despite the coexistence of two phases, the sample with 1?mm thickness shows excellent in-line transmittance in the visible to mid-infrared region (as high as 81% at 1100?nm). The upconversion and infrared emission under 980?nm exciting were measured and discussed as well.     

Large electrocaloric effect in two-step-SPS processed Pb(Sc0.25In0.25Nb0.25Ta0.25)O3 medium-entropy ceramics

Ferroelectric ceramic with a large electrocaloric (EC) effect at a very low electric field is very attractive in the next solid state refrigeration technology. In this work, two Pb(Sc_0.25In_0.25Nb_0.25Ta_0.25)O₃ (PSINT) medium-entropy ceramics were successfully synthesized by a spark plasma sintering (SPS) technology, including one-step-SPS processed and two-step-SPS processed samples. A large EC effect (△T ～ 0.85 K) with a high EC strength (△T/△E ～ 0.021 K cm/kV) around room temperature are obtained at a very low electric field (～40 kV/cm) in the two-step-SPS processed sample. Moreover, the working temperature range is very broad (～120 K), which can be responsible for the high relaxation degree of the dielectric peak. It can be believed that the PSINT medium-entropy ceramics can be promising candidates for application in the next-generation EC cooling devices.     

Evolution of core–rim structures and phase transformations in infra-red transmitting Y-α-SiAlON ceramics

Core–rim structures were observed as common features in Y-α-SiAlON ceramics hot-pressed between 1550?1950 °C. We found most dopants were taken into α’-rims, and a transition layer grown first on α-cores from liquid-phase over-saturated with metal solutes. Elongated β’-grain were formed as minor phase with α’- or AlN-cores thus only after the α’ matrix had consumed up all Y solutes, revealing that the α’ → β’ transformation is controlled by the transient liquid-phase and similar defects and dangling bonds could be detected in both SiAlON phases by cathodoluminescence. Quantitative assessment of Y_m/3Si_12?(m+n)Al_m+nO_nN_16?n demonstrates the multiphase evolution, initiated by over-saturation of Y solutes at low temperatures thus retaining α-phase as cores to lower the infra-red transmittance, dictated by homogenization of Al solutes at higher temperature. The elimination of those phase boundaries leads to better dopant and sintering design for achieving transparent and high-performance SiAlON ceramics.     

Low-temperature constrained sintering of YSZ electrolyte with Bi2O3 sintering sacrificial layer for anode-supported solid oxide fuel cells

Solid oxide fuel cells (SOFCs) have strong potential for next-generation energy conversion systems. However, their high processing temperature due to multi-layer ceramic components has been a major challenge for commercialization. In particular, the constrained sintering effect due to the rigid substrate in the fabrication process is a main reason to increase the sintering temperature of ceramic electrolyte. Herein, we develop a bi-layer sintering method composed of a Bi₂O₃ sintering sacrificial layer and YSZ main electrolyte layer to effectively lower the sintering temperature of the YSZ electrolyte even under the constrained sintering conditions. The Bi₂O₃ sintering functional layer applied on the YSZ electrolyte is designed to facilitate the densification of YSZ electrolyte at the significantly lowered sintering temperature and is removed after the sintering process to prevent the detrimental effects of residual sintering aids. Subsequent sublimation of Bi₂O₃ was confirmed after the sintering process and a dense YSZ monolayer was formed as a result of the sintering functional layer-assisted sintering process. The sintering behavior of the Bi₂O₃/YSZ bi-layer system was systematically analyzed, and material properties including the microstructure, crystallinity, and ionic conductivity were analyzed. The developed bi-layer sintered YSZ electrolyte was employed to fabricate anode-supported SOFCs, and a cell performance comparable to a conventional high temperature sintered (1400 °C) YSZ electrolyte was successfully demonstrated with significantly reduced sintering temperature (<1200 °C).     

Synergistic effect of binary fluoride sintering additives on the properties of silicon nitride ceramics

A variety of combinations of YF₃ and MgF₂ were used as sintering aids in the fabrication of Si₃N₄ ceramics via gas pressure sintering (GPS). The synergistic effects of YF₃ and MgF₂ on the liquid viscosity, mechanical properties, thermal conductivities, and grain growth kinetics of the Si₃N₄ ceramics were investigated. The results showed that appropriately adjusting the YF₃/MgF₂ ratio could decrease liquid viscosity, reducing the diffusion energy barrier of the solute atom and promoting mass transfer. Meanwhile, the chemical bonding strength in the grain boundary complexions formed by the metal cations also influenced grain boundary migration. Samples doped with 4 mol% YF₃ and 2 mol% MgF₂ achieved the lowest grain growth exponent (n = 2.9) and growth activation energy (Q = 616.7 ± 16.5 kJ mol^?1) as well as the highest thermal conductivity (83 W m^?1 K^?1) and fracture toughness (8.82 ± 0.13 MPa m^1/2).     

烧结时间对含铅玻璃制备微晶玻璃析晶及性能的影响

以铅玻璃与粉煤灰为原料，通过协同熔炼制备了微晶玻璃。通过XRD和SEM等手段研究了不同烧结时间下微晶玻璃的物相组成及显微结构，测定了微晶玻璃的密度、吸水率、维氏硬度和化学抗性。结果表明: 延长烧结时间对含铅玻璃加入量为40%(FG40)、50%(FG50)样品的晶相类型和晶化程度有影响，而对含铅玻璃加入量为60%(FG60)、70%(FG70)和80%(FG80)样品的影响较小。随着烧结时间延长，样品晶化程度提高，晶体长大，玻璃相减少。适宜的含铅玻璃加入量为50%~70%，对应的FG50、FG60、FG70样品最佳烧结时间分别为4 h、3 h、3 h。