Solid State Ionics最新文献

Poly(thiophene-3‑boronic acid) (PTBA) was studied as a promising active material for aqueous environments in this paper. Using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the solubility and electrochemical behavior of it was studied in a range of aqueous solutions. Fourier Transform Infrared Spectrometry (FTIR) results verify the successful synthesis. PTBA shows promising solubility qualities in certain pH ranges, especially in alkaline solutions. However, among alkaline, neutral, and acidic environments the best environment for redox properties of aqueous 1 mM PTBA is the neutral one. The peak current (i_p) of 1 mM PTBA for 100 mV/s in the neutral environment is 0.01 mA and half peak potential (E_p/2) is −0.1 V (vs Ag/AgCl). Diffusion coefficient of PTBA is found as 4.97 × 10⁻⁸ cm²/s. The impedance tests also confirm that the neutral solvent decreases the charge transfer resistance.

The mesoporous electrode material offers a high surface area, excellent porous texture, and optimal pore-size distribution, facilitating increased active sites for ion accretion and enhanced ionic diffusion rates. NiMoO₄, TiS₂, and their composites such as NT-1, NT-2, NT-3, and NT-4 composites have been prepared by hydrothermal approach to enhance the capacitance of supercapacitor electrodes. Different methodologies have been employed to analyze the optical, morphological and structural characteristics of the synthesized materials. X-ray diffraction was utilized to assess the crystalline nature of both the pristine materials and composites. Scanning electron microscopy examination confirmed the formation of mesoporous and irregular nanoparticles with sizes ranging from 50 to 100 nm. Fourier-transform infrared spectroscopy was employed to examine the stretching vibrations of the prepared samples. Through photoluminescence (PL) analysis, the energy band gap of the NT-1 composite was decisive to be 2.78 eV. The NT-1 composite exhibits an impressive specific capacitance of 1257.14 Fg⁻¹ at 1 Ag⁻¹, attributed to its huge surface area, efficient charge transfer, and synergistic effect while demonstrating remarkable stability after 5000 cycles with 92% capacitance retention. Therefore, NT-1 binary metal sulfide composite unleashes high-performance supercapacitors with remarkable specific capacitance and cyclic stability.

In-house electrospun La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ (LSCF) nanofibers have been tested through synchrotron x-ray diffraction and electrochemical impedance spectroscopy (EIS) in the 823–1173 K range, namely in the operating window of intermediate-temperature solid oxide fuel cells. Identical tests have been carried out on commercial LSCF powders, as a control sample. The results demonstrate that the electrospinning manufacturing procedure influences the crystalline properties of the perovskite. The rhombohedral structure (R), stable at room temperature, is retained by nanofibers throughout the whole temperature range, while a rhombohedral to cubic transition (R→C) is detected in powders at ⁓1023 K as a discontinuity in the rhombohedral angle α, accompanied by an abrupt change in oxygen occupation and microstrain. EIS data have a single trend in the nanofibers Arrhenius plot, and two different ones in powders, separated by a discontinuity at the structural transition temperature. Thus, a striking parallel is demonstrated between the variation with temperature of crystallographic features and electrochemical performance. Interestingly, this parallel is found for both nanofiber and granular electrodes. This opens up questions and new perspectives in attributing activation energies derived from EIS tests of LSCF materials to electrochemical processes and/or crystal structure variations.

All-solid-state lithium batteries (ASSB) are emerging as an effective and promising alternative to current technologies that use organic liquid electrolytes. Its main proposition is to mitigate the safety and environmental issues caused by the leakages and explosions of conventional cells through the development and use of solid electrolytes, in the form of polymer membranes, ceramic pellets, or even composites, which are a combination of both. In the present work, composite electrolytes of polyethylene oxide (PEO), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and Zr-doped niobium garnet oxides (Li_5+xLa₃Nb_2-xZr_xO₁₂ - LLNZ) were prepared. The addition of ceramic reduced the melting point and inhibited the formation of spherulite-type crystallization of the polymer. The ionic conductivities of the composites were slightly lower than the polymer but still high for composite electrolytes of this composition, around 10⁻⁴ S.cm⁻¹. The obtained results were analyzed considering the findings reported by other researchers, and some factors for a high-performance composite electrolyte were detailed. Additionally, all the fabricated composites showed a broad electrochemical window, some even above 5.0 V. Thus, electrochemical measurements were conducted with NMC811 as the cathode. The half-cell exhibited a specific capacity of 185 mAh.g⁻¹ at C/20 at 60 °C, and a capacity retention of 68% after 50 cycles at C/5. The results are promising and indicate the possibility of the use of high‑nickel cathodes in all-solid-state batteries to increase their energy density.

In the present work, gadolinium-doped ceria-based powders were co-fired with additions of 1% (w/w) of SiO₂, and 5% (w/w) of Y₂O₃ to test the role of yttrium ion on improving the grain boundary conductivity across the grain boundary regions of low grade gadolinia-doped ceria (CGO) electrolytes. The samples were prepared by hot press at low temperature (1000 °C) to minimize bulk dissolution of yttrium in the CGO lattice. Structural characterization by XRD of the prepared ceramics confirms a CGO single phase material with the fluorite type structure. All the samples were characterized by impedance spectroscopy as a function of temperature in air, in order to de-convolute different microstructural contributions to the overall electrical behaviour. The results showed, as expected, that the presence of small amounts of impurity of silica reduces the total conductivity, when compared with pure CGO ceramic sample. The grain boundary resistance of these ceramics, under low operating temperatures, has a large effect on the total conductivity and is related, on one hand with the presence of a space charge layer created by the local segregation of trivalent rare earth elements, and the consequently depletion of oxygen vacancies, and on the other hand by the blocking effect of the silicon impurity. However, the obtained results show that addition of yttria increases total conductivity when compared with impure samples without yttria. This effect was related with the partial recover of specific grain boundary conductivity, suggesting a preferential location of Si and Y cations on grain boundaries. The space charge potential values, calculated using impedance data, provided an approach to the promoting effect of recovering grain boundary conductivity by the yttrium ion.

In this study, A-site defective Ca_yTi_0.93Sc_0.07O_3-α oxides were prepared to examine their ionic conduction properties. The electrical conductivities of two typical compositions were measured as functions of oxygen partial pressure P_O2, temperature, and humidity. Additionally, phase transition, chemical expansion, and CO₂ tolerance were examined in Ca_0.985Ti_0.93Sc_0.07O_3-α using an atmosphere-controlled high-temperature X-ray diffraction. In Ca_0.947Ti_0.93Sc_0.07O_3-α, the ionic conduction domain over a wide range of P_O2 was observed at 500–800 °C, even though the humidity dependence of conductivities was confirmed only at 500 °C. Conversely, in Ca_0.985Ti_0.93Sc_0.07O_3-α, the conductivities were enhanced in humidified atmospheres at 500–800 °C, while the ionic conductivities in dry atmospheres were higher than those of 8YSZ. As protonic and oxide ionic conductivities are comparable, the proton-oxide ion mixed conduction can be considered to occur in Ca_0.985Ti_0.93Sc_0.07O_3-α. Therefore, a small percentage of Ca defect in Ca_yTi_0.93Sc_0.07O_3-α affects not only conductivity but also conductive ionic species. Furthermore, Ca_0.985Ti_0.93Sc_0.07O_3-α did not show any phase transition and chemical expansion with hydration up to 900 °C. The crystal phase of Ca_0.985Ti_0.93Sc_0.07O_3-α during the CO₂ tolerance test was observed to be stable. Therefore, the material properties of Ca_yTi_0.93Sc_0.07O_3-α suggest its high potential as electrolytes in high temperature electrochemical devices.

Lithium metal anodes are indispensable to realize the maximum energy density in future generation batteries. However, the lithium surface must be ‘protected’ to suppress its high reactivity and to stabilize its deposition and dissolution. Here, we report a process to form a lithium nitride (Li₃N) protective layer on lithium by a two-minute treatment in a dielectric barrier discharge (DBD) plasma. The process does not require low-pressure conditions or time-intensive post-treatments. The passivation layer is characterized by a unique, hexagonal bipyramid morphology, with α-Li₃N crystals stacked to form pillar-like structures. Such an arrangement is shown to be favorable for fast Li⁺ ion diffusion and dendrite prevention, as demonstrated by the stable Li plating/stripping of symmetric cells with passivated lithium (500 cycles compared to 150 cycles with bare lithium) at 1 mA/cm². Full cells with LiNi_0.33Mn_0.33Co_0.33O₂ (NMC111) cathode and passivated lithium anode retain 74% of their initial capacity after 300 cycles at 1C rate, by which time the cells with bare Li anode fail completely. This approach promises to be a practical solution for lithium passivation at industrial scale.

The stability and selectivity (balance between ionic conductivity and vanadium permeability) of the ion exchange membrane in vanadium redox flow batteries (VRFB) are critical factors that directly impact the battery's performance and lifetime. Herein, we synthesized an ether-free polybenzimidazole copolymer (mcPBI) with rigid benzene ring and flexible alicyclic structures in the polymer's backbone via solution condensation from 3,3′-diaminobenzidine, isophthalic acid and 1,4-cyclohexanedicarboxylic acid monomers. A series of sulfonated polybenzimidazoles (mcPBI-S-x) with long side chains and different grafting degrees were synthesized through grafting reactions, and membranes were prepared by the solution casting method. Microphase separation structure created by grafting accelerates ion transport. Protonated imidazole in an acidic environment enhances proton transport while impeding vanadium penetration due to the Donnan effect. Additionally, the ionic cross-linking between the sulfonic acid group and the imidazole group is in favor of dimensional stability maintenance. The ether-free polymer backbone is conducive to maintaining stability. The results show that all mcPBI-S-x membranes exhibit excellent ion selectivity. Specifically, the mcPBI-S-32% membrane demonstrates optimal ion selectivity (9.06 × 10⁷ S s cm⁻³), low area resistance of 0.45 Ω cm², vanadium permeability (0.76 × 10⁻¹⁰ cm² s⁻¹) and swelling ratio in sulfuric acid (4.3%). The battery with the mcPBI-S-32% membrane demonstrates a coulomb efficiency of 90.50%, a voltage efficiency of 85.69%, and an energy efficiency of 77.55% at a current density of 60 mA cm⁻². What's more, the membrane shows excellent chemical stability, and the chemical structure of mcPBI-S-32% characterized by ¹H NMR does not change after 200 cycles at 120 mA cm⁻².

This work explores green chemistry and the development of sustainable energy storage devices using non-toxic materials. In the fabrication process of electrodes activated carbon materials were used to create symmetrical electrodes. A solid polymer electrolyte (SPE) system is then formed through solution casting, utilizing chitosan (CHSN) and poly(2-ethyl-2-oxazoline) (POZ) as the polymer hosts to facilitate ionic transport with sodium chloride (NaCl) with the aid of plasticizer. Notably, the CSOZN5 system exhibits a relatively high conductivity of 3.59 × 10⁻⁴ S cm⁻¹. The non-Debye relaxation is indicated by the depressed semicircle, with a diameter below the real-axis and the asymmetry-broadness of tanδ. The electric and dielectric characteristics show similar trends with plasticizer concentration, with the highest dielectric constant recorded for the best ion-conducting sample. The electric modulus loss peak shift toward higher frequency indicated enhancement in the ionic movement for high plasticized systems. Through transference number measurement (TNM), the contribution of ions to the overall conductivity is identified, with the best ion-conducting plasticized CHSN:POZ:NaCl film demonstrating potential stability reaching 2.6 V. The capacitive behavior of the constructed electric double-layer capacitor (EDLC) is analyzed using the cyclic voltammetry (CV) test, revealing a specific capacitance (Cspe) of 9.11 F/g at 20 mV/s, signifying the possibility of green energy storage technologies with environmentally friendly materials.

Zinc metal anodes produce side reactions such as dendrite growth and surface corrosion during cycling, leading to premature battery failure. For this reason, we propose an anodic protection strategy for coating sodium carboxymethyl cellulose (CMC) hydrogel material on the surface of zinc foil. This non-conducting 3D porous interconnected network coating acts as a barrier to regulate the flux of zinc ions and electric field distribution, induces zinc to exhibit 3D deposition, and inhibits the growth of dendritic protrusions.The Zn@CMC anode possesses enhanced desolvation capability, which accelerates the rapid transfer of zinc ions, exhibits enhanced kinetics, and inhibits the occurrence of side reactions. The symmetric cell based on CMC hydrogel can be recycled for 1000 h at a current density of 0.5 mA cm⁻² with low voltage hysteresis, and the Zn@CMC//Na-doped VO₂ full cell can maintain a discharge specific capacity of 119 mAh g⁻¹ after 1500 cycles, which is of good practical performance. This study provides a new perspective for the introduction of CMC hydrogel for interfacial modification, which is of reference value for solving interfacial problems.