Conductivity Relaxation Research Articles

Origin of ργ/T scaling of primary and secondary conductivity relaxation times in mixture of water with protic ionic liquid.

Murali et al. [J. Phys. Chem. Lett., 2024, 15, 3376-3382] made ambient and high pressure dielectric measurements of a supercooled aqueous mixture of an acidic ionic liquid to find the presence of the primary (σ) conductivity relaxation together with the secondary (ν) conductivity relaxation originating from the water clusters confined by the cations and anions with relaxation times τσ and τν respectively. From the isothermal and isobaric conductivity relaxation data found on varying thermodynamic conditions (i.e. T and P) at constant τσ are the invariance of (i) the frequency dispersion or the Kohlrausch function exponent (1 - n) of the primary conductivity relaxation, and (ii) the ratio of the primary and secondary conductivity times, τσ/τν. This co-invariance of τσ, τν, and (1 - n) at constant τσ was observed before in non-aqueous ionic liquids, but it is found for the first time in aqueous ionic liquids. The new data together with PVT measurements enable Murali et al. to show additionally that both τσ and τν are functions of ργ/T with a single exponent γ = 0.58. The Coupling model is the only theory predicting the co-invariance of τσ, τν, and (1 - n) as well as the ργ/T scaling of both τσ and τν. It is applied herein to address and explain the data of the ionic liquid-water mixture.

Structural, morphological, electrical, and dielectric properties of Na2Cu5(Si2O7)2 for ASSIBs.

Solid inorganic electrolyte materials are fundamental components for constructing all-solid-state sodium-ion batteries. These solid electrolytes offer considerable benefits related to safety, electrochemical performance, and mechanical stability in comparison to liquid organic electrolyte systems. This study investigates the sodium ion conduction mechanism and relaxation kinetics in the sorosilicate material Na2Cu5(Si2O7)2, a potential solid electrolyte, using impedance spectroscopy. Analysis of the DC conductivity data demonstrates that sodium ion mobility follows Arrhenius behavior with a thermal activation energy barrier of 1.21 eV. This work highlights the importance of carefully choosing an appropriate equivalent circuit model to extract DC conductivity parameters from impedance data, given the contributions from both grain and grain boundary effects. Analysis of the AC conductivity and dielectric constant as a function of frequency and temperature demonstrates that ionic conduction takes place in this material through a process in which charge carriers overcome correlated energy barriers, known as correlated barrier hopping. The neutron diffraction patterns were analyzed using soft bond valence sum (BVS) techniques to map the possible ionic conduction pathways within the unit cell. Examination of the data points to obstructions in the sodium ion diffusion routes along the a-axis and diagonal of the bc plane within the triclinic unit cell. These bottlenecks likely contribute to the high activation energy and correspondingly low ionic conductivity observed. Analysis of dielectric properties by modulus verified that the ionic conduction relaxation phenomena exhibit thermal activation and a distribution of relaxation times. In summary, this work elucidates the microscopic ionic conduction mechanism in Na2Cu5(Si2O7)2 through extensive analysis encompassing DC/AC conductivity, electric modulus, and dielectric constant measurements. The insights gained into the ionic conduction mechanism will aid in engineering optimized ionic conductor materials for battery technologies.

Close-packing effect of water clusters within metal-organic framework pores on proton conductivity: a dielectric relaxation phenomenon in loose space and colossal dielectric permittivity.

Proton-conducting metal-organic frameworks (MOFs) have attracted tremendous attention for their promising application in proton-exchange membrane fuel cells. Water clusters play an extremely important role in the proton-conduction process and affect the proton conductivity of host materials. To date, the close-packing effect of water clusters within pores on proton conductivity due to the amorphous structure of commercial proton-exchange membranes is unclear. Herein, we prepared two crystalline MOFs containing different water clusters, namely, [Sm2(fum)3(H2O)4]·3H2O (Sm-fum-7H2O) and [Er2(fum)3(H2O)4]·8H2O (Er-fum-12H2O) (H2fum = fumaric acid), and regulated their proton conductivities by changing the water clusters. As expected, Sm-fum-7H2O showed a high proton conductivity of 6.89 × 10-4 S cm-1 at 333 K and ∼97% RH because of the close packing of the water clusters within the pores triggered by a lanthanide contraction effect, outperforming that of Er-fum-12H2O and some previously reported MOFs. Additionally, Sm-fum-7H2O and Er-fum-12H2O demonstrated high dielectric functions, reaching 2.22 × 103 and 1.42 × 105 at 102.5 Hz, respectively, making Er-fum-12H2O a highly dielectric material. More importantly, broadband dielectric spectroscopy measurements indicated that there was a dielectric relaxation process in Er-fum-12H2O with an activation energy of 0.59 eV. The present findings provide a better understanding of the crucial role of confined water clusters in proton conductivity and the novel phenomenon of the coexistence of proton conduction and dielectric relaxation in crystalline MOF materials.

Crystal structure, Hirshfeld surface analysis, conduction mechanism and electrical modulus study of the new organic-inorganic compound [C8H10NO]2HgBr4.

There has been a lot of interest in the development of a novel hybrid material based on mercury that has fascinating structural properties. In this paper, single crystals of [C8H10NO]2HgBr4 was successfully synthesized by the slow evaporation method at room temperature. In fact, the latter crystallizes in the orthorhombic system (Cmca space group) with cell parameters a = 20.824(2) Å, b = 15.352(1) Å and c = 13.700(1) Å and Z = 8. Its structure is constituted by one [C8H10NO]+ cation and one type of isolated anion [HgBr4]2- tetrabromomercurate(ii). The atomic arrangement presents an alternation of organic and inorganic layers along the a-axis. To maintain the cohesiveness of the structure, these components are joined via π⋯π interactions and hydrogen bonds (N-H⋯Br and N-H⋯O). A general network of hydrogen bonds ensures the interconnection of several entities. Greater knowledge of these interactions has been obtained based on the Hirshfeld surface analysis and 2D fingerprint plots. The analysis of complex impedance spectra shows that the electrical properties of the material are heavily dependent on frequency and temperature. The obtained results were analyzed by fitting the experimental data to an equivalent circuit model. The temperature dependence of conductivity and the relaxation frequency ωmax fulfill the Arrhenius relation and activation energies are estimated. The material follows Jonscher's universal dynamic law or here there is a decrease in the exponent 's' as the temperature increases. This result indicates that the Correlated Barrier Hopping (CBH) model represents the conduction mechanism. Besides, the non-Debye type conductivity relaxation is revealed by the electrical modulus analysis.

Exploration of the charge transport mechanism, complex impedance, dielectric/electric modulus and energy storage characteristics of the aloe vera (Aloe Barbadensis Miller) plant

Complex impedance spectra at room temperature in the frequency range of 8 Hz—5 MHz were measured on freshly cut leaf sections of the Aloe vera plant by AC impedance spectroscopy. They were analyzed using a classical ‘brickwork’ equivalent circuit composed of grain and grain boundary contributions commonly applied to solid-state materials. The obtained grain resistance/capacitance was 0.4 MΩ/72 pF and grain boundary resistance/ capacitance was 66.4 MΩ/50 nF. The determined conductivity changed according to the Jonscher power law with σ DC of 4.02 · 10–5 (Ωm)−1 and frequency constant of 0.92 characteristic for hopping as the conduction mechanism. Analysis of dielectric permittivity and electric modulus confirmed the non-Debye relaxation behavior. Nyquist plots for electric modulus revealed conductivity relaxation in the low frequency attributed to grain boundaries and impedance modulus displayed dielectric relaxation in the high frequency region associated with grains. A correlation has been established among the investigated parameters, morphology, and EIS-derived simulated parameters.

Investigation of dysprosium oxide substitution on physical, electrical and dielectric properties in sodium borosilicate glass system

Dysprosium oxide doped sodium borosilicate glasses were prepared in this study using a usual melt-quenching process. Further XRD, FTIR, density measurements, electrical conductivity, and dielectric properties were utilized to explore the prepared glassy samples. We found that all produced samples exhibit amorphous nature through X-ray diffraction. Increase in density and molar volume were found when dysprosium oxide concentration increased, which was ascribed to dysprosium oxide's greater molecular weight. Density data was used to calculate and explain several physical characteristics, including rare earth ion concentration (N), polaron radius (rp), internuclear distance (ri), and field strength (F).

Effect of doping of organo-soluble carbon dots on ionic relaxation and conductivity of planar anchored cyanobiphenyl based nematic liquid crystal

We demonstrate here the striking effect of organo-soluble carbon dots (CDs, diameter ∼7- 8 nm) on the tunability of ionic relaxation and conductivity of the host, planar anchored thermotropic nematic liquid crystal (5CB, 4-Cyano-4′-pentylbiphenyl). The optical texture, frequency, temperature, and concentration dependent dielectric studies of pristine 5CB and CDs-5CB composites have been performed using the polarising optical microscope and high-resolution dielectric spectroscopy, respectively. The doping of 0.5 wt% CDs into planar anchored 5CB is resulted into the vertical alignment confirmed through the cross-polarised optical microscope. The doping of CDs in 5CB liquid crystal is resulted into an unprecedented faster ionic relaxation with an abatement of the ionic amplitude at room temperature. The shift in the relaxation frequency for 0.5 wt% CDs-5CB composite (induced vertical alignment) as compared to pristine 5CB (planar aligned) at 28 °C (nematic) is found to be ∼13 folds which is further increased to ∼18 folds at 38 °C (isotropic). A similar trend in the conductivity curve is also observed which further confirms the significant enhancement in conductivity value with increase in temperature and concentration of dopant CDs. The observation of enhanced ionic conductivity and faster ionic relaxation in CDs-5CB composites as compared to pristine 5CB are attributed to the complete change of planar to vertical alignment by doping of CDs on planar anchored liquid crystal sample cells. It appears that the plausible strong interaction between hydrocarbon chains of CDs and 5CB molecules through anchored substrate surfaces with increasing concentration of CDs and decrease in rotational viscosity of host 5CB with increasing temperature certainly plays a pivotal role in the tuning of ionic relaxation and conductivity in the liquid crystal sample cells. We certainly believe that our results would catalyze the cognizance of the ionic relaxation and conductivity in CDs-5CB composites and other related systems. Moreover, such composites with tunable ionic relaxation/conductivity would be certainly helpful in the fabrication of various tuneable devices such as wave front corrector, low frequency oscillation generators, dynamic light scattering, and so on.

(Invited) Proton Surface Exchange Kinetics and Stability of Thin-Film Triple Conducting Oxides for Protonic Ceramic Electrolysis Cells

Protonic ceramic electrolysis cells (PCECs) have been attracting attention due to their ability to operate in the intermediate temperature (300 - 500 ˚C) sweet-spot. These temperatures enable fast kinetics, inexpensive materials (no precious metals; stainless interconnects), and lower operating voltage for producing green hydrogen, without the accelerated degradation that may be observed at higher temperatures. The steam electrodes often support triple conduction and thereby host the proton exchange / oxygen evolution process at the surface, where steam is split. Steam electrode materials development is at a relatively early stage, with open questions around the relationships among bulk composition, evolving surface chemistry, kinetic quantities, and degradation mechanisms. We are investigating the proton exchange surface coefficient (k) and its evolution over time on model thin film electrodes in order to ultimately develop highly active and long-term stable steam electrodes for PCECs.ABO3 perovskites with Ba on the A-site and nominally multivalent ions on the B-site are candidates for steam electrodes given the varied compositions in this class that can transport oxide ions, protons, and electronic species, and the lowering of hydration enthalpies by the basicity introduced by Ba. However, very few measurements of k exist for these materials, and the evolution of surface chemistry and thus k is poorly understood.In this work, we fabricated and compared two perovskite triple conducting oxides by growing geometrically well-defined films of Ba(Pr,Y)O3-x (BPY) and Ba(Co,Fe,Zr,Y)O3-x (BCFZY) with pulsed laser deposition. We examined the proton surface exchange coefficients (k-values) using simultaneous in-situ optical transmission relaxation and electrical conductivity relaxation measurements upon switching pH2O at a temperature of 400 ˚C, and continued these switches as a function of time to assess stability. To our knowledge, this is the first use of an optical transmission method to probe elevated temperature steam splitting kinetics, and we interpret the optical (and electrical) changes as indicative of redox during the hydrogenation process. The k-values of BPY thin films were approximately ten times higher than those of the BCFZY thin films, and BPY also retained higher k-values over time. The bulk and surface chemical compositions of BPY and BCFZY thin films before and after relaxation measurements were compared using Rutherford backscattering spectrometry, angle-resolved X-ray photoelectron spectroscopy, and scanning transmission electron microscopy with spectroscopy. Pronounced Ba enrichment and Si contamination (from the quartz tube) were evident at the surface of BPY by both S/TEM-EDS and XPS, whereas for BCFZY these surface chemical features were only detectable by XPS and absent in S/TEM-EDS. Implications for materials design of steam electrodes will be discussed, considering efficiency and lifetime.

Contribution of numerical modelling to design oxygen electrode for micro-solid oxide cells: A case study of high-performance nano-columnar La2NiO4 thin films

This article presents a numerical study that aims to guide the development of nano-columnar La2NiO4 thin films as high performing oxygen electrodes for micro-Solid Oxide Cell (μSOC). La2NiO4 thin films were deposited by Pulsed Injection Metal Organic Chemical Vapor Deposition (PI-MOCVD) and their performance is characterized by Electrochemical Impedance Spectroscopy (EIS) and Electrical Conductivity Relaxation (ECR). Excellent performance is obtained for 1 μm thick film with an Area Specific Resistance (ASR) of 0.12 Ω cm2 at 600 °C, making them suitable for low-temperature μSOCs. A Finite Element Method (FEM) model has been implemented and used to predict the ASR and impedance spectra in order to guide further optimization of the film thickness and morphology. After experimental validation of the model using various electrode thicknesses, the optimal value is estimated to be between 3 and 4 μm for the temperature range of 450–650 °C. For each temperature and thickness, the model can clearly predict whether the electrode is limited by the surface exchange reactions or the bulk diffusion. The simulations revealed that the gas diffusion process is not rate-limiting when the electrode thickness is below 5 μm and the temperature is below 650 °C. Furthermore, a geometrical parameters analysis study allowed to determine the ideal nano-columnar morphology for this promising electrode composition.

A way to limit the long-term degradation of solid oxide fuel cell cathode by decorating the surface with K2NiF4-Structure Pr4Ni3O10+δ phase

Prolonged annealing of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) at 700 °C for 1000 h resulted in phase segregation on the surface in the form of submicron-sized SrO on the grains and micron-sized CoFe2O4 particles near the grain boundaries during electrical conductivity relaxation (ECR) measurements. The presence of segregated particles results in a substantial decrease in the surface exchange coefficient, kchem. To mitigate this issue, the LSCF electrodes underwent a systematic coating process with the K2NiF4-structure Pr4Ni3O10+δ (PNO), while varying the loading content, thickness, and porosity. This is achieved by adjusting the gap between the nozzle exit and LSCF surface, ranging from 2 cm to 9 cm, coupled with the application of ultrasonic vibration of the nozzle chamber operating between 40 kHz and 180 kHz. Optimal surface coverage with a loading content of 0.28 mg cm−2 referred to as PNO5 results in a significant increase in kchem by up to one and a half order of magnitude compared to bare LSCF. The PNO coating effectively suppresses phase segregation during prolonged exposure, resulting in a substantial decrease in degradation. The improved performance is attributed to the optimal surface coverage of coated particulates, which enhances the active sites for oxygen reduction reaction (ORR) and the triple phase boundary (TPB) area. These exceptional characteristics position PNO coated LSCF as a highly promising cathode option for low temperature solid oxide fuel cells (SOFCs).

Investigation of the electrochemical performance of Mg-ion batteries based on PVDF-HFP thin polymer electrolyte films

In the present work, poly(vinylidene fluoride-hexafluoropropylene):magnesium trifluoromethanesulfonate (PVDF-HFP:MgTf) polymer electrolytic films with a porous structure were developed using the solution-casting method. With its high performance and versatility, PVDF-HFP has been widely employed in the development of solid polymer electrolyte films (SPEFs). In this study, metal salt particles are successfully included as an inorganic filler into solid PVDF-HFP films, reducing pore size and boosting the amorphous character of the films. Fourier transform infrared spectroscopy is used to examine the chemical structure of the produced SPEFs, and scanning electron microscopy is used to evaluate the surface morphology and locate pores in the SPEFs. The surface nature of the PVDF-HFP films and the PVDF-HFP:MgTf is confirmed by X-ray diffraction. The electrochemical stability of PVDF-HFP and PVDF-HFP:MgTf films is studied through a differential scanning calorimetry experiment. Results revealed that PVDF-HFP:MgT films could be stabilized when filled with electrolytes and electrodes and made less porous by adding inorganic salt particles. Further, electrochemical impedance spectroscopy is used to measure electrical conductivity between 303 and 423 K. At room temperature, PVDF-HFP and PVDF-HFP/Mg2+ SPEFs have optimal ionic conductivities of 3.38 × 10−7 and 1.08 × 10−6 SS ccmm−1−1 respectively. Ionic conductivity was found to increase with temperature. The modulus of the imaginary part of the loss tangent (M′ and M″) was found to be related to dielectric and conductivity relaxation.

High-temperature variable range hopping conduction and dielectric relaxation in CoFe2O4 ceramic

CoFe2O4 ceramic was fabricated using a sol-gel auto-combustion process. The cubic spinel structure with F d −3 m space group symmetry was confirmed through the Rietveld refinement of the XRD pattern of CoFe2O4 sintered at 800 °C for 4 h. The cobalt vacancies at the tetrahedral site were verified by electron density distribution calculated through the maximum entropy method. The impedance spectroscopy study revealed that the grain boundary was dominant compared to the grain in the electrical properties of CoFe2O4. The total dc resistivity was fitted by the variable range hopping (VRH) model, demonstrating that the charge carriers for conduction mechanism confirm to the VRH model. The density of localized states (N(EF)) near the Fermi level was found to be 1.07 × 1019 eV−1-cm−3. The hopping energy (EH) and hopping length (R) of the charge carriers were estimated to be 0.29 eV and 2.28 nm, respectively, at 473 K.

Temperature and frequency dependent response of electrical conduction and dielectric relaxation mechanism in CuCr2O4 tetragonally distorted spinel chromite

Herein, the polycrystalline CuCr2O4 (CCO) electro-ceramic was prepared via the sol-gel self-combustion route. The X-ray powder diffraction analysis at room temperature revealed that the CCO chromite was synthesized in a single phase tetragonally distorted normal spinel structure with I41/amd space group. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) investigated the polycrystalline nature of the compound. The microstructural analysis by field emission scanning electron microscopy (FESEM) explored the surface morphology of micron-sized grains (Gs) distinguished by well-pronounced grain boundaries (GBs) available for electrical response of the material. The color mapping images of elements by energy-dispersive X-ray spectroscopy (EDS) divulged the homogeneous distribution of elements in the compound. The surface chemistry of the compound was studied by X-ray photoelectron spectroscopy (XPS). This information helped in understanding the electronic states of the ions contributing to the electrical networks and mechanisms responsible for the charge transport within the CCO system. The dielectric relaxation and electrical transport properties were analyzed using complex impedance spectroscopy (CIS) over the experimental range of frequency and temperature from 40 Hz to 1 MHz and 243–493 K, respectively. The experimental complex impedance data were analyzed by RGQGRGBQGB equivalent circuit model which resolved the electro-active contributions of bulk and interface of the CCO spinel to its electrical dynamics. The dispersion in AC conductivity was explained by Jonscher's double power law which provided evidence of small polaron hopping (SPH) as a dominant transport mechanism governing electrical conduction in the compound. The temperature-dependent DC conductivity pattern exhibited an Arrhenius-like behavior that followed Mott and Davis's model of SPH. The analysis of complex electrical modulus M*(ω,T) professed the localized and de-localized movements of the charge carriers. The dielectric permittivity response of CCO followed Havriliak-Negami (HN) phenomenology that divulged the existence of non-Debye type dielectric relaxation processes. The interfacial polarization was observed to be accountable for the dispersion in dielectric loss spectra.

Investigation of electrical, dielectric, and relaxation phenomenon of Co–Cr substituted SrM hexaferrite: Validation of measured and simulated parameters

Chromium (Cr) and Cobalt (Co) substituted hexaferrite with composition Sr(CoCr)xFe(12−2x)O19 (x=0.0to 0.6) has been synthesized via the Sol-gel combustion technique. The phase purity, morphology, and electrical characteristics of all sintered hexaferrite have been analyzed. XRD measurements showed that all sintered hexaferrite exhibit a magnetoplumbite structure. The substitution of Cr–Co ions in a crystal lattice resulted in a meager decrease in lattice constant value ‘a’ and a considerable decrease in lattice constant value ‘c’. FTIR spectra revealed the existence of three precise absorption bands at 419.59, 539.71, and 580.37 cm−1 which were predicted to be due to Fe–O vibrations. Impedance spectroscopy has been carried out on a wide range of frequencies (20 Hz–2 MHz). The investigated parameters have been considerably affected by dopant-tuned morphology through a decrease in grain size and the formation of grain clusters. The loss tangent and dielectric constant of the Cr–Co substituted SrM hexaferrite is found to be increased with substitution. Substitution causes a decrease in the AC conductivity value in the high-frequency region from 9.57 × 10−4 to 3.05 × 10−4 Ω−1m−1. The non-Debye behavior is observed in the material by analyzing the dielectric and electric modulus spectra. The simultaneous contribution of grain/grain boundaries demonstrated by Cole-Cole plots (M″ vs M′) in the x = 0.4 sample is consistent with SEM micrographs. The charge transport mechanism that occurs in the synthesized samples can be explained with SEM/FESEM micrographs as well as with calculated values of grain and grain boundary resistance/capacitance from EIS software. The two incomplete semicircular arcs have been observed in the x = 0.6 sample in Z″ vs Z′ plots. The conductivity relaxation is significantly improved with Cr–Co substitution.

Label-free multimodal electro-thermo-mechanical (ETM) phenotyping as a novel biomarker to differentiate between normal, benign, and cancerous breast biopsy tissues.

Technologies for quick and label-free diagnosis of malignancies from breast tissues have the potential to be a significant adjunct to routine diagnostics. The biophysical phenotypes of breast tissues, such as its electrical, thermal, and mechanical properties (ETM), have the potential to serve as novel markers to differentiate between normal, benign, and malignant tissue. We report a system-of-biochips (SoB) integrated into a semi-automated mechatronic system that can characterize breast biopsy tissues using electro-thermo-mechanical sensing. The SoB, fabricated on silicon using microfabrication techniques, can measure the electrical impedance (Z), thermal conductivity (K), mechanical stiffness (k), and viscoelastic stress relaxation (%R) of the samples. The key sensing elements of the biochips include interdigitated electrodes, resistance temperature detectors, microheaters, and a micromachined diaphragm with piezoresistive bridges. Multi-modal ETM measurements performed on formalin-fixed tumour and adjacent normal breast biopsy samples from N = 14 subjects were able to differentiate between invasive ductal carcinoma (malignant), fibroadenoma (benign), and adjacent normal (healthy) tissues with a root mean square error of 0.2419 using a Gaussian process classifier. Carcinoma tissues were observed to have the highest mean impedance (110018.8 ± 20293.8 Ω) and stiffness (0.076 ± 0.009 kNm-1) and the lowest thermal conductivity (0.189 ± 0.019 Wm-1K-1) amongst the three groups, while the fibroadenoma samples had the highest percentage relaxation in normalized load (47.8 ± 5.12%). The work presents a novel strategy to characterize the multi-modal biophysical phenotype of breast biopsy tissues to aid in cancer diagnosis from small-sized tumour samples. The methodology envisions to supplement the existing technology gap in the analysis of breast tissue samples in the pathology laboratories to aid the diagnostic workflow.

AC Conduction Mechanism and Impedance Analysis of Conventional and Plasma‐Sintered Yttria‐Stabilized ZrO2@Mullite Composite

AbstractThe addition of 8 mol% of Y2O3 to the ZrO2@mullite composites stabilizes the metastable tetragonal phase of ZrO2 in conventional and plasma‐sintered Y2O3‐stabilized ZrO2@mullite composites. A fused, highly dense, and interconnected microstructure is formed in the case of plasma‐sintered Y2O3 stabilized ZrO2@mullite composite. At 1 MHz frequency, the room temperature and tanδ of (10.37 and 2.06) is obtained for the conventional Y2O3 stabilized ZrO2@mullite composite and that of (38.8 and 4.02) is observed for the plasma sintered Y2O3 stabilized ZrO2@mullite composite. The substitution of Y3+ in place of Zr4+ creates sufficiently large oxygen vacancies at the grain boundary regions of these composites endowed mostly with the ZrO2 phase. In conventional Y2O3‐ ZrO2@mullite composites, both dielectric relaxation as well as conductivity relaxation are observed due to the dynamic motion of dipoles and relaxation due to the presence of defect states and porous structures. This leads to higher grain boundary conductivity than the grain conductivity of these composites. Thermally activated conduction mechanisms exhibited in these composite materials are projected from the complex impedance and modulus analysis. The conventional and plasma sintered Y2O3‐ ZrO2@mullite composite has an optical bandgap of 3.26 and 3.58 eV, respectively.

Charge transport in highly acidic glass-forming protic ionic liquids tailored by zwitterionic precursors.

Highly acidic protic ionic liquids (PILs) are promising materials for potential electrochemical applications due to their high proton conductivity and excellent thermal stability. Still, little is known about the correlation between charge transport and structural dynamics as well as the proton transport mechanism despite the large body of literature on this topic. Here, we have examined the charge transport and structural dynamics by employing broadband dielectric spectroscopy in two highly acidic PILs in their supercooled liquid and glassy states, which included the same anion [TfO]- and different cations, [Tau]+ vs [Ahs]+. Unlike many other ionic liquids, the conductivity relaxation time τe of two studied PILs is substantially faster than the structural relaxation time τα. The decoupling behavior between charge transport and structural dynamics of two materials, which is manifested by a decoupling index Rτ, varies between 0.3 and 2.3 over the temperature range above Tg. Moreover, "Walden" plots of the molar conductivity vs the viscosity qualify both compounds as "Super ILs." All findings support the physical picture of large, polar, and orientationally correlated ion clusters, where the slow α-relaxation can be identified as structural relaxation associated with cooperative reorientations of the cluster macrodipole. In contrast, the shortest timescale for diffusive charge transport, τe, is 1-2 decades shorter than τα, implying that proton hopping is triggered by "single particle" (ions or ion pair) rotations and jumps on a sub-length scale of the cluster size, a dynamics being present even in the glassy state as indicated by a strong β-relaxation. These results demonstrate the practicality of employing highly acidic PILs in electrochemical fields.

Achieving Fast Oxygen Reduction on Oxide Electrodes by Creating 3D Multiscale Micro-Nano Structures for Low-Temperature Solid Oxide Fuel Cells.

Fast oxygen reduction reaction (ORR) at the cathode is a key requirement for the realization of low-temperature solid oxide fuel cells (SOFCs). While the design of three-dimensional (3D) structures has emerged as a new and promising approach to improving the electrochemical performance of SOFC cathodes, achieving versatile structures and structural stability is still challenging. In this study, we demonstrate a novel architectural design for a superior cathode with fast ORR activity. By employing a completely new fabrication process comprising a 3D printing technique and pulsed laser deposition (PLD), we design 3D La0.8Sr0.2CoO3-δ (LSC) micro-nano structures with the desired shape. 3D-printed yttria-stabilized ZrO2 (YSZ) microstructures significantly increase the ratio of surface area to volume while maintaining suitable ionic conductivity comparable to that of single-crystalline YSZ substrates. Scanning electron microscopy and energy dispersive X-ray microanalysis reveal the formation of crack- or void-free YSZ microstructures and the uniform deposition of LSC films by PLD on the YSZ microstructures. The 3D LSC micro-nano structures show significantly enhanced oxygen surface exchange coefficients (kchem) extracted from electrical conductivity relaxation (ECR) measurements by up to 3 orders of magnitude relative to the bulk LSC. Furthermore, electrochemical impedance spectroscopy measurements verify the kchem values from ECR and no directional difference in the measured ORR activity depending on the shape of 3D microstructures. The dramatic enhancement of the ORR activity of LSC is attributed to the increased film surface areas resulting from the 3D YSZ microstructures.

Manipulating fluorine induced bulky dipoles and their strong interaction to achieve high efficiency electric energy storage performance in polymer dielectrics

The pursuit of polymer dielectrics with elevated energy density frequently results in heightened energy loss, thereby hindering practical applications. To decouple the dependence of the high energy loss on the high energy storage performance, based on theoretical simulations, a bulky polar unit constructed from a fluorine atom substituted phenyl ring (4-FSt) is designed and copolymerized with methyl methacrylate (MMA). The fluorine atom is found to induce the dipole formation by deforming π-conjugated electrons distribution on the phenyl ring, which favors reversible polarization behaviors instead of conventional dipole orientation polarization under AC electric field and enhances the energy density of polymers. Meanwhile, the introduction of fluorine atoms possessing electron-withdrawing properties is confirmed to increase the electrons capturing ability and the dipole interactions, which significantly reduces the leakage conduction and orientation relaxation induced energy loss. As a result, the rather high energy discharging efficiency (over 88 %) could be finely maintained up to 825 MV m−1, and a discharge energy density of 16.6 J cm−3 is obtained, which exhibits significant advances over the reported polymer dielectrics. This work presents the first practice to decouple the dependence of high energy storage and energy loss in polymer dielectrics by manipulating the fluorine effect.

Significantly enhanced performance and conductivity mechanism in Nb/Mn co-doped CaBi4Ti4O15 ferroelectrics

With the rapid development of high-end industries, the demand for high-temperature piezoelectric materials is significantly increasing. However, realizing the ultra-high performance to meet more applications still faces major scientific and engineering challenges of our time. Here, a new Nb/Mn co-doped CaBi4Ti4O15 (CBT) high-temperature piezoelectric material system of CaBi4Ti4-x(Nb2/3Mn1/3)xO15 was synthesized by the conventional solid-state sintering method. The results show that the addition of the dopants tends to break the long-range ferroelectric chain and soften the flexibility of polarization, resulting in more distorted crystal structure and better ferroelectric properties of CBT ceramics. The ultra-high piezoelectric constant (d33 = 26.8 pC/N) is thus attained in CBT-based ceramics with x = 0.12, which is about several times larger than that of pure CBT ceramics. Moreover, numerous nano-sized layered domain structures that lie on the lateral plane of grains are observed in ceramics, with lower domain wall energy and better dynamic features under electric fields, mainly responsible for the origin of enhanced performance. Besides, excess dopants could make the conductivity mechanism of CBT ceramics transform from p-type to n-type, and also result in a shift of conduction relaxation mechanism from defect dipole rotation polarization to electron relaxation polarization. The work not only provides a promising candidate for high-temperature piezoelectric materials, but also opens a window for optimizing performance by tailoring domain structures using chemical modification.