Mixed Conductor Research Articles

A kinetic study on oxygen redox reaction of a double-perovskite reversible oxygen electrode—Part I: Experimental analysis

The carbon-free energy transition requires the spread of advanced technologies based on high-performing materials. In this framework and particularly referring to electrochemical energy converting systems, double perovskites are arousing more and more interest as mixed ionic electronic conductors with flexible manufacturing, appropriate tailoring for many tasks and high chemical stability. Among their possible applications, they form excellent oxygen electrodes in solid oxide cell technology used as fuel cells, steam/CO2 electrolysis cells and electrochemical air separation units. In view of the encouraging results shown by SmBa1−x Ca x Co2O5+δ co-doped double perovskite, this research work aims at a detailed analysis of SmBa0.8Ca0.2Co2O5+δ performance and the identification of kinetic paths for oxygen reduction and oxidation reactions. The electrochemical characterization was performed over a wide range of operation conditions to evaluate the electrode reversible behaviour and the interplay of the recognized phenomena governing the overall electrode kinetics.

Peculiar transient behaviors of organic electrochemical transistors governed by ion injection directionality

Despite the growing interest in dynamic behaviors at the frequency domain, there exist very few studies on molecular orientation-dependent transient responses of organic mixed ionic–electronic conductors. In this research, we investigated the effect of ion injection directionality on transient electrochemical transistor behaviors by developing a model mixed conductor system. Two polymers with similar electrical, ionic, and electrochemical characteristics but distinct backbone planarities and molecular orientations were successfully synthesized by varying the co-monomer unit (2,2’-bithiophene or phenylene) in conjunction with a novel 1,4-dithienylphenylene-based monomer. The comprehensive electrochemical analysis suggests that the molecular orientation affects the length of the ion-drift pathway, which is directly correlated with ion mobility, resulting in peculiar OECT transient responses. These results provide the general insight into molecular orientation-dependent ion movement characteristics as well as high-performance device design principles with fine-tuned transient responses.

Improving response performance of impedimetric NO2 sensor using NiO-YSZ mixed conductor porous layer

The mixed conductor porous layer was prepared by introducing the electronic conductor NiO into the oxygen ion conductor YSZ for the impedimetric NO2 sensor. By changing the ratio of YSZ/NiO in the porous layer, the morphology and electron-ion conduction properties of the mixed conductor porous layer were tuned to obtain the high-performance sensing electrode/electrolyte/gas three-phase boundary (TPB) and improve the response characteristics of the sensor. The results show that the number of pores in the porous layer decreases with increasing NiO doping, while the average pore size shows an opposite trend. The results of AC impedance and NO2-TPD measurement show that the introduction of NiO in the YSZ porous layer significantly improves the electrochemical activity of the sensor at TPB and the NO2 adsorption capacity, which in turn improves the sensitivity of the sensor. The sensor based on the YSZ:NiO= 1:0.5 (mass ratio) porous layer exhibits the highest Θ (ΔΘ = 19.13° for 300 ppm) and |Z| (S|Z|=0.35 for 300 ppm) response value. The sensor also has good anti-interference ability. The changes of ΔΘ caused by CH4, CO2, H2, NO and NH3 are 0.6%, 1.6%, − 2.6%, 3.3% and − 2.4%, and the Δ|Z| are 2.5%, 3.2%, − 2.7%, 5.6% and 1.2%. Meanwhile, the humidity has almost no effect on the |Z| and Θ response.

Conducting Polymer Nanoparticles with Intrinsic Aqueous Dispersibility for Conductive Hydrogels.

Conductive hydrogels are promising materials with mixed ionic-electronic conduction to interface living tissue (ionic signal transmission) with medical devices (electronic signal transmission). The hydrogel form factor also uniquely bridges the wet/soft biological environment with the dry/hard environment of electronics. The synthesis of hydrogels for bioelectronics requires scalable, biocompatible fillers with high electronic conductivity and compatibility with common aqueous hydrogel formulations/resins. Despite significant advances in the processing of carbon nanomaterials, fillers that satisfy all these requirements are lacking. Herein, intrinsically dispersible acid-crystalized PEDOT:PSS nanoparticles (ncrys-PEDOTX ) are reported which are processed through a facile and scalable nonsolvent induced phase separation method from commercial PEDOT:PSS without complex instrumentation. The particles feature conductivities of up to 410 S cm-1 , and when compared to other common conductive fillers, display remarkable dispersibility, enabling homogeneous incorporation at relatively high loadings within diverse aqueous biomaterial solutions without additives or surfactants. The aqueous dispersibility of the ncrys-PEDOTX particles also allows simple incorporation into resins designed for microstereolithography without sonication or surfactant optimization; complex biomedical structures with fine features (< 150 µm)areprinted with up to 10% particle loading . The ncrys-PEDOTX particles overcome the challenges of traditional conductive fillers, providing a scalable, biocompatible, plug-and-play platform for soft organic bioelectronic materials.

Research on overvoltage suppression of three-level converter based on two–three phase mixed conduction mode

Research on overvoltage suppression of three-level converter based on two–three phase mixed conduction mode

Mixed Ionic-Electronic Conducting Hydrogels with Carboxylated Carbon Nanotubes for High Performance Wearable Thermoelectric Harvesters.

Mixed ionic-electronic conducting (MIEC) thermoelectric (TE) materials offer higher ionic conductivity and ionic Seebeck coefficient compared to those of purely ionic-conducting TE materials. These characteristics make them suitable for direct use in thermoelectric generators (TEGs) as the charge carriers can be effectively transported from one electrode to the other via the external circuit. In the present study, MIEC hydrogels are fabricated via the chemical cross-linking of polyacrylamide (PAAM) and polydopamine (PDA) to form a double network. In addition, electrically conducting carboxylated carbon nanotubes (CNT-COOH) are dispersed evenly within the hydrogel via sonication and interaction with the PDA. Moreover, the electrical properties of the hydrogel are further improved via the in situ polymerization of polyaniline (PANI). The presence of CNT-COOH facilitates the ionic conductivity and enhances the ionic Seebeck coefficient via ionic-electronic interactions between sodium ions and carboxyl groups on CNT-COOH, which can be observed in X-ray photoelectron spectroscopy results, thereby promoting the charge transport properties. As a result, the optimum device exhibits a remarkable ionic conductivity of 175.3 mS cm-1 and a high ionic Seebeck coefficient of 18.6 mV K-1, giving an ionic power factor (PFi) of 6.06 mW m-1 K-2 with a correspondingly impressive ionic figure of merit (ZTi) of 2.65. These values represent significant achievements within the field of gel-state organic TE materials. Finally, a wearable module is fabricated by embedding the PAAM/PDA/CNT-COOH/PANI hydrogel into a poly(dimethylsiloxane) mold. This configuration yields a high power density of 171.4 mW m-2, thus highlighting the considerable potential for manufacturing TEGs for wearable devices capable of harnessing waste heat.

Versatile Mixed Ionic-Electronic Conducting Binders for High-Power, High-Energy Batteries

The increasingly extensive use of Lithium-Ion Batteries (LIBs) requires further optimization of the devices to make use of their maximum practical specific capacity. Although the binder occupies a small fraction of the electrode mass, it is one of the most crucial components to achieve improved cell performance and cycle life. Conducting polymers such as PEDOT:PSS have been already studied as binders for high-performance lithium-ion batteries (LIBs) but without addressing the structure-property relationships of the binder in the electrode. Herein, we develop mixed ionic-electronic conducting (MIEC) binders based on PEDOT:PSS (PPSS) and PEDOT:PDADMA-TFSI (PPTFSI) for Li-ion cathodes and we compare their performances with conventional formulations containing PVDF binder in Li||LFP cells. Furthermore, the influence of electrode formulations, including addition of conducting carbon (C), to balance the required porosity; and the Organic Ionic Plastic Cristal (OIPC) N-ethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide) (C2mpyrTFSI, O), to promote a synergistic effect of ionic and electronic conductivity enhancement; are analyzed. Finally, the versatility of these proposed binders is demonstrated with graphite||LFP full cells, high-voltage active material (NMC 111) as well as different electrolyte types (from liquid 1M LiTFSI in DOL/DME and ionic liquid based, to solid state membranes) showing the same trends, with improved performances in comparison with conventional formulations.

High-Performance Electrochemical Actuator under an Ultralow Driving Voltage with a Mixed Electronic-Ionic Conductive Metal-Organic Framework.

Although versatile deformation, high flexibility, and environmental friendliness of electrochemical actuators (EAs) have made them promising in bioinspired soft robots and biomedical devices, the relatively high driving voltages unfortunately impose great restrictions on their applications in low-energy and human-friendly electronics. Here, we find that the uses of a mixed electronic-ionic conductive metal-organic framework (c-MOF), i.e., Ni3(hexaiminotriphenylene)2 (Ni3(HITP)2), largely lower the driving voltage of EAs. The as-fabricated EA can work under a driving voltage as low as 0.1 V, representing the lowest value among those for the c-MOF-based EAs reported so far. The Ni3(HITP)2-based EA shows an excellent actuation performance such as a high bending strain difference of 0.48% (±0.5 V, 0.1 Hz) and long-term durability of >99% after 15,000 cycles due to the improved conductivity up to 1000 S·cm-1 and double-layer capacitance as high as 176.3 F·g-1 stemming from the mixed electronic-ionic conduction of Ni3(HITP)2.

Grain morphology‐dependent dielectric and piezoelectric properties of lead‐free KBT ceramics

AbstractK0.5Bi0.5TiO3 ceramics with cuboid (KBT‐C), rod (KBT‐R), and plate (KBT‐P)‐shaped grains were fabricated via solid‐state reaction and reactive template grain growth (using K2Ti6O13 and K0.5Bi4.5Ti4O15) methods, and the strong dependence of electrical properties on the grain morphology was demonstrated. The average grain sizes of KBT‐R, KBT‐P, and KBT‐C were ∼30 ± 10 μm, 7 ± 1 μm, and 350 ± 50 nm, respectively. While the room temperature dielectric constant decreased for KBT‐R (∼240) and KBT‐P (∼230) from ∼500 for KBT‐C, a significant enhancement in the piezoelectric charge coefficient (d33) was noticed for KBT‐R (∼95 pC/N) and KBT‐P (∼105 pC/N) samples compared to that of KBT‐C ceramic (∼60 pC/N). Accordingly, a large improvement in piezoelectric voltage coefficient (g33) of almost 300% in poled KBT‐R (∼45 × 10−3 Vm/N) and 400% in KBT‐P (∼54 × 10−3 Vm/N) samples over the KBT‐C ceramic was obtained. Interestingly, a significantly lower activation energy (Ea) for KBT‐C (∼0.71 eV) below the temperature of the dielectric maximum (Tm) was noticed compared to KBT‐R (∼1.07 eV) and KBT‐P (∼1.00 eV), suggesting a strong dependence of DC conduction on grain morphology. Furthermore, chronoamperometry measurements confirmed a mixed electronic and ionic conduction at higher temperatures in all samples.

Topotactically transformable antiphase boundaries with enhanced ionic conductivity

Engineering lattice defects have emerged as a promising approach to effectively modulate the functionality of devices. Particularly, antiphase boundaries (APBs) as planar defects have been considered major obstacles to optimizing the ionic conductivity of mixed ionic-electronic conductors (MIECs) in solid oxide fuel applications. Here our study identifies topotactically transformable APBs (tt-APBs) at the atomic level and demonstrates that they exhibit higher ionic conductivity at elevated temperatures as compared to perfect domains. In-situ observation at the atomic scale tracks dynamic oxygen migration across these tt-APBs, where the abundant interstitial sites between tetrahedrons facilitate the ionic migration. Furthermore, annealing in an oxidized atmosphere can lead to the formation of interstitial oxygen at these APBs. These pieces of evidence clearly clarify that the tt-APBs can contribute to oxygen conductivity as anion diffusion channels, while the topotactically non-transformable APBs cannot. The topotactic transformability opens the way of defect engineering strategies for improving ionic transportation in MIECs.

THERMODYNAMIC PROPERTIES OF SOME TERNARY COMPOUNDS OF THE ARGYRODITE FAMILY

Compounds of the argyrodite family are valuable environmentally friendly functional materials with mixed ion-electronic conductivity, thermoelectric, photovoltaic, optical, and other properties. This paper presents the results of a thermodynamic study of the Cu8GeS6 and Cu8GeSe6 compounds - representatives of this family using the EMF method with Cu4RbCl3I2 solid electrolyte in the 295-430 K temperature range. From the EMF measurement data, the partial molar functions of copper were calculated in both crystal modifications of the Cu8GeS6 and Cu8GeSe6 compounds, undergoing polymorphic transformations at 330 and 335 K, respectively. Based on solid-phase equilibria diagrams of the Cu-Ge-S(Se) systems, the potential-forming reactions responsible for the partial molar functions of copper in the alloys were determined and the thermodynamic functions of formation and standard entropies of both modifications of these compounds, as well as the thermodynamic functions of their polymorphic transitions, were calculated. The work also presents and analyzes the thermodynamic data for compounds of the argyrodite family available in the literature

Unidirectional Current in Layered Metal Hexacyanometallate Thin Films: Implication for Alternative Wet-Processed Electronic Materials.

Rectifying behavior of alternative electronic materials is demonstrated with layered structures of a crystalline coordination network whose mixed ionic and electronic conductivity can be manipulated by switching the redox state of coordinated transition-metal ions. The coordinated transition-metal ions can convey additional functionality such as (redox)catalysis or electrochromism. In order to obtain rectifying behavior and charge trapping, layered films of such materials are explored. Specifically, layered films of iron hexacyanoruthenate (Fe-HCR) and nickel hexacyanoferrate (Ni-HCF) were formed by the combination of different deposition procedures. They comprise electrodeposition during voltammetric cycles for Fe-HCR and Ni-HCF, layer-by-layer deposition of Ni-HCF without redox chemistry, and drop casting of presynthesized Ni-HCF nanoparticles. The obtained materials were structurally characterized by X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy for nanoparticles, and scanning force microscopy (SFM). Voltammetry in 1 mol L-1 KCl and current-voltage curves (I-V curves) recorded between a conductive SFM tip and the back electrode outside of an electrolyte solution demonstrated charge trapping and rectifying behavior based on the different formal potentials of the redox centers in the films.

Depletion Type Organic Electrochemical Transistors and the Gradual Channel Approximation

AbstractThe gradual channel approximation forms the foundation for the analysis of field‐effect transistors. It has been used to discuss transistors that are not necessarily based on the field‐effect as well, such as the organic electrochemical transistor (OECT). Here, the applicability of the gradual channel approximation for OECTs is studied by a 2D drift‐diffusion model. It is found that OECT switching can be described by two separate effects—a doping/dedoping mechanism and the formation of an electrostatic double layer at the interface between the mixed conductor and the electrolyte. The balance between these two mechanisms is determined by the morphology of the mixed conductor, in particular the question if ions move in the same phase and electric potential as the holes, or if separate ion and hole phases are formed. It is argued that the gradual channel approximation can only be used to describe electrostatic switching at the mixed conductor/electrolyte interface (the two‐phase model), but cannot be employed to analyze devices operating on a doping/de‐doping mechanism (the one‐phase model).

Application of Metal Oxide Nanoparticles in the Field of Potentiometric Sensors: A Review.

Recently, there has been rapid development of electrochemical sensors, and there have been numerous reports in the literature that describe new constructions with improved performance parameters. Undoubtedly, this is due to the fact that those sensors are characterized by very good analytical parameters, and at the same time, they are cheap and easy to use, which distinguishes them from other analytical tools. One of the trends observed in their development is the search for new functional materials. This review focuses on potentiometric sensors designed with the use of various metal oxides. Metal oxides, because of their remarkable properties including high electrical capacity and mixed ion-electron conductivity, have found applications as both sensing layers (e.g., of screen-printing pH sensors) or solid-contact layers and paste components in solid-contact and paste-ion-selective electrodes. All the mentioned applications of metal oxides are described in the scope of the paper. This paper presents a survey on the use of metal oxides in the field of the potentiometry method as both single-component layers and as a component of hybrid materials. Metal oxides are allowed to obtain potentiometric sensors of all-solid-state construction characterized by remarkable analytical parameters. These new types of sensors exhibit properties that are competitive with those of the commonly used conventional electrodes. Different construction solutions and various metal oxides were compared in the scope of this review based on their analytical parameters.

Ion migration mediated high Seebeck effect in halide perovskites and application in infrared detection

Thermoelectric materials play an important role in thermopower systems, thermal sensing and infrared photo-thermoelectric imaging. Ionic thermoelectric materials have recently attracted attentions considering their relatively high Seebeck coefficient. However, the ionic thermoelectric materials have to use liquid or hydrogels for ion conduction, and are susceptible to leakage, evaporation and portability issues. Metal halide perovskites possess low thermal conductivity and prominent ion migration characteristics, making them theoretically suitable candidates for thermoelectric conversion. Here we present the first-ever study of the ionic thermoelectric properties in typical solid perovskite composition MAPbI3, revealing an extremely high Seebeck coefficient of 35.7 mV/K. Furthermore, the assembled photo-thermoelectric detector of carbon/MAPbI3 single crystal/carbon demonstrated a high response (0.58 V/W) toward infrared light and the imaging test was well resolved. This research provides a novel avenue to investigate efficient thermoelectric devices based on ionic and electronic mixed conductors and develop photo-thermoelectric applications.

Carboxyl-Alkyl Functionalized Conjugated Polyelectrolytes for High Performance Organic Electrochemical Transistors.

Contemporary design principles for organic mixed ionic electronic conductors (OMIECs) are mostly based on the ethylene glycol moiety, which may not be representative of the OMIEC class as a whole. Furthermore, glycolated polymers can be difficult to synthesize and process effectively. As an emerging alternative, we present a series of polythiophenes functionalized with a hybrid carboxyl-alkyl side chain. By variation of the alkyl spacer length, a comprehensive evaluation of both the impact of carboxylic acid functionalization and alkyl spacer length was conducted. COOH-functionalization endows the polymer with preferential intrinsic low-swelling behavior and water processability to yield solvent-resistant conjugated polyelectrolytes while retaining substantial electroactivity in aqueous environments. Advanced in situ techniques, including time-resolved spectroelectrochemistry and Raman spectroscopy, are used to interrogate the materials' microstructure, ionic-electronic coupling, and operational stability in devices. To compare these materials' performance to state-of-the-art technology for the design of OMIECs, we benchmarked the materials and demonstrated significant application potential in both planar and interdigitated organic electrochemical transistors (OECTs). The polythiophene bearing carboxyl-butyl side chains exhibits greater electrochemical performance and faster doping kinetics within the polymer series, with a record-high OECT performance among conjugated polyelectrolytes ([μC*]pOECT = 107 ± 4 F cm-1 V-1 s-1). The results provide an enhanced understanding of structure-property relationships for conjugated polyelectrolytes operating in aqueous media and expand the materials options for future OMIEC development. Further, this work demonstrates the potential for conjugated polymers bearing alkyl-COOH side chains as a path toward robust OMIEC designs that may facilitate further facile (bio)chemical functionalization for a range of (bio)sensing applications.

Modulation of electronic and ionic conduction in mixed polymer conductors via additive engineering: Towards targeted applications under varying humidity

Polymer solids with mixed ion and electron transport hold great promise for next-generation organic electronics, and rational regulation of ionic/electronic contribution within these materials can enable a broadened spectrum of practical applications. However, a fundamental understanding of the conduction mechanisms and their correlations with morphological characteristics remains limited, especially under varying environmental humidity conditions. In the present work, simple additive engineering enables the effective regulation of electronic and ionic contribution in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) based conductors, giving rising to ion- and/or electron-dominant conductions. As a demonstration, PEDOT:PSS films with different electrical characteristics are successfully applied for thermal energy harvesting, healthcare monitoring and human motion detection upon humidity exposure. Combining operando alternating current (AC) impedance spectroscopy and grazing incidence small-angle X-ray scattering at low and high humidity levels, additive-dependent charge transport mechanisms are elucidated, and correlations between morphological alterations and conductivity evolutions are revealed. This work achieves highly tailorable PEDOT:PSS conduction utilizing Zonyl, dimethyl sulfoxide (DMSO) and carbon nanotubes (CNTs) as additives with distinct humidity responses and gains an in-depth comprehension of underlying mechanisms, which are expected to pave the way for next-generation organic electronics.

Crystallography Analysis on LSCF and LSM-based Perovskite Oxides

Perovskite oxide as a metal oxide offers an excellence on mixed ionic and electronic conductor (MIEC) properties which work simultaneously. The crystal structure of perovskite oxide plays the important role to achieve the superior performance. Generally, it formed a cubic which potentially distorted due to the ratio of metal ion constituents, the calcination temperature and the synthesis method used. Thus, this study presents chemical analysis of La0.7Sr0.3Co0.2Fe0.8O3-δ (LSCF) and La0.7Sr0.3MnO3-δ (LSM)-based perovskite oxides through crystallographic identification using Rietveld Refinement method (Rietica software) and material porosity analysis. The results show that the two types of perovskite oxide have different distorted crystal structures. Perovskite oxide LSCF produces hexagonal crystals and 63.98% rhombohedral dominance, while LSM remained significantly different from LSCF. LSM consist less hexagonal and 55.47% cubic structure. In addition, the pore characteristics indicate that macropores and pore volumes are more abundant in LSCF than LSM. This information can be used as a basis for the use of oxide materials as a separator of oxygen ions from the air, solid oxide fuel cells and catalyst for value-added chemical production from methane flue gas.

Identifiability of the mechanisms governing the reaction kinetics of MIEC electrodes in solid oxide cells

The oxygen reduction reaction (ORR) is the main phenomenon occurring in mixed ionic and electronic conductors (MIECs) used as air electrodes in solid oxide cells. Their optimisation requires the identification of the ORR regime, which is typically performed via electrochemical impedance spectroscopy (EIS). In this study we present a physics-based model to simulate the impedance spectra of p-type oxygen-deficient perovskite MIEC materials. The EIS response of four extreme kinetic scenarios, characterised by the rate-determining step (electron-transfer or ion-transfer) and the high/low surface coverage of adsorbed oxygen, is mechanistically interpreted for both dense films and porous electrodes. A strategy for kinetic identification is proposed based on distinctive EIS fingerprints at different oxygen partial pressures (pO2) and cathodic bias. However, distinguishing the kinetic scenarios is not free from ambiguity even in dense films since some scenarios are discriminated only via a quantitative analysis, which may be susceptible to experimental errors in real measurements, and reverse behaviours appear when combining cathodic bias with pO2 variation. More difficulties arise in porous electrodes since bulk oxygen vacancy transport interacts with the ORR response. Application of the proposed strategy using literature data for some common MIEC materials shows the typical challenges of kinetic identification when relying solely on EIS.

The Role of Surface Coating in P’2‐Na0.67Mn0.67Ni0.33O2: Enhancing Capacity and Stability of Layered Cathodes for Sodium‐ion Batteries

AbstractP’2‐Na0.67Mn0.67Ni0.33O2 (NMNO) is one of the most promising cathodic materials for new generation sodium‐ion batteries (SIBs). One drawback that is preventing its commercialization is however the high instability in the potential window 2.5–4.5 V vs. Na+/Na, caused by degradation reactions affecting the material's structure and composition. Herein we propose a strategy to overcome this weak spot introducing the surface coating of the material particles with inert magnesium oxide, that has been chosen as coating agent because of its low molecular weight. This protective layer is able to reduce the structural instability of the material without modifying the mixed conduction properties and thus globally stabilizing the electrochemical performances. In fact, the electrode of NMNO coated with 7 % of MgO, after an initial stabilization, was able to deliver over 90 mAh g−1 of reversible specific capacity at a current value of 50 mA g−1, with a capacity retention of 70 % after 250 cycles, to be compared with the 30 mAh g−1 of the uncoated material. The effect of the coating on the particles surface is here investigated with differential electrochemical mass spectrometry, to analyze the influence of the treatment on the electrode/electrolyte interphase.