SEARCH · Search NASA
Results for “electronic conductivity”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Factors Affecting the Electron Conductivity in Single Crystal Li 7 La 3 Zr 2 O 12 and Li 7 P 3 S 11
One of the serious challenges in all solid-state Li ion batteries is neutral Li intrusion into the solid-state electrolyte that can ultimately cause catastrophic failure. One possibility for this is due to n-type electron conductivity that induces the reaction Li + + e – → Li 0 at sites where the potential is less than the Li + /Li potential. This paper reports hybrid density functional theory calculations of the electronic conductivity in two prototype single crystalline solid-state electrolytes, cubic Li 7 La 3 Zr 2 O 12 (c-LLZO) and Li 7 P 3 S 11 (LPS). The formation energies of important point defects that can affect electron conductivity are determined, and we find that the mechanism of n-type electron conductivity for both solid-state electrolytes is via “small” electron polaron hopping, where the quotes signify that substantial Li ion rearrangement is associated with the polaron formation and its migration. In both electrolytes, the formation energies for the small polarons at the Fermi energy are too high to generate measurable electron conductivity at room temperature. For c-LLZO, the concentration of electron polarons necessary to ensure charge neutrality from positively charged oxygen vacancies formed in synthesis can be significantly higher. Hence, the electron conductivity could be significant when measured with ion-blocking metal electrodes, and we discuss how the synthesis conditions could affect this magnitude. However, in the solid-state battery, these polarons are replaced by negatively charged Li vacancies so that the electron conductivity should remain minimal. For LPS single crystals, the inherent minimal electron conductivity is independent of synthesis conditions. Here we also show that the cost of forming Li 0 in bulk c-LLZO is enormous due to strain effects so that it could only potentially form at voids, grain boundaries, or around vacancy defects which relax the lattice strain.
Implementing the donor–acceptor approach in electronically conducting copolymers via electropolymerization
Electropolymerization has become a convenient method for synthesizing and characterizing complex organic copolymers having intrinsic electronic conductivity, including the donor (D)–acceptor (A) class of electronically conducting polymers (ECPs). This review begins with an introduction to the electrosynthesis of common second-generation ECPs. The information obtainable from electroanalytical studies, charge carriers such as polarons (positive and negative) and bipolarons (positive and negative) and doping will be discussed. The evolutionary chain of ECPs is then presented. ECPs comprising electron-rich D and electron-deficient A moieties have been shown to possess intrinsic electronic conductivity and unique optical and electronic properties. They are third generation ECPs and electropolymerization of mixtures of D and A leads to stoichiometrically controlled block copolymers. These D–A type ECPs are discussed on the basis of selected representative materials. Since the discovery of electropolymerization as a powerful tool to synthesize copolymers of conjugated monomers with a pre-determined ratio of D and A repeat units present in the polymer, the field of D–A type ECPs has grown considerably and the literature available since 2004 to 2021 is summarized and tabulated. Electronic and optical properties of the materials determined by computational chemistry are presented. The data obtained from electrochemical and optical methods are compared with those obtained from computational methods and reasons for discrepancies are given. The literature on the concept of electropolymerization extended to synthesizing triblock and many-block copolymers is reviewed. Finally, applications of D–A polymers in optoelectronic devices (organic solar cells and field-effect transistors) and in bio-imaging are explained quoting appropriate examples.
Investigating Electron Conductivity Regimes in the Bacterial Cytochrome Wire OmcS
The anaerobic bacterium Geobacter sulfurreducens produces extracellular, electronically conductive cytochrome polymer wires that are conductive over micron length scales. Structure models from cryo-electron microscopy data show OmcS wires form a linear chain of hemes along the protein wire axis, which is proposed as the structural basis supporting their electronic properties. However, the mechanism by which this heme arrangement supports long-range electronic conduction remains unknown. Structure models from cryo-electron microscopy data show these wires form a linear chain of hemes along the protein wire axis, which is proposed as the structural basis supporting their electronic properties. Existing computational models using static heme redox potentials and coupling energies fail to explain experimental observations, predicting conductances 10,000 to 100,000 times lower than measured values. Here, we investigate how dynamic disorder affects site energies, interheme coupling, and long-range electronic conductivity within these cytochrome wires. We introduce an approach to extract charge carrier site information directly from Kohn–Sham density functional theory, without employing projector schemes, and show that site and coupling energies are highly sensitive to changes in interheme geometry and the surrounding electrostatic environment. Unlike models that incorporate dynamic disorder as a thermally averaged quantity, our quantum charge carrier model incorporates proxies for dynamic disorder through decoherence corrections, yielding predicted diffusion coefficient closer to what is expected from experiment and comparable with other organic-based electronic materials. Based on these simulations, we propose that the instantaneous fluctuations of the local electrostatic environment can transiently lift energy degeneracies and delocalize charge carriers. Furthermore, these studies reveal how incorporating dynamic fluctuations associated with the environment resolves the discrepancy between theory and experiment in microbial cytochrome wires and highlight design principles for bioinspired, heme-based conductive materials.
Roadmap for Sustainable Mixed Ionic–Electronic Conducting Membranes
Mixed ionic-electronic conducting (MIEC) membranes have gained growing interest recently for various promising environmental and energy applications, such as H 2 and O 2 production, CO 2 reduction, O 2 and H 2 separation, CO 2 separation, membrane reactors for production of chemicals, cathode development for solid oxide fuel cells, solar-driven evaporation and energy-saving regeneration as well as electrolyzer cells for power-to-X technologies. The purpose of this roadmap, written by international specialists in their fields, is to present a snapshot of the state-of-the-art, and provide opinions on the future challenges and opportunities in this complex multidisciplinary research field. As the fundamentals of using MIEC membranes for various applications become increasingly challenging tasks, particularly in view of the growing interdisciplinary nature of this field, a better understanding of the underlying physical and chemical processes is also crucial to enable the career advancement of the next generation of researchers. As an integrated and combined article, it is hoped that this roadmap, covering all these aspects, will be informative to support further progress in academics as well as in the industry-oriented research toward commercialization of MIEC membranes for different applications.
Understanding Chemo-Mechanical Stability of Protonic Ceramic Cells Through Electronic Conduction in the BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Electrolyte
BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ (BCZYYb) is a promising ceramic electrolyte for reversible protonic ceramic cells. It is reported that BCZYYb-based cells show excellent long-term durability, particularly in the electrolysis mode, in contrast to the cells based on the conventional electrolyte yttria-stabilized zirconia. In this study, we investigate the chemo-mechanical stability behavior (a low tendency of delamination) of the BCZYYb-based protonic ceramic cells in terms of local electronic conduction in the electrolyte. The local electronic conductivity of the BCZYYb electrolyte is determined using Pt-probe-embedded cells near each electrode interface. The BCZYYb electrolyte exhibits sufficient p-type conductivity (∼10 −3 S cm −1 ) near the oxygen electrode (corresponding p O 2 : 5.27–21 × 10 −2 atm) and n-type conductivity (∼10 −4 S cm −1 ) near the hydrogen electrode (corresponding p O 2 : 0.99–1.30 × 10 −24 atm) at 600 °C. A standard cell is prepared and tested over long-term in the fuel cell (at positive and negative voltages) and electrolysis modes. The cell exhibits stable performance without delamination or cracks in both operating modes, owing to local electronic conduction.
Mixed Ionic Electronic Conducting Quaternary Perovskites: Materials by Design for Solar Thermochemical Hydrogen
The innovative research conducted by Arizona State University and Princeton University in the project "Mixed Ionic-Electronic Conducting Quaternary Perovskites: Materials by Design for Solar Thermochemical Hydrogen" marks a significant stride forward in thermochemical water splitting. Through an intricate blend of computational design and experimental validation, the project delved into the promising potential of Mixed Ionic Electronic Conducting (MIEC) perovskites. These complex materials, characterized by their unique redox-active nature and adaptability in stoichiometry, present a promising frontier for efficient solar thermochemical hydrogen production. Firstly, the research enhanced the science by utilizing state-of-the-art computational methodologies to unravel the nuanced chemical potentials of MIEC perovskites. By simulating various off-stoichiometric scenarios and redox conditions, the team was able to predict material behaviors under diverse environmental conditions, a feat unachievable through conventional experimental methodologies alone. This approach not only fast-tracks the material screening process, significantly reducing the time from laboratory re-search to practical application, but also uncovers trends and correlations that are pivotal for future materials innovation. Regarding technical effectiveness, the project stands out in its economic feasibility. Traditional methods of materials discovery are often marred by high costs and extensive timeframes, owing to the iterative nature of experimental processes. However, by employing theoretical computations and validating these findings with targeted experiments, the project introduced a cost-effective paradigm for materials discovery and the first ever prediction, synthesis, and preliminary validation of a material solely from computational and theoretical considerations. This synergy between computation and experimentation expedites the discovery of optimal materials conducive to high-efficiency solar-to-hydrogen conversion processes. Furthermore, the public stands to benefit substantially from this research. The success of MIEC perovskites in solar thermochemical applications heralds a shift towards lower cost and lower electricity input for clean hydrogen production, hence potentially impacting climate and energy resilience. By improving the efficiency of solar-to-hydrogen conversions, the research paves the way for reduced dependency on fossil fuels, addressing the urgent global need for accessible and renewable energy sources. Moreover, the project's advancements contribute to scientific literacy in renewable energy technologies, empowering society through knowledge and spurring future innovations. In essence, this research project demonstrates significant progress in the realm of advanced water splitting through solar thermochemistry. Through its groundbreaking approaches in computational materials science and its implications for real-world applications, it holds the promise of a cleaner, more energy-resilient future.
Method of forming electronically conducting polymers on conducting and nonconducting substrates
The present invention provides electronically conducting polymer films formed from photosensitive formulations of pyrrole and an electron acceptor that have been selectively exposed to UV light, laser light, or electron beams. The formulations may include photoinitiators, flexibilizers, solvents and the like. These solutions can be used in applications including printed circuit boards and through-hole plating and enable direct metallization processes on non-conducting substrates. After forming the conductive polymer patterns, a printed wiring board can be formed by sensitizing the polymer with palladium and electrolytically depositing copper.
Electronically conducting polymers with silver grains
The present invention provides electronically conducting polymer films formed from photosensitive formulations of pyrrole and an electron acceptor that have been selectively exposed to UV light, laser light, or electron beams. The formulations may include photoinitiators, flexibilizers, solvents and the like. These solutions can be used in applications including printed circuit boards and through-hole plating and enable direct metallization processes on non-conducting substrates. After forming the conductive polymer patterns, a printed wiring board can be formed by sensitizing the polymer with palladium and electrolytically depositing copper.
Electronic conductivity in metal-graphene composites: the role of disordered carbon structures, defects, and impurities
Abstract This paper explores the transport properties of aluminum-carbon composite material via ab initio methods. Interfacial and electronic dynamics of the aluminum-graphene interface structure were investigated using models of amorphous graphene added to an aluminum matrix. We examine the impact on electronic conduction caused by the presence of nitrogen impurities within the interfacial amorphous graphene layer. We elucidate the conduction mechanisms by using a projection of the electronic conductivity into space.
Mitigating Electronic Conduction in Ceria‐Based Electrolytes via External Structure Design
Doped ceria electrolytes are the state of the art low‐temperature solid oxide electrolytes because of their high ionic conductivity and good material compatibility. However, cerium tends to reduce once exposed to reducing environments, leading to an increase in electronic conduction and a decrease in efficiency. Here, the leakage current is mitigated in ceria‐based electrolytes by controlling the defect chemistry through an engineered cathode side microstructure. This functional layer effectively addresses the problematic electronic conduction issue in ceria‐based electrolytes without adding significant ohmic resistance and increases the ionic transference number to over 0.93 in a thin 20 µm ceria‐based electrolyte at 500 °C, compared to a of 0.8 for an unmodified one. Based on this design, solid oxide fuel cells (SOFCs) are further demonstrated with the remarkable peak power density of 550 mW at 500 °C and excellent stability for over 2000 h. This approach enables a potential breakthrough in the development of ceria‐based low‐temperature solid oxide electrolytes.
Circularly Polarized Light-Induced Microwave Conductivity Measurement: Rapid Screening Technique of Electronic Conductivity in Chiral Molecular Materials
Here, we developed circularly polarized light-time-resolved microwave conductivity (CPL-TRMC) for investigation of the CPL-dependent photoinduced charge carrier dynamics in chiral materials with chiroptical properties. Chiral R- or S-perylenediimide (PDI) molecular thin films were paired with handedness-sorted (6,5) and (11,-5) single-walled carbon nanotube (SWCNT) films to compose a donor (D)-acceptor (A) system for the spin-dependent charge separation process, and the D-A system was examined through linear and circular polarization-dependent steady-state and time-resolved measurements. The R-PDI-(6,5) film exhibited strong enhancement in circular dichroism (CD) and revealed a reversed transient conductivity signal, relative to the polarity of CD in CPL-TRMC measurement upon excitation of the E 11 state, which is interpreted as arising from a spin-dependent initial charge separation process. Through linear polarization-dependent flash photolysis TRMC and circular polarization-resolved femtosecond transient absorption, we could deduce that sub-picosecond intertubular charge separation upon E 11 excitation in SWCNT was responsible for the spin-dependent photoconductivity transients observed in CPL-TRMC measurements.
Correlation among porosity, mechanical properties, morphology, electronic conductivity and electrochemical kinetics of dry-processed electrodes
Dry processing (DP) has received great interest recently, which poses many advantages over the conventional slurry-based processing. Here, this work investigates the effect of compression on electrode mechanical properties, morphology, electronic conductivity, and electrochemical kinetics. Similar to the slurry-based electrodes, LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC) cathodes with intermediate porosity (i.e., 32%) demonstrate lowest charge transfer resistance, highest electronic conductivity and best rate performance. Fracture of NMC secondary particles is observed in the dry processed NMC cathodes. Reducing electrode porosity results in more fracture in the NMC secondary particles.
Exploring the Role of Humidity, Temperature, and Mixed Ionic and Electronic Conductivity on SOFC Anode Electrocatalysis
Infiltration of nanoscale electrocatalysts into Ni/yttria-stabilized zirconia (Ni-YSZ) cermets has been shown to improve the electrochemical performance of solid oxide fuel cell (SOFC) anodes. While infiltrated electrodes in SOFCs result in improved cell performance, long-term operation leads to coarsening of the infiltrated nanoparticles and negates the short-term performance improvements. This study explores the roles of humidity, temperature, and number of cycles of nanocatalyst infiltration in improving mixed conduction within the Ni-YSZ electrode. Two mixed conduction phases were studied: Gd 0.1 Ce 0.9 O 2-δ (GDC) as an infiltrant into Ni-YSZ electrodes, and Ni/transition metal doped-YSZ electrodes infiltrated with Ni. Analysis of impedance data from these cells shows improved electrochemical performance in infiltrated cells with mixed conduction compared with infiltrated cells containing purely ionic and electronic conducting phases. Improved anode performance is attributed to the availability of electronic pathways through predominantly ionic-conducting phases to connect distant Ni nanoparticles and/or Ni grains.
Understanding metal propagation in solid electrolytes due to mixed ionic-electronic conduction
Metal penetration into a solid electrolyte (SE) is one of the critical problems impeding the practical application of solid-state batteries. In this study, we investigate the conditions under which electronic conductivity of the SE can lead to metal deposition and fracture within the SE. Three different stages for void filling (metal plating initiation, metal growth, and metal compression) in the SE are identified. We show that a micron-size isolated void in the SE near the anode can be quickly filled in by metal and fractured when the developed pressure in the void grows larger than the maximum pressure the SE material can sustain. We find that the anode voltage and applied current density play a significant role in determining the vulnerability to metal deposition. We discuss several strategies to prevent electronic conductivity-driven metal propagation in electrolytes that are not fully dense, including the densified layers between the anode and SE.
ELECTRON CONDUCTIVITY AT CYCLOTRON RESONANCE
Two distribution functions in the investigation of electron conductivity in a plasma at cyclotron resonance
Mixed ionic-electronic conductivity of high-nickel, single-crystal cathodes influencing the cycling stability of all-solid-state lithium-ion batteries
Removing cobalt lowers the electronic conductivity of high-nickel cathodes. A mismatch between electronic and ionic conductivities in the cathode composite leads to reaction inhomogeneity and peculiar cycling behavior in all-solid-state batteries.