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At least 145 records · Page 8

Development of an Accelerated Test Method for the Determination of Susceptibility to Atmospheric Corrosion

The theoretical rationale is presented for use of a repetitive cyclic current reversal voltammetric technique for characterization of localized corrosion processes, including atmospheric corrosion. Applicability of this proposed experimental protocol is applied to characterization of susceptibility to crevice and pitting corrosion, atmospheric corrosion and stress corrosion cracking. Criteria upon which relative susceptibility is based were determined and tested using two iron based alloys commonly in use at NASA-Kennedy; A36 (a low carbon steel) and 4130 (a low alloy steel). Practicality of the procedure was demonstrated by measuring changes in anodic polarization behavior during high frequency current reversal cycles of 25 cycles per second with 1 mA/sq cm current density amplitude in solutions containing Cl anions. The results demonstrated that, due to excessive polarization which affects conductivity of barrier corrosion product layers, A36 was less resistant to atmospheric corrosion than its 4130 counterpart; behavior which was also demonstrated during exposure tests.

Ambrose, John R.↗

The corrosion protection of 2219-T87 aluminum by organic and inorganic zinc-rich primers

The behavior of zinc-rich primer-coated 2219-T87 aluminum in a 3.5-percent Na-Cl was investigated using electrochemical techniques. The alternating current (ac) method of electro-chemical impedance spectroscopy (EIS), in the frequency range of 0.001 to 40,000 Hz, and the direct current (dc) method of polarization resistance (PR) were used to evaluate the characteristics of an organic, epoxy zinc-rich primer and an inorganic, ethyl silicate zinc-rich primer. A dc electrochemical galvanic corrosion test was also used to determine the corrosion current of each zinc-rich primer anode coupled to a 2219-T87 aluminum cathode. Duration of the EIS/PR and galvanic testing was 21 days and 24 h, respectively. the galvanic test results demonstrated a very high galvanic current between the aluminum cathode and both zinc-rich primer anodes (37.9 micro A/cm(exp 2) and 23.7 micro A/cm(exp 2) for the organic and inorganic primers, respectively). The PR results demonstrated a much higher corrosion rate of the zinc in the inorganic primer than in the organic primer, due primarily to the higher porosity in the former. Based on this investigation, the inorganic zinc-rich primer appears to provide superior galvanic protection and is recommended for additional study for application in the solid rocket booster aft skirt.

Danford, M. D.↗

The corrosion protection of AISI(TM) 1010 steel by organic and inorganic zinc-rich primers

The behavior of zinc-rich primer-coated AISI 1010 steel in 3.5-percent Na-Cl was investigated using electrochemical techniques. The alternating current (ac) method of electrochemical impedance spectroscopy (EIS), in the frequency range of 0.001 to 40,000 Hz, and the direct current (dc) method of polarization resistance (PR), were used to evaluate the characteristics of an organic, epoxy zinc-rich primer and an inorganic, ethyl silicate zinc-rich primer. A dc electromechanical galvanic corrosion test was also used to determine the corrosion current of each zinc-rich primer anode coupled to a 1010 steel cathode. Duration of the EIS/PR and galvanic testing was 21 days and 24 h, respectively. The galvanic test results demonstrated a very high current between the steel cathode and both zinc-rich primer anodes (38.8 and 135.2 microns A/sq cm for the organic and inorganic primers, respectively). The results of corrosion rate determinations demonstrated a much higher corrosion rate of the zinc in the inorganic primer than in the organic primer, due primarily to the higher porosity in the former. EIS equivalent circuit parameters confirmed this conclusion. Based on this investigation, the inorganic zinc-rich primer appears to provide superior galvanic protection and is recommended for additional study for application on solid rocket booster steel hardware.

Danford, M. D.↗

The Corrosion Protection of 2219-T87 Aluminum by Organic and Inorganic Zinc-Rich Primers

The behavior of zinc-rich primer-coated 2219-T87 aluminum in a 3.5-percent Na-Cl was investigated using electrochemical techniques. The alternating current (ac) method of electrochemical impedance spectroscopy (EIS), in the frequency range of 0.001 to 40,000 Hz, and the direct current (dc) method of polarization resistance (PR) were used to evaluate the characteristics of an organic, epoxy zinc-rich primer and an inorganic, ethyl silicate zinc-rich primer. A dc electrochemical galvanic corrosion test was also used to determine the corrosion current of each zinc-rich primer anode coupled to a 2219-T87 aluminum cathode. Duration of the EIS/PR and galvanic testing was 21 days and 24 h, respectively. The galvanic test results demonstrated a very high galvanic current between the aluminum cathode and both zinc-rich primer anodes (37.9 pA/CM2 and 23.7 pA/CM2 for the organic and inorganic primers, respectively). The PR results demonstrated a much higher corrosion rate of the zinc in the inorganic primer than in the organic primer, due primarily to the higher porosity in the former. Based on this investigation, the inorganic zinc-rich primer appears to provide superior galvanic protection and is recommended for additional study for application in the solid rocket booster aft skirt.

Danford, M. D.↗

RHETT/EPDM Flight Hollow Cathode

Under the sponsorship of the BMDO Russian Hall Electric Thruster Technology program two xenon hollow cathodes, a flight unit and a flight spare were fabricated, acceptance tested and delivered to the Naval Research Laboratory for use on the Electric Propulsion Demonstration Module. These hollow cathodes, based on the International Space Station plasma contactor design, were fabricated at the NASA Lewis Research Center for use with a D-55 anode layer thruster in the first on-orbit operational application of this technology. The 2.2 Ampere nominal emission current of this device was obtained with a xenon flow rate of 0.6 mg/s. Ignition of the cathode discharge was accomplished through preheating the active electron emitter with a resistive heating element before application of a 650 volt ignition pulse between the emitter and an external starting electrode. The successful acceptance testing of the Electric Propulsion Demonstration Module utilizing these cathodes demonstrated the suitability of cathodes based on barium impregnated inserts in an enclosed keeper configuration for use with Hall thruster propulsion systems.

Manzella, David↗

Visualizing diverse lithium growth and stripping behaviors in anode-free solid-state batteries with operando X-ray tomography

Anode-free solid-state batteries (SSBs), which eliminate the need for lithium metal use during cell assembly, have the potential to enable high energy densities and simplified manufacturing. However, the factors that control lithium growth/stripping at the anode current collector are not well understood. Here, we use operando X-ray microcomputed tomography to comprehensively image and quantify lithium deposition and stripping under various conditions in three different Li|Li 6 PS 5 Cl|current collector cells, revealing diverse behavior that depends on interface morphology, cell resistance, and solid-state electrolyte (SSE) microstructure. A cell with high resistance exhibits extensive lithium filament growth across the entire current collector interface, with filaments that grow around pre-existing pores in the SSE rather than lithium filling these pores. Lithium filament formation is partially reversible, with the cracks shrinking as lithium metal is stripped. Uniform lithium deposition is achievable at low current densities in low-resistance cells, whereas higher current densities in these cells cause an increase in interfacial roughness, which is correlated with subsequent filamentary growth at the edges of the cell. These results provide insight into filamentary vs. planar lithium growth and highlight that the evolution of lithium is sensitively dependent on SSE microstructure and electrochemical processes.

25 ENERGY STORAGE↗

Response of composite materials to the Space Station orbit environment

The rationale for selecting composite materials with an anodized aluminum foil coating for the Space Station is presented. Data on the effects of the space service environment on these materials are given. Results are also presented on the effect of optical properties of an aluminum/aluminum oxide coating on the thermal balance of the cylindrical structural members. The resistance of this coating to solar ultraviolet degradation is discussed.

Tompkins, S. S.↗

Hydroxide Exchange Membrane Carbon Capture (HEMCC) Using Nickel Hydroxide Batteries and Flow-through Membranes

Proposed is an electrochemical nickel hydroxide based hydroxide exchange membrane carbon capture (HEMCC) device for Direct Air Capture (DAC) of CO2. DAC has been identified as one of the key net negative carbon technologies to achieve net zero carbon emissions. Net negative carbon technologies are required to offset continued emissions from dilute CO2 sources such as agriculture and construction. The majority of current DAC technologies at scale (>1 KT∙yr-1) are adsorbent based technologies with significant energy cost. The traditional DAC energy cost is primarily driven by the temperature swing required to regenerate the sorbent and has been shown to be 1.8 MWh·ton-1 at the system level. Electrochemical pH swing devices are a growing research area for carbon capture devices with the goal of lowering the energy cost required for DAC. A pH gradient is built by generating OH- at the cathode and consuming OH- at the anode. An acid-base equilibrium with CO2 allows for the capture of CO2 at the cathode and release at the anode. This extends from other electrochemical CO2 capture devices based on pKa shifts of an electrochemically active organic species allowing for the capture and release of CO2. Electrochemical CO2 capture is considered promising based on potentially low energy costs to capture CO2 in comparison with current temperature swing adsorption technologies. This work explores Ni(OH)2 electrodes to produce the pH gradient for CO2 capture and release. At the cathode NiOOH is reduced to Ni(OH)2 while at the anode Ni(OH)2 is oxidized to NiOOH. The symmetrical electrodes allow for a low voltage requirement; the thermodynamic potential difference of standard electrochemical reactions is zero. Most of the voltage observed is to produce the pH gradient with the remainder driving the polarization of the electrodes. There is a resistance component as well, but this is small in comparison due to the low current densities used in the device, nominally 2 mA·cm-1. Two similar devices are presented, a traditional MEA (membrane electrode assembly) and a flow-through MEA. The traditional MEA separates the two Ni(OH)2 electrodes with an 80μm Piperion® membrane. While the flow-through membrane separates the electrodes with a three piece membrane consisting of two 80μm Piperion® membranes with a porous membrane between them. In the traditional MEA system air is passed over the cathode for capture, while the flow-through MEA the air is passed through the porous membrane isolated from the electrodes. The traditional MEA has been used to establish a baseline performance of the device and has been shown to capture CO2 at an energy cost of 1 MWh·ton-1 at the device level. An understanding has been built around the components of that energy cost including the relationship of flux to current density, effect of a regeneration process, transient battery behavior, and gas losses coinciding with changing the polarization of the batteries. The flow-through MEA looks to address of transient battery behavior and gas losses. It allows for denser, higher capacity electrodes, which can lean on traditional Ni-MH battery technology used in alkaline batteries used today. The higher capacities, limit the transient battery effect on flux in the device. Gas losses are addressed by having a continuous inlet air stream to the device and continuous outlet product.

Buchen, James↗

Double-injection, deep-impurity switch development

The overall objective of this program is the development of device design and process techniques for the fabrication of a double-injection, deep-impurity (DI)(2) silicon switch that operates in the 1-10 kV range with conduction current of 10 and 1A, respectively. Other major specifications include a holding voltage of 0 to 5 volts at 1 A anode current, 10 microsecond switching time, and power dissipation of 50 W at 75 C. This report describes work that shows how the results obtained at the University of Cincinnati under NASA Grant NSG-3022 have been applied to larger area and higher voltage devices. The investigations include theoretical, analytical, and experimental studies of device design and processing. Methods to introduce deep levels, such as Au diffusion and electron irradiation, have been carried out to "pin down' the Fermi level and control device-switching characteristics. Different anode, cathode, and gate configurations are presented. Techniques to control the surface electric field of planar structures used for (DI)(2) switches are examined. Various sections of this report describe the device design, wafer-processing techniques, and various measurements which include ac and dc characteristics, 4-point probe, and spreading resistance.

Selim, F. A.↗

Engineering Model Propellant Feed System Development for an Iodine Hall Thruster Demonstration Mission

CUBESATS are relatively new spacecraft platforms that are typically deployed from a launch vehicle as a secondary payload, providing low-cost access to space for a wide range of end-users. These satellites are comprised of building blocks having dimensions of 10x10x10 cu cm and a mass of 1.33 kg (a 1-U size). While providing low-cost access to space, a major operational limitation is the lack of a propulsion system that can fit within a CubeSat and is capable of executing high (Delta)v maneuvers. This makes it difficult to use CubeSats on missions requiring certain types of maneuvers (i.e. formation flying, spacecraft rendezvous). Recently, work has been performed investigating the use of iodine as a propellant for Hall-effect thrusters (HETs) 2 that could subsequently be used to provide a high specific impulse path to CubeSat propulsion. 3, 4 Iodine stores as a dense solid at very low pressures, making it acceptable as a propellant on a secondary payload. It has exceptionally high ρIsp (density times specific impulse), making it an enabling technology for small satellite near-term applications and providing the potential for systems-level advantages over mid-term high power electric propulsion options. Iodine flow can also be thermally regulated, subliming at relatively low temperature (< 100 C) to yield I2 vapor at or below 50 torr. At low power, the measured performance of an iodine-fed HET is very similar to that of a state-of-the-art xenon-fed thruster. Just as importantly, the current-voltage discharge characteristics of low power iodine-fed and xenon-fed thrusters are remarkably similar, potentially reducing development and qualifications costs by making it possible to use an already-qualified xenon-HET PPU in an iodine-fed system. Finally, a cold surface can be installed in a vacuum test chamber on which expended iodine propellant can deposit. In addition, the temperature doesn't have to be extremely cold to maintain a low vapor pressure in the vacuum chamber (it is under 10(exp −6) torr at −75 C), making it possible to 'cryopump' the propellant with lower-cost recirculating refrigerant-based systems as opposed to using liquid nitrogen or low temperature gaseous helium cryopanels. In the present paper, we describe the design and testing of the engineering model propellant feed system for iSAT (see Fig. 1). The feed system is based around an iodine propellant reservoir and two proportional control valves (PFCVs) that meter the iodine flow to the cathode and anode. The flow is split upstream of the PFCVs to both components can be fed from a common reservoir. Testing of the reservoir is reported to demonstrate that the design is capable of delivering the required propellant flow rates to operate the thruster. The tubing and reservoir are fabricated from hastelloy to resist corrosion by the heated gaseous iodine propellant. The reservoir, tubing, and PFCVs are heated to ensure the sublimed propellant will not re-deposit within the feed system. Heating is accomplished through a number of individual zones to control the overall power expended on heating the system and insulation is employed to minimize the amount of power used to heat the system prior to thruster operation.

Polzin, Kurt A.↗

Resistive Switching of Spinel Li 4 Ti 5 O 12 Lithium-Ion Battery Material for Neuromorphic Computing

The rapid rise of AI has exposed significant limitations in conventional Von Neumann computing architecture, particularly in regard to speed and energy efficiency. To address these challenges, researchers are exploring a brain-inspired neuromorphic architecture that mimics biological neural networks, enabling massive parallel processing with reduced power consumption for complex AI computational demands. Recent interest has focused on utilizing battery electrodes and solid electrolyte materials for their resistive switching properties in developing a neuromorphic architecture. These properties are precisely tuned through local- and bulk-level chemical composition modifications via voltage bias stimuli. In this study, we demonstrate fabricating a three-terminal lithium-ion electrochemical transistor based on lithium titanium oxide (Li 4 Ti 5 O 12 ), a popular lithium-ion battery anode material. We deposited and characterized LTO thin films using RF sputtering, demonstrating a 6 orders of magnitude increase in electronic conductivity upon lithiation, with conductivity plateauing after 20% lithiation. Density functional theory calculations revealed transformation from the insulating to conducting state, supported by experimental characterization through X-Ray Photoelectron Spectroscopy (XPS) and Direct Current (DC) polarization analyses. The fabricated transistor consisted of LTO as the channel layer, gold as source/drain terminals, lithium phosphorus oxynitride (LiPON) as the lithium-ion conductor, and copper as the gate terminal. The device exhibited clear hysteresis in transfer characteristics due to lithium insertion/extraction processes. Long-term potentiation (LTP) and long-term depression (LTD) measurements showed an asymmetric ratio of 1.425 and maximum/minimum conductance ratio of 7.83. When implemented in a deep neural network (DNN) for MNIST handwritten digit recognition, the device achieved 92.03% accuracy over 20 training epochs. Detailed transport mechanism analysis revealed the crucial role of oxygen vacancies and interface effects in device operation. Our preliminary findings establish LTO-based lithium-ion electrochemical transistors as promising candidates for energy-efficient neuromorphic computing applications, offering potential solutions to traditional Von Neumann architecture limitations.

25 ENERGY STORAGE↗

Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment

Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.

36 MATERIALS SCIENCE↗

Electrochemical Conversion of CO 2 to Methyl Formate in a Flow Electrolyzer with Mixed Propylene Carbonate/Methanol Catholyte

Despite the promise of electrochemical carbon dioxide reduction as a technology for the production of clean fuels and decarbonization of the chemical industry, research has mostly focused on aqueous systems with a relatively limited set of products that have been achieved via electrosynthesis. Increasingly, CO 2 electroreduction in nonaqueous solvents is being pursued to develop new avenues for expanding the suite of products that can be made with high selectivity. CO 2 reduction in alcohols coupled with in situ esterification to produce esters is one such route that utilizes nonaqueous electrolyte. To be practical, such electrochemical syntheses need to be translated to a high-performance reactor such as a flow electrolyzer. However, many organic solvents, such as alcohols, wet and flood porous electrodes, thus impeding reactor performance. In this work, methanol was mixed with propylene carbonate as a catholyte for a gas-fed CO 2 flow electrolyzer that avoided cathode flooding. Simultaneously, a dual aqueous anolyte was used for water oxidation as a scalable and sustainable anodic half-reaction. The performance effect of methanol concentration, catholyte acidity, CO 2 flow rate, and dilute water in the catholyte were investigated. With 10 vol % methanol in 90 vol % propylene carbonate, 63% faradaic efficiency for methyl formate ester product was sustained without cathode flooding. However, improvements are still needed to lower the cell resistance and further increase the operating current density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

GaAs shallow-homojunction solar cells

The feasibility of fabricating space resistant, high efficiency, light weight, low cost GaAs shallow homojunction solar cells for space application is investigated. The material preparation of ultrathin GaAs single crystal layers, and the fabrication of efficient GaAs solar cells on bulk GaAs substrates are discussed. Considerable progress was made in both areas, and conversion efficiency about 16% AMO was obtained using anodic oxide as a single layer antireflection coating. A computer design shows that even better cells can be obtained with double layer antireflection coating. Ultrathin, high efficiency solar cells were obtained from GaAs films prepared by the CLEFT process, with conversion efficiency as high as 17% at AMI from a 10 micrometers thick GaAs film. A organometallic CVD was designed and constructed.

Fan, J. C. C.↗

Galvanic Protected Anode Materials for Molten Regolith Electrolysis

This effort aimed to explore the use of refractory alloys as long-lifetime electrode materials for use in a molten regolith electrolysis (MRE) reactor, a technology that can produce oxygen (O2) from regolith. To find a material capable of withstanding the high temperatures and corrosive nature of molten regolith, first-principles thermodynamic calculations were performed on platinum group metals in the presence of iron (Fe) and silicon (Si) to determine favorable compositions for resisting unwanted secondary phases that could form on the surface of the material. As a result of these first-principles calculations, the kinetic properties of elements such as aluminum (Al), Fe, and Si can be more easily derived, which would provide insight into the longevity of such a material when used in an MRE reactor. The effort funded by this CIF project mapped the entire phase diagram of platinum group metals, which is beneficial not only to MRE where high temperatures and molten material are present, but also aerospace applications like turbine materials, terrestrial metal processing techniques, and energy storage applications. This project narrowed a broad spectrum of refractory metals down to a small list of alloys that would be able to survive not only the high temperatures of an MRE reactor, but also the thermodynamic forces that would cause inferior alloys to form secondary phases, which would ultimately consume the electrodes of the reactor. This research needs to be followed up with experimental demonstrations of these alloys in an MRE environment.

Kevin Grossman↗

NiFeCo-based catalysts in high current zero-gap anion exchange membrane water electrolyzers

Understanding degradation mechanisms in pure water anion exchange membrane water electrolyzers is essential for developing durable and precious metal-free hydrogen production systems, yet electronic, chemical, and transport-driven pathways often occur simultaneously at the anode. To separate these effects, we establish a morphology invariant Ni/Fe/Co thin film model catalyst platform using physical vapor deposition and systematically compare composition-dependent behavior under both pure water and 0.1 M KOH feeds. Devices were operated under industrially relevant current density conditions, galvanostatically at 1 A cm −2 for 24 hours; metal dissolution, ionomer oxidation, and resistance growth were quantified using inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy. Under pure-water operation, Ni-rich films showed voltage increases that correlated with rising total cell resistance (ΔV ≈ 243 mV, ΔR ≈ 0.17 Ω cm 2 ). Co-rich films maintained near constant voltages with minimal resistance change (ΔV < 10 mV, ΔR ≈ 0.03 Ω cm 2 ) but induced pronounced ionomer oxidation observed by XPS. In 0.1 M KOH, ionomer oxidation is suppressed, and impedance growth is minimized (<0.08 Ω cm 2 ) across all compositions, consistent with reduced transport limitations and improved ionic conduction relative to pure-water feeds. These results demonstrate how a controlled thin film model platform can isolate composition electrolyte relationships and provide mechanistic design principles for stable pure water anion exchange membrane electrolyzers.

Milenia Rojas Mendoza, B. [Stanford Univ., CA (Uni↗

Migratory gold resistive shorts - Chemical aspects of a failure mechanism

Integrated-circuit devices using the Ti/W/Au metal system are subject to failure mechanisms based on electrolytic corrosion. The migratory gold resistive short (MGRS) failure mode is one example of this mechanism and results in the formation of filamentary or dendritic deposits of gold between adjacent stripes on the IC chip. This reaction requires the presence of a sufficient amount of water, a bias voltage between adjacent stripes, and the activation of the cathodic (-) stripe. Gold ions are transported from anode to cathode through a film of moisture adsorbed on the surface of the chip; halide ions are probably involved in the transfer. Their presence is verified experimentally by X-ray photoelectron spectroscopy. Some of the chemical and electrostatic factors involved in the MGRS mechanism are discussed in this paper, including the questions of a threshold level of moisture and contamination.

Grunthaner, F. J.↗

Electrolytic gold plating, stripping, and ion transport dynamics through a solid-state iodide perovskite

The pronounced electrochemical reactivity between halide perovskites and metal electrodes can introduce mobile extrinsic metal ions which can cause device instability or enable novel functionalities. Here we systematically investigate the kinetics of gold cation (Au + ) migration in indium tin oxide (ITO)/methylammonium lead triiodide (MAPbI 3 )/Au model devices under long-term potentiostatic biasing. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) analyses reveal that Au + ions, electrochemically generated at the Au anode, traverse the perovskite layer with diffusion coefficients on the order of 10 −11 to 10 −10 cm 2 s −1 and are subsequently reduced at the cathode as Au 0 clusters, resembling metal plating behavior in electrolytic cells and solid-state batteries during charging. Furthermore, reversing the applied bias strips the plated Au 0 , revealing reversibility suitable for bipolar resistive switching devices and providing direct evidence of the electrochemical and ionic nature of Au transport within the perovskite matrix. Quantitatively determining diffusion coefficients and ion concentrations provides foundational inputs for future drift-diffusion modelling opportunities and allows us to relate our findings to implications on long term operation of devices like photovoltaic modules. These results clearly demonstrate the solid-state electrochemical nature of perovskite devices, highlight methods to be more quantitative about ion transport properties, provide and emphasize the importance of disentangling electro-, photo-, photoelectrochemical processes for understanding device performance and unlocking new functionalities.

14 SOLAR ENERGY↗