Carbonation cell materials compatibility
Material test and evaluation program for compatibility of materials with alkaline and acid electrolyte environments of carbonation cell system
Bannerton, N. P.↗
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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.
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Carbon monoxide detector
A sensitive carbon monoxide detector, developed specifically for spacecraft use, is described. An instrument range of 0 to 60 ppm CO in air was devised. The fuel cell type detector is used as a highly sensitive electrolysis cell for electrochemically detecting gases. The concept of an electrochemical CO detector is discussed and the CO oxidation behavior in phosphoric and sulfuric acid electrolytes is reported.
Holleck, G. L.↗
Improved wet-slug capacitor
Capacitor uses all-tantalum seals and straight, ungelled, 30-percent sulphuric acid electrolyte to reduce leakage from order of milliamperes to low-microampere region. Design offers better reliability in severe environments encountered in military and industrial electronics systems.
Ward, C. M.↗
Trioxane: A Fuel For Direct-Oxidation Fuel Cells
Trioxane identified as high-energy, nontoxic, solid substitute for formaldehyde as water-soluble fuel for use in direct-oxidation fuel cells. Found to undergo facile electrochemical oxidation to water and carbon dioxide at platinum and platinum-alloy electrodes in liquid-feed-type fuel cells that contain acid electrolytes or solid proton-exchange membrane electrolytes. Exhibits less crossover than do such conventional fuels as methanol and formaldehyde. Being solid at ambient temperature, trioxane offers significant advantages in handling and transportation. Synthesized from natural gas with relative ease.
Olah, George A.↗
Moisture-Induced Delayed Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales
While interfacial sulfur is the primary chemical factor affecting Al2O3 scale adhesion, moisture-induced delayed spallation appears as a secondary, but impressive, mechanistic detail. Similarities with bulk metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al(sub alloy)+3(H2O)(sub air) = Al(OH)(-) (sub 3) +3H(+) may be the operative mechanism. This proposal was tested on pre-oxidized Rene N5 by standard cathodic hydrogen charging in 1N H2SO4, as monitored by weight change, induced current, and microstructure. Cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the acid electrolyte produced neither scale spallation nor alloy dissolution. Thus, hydrogen charging was detrimental to alumina scale adhesion. Moisture-induced interfacial hydrogen embrittlement is concluded to be the cause of delayed scale spallation and desktop thermal barrier coating failures.
Smialek, James L.↗
Fe Coated Optical Fiber for Distributed Corrosion Monitoring in Soil and Aqueous Environment
Natural gas pipeline corrosion represents a substantial cost and safety concern during normal operations. Effective monitoring of corrosion is important to detect and mitigate pipeline risks before corrosion-related catastrophic events happen. Here, we describe the use of Fe-coated optical fiber sensors (OFS) for distributed corrosion monitoring where Fe acts as a corrosion proxy. By using an optical backscatterring reflectometer (OBR), corrosion was monitored based on the increase in backscattered intensity amplitude of the light being passed as Fe undergoes corrosion. The Fe-coated OFSs were prepared with a film thickness between 25-225 nm by an electroless plating approach and corroded by a CO2-saturated acidic electrolyte. The corrosion rate was approximately 2.5 mm/yr for Fe with a film thickness of 30 nm and increased with film thickness. Backscattering-based corrosion rates were supported by visible light transmission measurements, which have been previously demonstrated. Additionally, a correlation between the intermittent transmission and residual Fe film thickness during corrosion of Fe was established. Corrosion was measurable out to > 100 m which is a significant improvement over our previous work showing corrosion sensing at < 10 m. The corrosion sensor was also tested in soil at >1 ft depth. Fe-coated OFS was loaded into a Draka cable which provides mechanical support during fiber deployment and installation into either acidified soil, top-soil, or sandy soil.
aqueous environment↗
Fe-Coated Optical Fiber for Distributed Corrosion Monitoring in Soil and Aqueous Environments
Natural gas pipeline corrosion represents a substantial cost and safety concern during normal operations. The effective and real-time monitoring of corrosion is important to detect and mitigate pipeline risks before corrosion-related catastrophic events happen. Here, we describe the use of iron (Fe) coated optical fiber sensors (OFS) for distributed corrosion monitoring where Fe acts as a corrosion proxy. By using an optical backscattering reflectometer (OBR), corrosion was monitored based on the increase in the backscattered intensity amplitude of the light being passed as Fe underwent corrosion. The Fe-coated OFSs were prepared with a film thickness between 25–225 nanometers (nm) by an electroless plating approach and corroded by a carbon dioxide (CO2)-saturated acidic electrolyte. The corrosion rate (CR) was approximately 2.5 millimeters (mm)/year for Fe with a film thickness of 30 nm and increased with film thickness. Backscattering-based CRs were supported by visible light transmission measurements, which have been previously demonstrated. Additionally, a correlation between the intermittent transmission and residual Fe film thickness during the corrosion of Fe was established. The corrosion was measurable out to > 100 meters (m), which is a significant improvement over our previous work, which showed corrosion sensing at < 10 m. The corrosion sensor was also tested in soil at > 1 foot depth.
aqueous environment↗
Origin of Unusual Acidity and Li+ Diffusivity in a Series of Water-in-Salt Electrolytes.
Superconcentrated aqueous electrolytes ("water-in-salt" electrolytes, or WiSEs) enable various aqueous battery chemistries beyond the voltage limits imposed by the Pourbaix diagram of water. However, their detailed structural and transport properties remain unexplored and could be better understood through added studies. Here, we report on our observations of strong acidity (pH 2.4) induced by lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) at superconcentration (at 20 mol/kg). Multiple nuclear magnetic resonance (NMR) and pulsed-field gradient (PFG) diffusion NMR experiments, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations reveal that such acidity originates from the formation of nanometric ion-rich structures. The experimental and simulation results indicate the separation of water-rich and ion-rich domains at salt concentrations >= 5 m and the acidity arising therefrom is due to deprotonation of water molecules in the ion-rich domains. As such, the ion-rich domain is composed of hydrophobic -CF3 (of TFSI-) and hydrophilic hydroxyl (OH-) groups. At 20 m concentration, the tortuosity and radius of water diffusion channels are estimated to be similar to 10 and similar to 1 nm, respectively, which are close to values obtained from hydrated Nafion membranes that also have hydrophobic polytetrafluoroethylene (PTFE) backbones and hydrophilic channels consisting of SO3- ion cluster networks providing for the transport of ions and water. Thus, we have discovered the structural similarity between WiSE and hydrated Nafion membranes on the nanometer scale.
Han, Kee Sung↗
Investigations of the stability of GaAs for photoelectrochemical H 2 evolution in acidic or alkaline aqueous electrolytes
The long-term stability of p-GaAs photocathodes has been investigated for the hydrogen-evolution reaction (HER) in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq). Stability for the HER was evaluated using p-GaAs electrodes that were either etched or coated with active HER catalysts (Pt and CoP). Changes in surface characteristics of GaAs after exposure to electrochemical conditions were monitored by X-ray photoelectron spectroscopy (XPS), and electrode dissolution processes were evaluated by inductively coupled plasma mass spectrometry (ICP-MS). Consistent with thermodynamic predictions, after operation of the HER at pH 0 or pH 14, illuminated etched p-GaAs electrodes exhibited minimal dissolution while preserving a nearly stoichiometric surface. Electrodeposition or sputtering of Pt on the p-GaAs surface promoted the formation of excess As 0 via an interfacial reaction during the HER. The resulting non-stoichiometric As 0 -rich surface of p-GaAs/Pt electrodes caused a loss in photoactivity as well as substantial cathodic dark current. In contrast, p-GaAs electrodes coated with thin-film CoP catalysts did not display an increase in surficial As 0 after operation of the HER in acidic electrolytes. Minimization of deleterious interfacial reactions is thus critical to obtain extended stability in conjunction with high performance from p-GaAs photocathodes.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Cobalt‐Doped Bismuth Nanosheet Catalyst for Enhanced Electrochemical CO 2 Reduction to Electrolyte‐Free Formic Acid
Electrochemical carbon dioxide (CO 2 ) reduction reaction (CO 2 RR) to valuable liquid fuels, such as formic acid/formate (HCOOH/HCOO − ) is a promising strategy for carbon neutrality. Enhancing CO 2 RR activity while retaining high selectivity is critical for commercialization. To address this, we developed metal-doped bismuth (Bi) nanosheets via a facile hydrolysis method. These doped nanosheets efficiently generated high-purity HCOOH using a porous solid electrolyte (PSE) layer. Among the evaluated metal-doped Bi catalysts, Co-doped Bi demonstrated improved CO 2 RR performance compared to pristine Bi, achieving ~90 % HCOO − selectivity and boosted activity with a low overpotential of ~1.0 V at a current density of 200 mA cm −2 . In a solid electrolyte reactor, Co-doped Bi maintained HCOOH Faradaic efficiency of ~72 % after a 100-hour operation under a current density of 100 mA cm −2 , generating 0.1 M HCOOH at 3.2 V. Density functional theory (DFT) results revealed that Co-doped Bi required a lower applied potential for HCOOH generation from CO 2 , due to stronger binding energy to the key intermediates OCHO* compared to pure Bi. In conclusion, this study shows that metal doping in Bi nanosheets modifies the chemical composition, element distribution, and morphology, improving CO 2 RR catalytic activity performance by tuning surface adsorption affinity and reactivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Acid-in-Clay Electrolyte for Wide-Temperature-Range and Long-Cycle Proton Batteries
Explore the source record for details and available documents.
Wang, Shitong↗
Electrodeposition of near-equiatomic CoCuFeNi multi-principal element alloys from an acidic glycine-citrate-triton X100 aqueous electrolyte
Understanding the composition and morphology control of electrodeposited CoCuFeNi is the first step to finding a general strategy for developing electrodeposition processes of unconventional alloys with large redox potential differences and complicated deposition mechanisms. Here, in this work, we have successfully synthesized the near-equiatomic (<5 at% error) CoCuFeNi films with ~200nm thickness by electrodeposition from glycine-citrate-Triton X-100 acidic electrolytes. This system generally follows the Principle II in Brenner’s paradigm on alloy composition control in electrodeposition. X-ray diffraction (XRD) profiles show that the films only consist of one crystalline phase, different from the deposit from ammonia-citrate-boric acid electrolytes and the equilibrium phases predicted by CALPHAD. The near-equiatomic deposits at Ru substrates were successfully annealed at 400 ° C without significant intermixing between the substrate and the deposit, in which no phase separation of the crystalline phase was observed in its XRD profile. Xray photoelectron spectroscopy (XPS) reveals that some depositing elements (mainly Fe) exist as metal oxides. Cu is dissolved in the crystalline phases, stabilized by small crystalline domain size and the amorphous metal oxides inside the CoCuFeNi deposits.
CoCuFeNi↗
Role of electrolyte composition on the acid stability of mixed-metal oxygen evolution catalysts
Acid stability in catalysts that promote the oxygen evolution reaction (OER) may be achieved through either the introduction of electrolyte-modulated self-healing processes, or the fixation of OER active sites within stable, conductive oxide matricies. By varying the nature of the electrolyte, pH, buffer concentration, and ionic strength, the contributions of these two effects may be deconvoluted. In addition, we find that the nature of the buffer is capable of engendering OER with exceptional acid stability at moderate overpotentials.
14 SOLAR ENERGY↗
Implications of Fuel Crossover in Direct Methanol Fuel Cell
A new liquid-feed direct methanol fuel cell using proton-exchange membrane electrolyte was developed at JPL under an ARPA-sponsored program.
aqueous solutions methanol platinum alloy anode el↗
Advanced double layer capacitors
There is a need for large amounts of power to be delivered rapidly in a number of airborne and space systems. Conventional, portable power sources, such as batteries, are not suited to delivering high peak power pulses. The charge stored at the electrode-electrolyte double layer is, however, much more assessible on a short time scale. Devices exploiting this concept were fabricated using carbon and metal oxides (Pinnacle Research) as the electrodes and sulfuric acid as the electrolyte. The approach reported, replaces the liquid sulfuric acid electrolyte with a solid ionomer electrolyte. The challenge is to form a solid electrode-solid ionomer electrolyte composite which has a high capacitance per geometric area. The approach to maximize contact between the electrode particles and the ionomer was to impregnate the electrode particles using a liquid ionomer solution and to bond the solvent-free structure to a solid ionomer membrane. Ruthenium dioxide is the electrode material used. Three strategies are being pursued to provide for a high area electrode-ionomer contact: mixing of the RuOx with a small volume of ionomer solution followed by filtration to remove the solvent, and impregnation of the ionomer into an already formed RuOx electrode. RuOx powder and electrodes were examined by non-electrochemical techniques. X-ray diffraction has shown that the material is almost pure RuO2. The electrode structure depends on the processing technique used to introduce the Nafion. Impregnated electrodes have Nafion concentrated near the surface. Electrodes prepared by the evaporation method show large aggregates of crystals surrounded by Nafion.
Sarangapani, S.↗
Performance Leap of Lithium Metal Batteries in LiPF 6 Carbonate Electrolyte by a Phosphorus Pentoxide Acid Scavenger
Phosphorus pentoxide (P 2 O 5 ) is investigated as an acid scavenger to remove the acidic impurities in a commercial lithium hexafluorophosphate (LiPF 6 ) carbonate electrolyte to improve the electrochemical properties of Li metal batteries. Nuclear magnetic resonance (NMR) measurements reveal the detailed reaction mechanisms of P 2 O 5 with the LiPF 6 electrolyte and its impurities, which removes hydrogen fluoride (HF) and difluor-ophosphoric acid (HPO 2 F 2 ) and produces phosphorus oxyfluoride (POF 3 ), OF 2 P-O-PF 5 - anions, and ethyl difluorophosphate (C 2 H 5 OPOF 2 ) as new electrolyte species. The P 2 O 5 -modified LiPF 6 electrolyte is chemically compatible with a Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathode, generating a PO x F y -rich solid electrolyte interphase (SEI) that leads to highly reversible Li electrodeposition, while eliminating transition metal dissolution and cathode particle cracking. The excellent electrochemical properties of the P 2 O 5 -modified LiPF6 electrolytes are demonstrated on Li||NMC622 pouch cells with 0.4 Ah capacity, 50 mu m Li anode, 3 mAh cm -2 NMC622 cathode, and 3 g Ah -1 electrolyte/capacity ratio. The pouch cells can be galvanostatically cycled at C/3 for 230 cycles with 87.7% retention.
25 ENERGY STORAGE↗
Investigations of the stability of etched or platinized p-InP(100) photocathodes for solar-driven hydrogen evolution in acidic or alkaline aqueous electrolytes
Here, the stability of p-InP photocathodes performing the hydrogen-evolution reaction (HER) has been evaluated in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq), with a focus on identifying corrosion mechanisms. Stability for the solar-driven HER was evaluated using p-InP electrodes that were either etched or coated with an electrodeposited Pt catalyst (p-InP/Pt). Variables such as trace O 2 were systematically controlled during the measurements. Changes in surface characteristics after exposure to electrochemical conditions as well as electrode dissolution processes were monitored using X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). In either H 2 SO 4 or KOH, etched p-InP photoelectrodes corroded cathodically under illumination, forming metallic In 0 at the electrode surface. In contrast, electrodeposition of Pt kinetically stabilized illuminated p-InP photocathodes in both H 2 SO 4 and KOH by inhibiting the cathodic corrosion pathway. Notably, when held at 0 V vs. the reversible hydrogen electrode (RHE) in 1.0 M H 2 SO 4 (aq), p-InP/Pt exhibited a stable current density (J) of ~–18 mA cm –2 for >285 h under simulated 1 Sun illumination. The long-term current density vs. potential (J–E) behavior at pH 0 and pH 14 of p-InP/Pt photocathodes correlated with changes in the surface chemistry as well as the dissolution of p-InP. In acidic media, the J–E behavior of p-InP/Pt photocathodes remained nearly constant with time, but the surface of a p-InP/Pt electrodes gradually turned P-rich via a slow and continuous leaching of In ions. In alkaline electrolyte, the surface of p-InP/Pt electrodes was passivated by formation of an InO x layer that exhibited negligible dissolution but led to a substantial degradation in the J–E characteristics. Consequently, changes in the catalytic kinetics and surface stoichiometry are both important considerations for determining the corrosion chemistry and the long-term operational stability of InP photoelectrodes.
14 SOLAR ENERGY↗