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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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At least 361 records · Page 20

Comparison of chromium poisoning between lanthanum strontium manganite and lanthanum strontium ferrite composite cathodes in solid oxide fuel cells

Degradation mechanisms of chromium poisoning have been extensively investigated for last two decades on various cathode materials for solid oxide fuel cells. While most researchers used half-cell experiments to investigate the effects of chromium impurities, this paper compares the degradation phenomena of LSM-YSZ and LSF-GDC cathodes in full cells under different operating conditions, namely polarized current density and humidity over the cathode. Under cathodic load, performance degradation of LSF-GDC cathode is significantly less than that of LSM-YSZ cathode. Most interestingly, under humidified air condition, LSF-based cell hardly experiences performance degradation while LSM-based cell shows a catastrophic degradation. Cr deposition in LSM-based cells occurs mainly near the electrolyte under both dry and humidified air conditions. In contrast, Cr deposition in LSF-based cell concentrates at the cathode surface under dry air condition, but concentrates both at cathode surface and near electrolyte under humidified air condition. Microstructure analysis reveals Mn-associated Cr deposits in LSM-based cathode, and Sr- and Fe-associated Cr deposits in LSF-based cathode. With the help of distribution of relaxation time analysis, the different electrochemical behaviors of LSM- and LSF-based cells are carefully interpreted. The effects of electrochemical deposition, Sr surface segregation, and humidity on LSM- and LSF-based cathodes are discussed.

25 ENERGY STORAGE↗

Ultrafast Metal Electrodeposition Revealed by In Situ Optical Imaging and Theoretical Modeling towards Fast–Charging Zn Battery Chemistry

Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Importantly, understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast-charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn 2+ -ion diffusion. Moreover, steady-state Zn metal plating/ stripping with Coulombic efficiency above 99 % is achieved at 10-100 mA cm -2 in a reasonably high concentration (3 M) ZnSO 4 electrolyte. Significantly, a long-term cycling-stable Zn metal electrode is realized with a depth of discharge of 66.7% under 50 mA cm -2 in both Zn || Zn symmetrical cells and MnO 2 || Zn full cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trace levels of PtRu on NiMo foam electrodes towards hydrogen evolution reaction

Electrochemical water splitting plays a critical role in high purity hydrogen production. To lower capital cost and energy consumption, efficient catalysts are required to boost the hydrogen evolution reaction (HER), especially in alkaline media. Although PtRu alloy materials are still considered the state-of-the-art catalyst for the HER under alkaline media, large-scale application is hindered by its scarcity and high cost. NiMo alloy catalysts can be potential Pt-free alternatives to drive the sluggish kinetics of the HER under alkaline media, but their HER activity is still not ideal due to the limitation of Volmer step. Herein, we investigated the impact of trace levels of PtRu catalysts on NiMo electrodes towards the HER by incorporating advantages of both PtRu and NiMo catalysts to minimize cost and maintain a promising HER activity. Trace levels of PtRu catalysts from 0.0173 to 0.2648 mg cm −2 were loaded on commercial NiMo foam electrodes by a facile electrodeposition technique utilizing ppm concentration levels of PtRu in electrolyte. The results show that 0.0173 mg cm −2 PtRu loading on NiMo electrode can significantly enhance HER activity compared to the pristine NiMo foam electrode (Tafel slopes drop from ∼170 to ∼60 mV dec −1 ) due to the remarkable decline of energy barriers towards water dissociation and hydrogen adsorption. Meanwhile, the rate determining step (RDS) switches from the Volmer step to the Heyrovsky step when the PtRu loading increases to 0.0675 mg cm −2 . Promising catalytic stability is observed at 100 mA cm −2 over the course of 50 h with a PtRu loading of 0.1198 mg cm −2 . In conclusion, this work demonstrates a potential strategy to decrease the cost and simultaneously maintain superior HER performance by integrating trace levels of PtRu catalyst with NiMo foam electrodes.

Electrochemical water splitting↗

Refined Classical Force Field for Choline Chloride and Ethylene Glycol Mixtures over Wide Composition Range

In this work, a classical force field based on the General Amber Force Field (GAFF) was refined for the simulation of choline chloride (ChCl) and ethylene glycol (EG) mixtures over a wide composition range by scaling the partial charges and van der Waals parameters. The scaling factors were derived by fitting the simulation results to only eight experimental density and viscosity data points of pure EG, and ChCl/EG mixtures at 1:2, 1:4, and 1:6 molar ratios. Using the refined force field, properties essential for electrochemical applications such as density, viscosity, self-diffusion coefficient, and ionic conductivity were calculated, and excellent agreement to experimental results was found even for compositions and temperatures not used in the fitting procedure. In addition, new experimental data for density, viscosity, and ionic conductivity are reported as a function of temperature and composition for this mixture. To the best of our knowledge, this is the first classical force field developed for the study of ChCl/EG mixtures over a composition range that includes the eutectic point. Using the new model, the liquid dynamics was studied in terms of ionic conductivity. It was found that the dynamics in ChCl/EG mixtures with ChCl mole fraction higher than 20% is similar to that of ionic liquids, high temperature molten salts, and highly concentrated water-in-salt electrolytes.

25 ENERGY STORAGE↗

Permanent Nanobubbles in Water: Liquefied Hollow Carbon Spheres Break the Limiting Diffusion Current of Oxygen Reduction Reaction

Porous liquids have traditionally been designed with sterically hindered solvents. Alternatively, recent efforts rely on dispersing microporous frameworks in simpler solvents like water. Here we report a unique strategy to construct macroporous water by selectively incorporating hydrophilicity on the surfaces of hydrophobic hollow carbon spheres (HCS). Specifically, we show that the stable dispersion surface ionized HCS in water while retaining the inherent porosity. The electrocatalytic conversion of small gas molecules in aqueous electrolytes is limited by the concentration and diffusion rates of gas molecules in water. In this case, macroporous water exhibited 6 times gas uptake compared to nonporous (pure) water. Furthermore, by leveraging the high gas capacity and enhanced diffusion kinetics, the limiting diffusion current of oxygen reduction reaction (ORR) in macroporous water is 2 times that in nonporous water, offering promising prospects for sustainable energy conversion technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding extreme fast charge limitations in carbonate mixtures

Charging large format lithium ion batteries within ten to fifteen minutes requires changes to the electrolyte composition in addition to modification of electrode and cell architectures. Several approaches to address this need have been proposed; but there is not a lot of clarity on understanding which factors limit the performance of existing electrolytes. Furthermore, this work takes a closer look at the solvated components of a mixture of LiPF 6 in ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in the context of extreme fast charging and relates these findings to cell-level requirements. Molecular dynamics studies of the Gen-2 electrolyte compositions with increasing salt concentrations, have been performed to estimate transport properties like diffusivity, transference number and conductivity. Molecular-level differences in the structure of solvation shells under extreme LiPF 6 concentrations are probed here and some key aspects on solvent structure that help overcome barriers to Li + transport under extreme fast charge are discussed.

25 ENERGY STORAGE↗

Reversible Cl/Cl - redox in a spinel Mn 3 O 4 electrode

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn 3 O 4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn 2+ cations inserted in the first discharge and trapped in the Mn 3 O 4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl - redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl 3 ] - and [Cl 5 ] - , inside the Zn 2+ -trapped Mn 3 O 4 , and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reflection Optical Imaging to Study Oxygen Evolution Reactions

Discovery of high-efficiency water-splitting catalysts is critical for clean hydrogen fuel generation. Quantitative and reliable chemical imaging methods can play a crucial role in providing critical catalyst efficiency information for materials development and screening. Here, we developed a reflection optical imaging method to map the performance of transition metal oxide catalysts for oxygen evolution reaction (OER). The generated high concentration of oxygen in the electrolyte will decrease the refractive index of the solutions near the electrode and change the reflectivity of optical images. We successfully imaged and measured the OER on cobalt oxide, and the localized current density and overpotential distribution maps have been extracted. The oxidation and reduction of cobalt oxide can be imaged with our reflection optical imaging method as well. These maps showed that the catalytic activities are quite different at different locations, and some regions showed much higher activities. This is due to the non-uniformity created by the catalyst synthesis process and demonstrates the importance of using the optical imaging method to map the localized catalytic efficiency. In addition, the NiFe alloy’s OER catalytic activities have been studied as well. The proposed reflection optical imaging method could find many applications in catalyst activity measurement and screening.

Electrochemistry↗

All-vanadium sulfate acid redox flow battery system

All-vanadium sulfate redox flow battery systems have a catholyte and an anolyte comprising an aqueous supporting solution including chloride ions and phosphate ions. The aqueous supporting solution stabilizes and increases the solubility of vanadium species in the electrolyte, allowing an increased vanadium concentration over a desired operating temperature range. According to one example, the chloride ions are provided by MgCl2, and the phosphate ions are provided by (NH4)2HPO4.

25 ENERGY STORAGE↗

All-vanadium sulfate acid redox flow battery system

All-vanadium sulfate redox flow battery systems have a catholyte and an anolyte comprising an aqueous supporting solution including chloride ions and phosphate ions. The aqueous supporting solution stabilizes and increases the solubility of vanadium species in the electrolyte, allowing an increased vanadium concentration over a desired operating temperature range. According to one example, the chloride ions are provided by MgCl 2 , and the phosphate ions are provided by (NH 4 ) 2 HPO 4 .

Nie, Zimin↗

Effect of salt concentration profiles on protrusion growth in lithium-polymer-lithium cells

In this report, the formation of dendrites and other protrusions on lithium metal anodes is a subject of continued interest due to the potential to incorporate these anodes in next-generation rechargeable batteries with increased energy densities. Solid polymer electrolytes show improved stability against lithium metal compared to liquid carbonate electrolytes. We have studied the effect of salt concentration on the formation of protrusions formed on electrodeposited lithium through a rigid block copolymer electrolyte, polystyrene-block-poly(ethylene oxide) (PS-b-PEO or SEO), in a lithium-lithium symmetric cell. The cell lifetime decreases by a factor of 100 when salt concentration is increased by a factor of 5. Our main objective is to understand the reason for this observation. We show that this decrease is not due to a salt-induced change of the morphology of the block-copolymer electrolyte, nor is it due to a salt-induced change of mechanical properties. We use an approach based on Newman's concentrated solution theory to fully characterize ion transport in the block-copolymer electrolyte, and report the conductivity, salt diffusion coefficient, cation transference number, and thermodynamic factor. Neither cell lifetime nor protrusion density in failed cells correlate with any of these electrochemical parameters. However, the electrochemical parameters can be used to predict salt concentration profiles in our symmetric cells. We posit that an important parameter in protrusion growth is the magnitude of the salt concentration gradient, Δ. We observe a direct correlation between Δ and lithium protrusion growth.

25 ENERGY STORAGE↗

Revealing the Electrochemical Kinetics of Electrolytes in Nanosized LiFePO 4 Electrodes

Lithium-ion battery rate performance is ultimately limited by the electrolyte, yet the behaviors of electrolytes during high-rate (dis)charge remain elusive to electrochemical measurement. Herein, we develop and study a nanosized LiFePO 4 model system in which the electrolyte completely controls the electrochemical kinetics of the porous electrode. Impedance spectroscopy, cyclic voltammetry, and rate performance testing prove that ion transport in the electrolyte is the sole rate-limiting process, even in thin electrodes. A novel pseudo-steady-state extrapolation (S3E) method for Tafel analysis shows that LiFePO 4 obeys Butler-Volmer kinetics with a transfer coefficient of 3. The combination of these unexpectedly rapid interfacial kinetics and an activation barrier for phase transformation causes extreme reaction heterogeneity, which manifests as a moving reaction zone. Resistance versus capacity analysis enables direct measurement of electrolyte resistance growth during high-rate (dis)charge, revealing how the interaction between concentration polarization and a moving reaction zone controls electrolyte rate performance in LiFePO 4 electrodes. This work elucidates the profound impacts of the electrolyte on electrochemical measurements in porous battery electrodes: when the active material is not rate limiting, it is impossible to directly measure the intrinsic kinetics of the active material, but conversely, it becomes possible to directly measure the kinetics of the electrolyte.

Electrochemistry↗

Solvation governs cation transference in glyme-based lithium battery electrolytes

The efficacy of electrochemical systems is governed by the cation transference number, which represents the fraction of current carried by the working ion. Energy is wasted when field-induced motion also drives anions and solvent molecules, decreasing the transference number to near-zero. We present a systematic study of cation transference in a series of electrolytes: tetraglyme (TG), octaglyme (OG), and poly(ethylene oxide) (PEO) mixed with lithium bis(trifluoromethanesulfonyl)imide. In all three electrolytes, starting from the dilute salt concentration limit, the experimentally measured cation transference number decreases with increasing concentration, reaching a minimum between -0.1 and -0.2, before rising back to positive values. Explicit measurements of field-induced species' velocities by electrophoretic nuclear magnetic resonance indicate that negative cation transference numbers in TG and OG electrolytes are dictated by solvation interactions with minimal contribution from anion-cation interactions. Simulation-based solvation structures indicate that OG serves as a bridge between TG and PEO. Multi-charge positive clusters, which are negligible in TG, become increasingly important at higher chain lengths (OG and PEO). As migrating cations drag their solvation shells, this solvation-induced motion is amplified in glyme electrolytes because of covalent interactions between solvating glyme molecules and free glyme molecules.

Im, Julia↗

Ion Pairing and Redissociaton in Low-Permittivity Electrolytes for Multivalent Battery Applications

Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.

25 ENERGY STORAGE↗

Unique Conductivity Behavior in Water-In-Salt Electrolytes Driven by Ion Clusters

Understanding and predicting ion transport in aqueous electrolytes are crucial for advanced energy storage and biophysics, and many emergent technologies yet remain elusive. Herein, we introduce a unified framework to quantitatively describe and predict electrolyte conductivity that shifts from conventional molar concentration-based metrics to a volume fraction-based approach. Through analyzing a variety of electrolyte solutions via this perspective, we observe a universal conductivity peak at a 37% volume fraction. Small-angle X-ray scattering (SAXS) and molecular dynamics (MD) simulations reveal that nanometer-scale ion clusters drive this general behavior. Moreover, key geometric features of the ion transport pathwayssuch as pore size, tortuosity, and connectivityfollow a consistent dependence with respect to the volume fraction, reinforcing the argument for the universal conductivity trend. This paradigm shift opens new avenues for designing high-performance electrolytes and provides transformative insights for advancing studies in many fields, wherein molecular aggregates dictate transport properties.

Nguyen, Huong T. D.↗

Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface

The differential capacitance as a function of potential and composition for choline chloride (ChCl) and ethylene glycol (EG) at 1:2,1:4, 1:6, and 1:20 molar ratios were studied using electrochemical impedance spectroscopy (EIS) on glassy carbon. In addition, ChCl:EG at the known ethaline DES composition (1:2) and 1:20 molar ratio were studied on Au and Pt electrodes, and compared to glyceline (ChCl:glycerol, 1:2). The capacitance-potential curves on glassy carbon were best interpreted by the modified Gouy-Chapman model. A dampened U-shape was observed similar to dilute electrolytes, however, the non-negligible ionic and H-bonding interactions in these electrolytes resulted in ambiguity about the point of zero charge where capacitance was weakly dependent on potential. Additionally, the differential capacitance was independent of composition on glassy carbon due to limited availability of mobile free ions and constraints by solvated ion sizes within the interface. Increases in capacitance are observed with Au as a result of desolvation and specific adsorption of Cl, and with Pt upon decreased Cl concentrations. These results indicate DESs and H-bonded electrolytes with high salt concentrations are distinct from ionic liquids and present no pronounced over screening or crowding with applied potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methyl Carbamate-Lithium Salt Deep Eutectic Electrolyte for Lithium-Ion Batteries

Deep eutectic electrolytes (DEEs) represent a burgeoning field in electrolytes for energy storage applications. Compared to the more conventionally studied Li-ion electrolyte systems, these electrolytes offer numerous advantages, such as high ion concentration, costs, lower temperature operation, and safety. In this work, the formation of a novel eutectic electrolyte based on lithium salts and methyl carbamate was reported. These DEEs were formed via mixing lithium salts and low-cost methyl carbamate at ratios varying from 1:2 to 1:5 (mol:mol). Here, the DEE formed from methyl carbamate and lithium hexafluorophosphate (LiPF 6 ) at a 1:5 molar ratio generated a 4V stability window and a 25°C conductivity of up to 3.16E –3 S cm –1 . The DEE formed from methyl carbamate and lithium bis(trifluoromethane)sulfonimide (LiTFSI) at a 1:5 molar ratio generated a 3.2 V stability window and a 25°C conductivity of up to 2.87E –3 S cm –1 . The LiPF 6 DEE also demonstrated a discharge capacity of 128 mAh g –1 after 50 cycles with 93% discharge capacity retention at moderate cycling rates of 0.5C in a lithium titanate (LTO)/lithium iron phosphate (LFP) full cell. These results demonstrate the potential for methyl carbamate to generate eutectics from lithium salts and offer alternative electrolytes for use in low-temperature Li-ion battery applications.

25 ENERGY STORAGE↗

A hybrid analytical and numerical model for cross-over and performance decay in a unit cell vanadium redox flow battery

Developing an accurate and efficient model for cross-over is critical for improving the long-term performance of redox flow batteries (RFBs). Here, this work presents a hybrid analytical and numerical model that combines a two-dimensional analytical solution to the active species, a one-dimensional analytical model for cross-over mechanisms, and a zero-dimensional numerical model for outlet concentrations of reactants. By comparing with experiment over 41 cycles (ca. 144 h), the model reported a mean voltage difference of 0.0089 V, mean time difference of 14 s per cycle (of 3.5 h), maximum relative difference for capacity and energy of 1.34% and 1.63%, respectively. The predicted mean concentrations for V 2+ , V 3+ , and VO$_{2}^{+}$ in membrane are 65%~77% of measured values from the literature. Upon validation, the model reproduced behaviors in electrolyte imbalance similar to those observed in experiments and numerical models, and revealed the control of cross-over, self-discharge, stoichiometry of side reactions, and Coulombic efficiency on electrolyte imbalance. The model also demonstrates excellent computational efficiency for simulating 41 cycles (around 37,000 points) within 3~4 s. The demonstrated efficiency and accuracy for predicting cross-over and its impacts on voltage, capacity&energy decay, membrane concentrations, and electrolyte imbalance makes it a reliable tool for optimizing RFBs’ long-term performance.

25 ENERGY STORAGE↗