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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Impact of Platinum Primary Particle Loading on Fuel Cell Performance: Insights from Catalyst/Ionomer Ink Interactions

A variety of electrochemical energy conversion technologies, including fuel cells, rely on solution-processing techniques (via inks) to form their catalyst layers (CLs). The CLs are heterogeneous structures, often with uneven ion-conducting polymer (ionomer) coverage and underutilized catalysts. Various platinum-supported-on-carbon colloidal catalyst particles are used, but little is known about how or why changing the primary particle loading (PPL, or the weight fraction of platinum of the carbon-platinum catalyst particles) impacts performance. Here, by investigating the CL gas-transport resistance and zeta-potentials of the corresponding inks as a function of PPL, a direct correlation between the CL high current density performance and ink zeta-potential is observed. This correlation stems from likely changes in ionomer distributions and catalyst-particle agglomeration as a function of PPL, as revealed by pH, zeta-potential, and impedance measurements. These findings are critical to unraveling the ionomer distribution heterogeneity in ink-based CLs and enabling enhanced Pt utilization and improved device performance for fuel cells and related electrochemical devices.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Impact of Dispersion Solvent on Ionomer Thin Films and Membranes

Perfluorosulfonic acid (PFSA) ionomers are an important class of materials that many electrochemical devices rely on as their ion-conducting electrolyte. Often, PFSA films are prepared through solution-processing techniques. Previous research has demonstrated that the solvent environment affects PFSA dispersion conformation, but it is not clear to what extent (if at all) these conformational effects persist for thin films and membranes upon casting, nor how dispersion solvent impacts film formation during the drying process. Here in this paper, we explore these questions by systematically examining the effect of Thin Film all length scales affected by dispersion solvent water and n-propanol mixtures on PFSA thin-film formation and structure, membrane structure, and resulting properties. Using a combination of in situ, time-resolved grazing incidence X-ray scattering and tender wide-angle X-ray scattering, it is shown that films prepared from high-water-concentration dispersions exhibit stronger interactions and arrangement upon drying, and possess larger network domain sizes than those prepared from low-water-concentration dispersions. These stronger interactions likely manifest in greater network connectivity, as evidenced by enhanced conductivity for membranes and decreased water uptake for thin films. Significantly, these solvent-induced differences persist even after thermal annealing. It is clear that the dispersion solvent choice is a critical parameter controlling PFSA nano- and mesoscale structure and presents an important dial with which to direct PFSA macroscale properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Stable hydration in perfluorinated polyelectrolyte membranes such as Nafion is essential to maintain good ion conductivity and manage permeation, especially in vapor-fed devices where water content depends on relative humidity in a gas stream. Extensive studies in the literature have shown that Nafion hydration in water vapor is controlled by its interfacial transport resistance. Nafion forms a fluorine-rich layer at the polymer-gas interface, and it has been proposed that this layer blocks water transport due to its hydrophobicity. To develop a molecular-level description of the physics underlying transport resistance in this system, we have performed a computational reaction-diffusion kinetics study of water evaporation from Nafion. Two distinct models are examined, one mimicking the blocking function proposed in the literature and the other assuming that there is no blocking, treating instead water evaporation as a dynamic balance between uptake from the gas and desorption from the polymer surface. Simulation results are compared to time-dependent infrared data over a range of 100-0% relative humidity from the literature. Only the dynamic model successfully reproduces experimental observations. This indicates that the physical nature of interfacial transport resistance is not slow diffusion across an interfacial layer; rather, it is due to the competition between dehydration and rehydration. The simulation data provide details on the accompanying water distributions throughout the membrane and on interfacial kinetics, showing that they are characterized by strong fluctuations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

4 V Na Solid State Batteries Enabled by a Scalable Sodium Metal Oxyhalide Solid Electrolyte

All-solid-state sodium batteries (ASSSBs) are viable candidates for large scale energy storage that could vie with lithium. Ductile solid catholytes for such cells that can be prepared without extensive ball milling and directly paired with high voltage sodium cathodes are lacking, however. We report a new amorphous fast Na-ion conducting metal oxychloride that meets these criteria, synthesized through a scalable and low-cost route based on a spontaneous solid-state reaction with simple short mixing and 100 °C annealing. It has an ionic conductivity of 1.2 mS·cm–1 and low activation energy of 0.31 eV. Due to its dual O2–/Cl– framework, it exhibits a high anodic potential of 4 V vs Na+/Na and good chemical/electrochemical compatibility with high voltage sodium cathode materials. ASSSBs consisting of the oxychloride solid electrolyte paired with a high voltage P2–Na2/3Ni1/3Mn2/3O2 cathode showed stable long-term cycling with a 4.0 V vs Na3Sn cutoff potential and even to 4.3 V.

solid-state electrolyte, solid-state batteries, Nu↗
DOE OSTI2020

Electrolyte Oxidation Pathways in Lithium-Ion Batteries

The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO 2 /Li cells were cycled with a lithium-ion conducting glass–ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ~4.7 V vs Li/Li + for LiCoO 2 ), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterized, and a detailed reaction scheme is constructed to rationalize the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have a direct impact on understanding and mitigating degradation in high-voltage/higher-energy-density LiCoO 2 -based cells, and more generally for cells containing nickel-containing cathode materials (e.g., LiNi x Mn y Co z O 2 ; NMCs), as they lose oxygen at lower operating voltages.

25 ENERGY STORAGE↗
DOE OSTI2021

Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe 2+/3+ are introduced in the Li-ion conducting phase (Li 2 SnS 3 ). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li + extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen based dual anionic and cationic redox cathode avenue.

25 ENERGY STORAGE↗
DOE OSTI2022

An electrochemically stable homogeneous glassy electrolyte formed at room temperature for all-solid-state sodium batteries

All-solid-state sodium batteries (ASSSBs) are promising candidates for grid-scale energy storage. However, there are no commercialized ASSSBs yet, in part due to the lack of a low-cost, simple-to-fabricate solid electrolyte (SE) with electrochemical stability towards Na metal. In this work, we report a family of oxysulfide glass SEs (Na 3 PS 4-x O x , where 0 < x ≤ 60) that not only exhibit the highest critical current density among all Na-ion conducting sulfide-based SEs, but also enable high-performance ambient-temperature sodium-sulfur batteries. By forming bridging oxygen units, the Na 3 PS 4-x Ox SEs undergo pressure-induced sintering at room temperature, resulting in a fully homogeneous glass structure with robust mechanical properties. Furthermore, the self-passivating solid electrolyte interphase at the Na|SE interface is critical for interface stabilization and reversible Na plating and stripping. The new structural and compositional design strategies presented here provide a new paradigm in the development of safe, low-cost, energy-dense, and long-lifetime ASSSBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Grooved electrodes for high-power-density fuel cells

Proton exchange membrane fuel cells (PEMFCs) are leading candidates to decarbonize the transport sector, but widespread deployment will require improvements in lifetime, fuel economy and cost. Here we present the grooved electrode, an alternative electrode structure that enhances PEMFC performance and durability by coupling high ionomer (ion-conducting binder) content for improved H + transport with grooves for rapid O 2 transport. Grooved electrodes provide up to 50% higher performance than state-of-the-art conventional electrodes under standard operating conditions. Fuel cell diagnostics combined with multiphysics modelling demonstrate that grooved electrodes provide facile O 2 transport despite their high ionomer content, enabling improved reaction rate uniformity. Grooved electrodes also provide improved durability, with less performance loss after carbon corrosion compared with baseline electrodes. Machine learning analysis demonstrates the potential to further optimize grooved structures for next-generation PEMFCs with enhanced performance and durability, enabling smaller and cheaper fuel cell stacks with higher fuel efficiency.

25 ENERGY STORAGE↗
DOE OSTI2024

Computational discovery of fast interstitial oxygen conductors

New highly oxygen-active materials may enhance many energy-related technologies by enabling efficient oxygen-ion transport at lower temperatures, for example, below ~400 °C. Interstitial oxygen conductors have the potential to realize such performance but have received far less attention than vacancy-mediated conductors. Here, in this study, we combine physically motivated structure and property descriptors, ab initio simulations and experiments to demonstrate an approach to discover new fast interstitial oxygen conductors. Multiple new families were found, which adopt completely different structures from known oxygen conductors. From these families, we synthesized and studied oxygen kinetics in La 4 Mn 5 Si 4 O 22+δ , a representative member of the perrierite/chevkinite family. We found that La 4 Mn 5 Si 4 O 22+δ has higher oxygen-ion conductivity than the widely used yttria-stabilized ZrO 2 , and among the highest surface oxygen exchange rates at the intermediate temperature of known materials. The fast oxygen kinetics is the result of simultaneously active interstitial and interstitialcy diffusion pathways. We propose that the essential features for forming an effective interstitial oxygen conductor are the availability of electrons and structural flexibility, enabling a sufficient accessible volume. This work provides a powerful approach for understanding and discovering new interstitial oxygen conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Immune-compatible designs of semiconducting polymers for bioelectronics with suppressed foreign-body response

One of the greatest obstacles to achieving implantable electronics with long-term functionality and minimized inflammatory reactions is the immune-mediated foreign-body response (FBR). Recently, semiconducting polymers with mixed electron–ion conductivity have been demonstrated as promising candidates to achieve direct electrical interfacing on bio-tissues. However, there is limited understanding of their immune compatibility in vivo, and strategies for minimizing the FBR through molecular design remain underexplored. Here we introduce a set of molecular design strategies for enhancing the immune compatibility of semiconducting polymers. Specifically, we show that selenophene, when incorporated in the backbone, can mitigate the FBR by suppressing macrophage activation. In addition, side-chain functionalization with immunomodulatory groups decreases the FBR further by downregulating the expression of inflammatory biomarkers. Together, our synthesized polymers achieve suppression of the FBR by as much as 68% (as indicated by the collagen density). In the meantime, these immune-compatible designs still provide a high charge-carrier mobility of around 1 cm 2 V −1 s −1 . In conclusion, we anticipate that such immune-compatible design principles can be translated to a variety of conjugated polymers to suppress the FBR for implantable applications.

Li, Nan [University of Chicago, IL (United States)↗
DOE OSTI2022

Recovering carbon losses in CO 2 electrolysis using a solid electrolyte reactor

The practical implementation of electrochemical CO 2 reduction technology is greatly challenged by notable CO 2 crossover to the anode side, where the crossed-over CO 2 is mixed with O 2 , via interfacial carbonate formation in traditional CO 2 electrolysers. Here we report a porous solid electrolyte reactor strategy to efficiently recover these carbon losses. Furthermore, by creating a permeable and ion-conducting sulfonated polymer electrolyte between cathode and anode as a buffer layer, the crossover carbonate can combine with protons generated from the anode to re-form CO 2 gas for reuse without mixing with anodic O 2 . Using a silver nanowire catalyst for CO 2 reduction to CO, we demonstrated up to 90% recovery of the crossover CO 2 in an ultrahigh gas purity form (>99%), while delivering over 90% CO Faradaic efficiency under a 200 mA cm -2 current. A high continuous CO 2 conversion efficiency of over 90% was achieved by recycling the recovered CO 2 to the CO 2 input stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Phase evolution during lithium–indium halide superionic conductor dehydration

Select rare-earth alkali halides have demonstrated high lithium ion conductivity. The conductivity appears to be related to the stability of the crystal phase, ordering of the lithium sublattice and the amount of residual H 2 O. Li 3 InCl 6 can be synthesized from concentrated aqueous solution through controlled dehydration. In this work, we track Li 3 InCl 6 dehydration using a multimodal approach that combines thermogravimetric, spectroscopic, X-ray diffraction, and neutron scattering techniques. In situ X-ray diffraction suggests a single phase transition caused by dehydration, in disagreement with spectroscopic and thermodynamic measurements. Neutron scattering, being sensitive toward the H 2 O and Li sublattices, reveals multiple phase transitions. We show that the loss of the final trace H 2 O leads to strain and grain boundary formation. Thus, controlled dehydration may be a viable strategy for high-throughput processing for roll-to-roll manufacturing of REAH solid electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Gel composite electrolyte – an effective way to utilize ceramic fillers in lithium batteries

Achieving synergy between ion-conducting polymers and ceramics in a composite electrolyte has been proven to be difficult as the complicated ceramic/polymer interface presents challenges to understand and control. In this work, we report a strategy to utilize discrete ceramic fillers to form a gel composite electrolyte with enhanced transport properties for lithium metal batteries. The matrix of the composite membrane is crosslinked poly(ethylene oxide) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). The membrane is plasticized with tetraethylene glycol dimethyl ether (TEGDME). The incorporation of doped-lithium aluminum titanium phosphate particles (LICGC™) into the membrane greatly improves the membrane's cycling characteristics against the lithium electrode, exhibiting lower interfacial impedance, lower overpotential and higher rate capability. The underpinnings of the superior performance of the gel composite electrolyte are discussed in depth. LICGC™ can immobilize the TFSI - anions in the polymer matrix and simultaneously promote Li+ transport by increasing the plasticizer to Li + ratio. Further, the transport enhancement is achieved without sacrificing mechanical properties. The composite membrane shows significantly improved handleability and processability. This work sheds light on the design strategy for a safe electrolyte towards stable Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Challenge-driven printing strategies toward high-performance solid-state lithium batteries

Solid-state lithium batteries (SSLBs) are promising candidates for replacing traditional liquid-based Li-ion batteries and revolutionizing battery systems for electric vehicles and portable devices. However, longstanding issues such as form factors, interfacial contact resistance, balance between ion conductivity and mechanical strength, and manufacturing processability limit their applications. In this review we present how advanced printing technologies can help to mitigate typical problems in main components of SSLBs and improve device performance. Here we first introduce the common printing techniques for energy storage devices, then focus on the issues and corresponding printing strategies for anodes, cathodes, and solid-state electrolytes to guide the construction of energy-dense, free-form SSLBs. The features and effects of the printed structures are emphasized, as well. We conclude by discussing the problems associated with printing technologies and the potential research directions for printed solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

On the role of the zirconia/ceria interface in the degradation of solid oxide electrolysis cells

Gd-doped Ceria (GDC) barrier layers are widely used in solid oxide electrolysis cells to prevent reactions between the Y-stabilized Zirconia (YSZ) electrolyte and oxygen electrode. In some cases, electrolysis operation causes fracture near the GDC/YSZ interface. Here, we explain this effect using a numerical calculation, showing that a peak oxygen pressure is observed near the GDC/YSZ interface during electrolysis operation. Moreover, GDC/YSZ interdiffusion and possible zirconate phase formation occurring during electrode firing yield a low oxygen ion conductivity region that introduces a much higher peak oxygen partial pressure at the interdiffusion layer/YSZ interface, thereby exacerbating degradation. The results indicate that the peak pressure can be reduced and, thereby, damage can be mitigated by altering processing in order to minimize interdiffusion, decreasing the GDC layer thickness, and reducing oxygen electrode polarization resistance or altering electrolyte transport properties, e.g., changing the Gd doping level of GDC to increase the oxygen vacancy diffusivity.

Physics↗