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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Progress and Prospects of Inorganic Solid-State Electrolyte-Based All-Solid-State Pouch Cells

Here, all-solid-state batteries have piqued global research interest because of their unprecedented safety and high energy density. Significant advances have been made in achieving high room-temperature ionic conductivity and good air stability of solid-state electrolytes (SSEs), mitigating the challenges at the electrode–electrolyte interface, and developing feasible manufacturing processes. Along with the advances in fundamental study, all-solid-state pouch cells using inorganic SSEs have been widely demonstrated, revealing their immense potential for industrialization. This review provides an overview of inorganic all-solid-state pouch cells, focusing on ultrathin SSE membranes, sheet-type thick solid-state electrodes, and bipolar stacking. Moreover, several critical parameters directly influencing the energy density of all-solid-state Li-ion and lithium–sulfur pouch cells are outlined. Finally, perspectives on all-solid-state pouch cells are provided and specific metrics to meet certain energy density targets are specified. This review looks to facilitate the development of inorganic all-solid-state pouch cells with high energy density and excellent safety.

25 ENERGY STORAGE↗
DOE OSTI2024

Cation Migration and LSCF/SDC Decomposition Related to Long-Term Operation Mode as Revealed by Electron Microscopy

This study utilized energy dispersive spectroscopy (EDS) in a scanning electron microscope (SEM) and a scanning transmission electron microscope (STEM) in order to track cation migration and related particle decomposition for air electrode components of solid oxide cells. The influence of a Sm-doped ceria (SDC) barrier layers was assessed for three operation modes (fuel cell, electrolysis, reversible) over long time periods (1000-1500 hours). Composition profiles across air electrode/electrolyte interfaces indicated negligible accumulation of La/Sr cations to the yttria-stabilized zirconia (YSZ) electrolyte during operation. Instead, air electrode particles composed of SDC and/or La-Sr-Co-Fe-oxides (LSCF) exhibited decomposition by Sr evaporation and Sm migration to LSCF particle edges.

Picard, Yoosuf↗
DOE OSTI2023

Electrolyte Engineering Stabilizes Photoanodes Decorated with Molecular Catalysts

Molecular catalysts are promising oxygen evolution promoters in conjunction with photoanodes for solar water splitting. Maintaining the stability of both photoabsorber and cocatalyst is still a prime challenge, with many efforts tackling this issue through sophisticated material designs. Such approaches often mask the importance of the electrode-electrolyte interface and overlook easily tunable system parameters, such as the electrolyte environment, to improve efficiency. We provide a systematic study on the activity-stability relationship of a prominent Fe 2 O 3 photoanode modified with Ir molecular catalysts using in situ mass spectroscopy. After gaining detailed insights into the dissolution behavior of the Ir cocatalyst, a comprehensive pH study is conducted to probe the impact of the electrolyte on the performance. An inverse trend in Fe and Ir stability is found, with the best activity-stability synergy obtained at pH 9.7. The results bring awareness to the overall photostability and electrolyte engineering when advancing catalysts for solar water splitting.

14 SOLAR ENERGY↗
DOE OSTI2022

Resonant anomalous X-ray reflectivity for revealing ion distributions near electrodes

Energy storage devices–batteries, for example–consist of an electrolyte sandwiched between two charged electrodes through which current can pass. The metal ion organization at the electrode–electrolyte interface, commonly referred to as the electric double layer, determines the efficiency and stability of the device. There are two major challenges with experimentally characterizing the metal ion distribution at the interface.

42 ENGINEERING↗
DOE OSTI2020

The Effect of Artificial SEIs on Lithium Metal Anode Morphology and Conductivity

Lithium metal has often been termed the “holy grail” of battery technology, due to its high capacity (2,061 mAh/cm3) and low electrochemical potential (-3.04 V vs. SHE). However, lithium’s beneficially low potential also causes it to be highly reactive in the presence of organic solvents, making it difficult to harness the high energy capabilities for rechargeable batteries. Common failure of lithium metal batteries occurs by rapid dendrite growth leading to a hazardous short-circuit. Various methods have been brought forth to better understand the fundamental mechanisms of lithium metal batteries, as well as modifications made to better stabilize lithium metal. A common route of modification is done through interface engineering, with attempts to artificially provide a stable, homogeneous solid-electrolyte interface (SEI). The stability of the SEI has direct effects on the heterogeneity of the electrode surface, which initiates a waterfall effect of for progressive reactions such as dendrite growth, dead lithium accumulation, and electrolyte consumption. This work aims to produce a mixed LiI-LiF artificial SEI to improve ionic conductivity while retaining a high elastic modulus.

25 ENERGY STORAGE↗
DOE OSTI2021

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

The high-voltage, cobalt-free spinel cathode LiNi 0.5 Mn 1.5 O 4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm –2 displays a capacity retention of 90% over 300 cycles. Furthermore, the present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase, and making LNMO promising for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗
DOE OSTI2020

Reversible (De)Intercalation of Hydrated Zn 2+ in Mg 2+ -Stabilized V 2 O 5 Nanobelts with High Areal Capacity

The rechargeable aqueous zinc ion battery (ZIB) is regarded as one of the most promising candidates for large-scale energy storage applications due to its low-cost and eco-friendly properties. However, the development of a suitable cathode operating with high areal capacity and uncovering the relevant reaction mechanisms remain challenging. Herein, the application of Mg 0.26 V 2 O 5 ∙0.73H 2 O (MVO) nanobelts as a ZIB cathode is demonstrated. In situ FT-IR reveals the shift of OH stretching from 3350 cm -1 to 3200 cm -1 , corresponding to the hydration shell of Zn 2+ , while in situ Raman suggests the interlayer charges creening effect, which would boost the intercalation of hydrated Zn 2+ . Density function theory reveals that the hydrated Zn 2+ can lower the Coulombic repulsion at the electrode-electrolyte interface and circumvents the desolvation penalty of hydrated Zn 2+ during the (de)intercalation process. Additionally, excellent structure stability and large interlayer spacing guarantee the highly reversible (de)intercalation of hydrated Zn 2+ . Therefore, the MVO nanobelts exhibit a high areal capacity of 2.12 mAh cm -2 at 0.05 A g -1 , outstanding cycling stability of 2500 cycles at 10 A g -1 with a mass loading of 5 mg cm -2 . Finally, it is believed that the use of hydrated intercalation charge carriers will boost further studies in other multivalent rechargeable batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

From Pure to Seawater Electrolysis: Unveiling the Impact of Ionic Species and Contaminants on Electrocatalysis

Water electrolysis, including seawater splitting to produce hydrogen and oxygen, stands as a promising approach for the efficient storage of intermittent energy. However, the half-reactions of water splitting, the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), are known to be very sensitive toward the quality of water employed and are susceptible to contaminants originating from various sources, including the electrolyte or the electrodes. Those contaminants have a profound impact on the activity of these reactions of water splitting by modifying the electronic and physical structures of electrocatalysts as well as electrode–electrolyte interfaces. For seawater electrolysis, the unintentional presence of impurities, such as anions, cations, and organic compounds, affects the catalyst stability, selectivity, and activity. Despite the existence of numerous comprehensive reviews that delve into various aspects of catalysts and their structure–property relationships for several electrocatalytic reactions, the impact of contaminants has often been ignored. This critical review endeavors to address this issue by providing an overview of the diverse sources of contaminants influencing electrocatalytic water splitting and seawater splitting reactions, delineating the trends in electrochemical parameters and detailing different characterization methods for elucidating the physical and electronic changes of the electrode and electrolyte.

HER↗
DOE OSTI2022

Origin for electrochemically driven phase transformation in the oxygen electrode for a solid oxide cell

The next generation of fuel cells, electrolyzers, and batteries requires higher power, faster kinetics, and larger energy density, which necessitate the use of compositionally complex oxides to achieve multifunctionalities and activity. These compositionally complex oxides may change their phases and structures during an electrochemical process—a so-called “electrochemically driven phase transformation.” The origin for such a phase change has remained obscure. The aim of this paper is to present an experimental study and a theoretical analysis of phase evolution in praseodymium nickelates. Nickelate-based electrodes show up to 60 times greater phase transformation during operation when compared with thermally annealed ones. Theoretical analysis suggests that the presence of a reduced oxygen partial pressure at the interface between the oxygen electrode and the electrolyte is the origin for the phase change in an oxygen electrode. Guided by the theory, the addition of the electronic conduction in the interface layer leads to the significant suppression of phase change while improving cell performance and performance stability.

25 ENERGY STORAGE↗
DOE OSTI2021

Phase-Transition Interlayer Enables High-Performance Solid-State Sodium Batteries with Sulfide Solid Electrolyte

All-solid-state sodium (Na) batteries (ASSSBs) using sulfide-based solid electrolytes (SEs) have attracted intensive attention due to their superior safety, high energy density and low cost. However, interfacial issue is one of the biggest challenges to achieve high-performance sulfide-based ASSSBs due to the serious reactions between active Na metal and sulfide SEs at the interface. To address the interfacial challenges, we propose in this paper a simple and efficient approach by introducing a polymer electrolyte as an interlayer to stabilize the interface. Na 3 SbS 4 as a model sulfide SE is used to demonstrate the interlayer strategy to stabilize the interface by preventing the detrimental reactions and inhibiting Na dendrites. As a result, stable Na plating/stripping was observed in Na symmetric cells under the current density of 0.1 mA cm –2 . Moreover, ASSSBs with Na metal and TiS 2 electrode delivered long-term stability over 300 cycles remaining a specific capacity above 100 mAh g –1 , and FeS 2 ||Na cells exhibited an impressive specific capacity of up to 200 mAh g –1 after the 20th cycles. This work demonstrates an efficient strategy to address interfacial challenges between sulfide SEs and Na metal, which contributes to the development of ASSSBs in next-generation energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Active electrochemical interfaces stabilized through self-organized potential oscillations

Some electrochemical systems are known to have higher average efficiency when operated under an oscillatory regime. Given the compromise between activity and stability, the stability of electrochemical interfaces in a self-organized, oscillatory state must be taken into account. Here we evaluate the electro-oxidation of methanol and formic acid on platinum under regular and oscillatory conditions, and study the stability by following the Pt dissolution rates in situ with a stationary probe rotating disk electrode (SPRDE) coupled to an inductively coupled plasma mass spectrometer (ICP-MS). Generally speaking, as the electro-oxidation reaction proceeds, the platinum dissolution rate increases considerably. To guarantee Pt stability, the potential must be kept below 1.0 V vs. RHE. Interestingly, no dissolution is detectable when the electrode potential undergoes temporary self-organization, ensuring a stable and active interface.

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

Probing the electrical double layer by operando X‐ray photoelectron spectroscopy through a graphene‐carbon nanotube composite window

Abstract The electrical double layer is known to spontaneously form at the electrode‐electrolyte interface, impacting many important chemical and physical processes as well as applications including electrocatalysis, electroorganic synthesis, nanomaterial preparation, energy storage, and even emulsion stabilization. However, it has been challenging to study this fundamental phenomenon at the molecular level because the electrical double layer is deeply “buried” by the bulk electrolyte solution. Here, we report a quantitative probing of the electrical double layer of ionic liquids from the solid side of a photoelectron‐transparent graphene‐carbon nanotube hybrid membrane electrode using X‐ray photoelectron spectroscopy. The membrane window is ultrathin (1‐1.5 nm), large (~1 cm 2 ), and robust, enabling a tight seal of the electrolyte and quantitative measurement with excellent photoelectron signals. By operando monitoring the population changes of cations and anions in response to the applied electrical potentials, we experimentally resolve the chemical structure and dynamics of the electrical double layer, which corroborate results from molecular dynamics simulations. image

Wang, Peng↗
DOE OSTI2023

The role of ionic liquids in resolving the interfacial chemistry for (quasi-) solid-state batteries

Interfacial issues impede the advancement of current solid state battery technology; thus, interface engineering approaches are necessary to enable solid-state configuration. The advantage of solid-state cells stems from their low flammability and high electrochemical stability. Ionic liquids are viscous and nonflammable compounds that possess the requisite physical properties while optimizing the interface between solid electrodes and solid electrolytes, accelerating interfacial ion transport and enabling the fabrication of engineered interphases via the supply of robust chemical building blocks. In conclusion, this review summarizes the roles of ionic liquids in solid-state batteries focusing on the interface, with insights into their functionality as well as highlighting their applicability in the next generation battery systems.

25 ENERGY STORAGE↗
DOE OSTI2025

Deepening the LUMO: Brominated Naphthalene Diimide Electron Transport Layers for Low-Hysteresis Perovskite Solar Cells

Precise energy level alignment at the interfaces between the charge transport layers, active layer, and electrodes plays a key role in maximizing photovoltaic performance and operational stability in perovskite solar cells (PSCs). Organic electron transport layers (ETLs) have received little attention compared to their inorganic counterparts but offer the unique advantage of facile functionalization for fine-tuning of electronic properties. Here, we report the design, synthesis, and characterization of two benzyl-phosphonic acid (BnPA)-functionalized naphthalene diimide (NDI) derivatives, NDI-(BnPA) 2 and Br 2 -NDI-(BnPA) 2 as organic ETLs for PSCs in an n-i-p device configuration. Bromination of the NDI core at the 4,9-positions deepens the lowest unoccupied molecular orbital (LUMO) in Br 2 -NDI-(BnPA) 2 by 0.29 eV, enabling improved energy alignment with the conduction band minimum of the perovskite. Devices incorporating Br 2 -NDI-(BnPA) 2 demonstrated enhanced short-circuit current density (JSC), reduced hysteresis, and a maximum power conversion efficiency of 13.67%, compared to 13.20% for the unsubstituted NDI-(BnPA) 2 analog. The deeper LUMO of Br 2 -NDI-(BnPA) 2 is hypothesized to facilitate more efficient electron extraction, suppress interfacial charge accumulation, and reduce field-driven ion migration, collectively contributing to the observed reduction in hysteresis. These results highlight the effectiveness of combining molecular-level LUMO tuning with robust interfacial anchoring to advance the performance and durability of organic ETLs in PSCs.

Deposition↗
DOE OSTI2024

Solvation Environment and Interface Dynamics of Li 2 B 12 H 12 and Li 2 B 12 F 12 Electrolytes Uncovered by Theory and Operando Optical and FTIR Spectroelectrochemistry

In this work, we evaluated two closo-borate salts (Li 2 B 12 H 12 and Li 2 B 12 F 12 ) in propylene carbonate from theoretical and experimental perspectives to understand how the coordination environment influences their spectroscopic and electrochemical properties. The coordination environments of the closo-borate salts were modeled via density functional theory (DFT) and molecular dynamics (MD). Vibrational spectra calculated from the predicted coordination environments are in agreement with experimentally measured steady-state FTIR data. This theoretical investigation also suggested that Li 2 B 12 F 12 would possess a higher ionic conductivity than Li 2 B 12 H 12 , which was corroborated experimentally. Additionally, an electrochemical cell was designed and fabricated that enabled operando optical and FTIR spectroelectrochemical (OP-IR-SEC) measurements. This allowed for the simultaneous measurement of the relative changes of species at a lithium electrode-liquid electrolyte interface and the visualization of lithium plating at the electrode surface. This technique could provide new chemical insights and potentially link optical changes at the electrode–electrolyte interface to specific chemical species in similar electrochemical systems. The Li 2 B 12 F 12 electrolyte was found to have a higher thermal stability, which may find utility in applications for batteries that are subject to high-temperature conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Influence of Water Transport Across Microscale Bipolar Interfaces on the Performance of Direct Borohydride Fuel Cells

Direct borohydride fuel cells (DBFCs) can operate at double the voltage of proton exchange membrane fuel cells (PEMFCs) by employing an alkaline NaBH 4 fuel feed and an acidic H 2 O 2 oxidant feed. The pH-gradient-enabled microscale bipolar interface (PMBI) facilitates the creation and maintenance of an alkaline environment at the anode and an acidic environment at the cathode for the borohydride oxidation and peroxide reduction reactions. However, given the need to dissociate water at the interface to ensure ionic conduction, PMBI can be efficient only when anion exchange ionomer (AEI) moieties enable fast water transport for autoprotolysis. Herein, a series of polynorbornene-based AEIs with a range of water uptake values are examined to unravel the optimum water uptake required to enable high performance DBFCs. The DBFC with PMBI configuration containing the optimal AEI composition delivers a current density of 302 mA cm –2 at 1.5 V and a peak power density of 580 mW cm –2 at 1 V. This AEI composition exhibits high hydroxide ionic conductivity of 90.7 mS cm –1 at 80 °C with an IEC of 2.01 mequiv g –1 and demonstrates impressive chemical stability by retaining 98.75% of its initial ionic conductivity after immersion into anolyte (3 M KOH and 1.5 M NaBH 4 ) at 70 °C for 536 h.

25 ENERGY STORAGE↗