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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Cathode additives for lithium-ion batteries

In some implementations, a cathode is formed by (1) providing a cathode additive including (a) a matrix including a lithium compound, and (b) metal nanostructures embedded in the matrix; and (2) combining the cathode additive with a cathode active material to form a mixture. In other implementations, a cathode is formed by (1) providing a cathode additive including a compound of lithium and at least one non-metal or metalloid; and (2) combining the cathode additive with a cathode active material to form a mixture.

25 ENERGY STORAGE↗
DOE OSTI2025

Screening and Development of Sacrificial Cathode Additives for Lithium‐Ion Batteries

Abstract This work presents a computational screening approach to identify Li‐rich transition‐metal oxide sacrificial cathode additives and provides experimental validation of antifluorite‐structured Li 6 MnO 4 as a potential candidate. Initial attempts to synthesize this compound result in low purity (≤40% by weight) owing to close thermodynamic competition with Li 2 O and MnO at low temperature. However, it is shown that a much higher purity of 85% by weight can be achieved by combining Li excess with rapid cooling from high temperature, which effectively stabilizes the Li 6 MnO 4 phase. The synthesized product delivers a high irreversible Li release capacity that exceeds 700 mAh g −1 by utilizing combined Mn oxidation (Mn 2+/3+ and Mn 3+/4+ ) and O oxidation. These results demonstrate that Li 6 MnO 4 may therefore be useful as a potential sacrificial cathode additive in Li‐ion batteries and motivate further investigation of other structurally‐related compounds. While attempts were made to synthesize two additional compounds among computationally screened candidates, it was not successful to experimentally realize the two candidates. The difficulty of experimental realization of the newly predicted materials remains a challenge and it is suggested that more efforts need to be devoted to developing computational techniques to precisely predict synthesizability and propose potential synthetic routes of the predicted materials.

Kim, Haegyeom↗
DOE OSTI2021

Li2O-Based Cathode Additives Enabling Prelithiation of Si Anodes

Low first-cycle Coulombic efficiency is especially poor for silicon (Si)-based anodes due to the high surface area of the Si-active material and extensive electrolyte decomposition during the initial cycles forming the solid electrolyte interphase (SEI). Therefore, developing successful prelithiation methods will greatly benefit the development of lithium-ion batteries (LiBs) utilizing Si anodes. In pursuit of this goal, in this study, lithium oxide (Li2O) was added to a LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode using a scalable ball-milling approach to compensate for the initial Li loss at the anode. Different milling conditions were tested to evaluate the impact of particle morphology on the additive performance. In addition, Co3O4, a well-known oxygen evolution reaction catalyst, was introduced to facilitate the activation of Li2O. The Li2O + Co3O4 additives successfully delivered an additional capacity of 1116 mAh/gLi2O when charged up to 4.3 V in half cells and 1035 mAh/gLi2O when charged up to 4.1 V in full cells using Si anodes.

25 ENERGY STORAGE↗
NASA NTRS1995

Preventing Overcharge And Overdischarge Of Lithium Cells

Secondary lithium cells operating at ambient temperature protected against overcharge and overdischarge by use of cathode additives acting as sources and sinks of electroactive chemical species, which is lithium. Additive in cathode limits excursion of voltage of cell during both overcharge and overdischarge. In addition to protecting cell, also serves as part of state-of-charge indicator: attainment of greater or lesser limiting voltage indicates end of charge or end of discharge, respectively. Concept applied to Li/TiS2 system, and also applicable to such other lithium systems as Li/MoS2, Li/NbSe3, and Li/V2O5.

Huang, Chen-Kuo↗
NASA NTRS1994

Overcharge and overdischarge protection of ambient temperature secondary lithium cells

A cathode additive is provided for protecting an ambient temperature secondary lithium cell from overcharging or overdischarging. The cathode additive is chosen to create an upper voltage plateau which is slightly higher than a characteristic charge cutoff voltage of the cathode of the cell. The cathode additive additionally creates a lower voltage plateau which is slightly lower than the characteristic discharge cutoff voltage of the cell. Preferably, the cathode additive is a transition metal oxide or a sulfide and may, for example, include a mixture of Li2Mn2O4 and Li(0.1)MoO2.

Huang, Chen-Kuo↗
DOE OSTI2021

Townsend to glow discharge transition for a nanosecond pulse plasma in helium: space charge formation and resulting electric field dynamics

Stark polarization spectroscopy is used to investigate the temporal evolution of the electric field distribution in the cathode region of a nanosecond pulsed discharge in helium at 120 Torr. The measurements are performed on the He I transition at 492.19 nm, during the early stages of the discharge formation. The experimental results are compared with the predictions of a 1D fluid model. Time-resolved ICCD images show that the discharge develops as a diffuse, cathode-directed ionization wave with a Townsend-like feature before transitioning into a glow-like structure. Near anode instabilities characterized by filament formation were observed near the high voltage electrode. Within 30 ns, a reduction of the sheath thickness to about 250 μm is observed, coinciding with a gradual increase of the discharge current and proportional increase in electric field at the cathode. Additionally, the cathode electric field corresponding to this sheath with a thickness of 250 μm is about 40 kV cm -1 . A subsequent steep increase of the discharge current leads to a further reduction of the sheath width. The electric field evolution as obtained by the fluid model is in excellent agreement with the measurements and shows that an enhanced ionization near the cathode is causing the space charge formation responsible for the increase in electric field.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Prelithiation of Lithium Peroxide for Silicon Anode: Achieving a High Activation Rate

The use of lithium peroxide (Li2O2) as a cost-effective low-weight prelithiation cathode additive was successfully demonstrated. Through a series of studies on the chemical stability of Li2O2 and the activation process of Li2O2 on the cathode, we revealed that Li2O2 is more compatible with conventional electrolyte and cathode laminate slurry than lithium oxide. Due to the significantlysmaller size of commercial Li2O2, it can beused directly as a cathode additive. Moreover, the activation of Li2O2 on the cathode leads to the impedance growthof the cathode possibly resulting from the release of dioxygen andevacuation of Li2O2 inside the cathode. Withthe introduction of a new Li2O2 spread-coatingtechnique on the cathode, the capacity loss was suppressed. Si||NMCfull cells using Li2O2 spread-coated cathodedemonstrated a highly promising activation rate of Li2O2 and significantly enhanced specific capacity and cyclingstability compared to the uncoated full cells.

cathode additive↗
NASA NTRS2018

The Effects of Background Pressure on SPT-140 Thruster Performance at Multiple Power Levels

NASA's planned Psyche mission is scheduled to launch in 2022 and begin a 3.5-year cruise to the metallic asteroid Psyche, where it would examine this unique body. The baseline spacecraft design is a hybrid of JPL's deep-space heritage subsystems with commercial partner SSL's power, structure, and SPT-140 electric propulsion subsystems. Since the deep-space implementation of the SPT-140 differs from the commercial implementation, primarily in the need for deep power throttling, characterization of the system at lower powers is necessary. One specific area of interest is the sensitivity of thruster performance to background pressure in ground-based test facilities, which can have an impact on the prediction of in-space performance. Measurements of this pressure dependence were performed on a qualification-model SPT-140 thruster over the 0.9-4.5 kW range of interest for the Psyche mission. Thrust sensitivity to pressure, in an absolute sense, was largest at 4.5 kW and decreased with power until there was little-to-no measurable effect at 0.9 kW. In a relative sense, thrust sensitivity was similar at all powers above 0.9 kW with about 2-4% higher thrust measured at 10 μTorr than at the lowest operating pressure. Thruster stability margin, examined as a function of magnet current, did not have a strong dependence on facility pressure. Finally, an investigation of low-power operation at the lowest facility pressure showed that a combination of added cathode keeper current and additional cathode propellant flow significantly mitigated the larger negative cathode-to-ground voltages that were observed. These test results, combined with thruster life test results, inform the selection of proper low-power operating conditions for Psyche.

Snyder, John S.↗
NASA NTRS2018

The Effects of Background Pressure on SPT-140 Hall Thruster Performance

NASA’s planned Psyche mission is scheduled to launch in 2022 and begin a 3.5-year cruise to the metallic asteroid Psyche, where it would examine this unique body. The baseline spacecraft design is a hybrid of JPL’s deep-space heritage subsystems with commercial partner SSL’s power, structure, and SPT-140 electric propulsion subsystems. Since the deepspace implementation of the SPT-140 differs from the commercial implementation, primarily in the need for deep power throttling, characterization of the system at lower powers is necessary. One specific area of interest is the sensitivity of thruster performance to background pressure in ground-based test facilities, which can have an impact on the prediction of in-space performance. Measurements of this pressure dependence were performed on a qualification-model SPT-140 thruster over the 0.9-4.5 kW range of interest for the Psyche mission. Thrust sensitivity to pressure, in an absolute sense, was largest at 4.5 kW and decreased with power until there was little-to-no measurable effect at 0.9 kW. In a relative sense, thrust sensitivity was similar at all powers above 0.9 kW with about 2-4% higher thrust measured at 10 µ µTorr than at the lowest operating pressure. Thruster magnetic field sensitivity, examined as a function of magnet current, did not have a strong dependence on facility pressure. Finally, an investigation of low-power operation at the lowest facility pressure showed that a combination of added cathode keeper current and additional cathode propellant flow significantly mitigated the larger negative cathode-to-ground voltages that were observed. These test results, combined with thruster life test results, inform the selection of proper low-power operating conditions for Psyche.

Mackey, Jonathan A.↗
DOE OSTI2022

Flexible 2D Boron Imidazolate Framework for Polysulfide Adsorption in Lithium–Sulfur Batteries

We report the "polysulfide shuttle," a process initiated by the dissolution of polysulfides, is recognized to be one of the major failure mechanisms of lithium-sulfur (Li-S) batteries. Much research effort has been dedicated toward efficient cathode additives and host materials to suppress the leaching of polysulfide species. Herein, we report a new 2D metal-organic framework constituted by a tritopic ligand, boron imidazolate ([BH(Im) 3 ] - , Im = imidazole), and Co 2+ ions for lithium polysulfide adsorption. The cobalt imidazolate framework (CoN 6 -BIF) contains octahedrally coordinated Co centers that form two-dimensional layers in the a,b plane. Composite cathodes containing CoN 6 -BIF exhibited high sulfur utilization and capacity retention, resulting in improved specific capacity and cycle life compared to sulfur/carbon controls. Density functional theory (DFT) calculations suggest that CoN 6 -BIF linkers are rotationally flexible, allowing the framework to accommodate polysulfide in the expanded pores. This unusual property of BIFs opens up new avenues for exploring flexible metal-organic frameworks (MOFs) and their applications to energy storage.

25 ENERGY STORAGE↗
DOE OSTI2026

Influence of solvents on electrochemical stability window of ionic liquid solutions

The electrochemical stability window (ESW) defines the voltage range within which an electrolyte remains stable against oxidation and reduction, serving as a key descriptor for ionic liquid (IL)-based systems. The ESWs of 15 ILs with diverse cation-anion combinations were systematically investigated, both in their neat forms and as binary mixtures with three representative solvents, i.e., propylene carbonate (PC), ethylene glycol (EG), and tetrahydrofuran (THF). Cyclic voltammetry on a glassy carbon electrode determined anodic and cathodic stability limits, revealing that ESW protection in IL-solvent mixtures strongly depends on solvent polarity, proticity, and IL compatibility. PC, with a high dielectric constant and aprotic character, broadened anodic limits and moderately stabilized cathodic limits. THF maintained compact interfacial structure, offering additional cathodic protection, whereas EG, being protic, reduced ESWs via proton-coupled electron transfer and hydrogen evolution. The solvent protection trend followed by PC > THF > EG, with bulky, hydrophobic cations ([HMIM] + , [BMPYRR] + ) and weakly coordinating anions ([NTF 2 ] - , [DCA] - , [DEP] - ) showing the highest ESW protection for 50 mol% IL in these solvents. Among the neat ILs, [EMIM][DEP], [HMIM][PF 6 ], and [BMPYRR][DCA] showed wide ESWs of ∼5.5 V. These results provide valuable insight into solvent-modulated electrochemical stability, enabling rational design of IL-based electrolytes for energy storage and electrosynthesis.

25 ENERGY STORAGE↗
DOE OSTI2024

Research Progress and Perspectives on Pre‐Sodiation Strategies for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) with abundant elements have garnered significant attention from researches as a promise compensation to lithium‐ion batteries (LIBs). However, the large‐scale commercial application of SIBs is partially hindered by the limited initial coulombic efficiency (ICE) due to the irreversible formation of solid electrolyte interphase (SEI) and intercalation into the defects in the anode. Similar to pre‐lithiation techniques, pre‐sodiation approaches are considered to be one of the most direct and effective way to compensate for the loss of active sodium at the anode side of SIBs during the initial cycle. In this context, additional sodium ions are pre‐injected to the cathode/anode material by chemical/electrochemical methods, aiming to improve battery span life and energy density. Here, this review delves into the necessity and impact of pre‐sodiation techniques, compiling the latest research progress, for instance, self‐sacrificing cathode additives, over‐sodiated cathode materials, direct contact and solution chemical pre‐sodiation. Notably, the research mechanisms underlying solution chemical pre‐sodiation are highlighted. This comprehensive overview aims to foster a deeper understanding of the pre‐sodiation techniques and expects to provide guidance for realizing the commercial application of high energy density sodium‐ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Corrosion Mitigation and Increased Discharge Capacity in Aqueous Processed Thick Cathodes using Phosphoric Acid Additives

Aqueous processed cathodes for lithium-ion batteries are favorable for both cost and environmental reasons; however, these electrodes still face significant problems with increasing areal capacities (i.e. thickness). Highly basic slurry conditions (pH in excess of 12) corrode the current collector surface and evolve hydrogen gas. Consequently, bubbling at the electrode interface causes substantial damage to the dried electrode. As the loading of these electrodes is increased, damage becomes severe and results in lack of adhesion and cohesion. Here introduction of phosphoric acid to combat the rise in pH and suppress the corrosion at the current collector surface is investigated. Phosphoric acid was added in increments of 0.5, 1.0, and 1.5 wt% and the subsequent effects on slurry rheology, particle size, adhesion, and electrochemical cycling were investigated. A technique is reported for obtaining thick (6-8 mAh/cm2) cathodes that exhibit reduced surface cracking and improved rate performance as compared to control samples.

Kukay, Alexander↗
DOE OSTI2022

Achieving SEI preformed graphite in flow cell to mitigate initial lithium loss

The irreversible lithium loss due to the formation of solid electrolyte interphase (SEI) in the initial cycle on the graphite anode greatly reduces the overall cell energy density of lithium ion batteries, that is, the lost Li ions from forming SEI lead to the decrease of Li ions for the intercalation. The method of cathode prelithiation has been widely explored to compensate this lithium loss. However, these cathode additives with high lithium contents inevitably lower the loading of the cathode active materials. In this work, we report a novel approach to solve this challenge, a facile graphite prelithiation method by preforming SEI layers on the surface of graphite powders (Pre-SEI graphite) utilizing a specially designed flow cell. The Li accommodation in the graphite anode can be controlled by the operating time and current density in the flow cell for the electrochemical SEI formation. As a result, we demonstrate a 10% initial Columbic efficiency increase of the LiFePO 4 electrode in a full cell configuration using the Pre-SEI graphite, compared with the pristine graphite anode. The electrochemical preformation of SEI on the graphite powders offers a complete solution to offset initial lithium loss without a sacrifice of active cathode material loading.

25 ENERGY STORAGE↗
DOE OSTI2023

Fuel cell cathode and fuel cell system including a polymeric additive

A cathode configured for use within a fuel cell system is provided. The cathode includes a cathode substrate. The cathode further includes a coating disposed upon the cathode substrate and including a fluorocarbon polymer additive configured for sintering at a temperature of less than 200° C. The fluorocarbon polymer additive may be mixed with a catalyst ink coating or may be applied separately as a topcoat layer.

Ramaswamy, Nagappan↗
DOE OSTI2023

Cathode regeneration and upcycling of spent LIBs: toward sustainability

‘Green ambition towards sustainability’ is one of the hot research topics of the 21st century. With the sharp steering of the energy infrastructure toward fulfilling this radical expectation, the last decade has seen a global trend toward diversified sustainable renewable energy sources (such as solar, wind, and hydroelectric power) and electrification. Lithium-ion batteries (LIBs) are playing a significant role in this energy revolution. However, with the massive scale of the production of LIBs and their eventual retirement, attention has been turned to the erratic supply of raw materials used to manufacture these batteries and their disposal. Cathode regeneration technology is likely to be an optimal solution for the disposal of waste cathodes, aimed at non-destructively repairing and straightforwardly reusing degraded cathode materials for re-manufacturing LIBs with a shortened circular process, reasonable profits, and excellent efficiency. Additionally, cathode upcycling technology, aimed at upgrading the electrochemical performance of degraded materials, can be well adapted to the upgrading of battery chemistry and show excellent flexibility and potential for transforming the LIB industry from a resource-based to a circular economy. Thus, a holistic perspective based on the complete life cycle of LIBs is encouraged, and sustainability must be at the forefront regarding battery and pack design, raw material acquisition, materials synthesis, manufacturing, operating, retiring, and recycling processes of LIBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Topotaxially grown composite cathodes for cobalt-free high-energy long-life Li-ion batteries

The vehicle industry’s increasing demand for electrification necessitates the removal of expensive and rare cobalt from current high-energy batteries. However, eliminating cobalt poses challenges due to its vital role in maintaining the layered structural ordering and cycling stability of commonly used Li(NiMnCo)O 2 cathodes. As an alternative to conventional layered oxide designs, we report a lithium nickelate cathode with a composite structure comprising major stoichiometric layered and minor rocksalt phases within the same oxygen lattice. This material outperforms conventional designs by maintaining stable battery operation at voltages up to 4.8 V vs. Li|Li + , with 88% capacity retention after 1000 cycles at 2C. The topotaxial-growth-enabled interlock between the two components mitigates chemo-mechanical degradation, offering a promising pathway to cobalt-free cathodes. Additionally, we reveal a miscibility gap in the Li-Ni-O system that enables kinetic adjustment of composition and structure during sintering, thereby tuning the functionality of high-energy cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Understanding implications of cathode architecture on energy density of solid-state batteries

Next generation solid-state batteries (SSB) will need to leverage high voltage cathodes, as well as metallic anodes to achieve the realistic performance targets necessary to replace liquid electrolyte-based batteries in cutting-edge applications including electric vehicles. However, limitations arising from mass and charge transports, kinetics and chemo-mechanical degradation at the electrode | electrolyte interface limit the performance of present day SSBs. Optimizing composite cathode architecture, which is an integral part of solid-state batteries, is vital to realize the high-energy density and high-performance goals for next-generation solid-state batteries. Additionally, cathode architecture needs to be optimized for high loadings of active material, well-percolated ion and electron transport pathways and increased resilience against electrochemical stresses. This paper provides a first report of framework for geometric modeling of composite cathode architectures and evaluates the impact of cathode architecture on cell-level energy density using hierarchical models. Packing around primary and secondary active material particles are simulated for a range of active material particle size and solid electrolyte size distributions in the composite cathode. Impact of packing architecture on processing parameters of a given cathode composition and thickness, as well as on achievable energy density is evaluated for a range of commonly used solid electrolyte and cathode materials. Overall, the proposed framework offers a facile exploratory methodology for establishing initial metrics for scalable processing of practical and competent SSBs.

25 ENERGY STORAGE↗