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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 OSTI2025

A Perspective on Pathways Toward Commercial Sodium‐Ion Batteries

Lithium-ion batteries (LIBs) have been widely adopted in the automotive industry, with an annual global production exceeding 1000 GWh. Despite their success, the escalating demand for LIBs has created concerns on supply chain issues related to key elements, such as lithium, cobalt, and nickel. Sodium-ion batteries (SIBs) are emerging as a promising alternative due to the high abundance and low cost of sodium and other raw materials. Nevertheless, the commercialization of SIBs, particularly for grid storage and automotive applications, faces significant hurdles. This perspective article aims to identify the critical challenges in making SIBs viable from both chemical and techno-economic perspectives. First, a brief comparison of the materials chemistry, working mechanisms, and cost between mainstream LIB systems and prospective SIB systems is provided. The intrinsic challenges of SIBs regarding storage stability, capacity utilization, cycle stability, calendar life, and safe operation of cathode, electrolyte, and anode materials are discussed. Furthermore, issues related to the scalability of material production, materials engineering feasibility, and energy-dense electrode design and fabrication are illustrated. Finally, promising pathways are listed and discussed toward achieving high-energy-density, stable, cost-effective SIBs.

25 ENERGY STORAGE↗
NASA NTRS1974

Cold cathodes for sealed-off CO2 lasers

Cold cathodes for CO2 lasers should possess a very low sputtering rate, have a minimum of negative ions in the sputtering products, and consume no oxygen. These conditions can be satisfied by selecting cathode materials from those elements of group I in the periodic table which form semiconducting oxide layers and then exposing these elements to a reducing gas mixture. Experimental results show that silver, internally oxidized silver-copper alloys, and pure copper satisfy most of these requirements in He-CO2-CO-Xe gas mixtures. Infrared CO and CO2 gas analysis performed on simple gas discharge tubes using such cathodes indicate that laser lives of 10,000 hr can be expected.

Hochuli, U. E.↗
DOE OSTI2021

Degradation Diagnostics from the Subsurface of Lithium-Ion Battery Electrodes

Despite the long-established rocking-chair theory of lithium-ion batteries (LIBs), developing novel characterization methodology with higher spatiotemporal resolution facilitates a better understanding of the solid electrolyte interphase studies to shape the reaction mechanisms. In this work, we develop a Xenon ion plasma focused ion beam (Xe + PFIB)-based characterization technique to probe the cross-sectional interface of both ternary cathode and graphite anode electrodes, with the focus on revealing the chemical composition and distribution underneath the electrode surface by in-depth analysis of secondary ions. Particularly, the lithium fluoride is detected in the pristine cathode prior to contact with the electrolyte, reflecting that the electrode degradation is in the form of the loss of lithium inventory during electrode preparation. This degradation is related to the hydrolysis of the cathode material and the decomposition of the PVDF binder. Here, through the quantitative analysis of the transition-metal degradation products, manganese is found to be the dominant element in the newly formed inactive fluoride deposition on the cathode, while no transition metal signal can be found inside the anode electrode. These insights at high resolution implemented via a PFIB-based characterization technique not only enrich the understanding of the degradation mechanism in the LIBs but also identify and enable a high-sensitivity methodology to obtain the chemical survey at the subsurface, which will help remove the capacity-fade observed in most LIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

A scalable approach of using biomass derived glycerol to synthesize cathode materials for lithium-ion batteries

Glycerol, a main byproduct of biodiesel, was used as the fuel agent in a scalable flame-assisted spray pyrolysis approach to synthesize micron-size cathode materials. Single droplet combustion, particle morphology, and electrochemical performance were examined considering the effects of salt concentration, water addition, and post-annealing time on synthesizing Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 (NCM111) cathode materials. Single droplet tests showed that a sufficient amount of water in the glycerol-based precursor could delay droplet inflation and ignition. Moreover, using a two-fluid atomization nozzle, spray tests demonstrated that adding water would result in less wrinkled and more uniform particles. Nevertheless, increasing water proportion in the precursor could reduce the reaction heat, resulting in that samples prepared with water addition needed longer post-annealing time to improve their electrochemical performance. Using the precursor without water, the best performed NCM111 cathode material was synthesized with only 2 h of post-annealing. It has a discharge capacity of 163.3 mAh/g at 0.1C and 85.5% capacity retention at 1C after 100 cycles. Furthermore, the current work confirmed the capability of using glycerol as a sustainable fuel agent to synthesize NCM111 cathode materials, and also provided basic conditions for the development of large-scale production in the future.

25 ENERGY STORAGE↗
DOE OSTI2023

Unraveling the nature of sulfide ions in hydrometallurgical recycling of NCM622 cathode material

The use of lithium-ion batteries (LIBs) has increased dramatically since its initial inception in the late 20th century. Such a surge in the LIB market and industry has resulted in a huge demand for mineral resources. Besides, the large scale of production will lead to massive amounts of waste batteries in the end. As such, recycling is seen as an end-of-pipe process to resolve sustainability and environmental concerns. The hydrometallurgical recycling is considered to be the most prominent method to recover cathode materials from spent LIBs owing to its high leaching efficiency and low energy costs. A series of procedures including pretreatment of the spent LIBs, acid leaching of the black mass, chemical co-precipitation of the hydroxide precursor, and sintering of the cathode active material need to be operated precisely. In this aspect, the impurities introduced during the process could pose a serious threat to the reaction stability as well as recycling consistency. Here, the impact of sulfide ions on recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode material with the method of hydrometallurgy is first investigated in detail. This study shows that hydrometallurgical process is not obviously influenced by sulfide impurity. No signs of secondary phase or impurity inclusion are spotted in synthesized cathodes. Under 5 at % sulfide concentration conditions, the obtained NCM622 cathode exhibits a capacity of 159.4 mAh/g after 100 cycles at 1/3C, which is at the same level as virgin benchmark. The difference in rate performance between cathodes with and without additional sulfide is less than 2 % or even smaller. In short, the results indicate a neutral status of sulfide ions in hydrometallurgical recycling.

25 ENERGY STORAGE↗
DOE OSTI2024

Degradation Mechanism of Phosphate‐Based Li‐NASICON Conductors in Alkaline Environment

NASICON-type Li conductors (Li-NASICON) have traditionally been regarded as promising candidates for solid-state Li-air battery applications because of their stability in water and ambient air. However, the presence of water in the cathode of a Li-air battery can induce a highly alkaline environment by modifying the discharge product from Li 2 O 2 to LiOH which can potentially degrade cathode and separator materials. This study investigates the alkaline stability of common Li-NASICON chemistries through a systematic experimental study of LiTi x Ge 2-x (PO 4 ) 3 (LTGP) with varying x = 0–2.0. Density functional theory calculations are combined to gain a mechanistic understanding of the alkaline instability. It is demonstrated that the instability of LTGP in an alkaline environment is mainly driven by the dissolution of PO 4 3– groups, which subsequently precipitate as Li 3 PO 4 . The introduction of Ti facilitates the formation of a Ti-rich compound on the surface that eventually passivates the material, but only after significant bulk degradation. Consequently, phosphate-based Li-NASICON materials exhibit limited alkaline stability, raising concerns about their viability in humid Li-air batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Revisiting Discharge Mechanism of CF x as a High Energy Density Cathode Material for Lithium Primary Battery

Lithium/fluorinated graphite (Li/CFx) primary batteries show great promise for applications in a wide range of energy storage systems due to their high energy density (>2100 Wh kg –1 ) and low self-discharge rate (<0.5% per year at 25 °C). While the electrochemical performance of the CF x cathode is indeed promising, the discharge reaction mechanism is not thoroughly understood to date. In this article, a multiscale investigation of the CF x discharge mechanism is performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, cross-sectional focused ion beam, high-resolution transmission electron microscopy, and scanning transmission electron microscopy with electron energy loss spectroscopy are utilized to investigate this system. Results show no metallic lithium deposition or intercalation during the discharge reaction. Crystalline lithium fluoride particles uniformly distributed with <10 nm sizes into the CF x layers, and carbon with lower sp2 content similar to the hard-carbon structure are the products during discharge. This article deepens the understanding of CF x as a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Polypeptide organic radical batteries

In only a few decades, lithium-ion batteries have revolutionized technologies, enabling the proliferation of portable devices and electric vehicles, with substantial benefits for society. However, the rapid growth in technology has highlighted the ethical and environmental challenges of mining lithium, cobalt and other mineral ore resources, and the issues associated with the safe usage and non-hazardous disposal of batteries. Only a small fraction of lithium-ion batteries are recycled, further exacerbating global material supply of strategic elements. A potential alternative is to use organic-based redox-active materials to develop rechargeable batteries that originate from ethically sourced, sustainable materials and enable on-demand deconstruction and reconstruction. Making such batteries is challenging because the active materials must be stable during operation but degradable at end of life. Further, the degradation products should be either environmentally benign or recyclable for reconstruction into a new battery. Here we demonstrate a metal-free, polypeptide-based battery, in which viologens and nitroxide radicals are incorporated as redox-active groups along polypeptide backbones to function as anode and cathode materials, respectively. These redox-active polypeptides perform as active materials that are stable during battery operation and subsequently degrade on demand in acidic conditions to generate amino acids, other building blocks and degradation products. Here, such a polypeptide-based battery is a first step to addressing the need for alternative chemistries for green and sustainable batteries in a future circular economy.

25 ENERGY STORAGE↗
DOE OSTI2023

Roles of Mn and Co in the Air Synthesizability of Layered Oxide Cathodes for Lithium-Based Batteries

High-nickel layered oxides (LiNi 1-x-y Mn x Co y O 2 ) are the prevailing cathode materials for high-energy-density lithium-based batteries, but they are plagued with deleterious surface air instabilities stemming from residual lithium formation. These issues severely hinder mass production as cathode calcination is limited to a flowing oxygen atmosphere, which entails high manufacturing costs as opposed to simpler and more economical air calcination. Here, while higher Ni contents are known to worsen air instabilities, the influence of Mn and Co contents on impacting these phenomena are less elucidated. We herein present the synthesis in ambient air and flowing oxygen atmospheres of three cathode variants with the same Ni contents, but varying Mn and Co contents: LiNi 0.7 Mn 0.3 O 2 , LiNi 0.7 Mn 0.15 Co 0.15 O 2 , and LiNi 0.7 Co 0.3 O 2 . It is found that the critical parameter influencing the air stability of the cathodes is the average Ni oxidation state, which is greatly dependent on the Mn and Co contents. Substitution of Mn for Ni drives down the Ni oxidation state as Mn exists as Mn4 + and reduces surface residual lithium formation, which vastly improves the overall air stability and, therefore, the synthesizability in air, but with a penalty of lowered capacity. In contrast, substitution of Co for Ni maintains Ni 3+ as Co exists as Co 3+ , offering increased initial capacity, but worsens the air stability and cyclability as the driving force for residual lithium formation and surface reactivity is increased.

25 ENERGY STORAGE↗
DOE OSTI2021

Effect of cathode on crosstalk in Si-based lithium-ion cells

Crosstalk between the cathode and the anode in Li-ion batteries has a great impact on performance, safety and cycle lifetime. However, a systematic investigation of crosstalk behavior in silicon (Si)-based cells with various cathode materials has not been reported. We investigated the crosstalk behavior of a Si anode coupled with one of the following cathodes—LiCoO 2 (LCO), LiNi 0.5 Mn 0.3 Co 0.2 (NMC532), and LiFePO 4 (LFP)—in a full cell. For each electrochemical couple, we compared electrolyte decomposition products, solid electrolyte interphase (SEI) chemistry, and degradation mechanisms during cycling. From a very early stage of cycling, each couple showed different crosstalk behavior; different electrolyte decomposition products and SEI chemistry on the Si anodes were seen. Specifically, the formation and growth mechanism of Si SEI differ depending on cathode materials. For the LFP system, the Si SEI rich in LiF and inorganic species, which is stable and robust. It forms at an early stage of cycle. As a result, the SEI of Si from the LFP system well tolerates SEI breakage due to mechanical changes of Si and suppresses Li loss, resulting in stable cycle life.

25 ENERGY STORAGE↗
DOE OSTI2023

Direct recycling of spent nickel-rich cathodes in reciprocal ternary molten salts

Lithium-ion batteries (LIBs) have revolutionized portable electronics and electric vehicles (EVs), but the growing accumulation of end-of-life (EOL) batteries poses environmental challenges. Recycling high-value cathodes from EOL LIBs can minimize waste and reduce the need for mining critical minerals. Here, this study focuses on the direct recycling of Ni-rich cathodes, particularly lithium-manganese-cobalt-oxide (NMC) 622 in a “reciprocal ternary molten salts (RTMS)" system. The ionothermal relithiation in the RTMS system successfully restores the layered structure, lithium content, and electrochemical performance of the NMC 622 cathode, comparable to the pristine material. The cost analysis reveals that cathode regeneration through ionothermal relithiation is more economical than virgin production or conventional recycling methods.

25 ENERGY STORAGE↗
DOE OSTI2022

Micro cavity fission chamber radiation detection system

A radiation detector to monitor the neutron flux of a nuclear reactor or other high-radiation environment, that can withstand the high temperatures and radiation fields of such environment, is provided. A small dielectric substrate with a low neutron-activation cross section is provided. The substrate is coated with a neutron conversion material, such as uranium oxide or thorium oxide. One or more substrates form a micro-sized detection cavity that is filled with a detection gas. A voltage is provided across anode and cathode wires in the detection cavity. A neutron absorbed in the conversion material may release reaction products into the gas, causing ionization of the gas which then produces a current or voltage signal. The small detector volume minimizes energy deposition into the detection gas by competing particles such as gamma rays, fast electrons, and beta particles, and therefore minimizes false counts while retaining large signals from neutron interactions.

McGregor, Douglas S.↗
DOE OSTI2022

The Effects of Phosphate Impurity on Recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Material via a Hydrometallurgy Method

From portable electronics to electric vehicles, lithium-ion batteries have been deeply integrated into our daily life and industrial fields for a few decades. The booming field of battery manufacturing could lead to shortages in resources and massive accumulation of battery waste, hindering sustainable development. Therefore, hydrometallurgy-based approaches have been widely used in industrial recycling to recover cathode materials due to their high efficiency and throughput. Further, impurities have always been a great challenge for hydrometallurgical recycling, introducing challenges to maintain the consistency of product quality because of potential unintended effects caused by impurities. Herein, after comprehensive investigation, we first report the impacts of phosphate impurity on a recycled LiNi 0.6 Co 0.2 Mn 0.2 O 2 ("NCM622") cathode via a hydrometallurgy method. We demonstrate that a passivation layer of Li 3 PO 4 is formed at grain boundaries during sintering, which significantly raises the activation barrier and hinders lithium diffusion. In addition, the distinct degradation of cathode electrochemical properties is observed from poor particle morphology and high cation mixing as a result of phosphate impurity. Cathode powders with 1 at. % phosphate impurity retain a capacity of 146 mAh/g after 100 cycles at 0.33C, 6% less than that of a virgin cathode. Furthermore, cathodes with higher phosphate concentrations perform even worse in electrochemical tests. Therefore, phosphate impurities are detrimental to the hydrometallurgical recycling of NCM cathode materials and need to be excluded from the recycling process.

25 ENERGY STORAGE↗
DOE OSTI2020

Zincate-Blocking-Functionalized Polysulfone Separators for Secondary Zn–MnO 2 Batteries

Alkaline zinc–manganese dioxide (Zn–MnO 2 ) batteries are well suited for grid storage applications because of their inherently safe, aqueous electrolyte and established materials supply chain, resulting in low production costs. With recent advances in the development of Cu/Bi-stabilized birnessite cathodes capable of the full 2-electron capacity equivalent of MnO 2 (617 mA h/g), there is a need for selective separators that prevent zincate (Zn(OH) 4 ) 2– transport from the anode to the cathode during cycling, as this electrode system fails in the presence of dissolved zinc. In this work, we present the synthesis of N-butylimidazolium-functionalized polysulfone (NBI-PSU)-based separators and evaluate their ability to selectively transport hydroxide over zincate. We then examine their impact on the cycling of high depth of discharge Zn/(Cu/Bi–MnO 2 ) batteries when inserted in between the cathode and anode. Initially, we establish our membranes’ selectivity by performing zincate and hydroxide diffusion tests, showing a marked improvement in zincate-blocking (D Zn (cm 2 /min): 0.17 ± 0.04 × 10 –6 for 50-PSU, our most selective separator vs 2.0 ± 0.8 × 10 –6 for Cellophane 350P00 and 5.7 ± 0.8 × 10 –6 for Celgard 3501), while maintaining similar crossover rates for hydroxide (D OH (cm 2 /min): 9.4 ± 0.1 × 10 –6 for 50-PSU vs 17 ± 0.5 × 10 –6 for Cellophane 350P00 and 6.7 ± 0.6 × 10 –6 for Celgard 3501). We then implement our membranes into cells and observe an improvement in cycle life over control cells containing only the commercial separators (cell lifetime extended from 21 to 79 cycles).

crossover↗
DOE OSTI2024

Life-cycle analysis of lithium chemical production in the United States

To achieve its ambitious national decarbonization goals, the United States has incentivized the domestic production of materials critical to decarbonization technologies, including lithium-ion batteries (LIBs). These materials include battery-grade lithium chemicals (Li-chemicals), for which the U.S. is encouraging domestic production from resources (sedimentary clays and low Li-content brines (LLCBs)) that differ substantially from conventional sources (Salar brines and spodumene ores). Here, we conduct the first-ever comparative life-cycle analysis of Li-chemical production from all alternative resources (in the U.S.) and conventional sources based on data from company literature for U.S.-related production efforts. Two energy sources (electricity and natural gas), four material inputs (HCl, NaOH, Na 2 CO 3 , and CaO), and process carbon emissions dominate the life-cycle impacts (≥90% share) of U.S.-based Li-chemical production. Comparatively, the life-cycle impacts of alternative sources-based Li-chemicals lie between those for Li-chemical production from Salar brines and from spodumene ores. At the battery level, the shift in Li-chemical sourcing causes a notable change in LIB's life-cycle impacts (by ~5–15%), independent of the cathode chemistry employed. Our study highlights the relevance of a decarbonized electric grid and the capture and sequestration of process carbon emissions generated during Li-chemical and upstream material production in decarbonizing Li-chemical production from alternative sources. Further decarbonization would necessitate using decarbonized material inputs and a shift away from natural gas towards renewable energy for alternative resource-based Li-chemical production processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells

MoO3 has shown promise as a cathode material that can extend the upper limit of operating temperature of rechargeable lithium thin-film electrochemical cells. Cells of this type are undergoing development for use as energy sources in cellular telephones, wireless medical sensors, and other, similarly sized portable electronic products. The LiCoO2 and LiMn2O4 cathodes heretofore used in these cells exhibit outstanding cycle lives (of the order of hundreds of thousands of cycles) at room temperature, but operation at higher temperatures reduces their cycle lives substantially: for example, at a temperature of 150 C, cells containing LiCoO2 cathodes lose half their capacities in 100 charge/discharge cycles. The superiority of MoO3 as a cathode material was demonstrated in experiments on lithium thin-film cells fabricated on glass slides. Each cell included a layer of Ti (for adhesion to the glass slide), a patterned layer of Pt that served as a cathode current collector, a cathode layer of MoO3, a solid electrolyte layer of Li3.3 PO3.8 N0.22 ("LiPON"), and an anode layer of Li. All the layers were deposited by magnetron sputtering except for the Li layer, which was deposited by thermal evaporation. These cells, along with similar ones containing LiCoO2 cathodes, were subjected to several tests, including measurements of specific capacity in charge/discharge cycling at a temperature of 150 C. The results of these measurements, plotted in the figure, showed that whereas specific capacity of the cells containing LiCoO2 cathodes faded to about half its initial value after only 100 cycles, the specific capacity of the cells containing the MoO3 cathodes faded only slightly during the first few hundred cycles and thereafter not only recovered to its initial value but continued to increase up to at least 5,500 cycles.

West, William↗
NASA NTRS2010

Performance Testing of Molten Regolith Electrolysis with Transfer of Molten Material for the Production of Oxygen and Metals on the Moon

Previously, we have demonstrated the production of oxygen by electrolysis of molten regolith simulants at temperatures near 1600 C. Using an inert anode and suitable cathode, direct electrolysis (no supporting electrolyte) of the molten silicate is carried out, resulting in the production of molten metallic products at the cathode and oxygen gas at the anode. Initial direct measurements of current efficiency have confirmed that the process offer potential advantages of high oxygen production rates in a smaller footprint facility landed on the moon, with a minimum of consumables brought from Earth. We now report the results of a scale-up effort toward the goal of achieving production rates equivalent to 1 metric ton O2/year, a benchmark established for the support of a lunar base. We previously reported on the electrochemical behavior of the molten electrolyte as dependent on anode material, sweep rate and electrolyte composition in batches of 20-200g and at currents of less than 0.5 A. In this paper, we present the results of experiments performed at currents up to 10 Amperes) and in larger volumes of regolith simulant (500 g - 1 kg) for longer durations of electrolysis. The technical development of critical design components is described, including: inert anodes capable of passing continuous currents of several Amperes, container materials selection, direct gas analysis capability to determine the gas components co-evolving with oxygen. To allow a continuous process, a system has been designed and tested to enable the withdrawal of cathodically-reduced molten metals and spent molten oxide electrolyte. The performance of the withdrawal system is presented and critiqued. The design of the electrolytic cell and the configuration of the furnace were supported by modeling the thermal environment of the system in an effort to realize a balance between external heating and internal joule heating. We will discuss the impact these simulations and experimental findings have on the design of a suitable prototype for lunar applications

Sibille, Laurent↗
DOE OSTI2021

Direct Recycling R&D at the ReCell Center

The expected rapid growth in electric vehicle deployment will inevitably be followed by a corresponding rise in the supply of end-of-life vehicles and their lithium-ion batteries (LIBs). The batteries may be reused, but will eventually be spent and provide a potential domestic resource that can help supply materials for future battery production. However, commercial recycling processes depend on profits from recovery of cobalt, use of which is being reduced in new cathode chemistries. The U.S. Department of Energy, therefore, established the ReCell Center in early 2019 to develop robust LIB recycling technology that would be economical even for batteries that contain no cobalt. The central feature of the technology is recovery of the cathode material with its unique crystalline cathode morphology intact in order to retain its value and functionality. Other materials are recovered as well in order to maximize revenues and minimize waste-handling costs. Analysis and modeling serve to evaluate and compare process options so that we can identify those that will be most economical while still minimizing energy use and environmental impacts. This paper provides background and describes highlights of the center’s first 2 years of operation.

Gaines, Linda (ORCID:0000000237263387)↗