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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Salt-rich solid electrolyte interphase for safer high-energy-density Li metal batteries with limited Li excess

We propose a carbonate-based electrolyte optimized with dual cations and ionic liquid for high-efficiency Li metal batteries with a high-voltage cathode. An average coulombic efficiency of Li deposition of 99.6% is achieved due to the salt-rich solid electrolyte interphase and Na guided uniform Li plating. The Li||NCM811 cells can be cycled with limited Li (N/P = 1) over 90 cycles. An additional advantage is that it improves the thermal stability of the NCM811 cathode.

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

Dual Functional Ni3S2@Ni Core-Shell Nanoparticles Decorating Nanoporous Carbon as Cathode Scaffolds for Lithium-Sulfur Battery with Lean Electrolytes

Lithium-sulfur batteries are very promising for next-generation energy storage. However, most studies use flooded electrolytes to achieve a high specific capacity at the expense of lowering the specific energy. Understanding lithium-sulfur battery performance with lean electrolytes is highly desirable. Herein, a modified Pechini method is developed to synthesize a nanoporous carbon host decorated with Ni3S2@Ni particles. Such a cathode delivers enhanced specific capacities with extended cycling life in lean electrolytes, due to the dual functions of the Ni3S2 shell, which can both facilitate reaction kinetics and promote electrolyte wetting. This work highlights a strategy to rationally design cathodes for highenergy lithium-sulfur batteries.

Zhang, Yulun↗
NASA NTRS2009

Performance Demonstration of Mcmb-LiNiCoO2 Cells Containing Electrolytes Designed for Wide Operating Temperature Range

With the intent of improving the performance of Li-ion cells over a wide operating temperature range, we have investigated the use of co-solvents to improve the properties of electrolyte formulations. In the current study, we have focused upon evaluating promising electrolytes which have been incorporated into large capacity (7 Ah) prototype Li-ion cells, fabricated by Yardney Technical Products, Inc. The electrolytes selected for performance evaluation include the use of a number of esters as co-solvents, including methyl propionate (MP), ethyl propionate (EP), ethyl butyrate (EB), propyl butyrate (PB), and 2,2,2-trifluoroethyl butyrate (TFEB). The performance of the prototype cells containing the ester-based electrolytes was compared with an extensive data base generated on cells containing previously developed all carbonate-based electrolytes. A number of performance tests were performed, including determining (i) the discharge rate capacity over a wide range of temperatures, (ii) the charge characteristics, (iii) the cycle life characteristics under various conditions, and (iv) the impedance characteristics.

Smart, M. C.↗
NASA NTRS2000

Electrolytes for Li-Ion Cells in Low Temperature Applications

Prototype AA-size lithium-ion cells have been demonstrated to operate effectively at temperatures as low as -30 to -40 C. These improvements in low temperature cell performance have been realized by the incorporation of ethylene carbonate-based electrolytes which possess low melting, low viscosity cosolvents, such as methyl acetate, ethyl acetate, gamma-butyrolactone, and ethyl methyl carbonate. The cells containing a 0.75M LiPF6 EC+DEC+DMC+EMC (1:1:1:1) electrolyte displayed the best performance at -30 C (> 90% of the room temperature capacity at approximately C/15 rate), whereas, at -40 C the cells with the 0.75M LiPF6 EC+DEC+DMC+MA (1:1:1:1) and 0.75M LiPF6 EC+DEC+DMC+EA (1:1:1:1) electrolytes showed superior performance.

Smart, M. C.↗
NASA NTRS1979

Carbon dioxide electrolysis using a ceramic electrolyte

This paper discusses the results of an experimental study of the electrical aspects of carbon dioxide electrolysis using a ceramic electrolyte. The electrolyte compositions used in this study are 8% Y2O3 stabilized ZrO2, 7.5% CaO stabilized ZrO2, and 5% Y2O3 stabilized ThO2. Results indicate that the 8% Y2O3 stabilized ZrO2 is the best material to use for electrolysis, in terms of current as a function of voltage and temperature, and in terms of efficiency of oxide ion flow through it. The poorest results were obtained with the 5% Y2O3 stabilized ThO2 composition. An electrolysis system which might be employed to reclaim oxygen and carbon from effluents of space manufacturing, assuming that an industry would have to electrolyze 258,000 tonnes of CO2 per year, is predicted to require a total cell area of 110,000 sq m of 1 mm thickness and electrical capacity of 441 MW.

Erstfeld, T. E.↗
DOE OSTI2022

Dual Passivation of Cathode and Anode through Electrode–Electrolyte Interface Engineering Enables Long-Lifespan Li Metal–SPAN Batteries

The reliability and durability of lithium metal (Li 0 )–sulfur batteries are largely limited by the undesired Li 0 plating-stripping irreversibility and the detrimental polysulfide dissolution, yet approaches that can simultaneously address the above anodic and cathodic problems are scarce. In this study, we report the stable operation of a Li 0 -SPAN (sulfurized polyacrylonitrile) battery via an anode–cathode dual-passivation approach. By combination of a fluorinated localized high concentration electrolyte (LHCE) and a Li 3 N-forming additive (TMS-N 3 ), robust and highly conductive electrode passivation layers are formed in situ on the surface of both the Li 0 anode and the SPAN cathode. The resulting highly reversible, dendrite-free, and high-density Li 0 plating morphology enables a high Coulombic efficiency of 99.4%. Advanced tender energy X-ray spectroscopy also reveals the eliminated Li 2 S formation and minimized polysulfide dissolution in SPAN cathodes, leading to a high capacity of 580 mAh/g SPAN and stable cycling with negligible capacity decay (0.7%) for 800 cycles. This electrode–electrolyte interphase engineering strategy has tackled the major limitations of Li–S batteries in both ether- and carbonate-based electrolyte systems and under a wide temperature range from –10 to +50 °C, thus providing insightful guidelines for the rational design of highly durable and high-energy-density Li 0 -S batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

High-Nickel Cathode Materials for High-Energy, Long-Life, Low-Cost Lithium-Ion Batteries (Final Report)

The overall goal of this project is to produce Li-ion cells, which deliver at least 600 Wh kg -1 at the cathode level with usable lifetimes of at least 1,000 cycles or 15 years of storage (calendar life). A secondary goal of this project is to minimize the use of cobalt in the cathode, with the ultimate goal of eliminating cobalt entirely. To develop such a cathode, the University of Texas at Austin (UT Austin) team extensively investigated the structural, physical, and chemical properties of layered oxide materials. A panel of dopant elements were surveyed with an emphasis on identifying those, which impart electrochemical and thermal stability. Of those tested, Al and Mg showed the greatest performance improvements while still being easily incorporated into the cathode through simple alterations of the precursor coprecipitation method. Other dopants, such as Ta, Nb, B, and F significantly improved cathode performance, yet their mode of incorporation required additional processing which negated their use under scaled-up conditions. From this work, a first-generation cathode LiNi 0.85 Mn 0.075 Co 0.05 Al 0.02 Mg 0.005 O 2 (NMCAM-85) was produced and an initial set of 2 Ah cells was fabricated by Tesla Inc. These cells delivered 650 Wh kg -1 and a cycle life of just over 700 cycles. Further improvements were garnered through careful study of electrolyte additives. A tailored, ethylene carbonate (EC)-free electrolyte was developed, which improved capacity retention from 60% to 82% after 500 cycles in model LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA-90) full cells. This study identified the additives fluoroethylene carbonate (FEC) and lithium difluorophosphate (LiPO 2 F 2 ) as beneficial additives, which were included in the electrolyte for the end-of-project cells. The UT Austin team developed a high-Ni layered oxide cathode LiNi 0.85 Mn 0.1 Al 0.05 Mg 0.005 O 2 (NMAM-85) capable of meeting the project goals. This cathode was synthesized in kilogram quantities and delivered to Tesla for fabrication into 2 Ah pouch cells for DOE testing. These large-format cells achieved 630 Wh kg -1 at the cathode level under the designated testing parameters, meeting the project goal with a completely cobalt-free cathode. The large-format cells are currently undergoing cycle life and calendar life evaluation at Idaho National Lab.

25 ENERGY STORAGE↗
DOE OSTI2022

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗
DOE OSTI2023

In situ microscopy and spectroscopy characterization of microsized Sn anode for sodium-ion batteries

Microsized Sn is a promising anode material for sodium-ion batteries in terms of cost, specific capacity, and volumetric energy density, which however suffers from huge volume changes and rapid cell degradation upon cycling. Despite recent advances via nanostructured electrode design and interface engineering, the correlation between mechanical stability, solid-electrolyte interphase (SEI) and reaction kinetics/reversibility remains controversial and elusive. Here, in this work, by combining in situ scanning electron microcopy and X-ray absorption spectroscopy as well as X-ray photoelectron spectroscopy, we have investigated the underlying electro-chemo-mechanical behavior and their coupling effects during charge/discharge of microsized Sn anode. Our results revealed that microsized Sn is pulverized into nanoparticles with simultaneous formation of numerous voids and pores upon the 1st charge/discharge, while the electrolytes composition plays a critical role on the consequent parasitic reactions and eventually the sodiation/de-sodiation reversibility. In contrast to carbonate-based electrolytes, ether-based electrolytes enabled formation of inorganic species dominated SEI with improved mechanical strength, thus leading to higher specific capacity and improved cycling stability. The present findings are crucial for future development of microsized anode materials for rechargeable batteries with high volumetric energy density.

25 ENERGY STORAGE↗
DOE OSTI2023

Elucidating the Effects of Temperature on Nonaqueous Redox Flow Cell Cycling Performance

The impact of cell temperature is a relatively underexplored area within the burgeoning field of nonaqueous redox flow batteries (NAqRFBs). Here, we investigate the effect of elevated temperature on the performance of nonaqueous redox electrolytes and associated flow cells. Using a model compound, N-(2-(2-methoxyethoxy)-ethyl)phenothiazine (MEEPT), in a propylene-carbonate-based electrolyte, we experimentally measure the temperature dependence of relevant physicochemical properties (i.e., electrolyte conductivity, viscosity, diffusivity) and electrochemical characteristics (i.e., chemical and electrochemical reversibility) across a temperature range of 30 °C to 70 °C. We then perform flow cell studies, finding that while ohmic and mass transport resistances decrease significantly with increases in temperature for the MEEPT/MEEPT +· redox couple, accessible electrolyte capacity gradually reduces at temperatures > 50 °C. Ex-situ, post-test characterization using microelectrode voltammetry suggests that this capacity fade is due to instability of the MEEPT radical cation. Finally, using MEEPT as a posolyte and a model viologen negolyte (bis(2-(2-methoxyethoxy)ethyl)viologen), we assemble a full cell and perform polarization analyses, observing a 2× increase in the peak power density when the operating temperature is increased from 30 °C to 70 °C. Broadly, this work highlights opportunities for systematic engineering of nonaqueous electrolytes and flow cells for higher power operation at elevated temperatures.

Electrochemistry↗
NASA NTRS2007

Performance of Low Temperature Electrolytes in Experimental and Prototype Li-Ion Cells

Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with ethylene carbonate-based electrolytes optimized for low temperature in experimental MCMB-LiNixCo1_x0 2 cells. In addition to obtaining discharge and charge rate performance data at various temperatures, electrochemical measurements were performed on individual electrodes (made possible by the incorporation of Li reference electrodes), including EIS, linear polarization and Tafel polarization measurements. The combination of techniques enables the elucidation of various trends associated with electrolyte composition. In addition to investigating the behavior in experimental cells, the performance of many promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

Li-ion batteries↗
NASA NTRS2008

Assessment of Various Low Temperature Electrolytes in Prototype Li-Ion Cells Developed for ESMD Applications

Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with six different ethylene carbonate-based electrolytes optimized for low temperature. In addition to investigating the behavior in experimental cells initially, the performance of these promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells, manufactured by Yardney Technical Products and Saft America, Inc. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

Wide Operating Temperature Electrolytes↗
DOE OSTI2021

Probing the thermodynamics and kinetics of ethylene carbonate reduction at the electrode–electrolyte interface with molecular simulations

Understanding the formation of the solid-electrolyte interphase (SEI) in lithium-ion batteries (LIBs) is an ongoing area of research due to its high degree of complexity and the difficulties encountered by experimental studies. Herein, we investigate the initial stage of SEI growth, the reduction reaction of ethylene carbonate (EC), from both a thermodynamic and kinetic approach with theory and molecular simulation. We employed both the potential distribution theorem (PDT) and the SMD implicit solvent model to EC solvation for the estimation of reduction potentials of Li$^+$, EC, and Li$^+$-solvating EC (s-EC), as well as reduction rate constants of EC and s-EC. We find that solvation effects greatly influence these quantities of interest, particularly the Li$^+$/Li reference electrode potential in EC solvent. Further, we also compute the inner- and outer-sphere reorganization energies for both EC and s-EC at the interface of liquid EC and a hydroxyl-terminated graphite surface, where total reorganization energies are predicted to be 76.6 and 88.9 kcal/mol, respectively. With the computed reorganization energies, we estimate reduction rate constants across a range of overpotentials and show that EC has a larger electron transfer rate constant than s-EC at equilibrium, despite s-EC being more thermodynamically favorable. Furthermore, this manuscript demonstrates how ion solvation effects largely govern the prediction of reduction potentials and electron transfer rate constants at the electrode-electrolyte interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Development of cathode-electrolyte-interphase for safer lithium batteries

Accompanied by the adoption of aggressive cathodes to continuously improve batteries energy density, enhancing their safety is becoming increasingly urgent for the electric vehicle development. In-situ controllable formation of robust cathode-electrolyte interphase (CEI) with high inorganic content seems to be the most promising strategy to address the thermal runaway concerns. Moreover, the in-situ formation strategy via suitable electrolyte replacement or electrolyte additives is extremely simple yet effective, especially for industrial manufacture of batteries. Here, this paper briefly reviews recent advanced CEIs formed by conventional carbonate-based electrolytes, fluorinated electrolytes, concentrated electrolytes, and solid state electrolytes. The focus on the thermal stability of the cathodes after CEI modification, and at the same time conduct safety tests at the material, cell, and module levels for comprehensive evaluation are encouraged. The review will provide inspiration for future developments in battery safety and push forward the practical applications of newly developed high-energy density batteries.

25 ENERGY STORAGE↗
NASA NTRS1988

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

Isenberg, Arnold O.↗
DOE OSTI2024

Tailoring Solvation Solvent in Localized High-Concentration Electrolytes for Lithium||Sulfurized Polyacrylonitrile

Sulfurized polyacrylonitrile (SPAN) is a promising cathode material for lithium-sulfur (Li-S) batteries due to its significantly reduced polysulfide (PS) dissolution compared to the elemental S cathode. Although conventional carbonate-based electrolytes is stable with SPAN electrodes, it is less stable with Li metal anode (LMA). Recently, localized high-concentration electrolytes (LHCEs) have been developed to improve the stability of LMA. Here, we report a new strategy to further improve the performance of LI||SPAN batteries by replacing the conventional solvating solvent 1,2-dimethoxyethane (DME) in the LHCE with a new solvating solvent, 1,2-diethoxyethane (DEE), the new LHCEs exhibits less reactivity against Li 2 S 2 , alleviates PS dissolution, forms a better cathode-electrolyte interphase layer on the SPAN, and enhances structure reversibility even at elevated temperature (ET, 45°C). With the same salt and diluent as in other LHCEs, the LHCE with DEE leads to better performance in Li||SPAN batteries (with 82.9% capacity retention after 300 cycles at ET), preservation of SPAN cathode structure, and suppression of the volume change of LMA. The similar strategy on tailoring the solvating solvents in LHCEs can also be used in other rechargeable batteries to improve their performances.

1,2-diethoxyethane↗
DOE OSTI2024

Mitigating Calendar Aging in Si-NMC Batteries with Advanced Dual-Salt Glyme Electrolytes

In addressing the critical challenge of calendar aging in silicon (Si)-based lithium-ion batteries, this study introduces a groundbreaking strategy utilizing glyme-type dual-salt electrolytes (lithium bis(trifluoromethanesulfonyl)imide [LiTFSI] and lithium difluoro(oxalato)borate [LiDFOB]). These electrolytes are demonstrated to significantly mitigate parasitic reactions and capacity loss in Si-NMC (lithium nickel manganese cobalt oxide) full cells, especially when compared with traditional carbonate-based electrolytes. Further, our exhaustive mechanistic analysis reveals that such electrolytes not only preserve the integrity of the Si anode but also improve the cathode/electrolyte interphases (CEI) through the formation of a conformal coating on the high-voltage cathode surface. This dual-salt approach, enhanced by the addition of a phosphate additive, effectively decelerates calendar aging, marking a substantial advance in the quest for durable and reliable Si-based energy storage technologies. The findings underscore the vital role of electrolyte composition in extending the calendar life of Si batteries, offering an alternative avenue toward maximizing the performance and longevity of next-generation Li-Si batteries.

36 MATERIALS SCIENCE↗