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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Enabling Conversion-Type Iron Fluoride Cathode by Halide-Based Solid Electrolyte

The practical application of low-cost and energy-dense iron fluoride cathodes has been hindered by the first cycle electrochemical irreversibility, cycling instability, and large voltage hysteresis. Here, we report that these challenges may be overcome by the utilization of halide-based solid electrolytes (SEs). The excellent electrochemical stability of halide-based SEs enables a complete conversion and deconversion of FeF 2 which cannot be achieved with sulfide-based SEs. Due to restricted and reversible decomposition of SE, prevention of Fe dissolution, mechanical confinement of active material, as well as improved electrode kinetics, solid-state FeF 2 cathode with halide-based SE demonstrated superior electrochemical performance compared with FeF 2 electrodes in liquid electrolytes, with a high 1st cycle coulombic efficiency (~100 %), high specific capacity (~600 mAh/g), long cycle life (>100 cycles) and high-rate performance (up to 2C). In conclusion, our results suggest solidifying the batteries may be a viable approach to addressing the long-standing key challenges of iron fluoride cathodes.

25 ENERGY STORAGE↗
DOE OSTI2019

Elucidation of Anionic and Cationic Redox Reactions in a Prototype Sodium-Layered Oxide Cathode

The ever-increasing demand for large-scale energy storage has driven the prosperous investigation of sodium-ion batteries (NIBs). As a promising cathode candidate for NIBs, P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 (NaNMO), a prototype sodium-layered oxide, has attracted extensive attention because of its high operating voltage and high capacity density. Although its electrochemical properties have been extensively investigated, the fundamental charge compensation mechanism, that is, the cationic and anionic redox reactions, is still elusive. In this report, we have systematically investigated the transition metal and oxygen redox reactions of NaNMO nanoflakes using bulk-sensitive soft X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering from an atomic-level view. We show that the bulk Mn 3+ /Mn 4+ redox couple emerges from the first discharge process with the increment of inactive Mn 3+ upon cycling, which may have a negative effect on the cyclability. In contrast, the bulk Ni redox mainly stems from the Ni 2+ /Ni 3+ redox couple, in contrast to the conventional wisdom of the Ni 2+ /Ni 4+ redox couple. The quantitative analysis provides unambiguous evidence for the continuous reduction of the average valence state of Mn and Ni over extended cycles, leading to the voltage fading. In addition, we reveal that the oxygen anions also participate in the charge compensation process mainly through irreversible oxygen release rather than reversible lattice oxygen redox. Such understanding is vital for the precise design and optimization of NaNMO electrodes for rechargeable NIBs with outstanding performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Surface Stabilization with Fluorine of Layered Ultrahigh-Nickel Oxide Cathodes for Lithium-Ion Batteries

High-nickel layered oxide cathodes are key to meet the demands of the electric vehicle industry because of their high specific capacity. However, commercialization of these materials is hindered by critical challenges, such as phase transitions, particle cracking, aggressive surface reactivity, and thermal instability. Cation doping along with surface coating has proven to be an effective way to circumvent some of these issues to a large extent. Herein, fluorine coating is employed on a high-nickel Li[Ni 0.95 Mn 0.015 Co 0.02 Al 0.01 Mg 0.005 ]O 2 (NMCAM) cathode via a solution route. Detailed structural and electrochemical analyses indicate fluorine largely decorates the surface at low enough calcination temperatures. The cathode with 1 mol % fluorine coating exhibits a capacity retention of 71% after 500 cycles as compared to 59% for the control sample when cycled to a high cutoff voltage of 4.3 V in a full cell configuration with graphite anode. Post-mortem analysis of cycled electrodes reveals that surface reactivity is a major contributor to capacity fade as compared to particle cracking. Fluorine coating reduces surface reactivity and the depth to which rock-salt phase is formed on the surface during cycling. The thermal stability is also enhanced after fluorine coating as the material shows less heat release at high states of charge. Furthermore, this work demonstrates an effective, economical, and scalable way to stabilize the surface with fluorine and enhance the electrochemical performance of high-nickel cathodes.

25 ENERGY STORAGE↗
DOE OSTI2026

Phase Transformation Enables Stable Cycling and Fast Charging of Cation-Disordered Rocksalt Cathodes

Developing high-capacity, long-life cathodes is critical to overcome the energy limitations of current Li-ion batteries. In this work, we report a Li-excess cation-disordered rocksalt (DRX) cathode, Li 1.167 Mn0.7Ti 0.133 O 1.8 F 0.2 (M 0.7 F 0.2 ), which demonstrates excellent electrochemical performance. This cathode delivers a capacity approaching 250 mAh g –1 and maintains 200 mAh g –1 over 200 cycles with an average discharge voltage of 3.1 V at 2 V cutoff. The formation of a spinel-like phase during cycling enables fast charging, achieving over 240 mAh g –1 at 2C for 100 cycles. Combined X-ray absorption spectroscopy and transmission electron microscopy reveal reversible electrochemical redox processes and stable Mn local structures during 2 V discharge. These results highlight the potential of DRX cathodes for next-generation Li-ion batteries and provide insights into strategies to overcome kinetic limitations and optimize the cathode-electrolyte interface.

25 ENERGY STORAGE↗
DOE OSTI2025

Constructing synthetic organosulfur additive for high voltage lithium-ion batteries

Despite its high anodic stability, common organosulfur solvents such as ethyl methyl sulfone and sulfolane typically exhibit poor solid-electrolyte interphase (SEI) formation capability. Here, to address this, the fluorinated organic sulfate 4-(trifluoromethyl)-1,3,2-dioxathiolane 2,2-dioxide (TFDTD) was developed as an effective additive for tailoring organosulfur-based electrolytes in lithium-ion batteries. This development was guided by the functionality selection principle and careful evaluation of feasibility in organic synthesis. TFDTD can be readily synthesized through the reaction between trifluoropropylene glycol and sulfuryl chloride. The ring structure of the organic sulfate enables the formation of a stable SEI on the anode, while the fluorination of the sulfate not only enhances its chemical stability and oxidation potential, but also its effectiveness to protect the anode by increasing its reduction potential, rendering it preferentially reduced on the anode surface before the decomposition of other electrolyte components. Introducing TFDTD facilitates the generation of a robust solidelectrolyte interphase on the graphite anode, significantly enhancing cell performance. Moreover, coupling the use of TFDTD with vinylene carbonate provides further protection on the cathode surface, enabling exceptionally stable, high-voltage, long-term cycling of Gr||NMC full cells.

Functionality selection principle↗
DOE OSTI2021

Modulating the Surface Ligand Orientation for Stabilized Anionic Redox in Li‐Rich Oxide Cathodes

Abstract Anionic redox chemistry is emerging as a key concept in the development of high‐energy lithium‐ion batteries, as it enables a nearly doubled charge storage capacity, aiding the development of high‐capacity batteries. However, the anionic reactivity is frequently irreversible from charge to discharge, leading to rapid decay of the capacity and voltage of batteries over long‐term cycling. Although the possibility of controlling the anionic redox reactions by tuning the geometric and electronic structures has recently been proposed, the implementation of this strategy is still a critical challenge. Herein, a strategy is proposed to improve the anionic redox reversibility of a model anionic redox active cathode material, Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 , by tuning the surface ligand geometry via the growth of a lattice‐compatible spinel LiCoO 2 coating layer on the particle surface. Detailed local structure and first principles investigations reveal that the shape and orientation of the octahedral layer in the host lattice are modified. Accordingly, a two‐band oxygen redox behavior is triggered in the ligand‐orientation‐regulated Li‐rich cathode, leading to enhanced reversibility, and thus, remarkably improved capacity and voltage retention over cycling. This study highlights the importance of controllable ligand orientation, carving a new path for the development and design of Li‐rich cathodes in the future.

Liu, Yanchen↗
DOE OSTI2020

Full Concentration Gradient-Tailored Li-Rich Layered Oxides for High-Energy Lithium-Ion Batteries

Lithium-rich layered oxides (LLOs) are prospective cathode materials for next-generation lithium-ion batteries (LIBs), but severe voltage decay and energy attenuation with cycling still hinder their practical applications. In this study, a series of full concentration gradient-tailored agglomerated-sphere LLOs are designed with linearly decreasing Mn and linearly increasing Ni and Co from the particle center to the surface. The gradient-tailored LLOs exhibit noticeably reduced voltage decay, enhanced rate performance, improved cycle stability, and thermal stability. Without any material modifications or electrolyte optimizations, the gradient-tailored LLO with medium-slope shows the best electrochemical performance, with a very low average voltage decay of 0.8 mV per cycle as well as a capacity retention of 88.4% within 200 cycles at 200 mA g –1 . These excellent findings are due to spinel structure suppression, electrochemical stress optimization, and Jahn-Teller effect inhibition. Further investigation shows that the gradient-tailored LLO reduces the thermal release percentage by as much as about 41% when the battery is charged to 4.4 V. This study provides an effective method to suppress the voltage decay of LLOs for further practical utilization in LIBs and also puts forward a bulk-structure design strategy to prepare better electrode materials for different rechargeable batteries.

36 MATERIALS SCIENCE↗
NASA NTRS2014

Controllers for Battery Chargers and Battery Chargers Therefrom

A controller for a battery charger that includes a power converter has parametric sensors for providing a sensed Vin signal, a sensed Vout signal and a sensed Iout signal. A battery current regulator (BCR) is coupled to receive the sensed Iout signal and an Iout reference, and outputs a first duty cycle control signal. An input voltage regulator (IVR) receives the sensed Vin signal and a Vin reference. The IVR provides a second duty cycle control signal. A processor receives the sensed Iout signal and utilizes a Maximum Power Point Tracking (MPPT) algorithm, and provides the Vin reference to the IVR. A selection block forwards one of the first and second duty cycle control signals as a duty cycle control signal to the power converter. Dynamic switching between the first and second duty cycle control signals maximizes the power delivered to the battery.

Elmes, John↗
DOE OSTI2026

Novel Organosulfur-Based Electrolytes for Safe Operation of High Voltage Li-ion Batteries over a Wide Operating Temperature

This project addresses the failure of conventional electrolytes and enables high-voltage operation of lithium-ion batteries (LIBs) by developing a novel organosulfur-based electrolyte system. To achieve this goal, we first designed and synthesized new organosulfur solvents that functionalized with strong electron-withdrawing groups such as fluoroalkyl and cyano substituents. Through regio-specific molecular engineering, supported by theoretical calculations, we lowered the highest occupied molecular orbital (HOMO) energy levels of these molecules to increase their anodic stability for high-voltage operation. We then optimized the formulation of the organosulfur-based electrolyte with additives, co-solvents and salts tailored to the newly synthesized solvent molecules. In parallel, we utilized advanced spectroscopic techniques—including in situ FTIR, EIS, and DEMS—to thoroughly elucidate the mechanisms of interaction between the electrolyte and electrode materials. Finally, we evaluated 2 Ah pouch cells under both normal and extreme conditions. Pouch cells with the newly developed electrolyte system demonstrated >90% capacity retention after 500 cycles under 4.5 V operating voltage, >80% capacity retention after 1000 cycles in coin cell level. In addition, the cells exhibited high safety and reliable operation capability over a wide temperature range from −30 °C to +45 °C.

25 ENERGY STORAGE↗
DOE OSTI2023

Operation of Layered LiCoO 2 to Higher Voltages with a Localized Saturated Electrolyte

The commercialization of lithium-ion batteries started with the layered LiCoO 2 (LCO) cathode for portable electronics, but only 50% of its theoretical capacity can be used in practical cells due to detrimental surface and bulk degradations when charged to high voltages. Here we demonstrate here that the stability of electrolyte plays a critical role in the performance of LCO at high voltages by employing a localized saturated electrolyte (LSE). With a cutoff voltage of 4.5 V, LCO achieves an initial 1C discharge capacity of 176 mA h g -1 and a capacity retention of 80% over 230 cycles. Even with a cutoff voltage of 4.6 V, LCO with 2% aluminum doping displays an initial discharge capacity of 189 mA h g -1 at 1C rate with 80% capacity retention over 137 cycles. With extensive analytical characterization, we show that the improved cycling stability stems from a suppression of the O3 to H1-3 phase transition as well as a robust inorganic-rich cathode-electrolyte interphase (CEI) facilitated by the LSE. This work highlights the importance of protecting the surface as well as the bulk with appropriate electrolytes for the high-voltage, higher-energy-density operation of LCO.

25 ENERGY STORAGE↗
DOE OSTI2023

Fluorinated High-Voltage Electrolytes To Stabilize Nickel-Rich Lithium Batteries

As state-of-the-art (SOA) lithium-ion (Li-ion) batteries approach their specific energy limit (~250 Wh kg -1 ), layer-structured, nickel-rich (Ni-rich) lithium transition metal oxide-based cathode materials, e. g., LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), have attracted great interest owing to their practical high specific capacities (>200 mAhg -1 ). Coupled with their high average discharge voltages (~4 V vs Li/Li + ), Ni-rich cathode-based lithium batteries possess a great potential to achieve much higher specific energies (>350 Wh kg -1 at the cell level) than the SOA Li-ion counterparts. In addition, Ni-rich oxides are low-cost battery cathode materials due to their low cobalt contents. However, Ni-rich cathode-based lithium batteries suffer quick capacity degradations upon cycling, particularly at high upper cutoff voltages (e.g., ≥= 4.5 V vs Li/Li + ), due to crystal structure changes of the active cathode materials and parasitic side reactions at the electrolyte/electrode interfaces. In this study, a fluorinated-solvent-based, high-voltage stable electrolyte (HVE), i.e., 1 M Li bis(trifluoromethanesulfonyl)imide (LiTFSI) in fluoroethylene carbonate (FEC), bis(2,2,2-trifluoroethyl) carbonate (FDEC), and methyl (2,2,2-trifluoroethyl) carbonate (FEMC) with Li difluoro(oxalate)borate (LiDFOB) additive, was formulated and evaluated in Li/NMC811 battery cells. Further, to the best of our knowledge, this class of electrolyte has not been investigated for Ni-rich cathode-based lithium batteries. Li/NMC811 cells with HVE exhibited a superior long-term cycle performance stability, maintaining ~80% capacity after ~500 cycles at a high cutoff voltage of 4.5 V (vs Li/Li + ) than a baseline carbonate-solvent-based electrolyte (BE). The superior cycle stability of the Li/NMC811 cells is attributed to the inherently high-voltage stability of HVE, supported by the physical and electrochemical analyses. This conclusion is supported by our density functional theory (DFT) modeling where HVE shows a less tendency of deprotonation/oxidation than BE, leading to the observed cycle stability. The findings in this study are important to help tackle the technical challenges facing Ni-rich cathode-based lithium batteries to realize their high energy density potentials with a long cycle life.

25 ENERGY STORAGE↗
NASA NTRS1991

Nickel-hydrogen LEO cycling at 20-50 percent DOD

Two NiH2 two-cell packs made up of engineering cells built according to the Hubble Space Telescope design (EPI RNH 90-3) are currently being low-earth-orbit (LEO) cycled at 20-50 percent depth of discharge (DOD). The cells were manufactured by Eagle-Picher Industries, Inc., and activated with electrolyte (KOH) concentrations of 26 percent (pack No.1) and 31 percent (pack No.2), for use during evaluation of the HST cell design. The cells have been grouped according to electrolyte concentration but follow the same test schedule for comparison. This test was set up to study the behavior of NiH2 cells having differing electrolyte concentrations, when operated at relatively high DOD (20-50 percent) in a LEO cycling program. The test was designed specifically to allow the cells to pick their own recharge ratio for varying DOD and varying EOC (end of charge) voltages. The cells are being cycled in a simulated 96-min orbit with 60-min charge and 36-min discharge where an EOC cutoff voltage controls high-rate charging. EOC cutoff voltages vary between 1.48 V and 1.56 V.

Lowery, John E.↗
DOE OSTI2019

Evaluation of Gas Formation and Consumption Driven by Crossover Effect in High-Voltage Lithium-Ion Batteries with Ni-Rich NMC Cathodes

Gas formation during lithium-ion battery (LIB) cycling impacts the stability and safety of these batteries, especially for those containing Ni-rich NMC cathodes. In this paper, the cycling performance and gassing behavior of NMC811/graphite full cells with 4.2 and 4.4 V upper cutoff voltages were first compared. We report cells with a 4.2 V upper cutoff voltage had good cycling stability, exhibiting a capacity retention of 96.8% after 100 cycles and generated little gas. On the other hand, cells with a 4.4 V upper cutoff voltage lost over 25% of initial capacity after 100 cycles and generated large amounts of gas in the first 10 cycles. Electrochemical cycling of anode and cathode symmetric cells was implemented to isolate gases formed at the electrode. Gas chromatography–mass spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning transmission electron microscopy were used to characterize the gas formation and associated material surfaces and structural properties. It was found that CO2 and fluorinated alkanes were the dominant gases evolved on the cathode side during cycling to 4.4 V. Gas crossover to the anode led to the depletion of gaseous products, which stabilized the cell performance to some extent. However, the growing surface reconstruction layer at the cathode, the thickening of the solid electrolyte interphase layer at the anode, and the gradual depletion of lithium inventory collectively contributed to the continuous capacity loss of full cells cycled to 4.4 V.

25 ENERGY STORAGE↗
DOE OSTI2024

Alkali‐Ion‐Assisted Activation of ε‐VOPO 4 as a Cathode Material for Mg‐Ion Batteries

Abstract Rechargeable multivalent‐ion batteries are attractive alternatives to Li‐ion batteries to mitigate their issues with metal resources and metal anodes. However, many challenges remain before they can be practically used due to the low solid‐state mobility of multivalent ions. In this study, a promising material identified by high‐throughput computational screening is investigated, ε‐VOPO 4 , as a Mg cathode. The experimental and computational evaluation of ε‐VOPO 4 suggests that it may provide an energy density of >200 Wh kg −1 based on the average voltage of a complete cycle, significantly more than that of well‐known Chevrel compounds. Furthermore, this study finds that Mg‐ion diffusion can be enhanced by co‐intercalation of Li or Na, pointing at interesting correlation dynamics of slow and fast ions.

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

Promoting reversibility of layered potassium cathode through interstitial doping

With the increasing needs for large-scale and low-cost energy storage devices, Mn-based layered oxide cathodes have achieved considerable researching interests for potassium-ion batteries owing to their high energy density, abundant resource and low toxicity. However, their developments are challenged by the absence of suitable cathode materials to tolerate large-sized K-ion insertion/extraction and the presence of Jahn-Teller distortion of Mn 3+ . To address this issue, here we present a strategy of embedding boron into interstitial tetrahedral sites to obtain a P3-K 0.5 Mn 0.8 Co 0.2 B 0.1 O 2 cathode. Strong B-O covalent bonds facilitate the construction of robust orthorhombic framework and alleviate the undesired elongation of Mn-O bonds, contributing to excellent electrochemical performance. In addition, boron ions are verified to promote the formation of a homogeneous cathode electrolyte interphase layer, improving interfacial stability and realizing highly reversible cycling in a wide voltage range (1.4-4.3 V). This strategy provides a new pathway towards the development of high-performance cathode materials for potassium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Understanding Solvation Behavior of the Saturated Electrolytes with Small/Wide-Angle X-ray Scattering and Raman Spectroscopy

Concentrated electrolytes are attracting significant attention because the solvation structures could stabilize the interface, encouraging novel electrolyte development for high-voltage and long-cycle-life batteries. Saturated electrolytes, which have the highest salt concentrations, have been rarely studied because of their shortcomings of high viscosity and low ionic conductivity. Nevertheless, the exciting solvation structure in saturated solution is still worth studying, significantly broadening the comprehensive understanding of the solvation processes. In this work, we investigate the saturated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dissolved in seven different organic solvents, including propylene carbonate (PC), tetrahydrofuran (THF), acetonitrile (ACN), dimethylformamide (DMF), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (Diglyme), and tetraethylene glycol dimethyl ether (Tetraglyme). The combined small/wide-angle X-ray scattering and Raman spectroscopy are employed to study the global and local solvation structure. Here, this work demonstrates a method for detecting the structure of liquids, which will facilitate the study of structure–performance relationships and the screening of new electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗