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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

4.6 V Moisture‐Tolerant Electrolytes for Lithium‐Ion Batteries

Abstract Commercial LiPF 6 ‐based electrolytes face limitations in oxidation stability (4.2 V) and water tolerance (10 ppm). While replacing LiPF 6 with lithium bis(trifluoromethane)sulfonimide (LiTFSI) improves water tolerance, it induces Al current collector corrosion above 3.7 V vs. Li/Li + . To address this, lithium cyano(trifluoromethanesulfonyl)imide (LiCTFSI) is proposed here as a non‐corrosive, moisture‐tolerant alternative. The 2.0 M LiCTFSI/propylene carbonate (PC)‐fluoroethylene carbonate (FEC) (7:3 by volume) electrolyte enables LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathodes to reach 210 mAh g −1 (2.8‐4.6 V) with a cycle life of 500. Full cells with NCM811||graphite (2.0 mAh cm −2 ) show 77.8% capacity retention after 500 cycles. Even with 2000 ppm moisture in the electrolyte, full cells maintain high cycling stability, reducing the need for costly dry rooms. The electrolyte’s low freezing point and high thermal stability enable the operation from ‐20 °C to 60 °C, delivering 168 mAh g −1 at ‐20 °C and retaining 94% capacity after 100 cycles at 60 °C. In contrast, cells with commercial LiPF 6 electrolyte deliver 71 mAh g −1 at ‐20°C and retain 52.7% after 100 cycles at 60 °C. This novel salt offers a cost‐effective solution for developing robust, high‐performance batteries suitable for extreme conditions.

Zhang, Nan↗
DOE OSTI2026

Impact of Anode to Cathode Crossover in Lithium‐metal Batteries With High‐Nickel Cathodes

The advancement of high-energy-density lithium-metal batteries (LMBs) is hindered by the chemical instability of both lithium-metal anode and high-nickel layered oxide cathodes. While cathode-to-anode crossover is well-documented, the reverse process of anode-to-cathode crossover remains underexplored. Here, we systematically investigate such crossovers and the degradation pathway in pouch cells with a localized high-concentration electrolyte, comparing NMC622, NMC811, and NMC90 cathodes paired with lithium-metal and graphite anodes. Despite delivering higher initial capacities, LMBs exhibit faster capacity fade under long-term cycling at 45 °C. To isolate cathode-side degradation, galvanostatic electrochemical impedance spectroscopy (GEIS) measurements of cycled cathodes paired with delithiated lithium iron phosphate (LFP) counter electrodes reveal significantly higher charge-transfer resistance in cathodes cycled with lithium-metal. Surface characterization via X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) reveals greater electrolyte decomposition on cathodes cycled with lithium metal, leading to thicker, more organic-rich cathode–electrolyte interphases (CEIs), consistent with the elevated charge-transfer resistance observed in GEIS measurements. Notably, NMC90 shows the most pronounced CEI thickening, linking higher cathode surface reactivity to greater susceptibility to anode-to-cathode crossover. This work presents compelling evidence of crosstalk degradation originating from lithium-metal anodes and underscores the importance of cross-interface stability for the design of durable LMBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Self‐Assembly and Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces

Abstract Two‐dimensional (2D) conductive metal‐organic frameworks (MOF) represent a unique class of electrode materials with high capacity and power density. Understanding molecular mechanisms and pathways for heterogeneous nucleation of 2D π‐conjugated MOFs is highly desirable for controlling the structure and properties of conductive MOFs on solid substrates. Herein, a systematic study of nucleation and growth of 2D π‐conjugated Ni‐catecholate (Ni‐CAT‐1) MOFs on highly oriented pyrolytic graphite (HOPG) and copper substrates is reported. It is discovered that the nucleation density and growth kinetics of the MOF film can be controlled by varying substrate interactions with the organic linker. Specifically, π–π interactions between the linker and the HOPG dictate lower nucleation density, whereas π–metal interactions between the linker and the copper substrate dictate faster nucleation and higher nucleation densities. These studies reveal the key mechanism for Ni‐CAT‐1 nucleation on different surfaces and provide insights into interfacial control over the growth of other 2D π‐conjugated MOF films on solid substrates to inform synthesis of functional materials.

2D materials↗
DOE OSTI2024

Role of Solvent in the Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces

Abstract A controlled growth of two‐dimensional (2D) π‐conjugated metal‐organic frameworks (MOFs) on solid substrates can open exciting opportunities for the application of 2D MOFs as optoelectronic devices. Some factors like solvent composition and type of substrates are known to influence the properties of solution‐processed 2D MOF crystals; however, a mechanistic understanding of how interactions between solvent, substrate, and precursors affect heterogeneous nucleation has been limited. Here, it is reported that the structure of Ni‐catecholate (Ni‐CAT‐1) MOFs at a solid–liquid interface is controlled by solvent–substrate and solvent–MOF precursor interactions. Specifically, the structure of the MOF film can be controlled by varying the affinity of the solvent to the substrate. As a fraction of N , N ‐dimethylformamide (DMF) in a binary solvent mixture of water and DMF increases, the arrangement of Ni‐CAT‐1 crystals varies from vertically aligned nanorods to the graphite substrate to less ordered nanorods with the lower initial nucleation number density of Ni‐CAT‐1 crystals on the surface.

2D materials↗
DOE OSTI2023

Thermally Responsive Hydrogels for Passive Temperature Regulation under Direct Sunlight

By spontaneously emitting midinfrared radiation to outer space through the atmospheric window and reflecting sunlight, daytime radiative coolers achieve notable passive cooling performance. However, existing daytime radiative cooling systems generally lack the ability to adaptively switch between heating and cooling states based on ambient conditions. Herein a passive thermal regulation system that features a temperature‐dependent switchable solar reflectance from 0.05 (low temperature) to 0.8 (high temperature) is presented. This, along with a ≈0.95 midinfrared emittance, it enables automatic switching between radiative cooling and solar heating. Switchablity is enabled using a poly( N ‐isopropylacrylamide) (PNIPAM) hydrogel which exhibits high solar scattering above its tunable lower critical solution temperature (LCST) and transparency below its LCST. The lower part of the hydrogel is loaded with graphite to absorb solar energy in the heating state. In testing under sunny and partly cloudy outside conditions, this system maintains a temperature close to the set LCST.

Xie, Dajie↗
DOE OSTI2021

Structural Evolution and Transition Dynamics in Lithium Ion Battery under Fast Charging: An Operando Neutron Diffraction Investigation

Abstract Fast charging (<15 min) of lithium‐ion batteries (LIBs) for electrical vehicles (EVs) is widely seen as the key factor that will greatly stimulate the EV markets, and its realization is mainly hindered by the sluggish diffusion of Li + . To have a mechanistic understanding of Li + diffusion within LIBs, in this study, structural evolutions of electrodes for a Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) || graphite cylindrical cell with high areal loading (2.78 mAh cm −2 ) are developed for operando neutron powder diffraction study at different charging rates. Via sequential Rietveld refinements, changes in structures of NMC622 and Li x C 6 are obtained during moderate and fast charging (from 0.27 C to 4.4 C). NMC622 exhibits the same structural evolution regardless of C‐rates. For phase transitions of Li x C 6 , the stage I (LiC 6 ) phase emerges earlier during the stepwise intercalation at a lower state of charge when charging rate is increased. It is also found that the stage II (LiC 12 ) → stage I (LiC 6 ) transition is the rate‐limiting step during fast charging. The LiC 12 → LiC 6 transition mechanism is further analyzed using the Johnson–Mehl–Avrami–Kolmogorov model. It is concluded as a diffusion‐controlled, 1D phase transition with decreasing nucleation kinetics under increasing chargingrates.

25 ENERGY STORAGE↗
DOE OSTI2025

High‐Temperature Single‐Photon Emission From Covalently Functionalized van der Waals Heterostructures

Two-dimensional (2D) transition metal dichalcogenides (TMDs) such as tungsten diselenide (WSe 2 ) are attractive nanomaterials for quantum information applications due to single-photon emission (SPE) from intrinsic atomic defects. Defect and strain engineering techniques have been developed to produce high purity, deterministically placed SPE in WSe 2 . However, a major challenge in the application of these techniques is the low temperature required to observe defect-bound TMD exciton emission, typically limiting SPE to T < 30 K. SPE at higher temperatures either loses purity or requires integration into complex devices such as optical cavities. Here, 2D heterostructure engineering and molecular functionalization are combined to achieve high purity (>90%) SPE in strained WSe 2 persisting to over T = 90 K. Covalent diazonium functionalization of graphite in layered WSe 2 /graphite heterostructures maintains high purity up to T = 90 K and single-photon source integrity up to T = 115 K. This method preserves the best qualities of SPE from WSe 2 while increasing working temperature to more than three times the typical range. This work demonstrates the versatility of surface functionalization and heterostructure design to synergistically improve the properties of quantum emission and offers new insights into the phenomenon of SPE from 2D materials.

2D materials↗
DOE OSTI2020

Multimodal Nanoscale Tomographic Imaging for Battery Electrodes

Accurate representations of the 3D structure within a lithium-ion battery are key to understanding performance limitations. However, obtaining exact reconstructions of electrodes, where the active particles, the carbon black and polymeric binder domain, and the pore space are visualized is challenging. In this work, it is shown that multimodal imaging can be used to overcome this challenge. High-resolution ptychographic X-ray computed tomography are combined with lower resolution but higher contrast transmission X-ray tomographic microscopy to obtain 3D reconstructions of pristine and cycled graphite-silicon composite electrodes. This cross-correlation enables quantitative analysis of the surface of active particles, including the heterogeneity of carbon-black and binder domain and solid-electrolyte interphase coverage. Capturing the active particles as well as the carbon black-binder domain allows using these segmented structures for electrochemical simulations to highlight the influence of the particle embedding on local state of charge heterogeneities.

25 ENERGY STORAGE↗
DOE OSTI2020

Advanced electrolytes for fast-charging high-voltage lithium-ion batteries in wide-temperature range

LiNixMnyCo1-x-yO2 (NMC) cathode materials with Ni=0.8 have attracted great interest for application in high energy-density lithium (Li)-ion batteries (LIBs) because of their high specific capacities at high voltages. However, the practical application of Ni-rich NMC in LIBs under high charge voltages (e.g. 4.4 V and above) still faces big challenges due to the severe capacity fading, which is directly related to the instability of the cathode/electrolyte interface. In this work, we develop new localized high-concentration electrolytes (LHCEs) based on carbonate solvents, which are compatible with graphite (Gr) anode and have a high oxidation potential over 4.9 V vs. Li/Li+. The optimal LHCE enables the Gr||NMC811 cells with 2.8 mAh cm-2 cathode areal capacity loading to achieve an excellent cycling stability over 600 cycles with a capacity retention of 94.2 % under a charge cut-off voltage of 4.4 V at 25 ?C, good rate capabilities under fast charging or discharging up to 3C rate, and superior low-temperature discharge performance down to -30 ?C with a capacity retention of 85.6% at C/5 rate. The findings in this work shed light a very promising strategy to develop new electrolytes for practical high-energy LIBs with Ni-rich NMC cathodes.

Zhang, Xianhui↗
DOE OSTI2020

Stabilized Co-Free Li-Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Li-rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g –1 . However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well-known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full-cell performance degradation. In this study, an artificial surface prereconstruction (ASR) for Li 1.2 Mn 0.6 Ni 0.2 O 2 particles with a molten-molybdate leaching is conducted, which creates a crystal-dense anion-redox-free LiMn 1.5 Ni 0.5 O 4 shell that completely encloses the LXMO lattice (ASR-LXMO). Differential electrochemical mass spectroscopy and soft X-ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR-LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR-LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g –1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full-cell matched with a commercial graphite anode and lean (2 g A –1 h –1 ) electrolyte, ASR-LXMO shows high capacity retention of 76% after 125 cycles in full-cell cycling.

25 ENERGY STORAGE↗
DOE OSTI2021

A Review of Existing and Emerging Methods for Lithium Detection and Characterization in Li-Ion and Li-Metal Batteries

Whether attempting to eliminate parasitic Li metal plating on graphite (and other Li-ion anodes) or enabling stable, uniform Li metal formation in ‘anode-free’ Li battery configurations, the detection and characterization (morphology, microstructure, chemistry) of Li that cannot be reversibly cycled is essential to understand the behavior and degradation of rechargeable batteries. In this review, various approaches used to detect and characterize the formation of Li in batteries are discussed. Each technique has its unique set of advantages and limitations, and works towards solving only part of the full puzzle of battery degradation. Going forward, multimodal characterization holds the most promise towards addressing two pressing concerns in the implementation of the next generation of batteries in the transportation sector (viz. reducing recharging times and increasing the available capacity per recharge without sacrificing cycle life). Such characterizations involve combining several techniques (experimental- and/or modeling-based) in order to exploit their respective advantages and allow a more comprehensive view of cell degradation and the role of Li metal formation in it. Additionally, it is also discussed which individual techniques, or combinations thereof, can be implemented in real-world battery management systems on-board electric vehicles for early detection of potential battery degradation that would lead to failure.

25 ENERGY STORAGE↗
DOE OSTI2021

High-Voltage and High-Safety Practical Lithium Batteries with Ethylene Carbonate-Free Electrolyte

Serious safety issues are impeding the widespread adoption of high-energy lithium-ion batteries for transportation electrification and large-scale grid storage. Herein, a triple-salt ethylene carbonate (EC) free electrolyte for high-safety and high-energy pouch-type LiNi 0.8 Mn 0.1 Co 0.1 O 2 |graphite (NMC811|Gr) cells is reported. This EC-free electrolyte can effectively stabilize the NMC811 surface under high potential (up to 4.5 V), as well as generate a stable interphase to achieve a superior compatibility with the Gr anode. The electrolyte strategy enables significantly enhanced intrinsic safety (trigger temperature of thermal runaway (TR) increased by 67.0 °C), excellent electrochemical properties (4.2V, ≈100% after 200 cycles), and superior high voltage stability (4.5 V, 82.1% after 200 cycles). Furthermore, the work opens up a new avenue for developing novel electrolyte systems to build safer high-energy batteries for practical applications.

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 OSTI2022

Over-Potential Tailored Thin and Dense Lithium Carbonate Growth in Solid Electrolyte Interphase for Advanced Lithium Ion Batteries

A stable solid electrolyte interphase (SEI) is highly desired to prevent parasitic reactions during normal operation of lithium-ion batteries (LIBs). Lithium carbonate (Li 2 CO 3 ) is one of the most significant components for smooth SEI passivation layers; while the formation mechanism and special distribution of the Li 2 CO 3 layer has not yet been illustrated. In this study, an over-potential tailored Li 2 CO 3 growth mechanism based on the typical hard carbon anode is demonstrated. With an increase in the over-potential, the size of Li 2 CO 3 decreases gradually as the amount increases. When the over-potential is large (potential at 0.01 V), a Li 2 CO 3 -rich thin and dense inorganic layer with the average thickness of 4.4 nm in the SEI is constructed. The special SEI the completely wraps the boundaries of the anode enables a larger Li-ion de-solvation energy barrier and a lower Li-ion diffusion energy barrier, which supports low self-discharge behavior and a fast kinetic rate at the anode. More generally, this Li 2 CO 3 growth mechanism is also applicable to commercialized graphite anodes and similar results are also obtained. Therefore, this work provides a new insight into the Li 2 CO 3 growth mechanism in SEIs, as well as a guideline for the design of stable artificial SEIs.

25 ENERGY STORAGE↗
DOE OSTI2022

Insights into the Crossover Effects in Cells with High‐Nickel Layered Oxide Cathodes and Silicon/Graphite Composite Anodes

Abstract Silicon anodes are regarded as one of the most promising alternatives to graphite (Gr) anodes due to their ultrahigh capacity, abundance, and low cost. Coupling Si‐based anodes with high‐nickel layered oxide cathodes LiNi x Mn y Co 1− x − y O 2 (NMC, x ≥ 0.8) can enhance the driving range for electric vehicles. Transition‐metal (TM) ion dissolution and deposition has been a long‐known failure mode for Gr‐based lithium‐ion batteries. However, the mechanistic insight associated with TM ion deposition on Si‐based anodes has rarely been reported. Herein, the impact of in situ deposited TM ions on SiO x /Gr composite anodes and the individual influences of Ni, Mn, and Co on the structural and electrochemical stability along with the underlying degradation mechanisms are presented. TM ion dissolution causes a greater deleterious impact on Si than on Gr, with different TM ions exhibiting different influences on anode‐electrolyte interphase formation. Specifically, Ni deposit induces more aggressive salt decomposition; Co deposit has negligible effect on salt decomposition, but significantly accelerates solvent decomposition; and Mn deposit aggravates both salt and solvent decompositions, resulting in worse full cell performance. The extent of degradation decreases in the order Mn 2+ > Ni 2+ > Co 2+ . The systematic comparisons presented can guide further development of high energy systems.

Zhang, Xianhui↗