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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Kinetics of intercalation of lithium into NbSe3 and TiS2 cathodes

Titanium disulfide and niobium triselenide are two well-studied candidate materials for positive electrodes in rechargeable lithium cells. A comparative study of the kinetics of intercalation of lithium in both the cathodes is made here based on various electrochemical techniques, i.e., linear polarization, potentiodynamic polarization, and ac impedance under different experimental conditions such as prismatic or disk configuration of fresh, partially discharged, or cycled electrode. Further, the diffusion coefficients of lithium ions in these cathodes are estimated under these conditions using conventional techniques, i.e., ac impedance, chronocoulometry, chronoamperometry, and current pulse relaxation. Based on the values of the diffusion coefficients, the applicability of these methods for the determination of diffusion coefficients is discussed.

Ratnakumar, B. V.↗
DOE OSTI2021

Rapid Charging Made Practical in Graphite-Based Lithium Batteries: Surface-Acoustic Wave Turbulent Electrolyte Mixing to Overcome Diffusion Limited Charging Rates

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer's depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles.

25 ENERGY STORAGE↗
DOE OSTI2024

Designing Particle Morphologies for Materials with Solid Transport Limitations: A Case Study of Lithium and Manganese Rich Cathode Oxides

A lithium and manganese rich nickel-manganese-cobalt oxide (LMR-NMC) cathode is a promising candidate for next-generation batteries due to its high specific capacity, low cost, and low cobalt content. However, the material suffers from poor rate capability due to the diffusion limitations of lithium in the cathode particles. Understanding the material performance requires careful control of the morphology of the cathode particles, taking into account the primary and agglomerated diffusion pathways and the presence of pores, some of which could be closed from electrolyte infiltration. Here, in this study, we use a microstructure-based mathematical model combined with experimental data to understand the role of the complex cathode particle morphology in the rate performance of the material. Scanning electron microscopy images of cathodes made under different synthesis conditions, which results in different agglomerate morphologies, serve as the input into the mathematical model. The model is then compared to rate data to understand the controlling parameters. The presence of intra-agglomerate closed pores results in a large agglomerate diffusion length in comparison to the ideal condition, where the primary particles are agglomerated in an open and dispersed manner such that the entire interfacial area is available for electrochemical reaction. Smaller primary and agglomerate diffusion lengths result in better electrochemical performance. This points us toward designing the morphology of the cathode particles to compensate for the diffusion limitation of LMR-NMC while maximizing the density.

Tewari, Deepti↗
NASA NTRS2003

Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

Manzo, Michelle A.↗
NASA NTRS2004

Thermal characteristics of Lithium-ion batteries

Lithium-ion batteries have a very promising future for space applications. Currently they are being used on a few GEO satellites, and were used on the two recent Mars rovers Spirit and Opportunity. There are still problem that exist that need to be addressed before these batteries can fully take flight. One of the problems is that the cycle life of these batteries needs to be increased. battery. Research is being focused on the chemistry of the materials inside the battery. This includes the anode, cathode, and the cell electrolyte solution. These components can undergo unwanted chemical reactions inside the cell that deteriorate the materials of the battery. During discharge/ charge cycles there is heat dissipated in the cell, and the battery heats up and its temperature increases. An increase in temperature can speed up any unwanted reactions in the cell. Exothermic reactions cause the temperature to increase; therefore increasing the reaction rate will cause the increase of the temperature inside the cell to occur at a faster rate. If the temperature gets too high thermal runaway will occur, and the cell can explode. The material that separates the electrode from the electrolyte is a non-conducting polymer. At high temperatures the separator will melt and the battery will be destroyed. The separator also contains small pores that allow lithium ions to diffuse through during charge and discharge. High temperatures can cause these pores to close up, permanently damaging the cell. My job at NASA Glenn research center this summer will be to perform thermal characterization tests on an 18650 type lithium-ion battery. High temperatures cause the chemicals inside lithium ion batteries to spontaneously react with each other. My task is to conduct experiments to determine the temperature that the reaction takes place at, what components in the cell are reacting and the mechanism of the reaction. The experiments will be conducted using an accelerating rate calorimeter (ARC), which uses a heat-wait-search mode until an exothermic reaction is detected. After an exotherm is found the calorimeter maintains an adiabatic environment around a bomb which holds the test sample. The ARC will help identify important reactions and what temperature these exothermic reactions take place at. In order fully understand the battery, we are first going to take apart the battery and test the individual components of the battery using the ARC. I will first conduct a test on the electrolyte solution by itself. We will then test the electrolyte solution with the anode. We would like to see how the electrolyte solution reacts with the anode and its binder material. The next would be the same test using the cathode instead of the anode. By comparing the results of the electrolyte, electrolyte with anode, and the electrolyte with the cathode we can determine the reactions that are taking place due to each component. Using the heat capacity of the each individual sample and the temperature by which the sample increases, kinetic and thermo-dynamical information can then be found. A Gas chromatograph could be used to help with the task of identifying the by-products at the end of each test. One way of increasing the cycle life is to increase the stability of the materials inside the

Hauser, Dan↗
DOE OSTI2021

Rapid charging made practical in graphite-based lithium batteries: surface-acoustic wave turbulent electrolyte mixing to overcome diffusion limited charging rates [Final Report]

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer’s depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li+ ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles. 0.1. Turbulent acoustic streaming mixes the electrolyte during charging—even with separator Our proposed 100-MHz SAW device used to recirculate the electrolyte is compatible with lithium- ion battery electrochemistry, as it is made in our lab of single-crystal lithium niobate. Their solution is straightforward to drive from a DC power source alongside the signal provided during battery charging. The device is only needed during charging and does not consume power dur- ing battery discharge. Uniquely, SAW generates extreme accelerations of over 1 billion meters per second squared in the fluid, driving turbulent mixing from centimeter to submicron length scales, even through the porous separator materials that tend to be used in batteries, all while avoiding interfering with the anode’s solid electrolyte interphase layer that forms during use. By employing novel fluid mechanics, the investigators are proposing a new direction for battery research away from direct use of materials science and electrochemistry. The chemistry agnostic solution may be employed in any battery chemistry that makes use of liquid electrolytes, providing a broader transformative benefit to the battery research community. They are to produce a series of prismatic and 20700-cell sized 2 Ah batteries capable of being charged and discharged at least 500 times without more than 20% loss in battery capacity, and to provide analysis tools useful to the battery research and development community for adopting this approach for other battery chemistries and configurations.

25 ENERGY STORAGE↗
DOE OSTI2025

Decoupling Li out-diffusion and surface diffusion in the lithiation-assisted epitaxial growth of lithium tungstate

Lithiation-assisted epitaxy offers a flexible and robust approach for synthesizing high-quality Li-containing materials and interfaces with precise control. Here, in this study, we use lithium tungstate (Li x WO 3+x/2 , where x = 0 to 2) as a model system to investigate the intertwined effects of Li out-diffusion-induced compositional changes and surface-diffusion-induced morphological changes. By systematically varying synthesis and processing conditions, we uncover their impact on lithium tungstate film formation. Comprehensive characterizations, including X-ray diffraction, atomic force microscopy, X-ray photoemission spectroscopy and time-of-flight secondary ion mass spectrometry, reveal that low-temperature growth (< 300 °C) followed by high-temperature annealing yields continuous lithium tungstate films with significantly reduced surface roughness. In contrast, high-temperature deposition (≥ 300 °C) accelerates surface diffusion and Li out-diffusion, leading to island formation. Furthermore, in situ scanning transmission electron microscopy demonstrates the beam sensitivity of Li 2 WO 4 and reveals a phase transition from Li 2 WO 4 to LiWO 3.5 under prolonged electron beam exposure. These findings deepen our understanding of how to control composition and morphology of Li-containing films, providing valuable insights for the design and integration of energy materials.

Shi, Jueli [Pacific Northwest National Laboratory ↗
DOE OSTI2020

Enabling fast charging of lithium-ion batteries through secondary- /dual- pore network: Part I - Analytical diffusion model

Battery performance is strongly correlated with electrode microstructural properties. Enabling fast charging of lithium-ion batteries requires improved through-plane ionic diffusion that can be achieved through, among other strategies, structured electrodes with a secondary- or dual-pore network (SPN). In this work, an analytical model investigates the impact of such an SPN on ionic diffusion with a composite electrode, considering various pore-channel geometries and comparing to standard electrodes with identical gravimetric- and volumetric-specific theoretical capacities. Relevant SPN design parameters and tortuosity coefficients are identified according to three optimization objectives that aim to balance the improved overall through-plane diffusion, thanks to the coarse aligned channels, and degraded in-plane diffusion because of the porous matrix densification required to maintain gravimetric- and volumetric-specific theoretical capacities. The model indicates that a relatively low amount of SPN is required and that electrodes with high through-plane tortuosity and low in-plane tortuosity benefit most from such architecture.

25 ENERGY STORAGE↗
DOE OSTI2020

Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries

Metal fluorides present a high redox potential among the conversion-type compounds, which make them specially work as cathode materials of lithium ion batteries. To mitigate the notorious cycling instability of conversion-type materials, substitutions of anion and cation have been proposed but the role of foreign elements in reaction pathway is not fully evaluated. In this work, we explored the lithiation pathway of a rutile-Fe 0.9 Co 0.1 OF cathode with multimodal analysis, including ex situ and in situ transmission electron microscopy and synchrotron X-ray techniques. Our work revealed a prolonged intercalation–extrusion–cation disordering process during phase transformations from the rutile phase to rocksalt phase, which microscopically corresponds to topotactic rearrangement of Fe/Co–O/F octahedra. During this process, the diffusion channels of lithium transformed from 3D to 2D while the corner-sharing octahedron changed to edge-sharing octahedron. DFT calculations indicate that the Co and O cosubstitution of the Fe 0.9 Co 0.1 OF cathode can improve its structural stability by stabilizing the thermodynamic semistable phases and reducing the thermodynamic potentials. We anticipate that our study will inspire further explorations on untraditional intercalation systems for secondary battery applications.

25 ENERGY STORAGE↗
NASA NTRS1972

Development and pilot line production of lithium doped silicon solar cells

The work performed over the period of September 1971 to August 1972 to develop production processes for fabrication of lithium doped P/N cells is described. The BCl3 diffusion without 02 was selected as the optimum diffusion process for fabrication of lithium doped cells. An 8-2-7 (warm up - deposition - drive-in time in minutes) diffusion schedule at 1055 C was used for the first two lots (300 cells each) delivered to JPL. Cell efficiencies ranged from 11.0 to 13.7% based on an AMO of 135.3 mW/sq cm. These high efficiencies were obtained using from 10 to 40 cells per boron diffusion; increasing the quantity beyond 40 resulted in lower outputs. At this point, the emphasis was placed on investigation of a BCl3 with 02 diffusion. Through evaluation of the effects of diffusion time and temperature, gas flow rates, and desposition plus drive-in vs. continuous deposition and no drive-in cycles, diffusion parameters were determined which produced short circuit currents of 136 + or - 4 mA for ten cells spaced along 12 in. of the diffusion boat. The quantity was increased to 60, 100, and 150 cell diffusions with no more variation in cell short circuit current than observed with 10 cells.

Payne, P. A.↗
DOE OSTI2020

Accommodation of Silicon in an Interconnected Copper Network for Robust Li-Ion Storage

Silicon (Si)-based materials are one of the most promising anodes to be applied in rechargeable lithium ion batteries. However, the active Si/electrolyte interface causes continuous side reactions and poor conductivity, which significantly decreases the cycling stability. Cu is the only metallic current collector that has been known to promote electron conduction and lithium-ion transfer without alloying reaction occurrence. However, to the best current knowledge, scalable interface engineering incorporating Cu has not been reported. In this study, this conductive Cu interface (CCI) is constructed through a self-assembly carbothermic reduction method to achieve efficient protection of Si/electrolyte interfaces while allowing for fast Li + diffusion. The energy barrier of lithium-ion diffusion through Cu is calculated to be 0.1965 eV, which is much lower than that through Au, Fe, and Ni films. Benefiting from the enhanced interfacial protection and kinetics of Si with CCI, a fading rate of only 0.068% is maintained for 1000 cycles and an aerial capacity of 4.78 mAh cm -2 is achieved after 280 cycles, which is comparable to the industry standards required for practical application.

36 MATERIALS SCIENCE↗
DOE OSTI2025

On Rate-Limiting Mechanisms in NMC Cathodes: The Interplay of Low and High Current Constraints

In this study, we investigate the rate performance limits in LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes for lithium-ion batteries, focusing on how cathode thickness, porosity, and threshold voltage impact discharge capacity. By conducting galvanostatic discharge experiments across a wide range of current densities using cathodes of varying thicknesses and porosities, we identify two distinct rate-limiting mechanisms: ionic liquid-diffusion and Ohmic/charge-transfer limitations. Our findings show that thick, dense cathodes are primarily limited by lithium diffusion in the electrolyte, while thinner and more porous cathodes are dominated by Ohmic/charge-transfer limitations, particularly at higher lower cutoff voltages. Crucially, these results allow us to identify the rate-limiting mechanisms in different cathode configurations, offering clear insights into how cathode design can be optimized for improved performance. Understanding these mechanisms is essential for designing next-generation batteries with enhanced rate performance, which is critical for applications such as electric vehicles and renewable energy storage systems.

Brischetto, Martin (ORCID:0000000339865813)↗
NASA NTRS1991

Finite linear diffusion model for design of overcharge protection for rechargeable lithium batteries

The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. The model has been experimentally verified using 1,1-prime-dimethylferrocene as a redox additive. The theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

Narayanan, S. R.↗
DOE OSTI2020

Concentration dependent properties and plastic deformation facilitate instability of the solid-electrolyte interphase in Li-ion batteries

Lithium-ion batteries (LIBs) often suffer from capacity fading and poor cyclic performance due to mechanical degradation of the solid-electrolyte interphase (SEI). Here we perform numerical simulations and theoretical analysis to elucidate the role of plasticity in wrinkling and ratcheting behaviors of an SEI/electrode system. A coupled diffusion and finite deformation framework is formulated and numerically implemented as a user-element subroutine (UEL) to describe transient lithium diffusion and accompanying elastic–viscoplastic deformation of the electrode. It is found that concentration dependent properties and plastic deformation facilitate wrinkling in such a system. A wrinkled morphology may further lead to ratcheting and related failure under cycling. A phase diagram of four types of cyclic behaviorsis identified in terms of the charging rate and time. Our analysis suggests several potential strategies to avoid wrinkling and ratcheting instabilities, such as charging/discharging the electrode at a sufficiently slow rate, and/or introducing a thick artificial SEI with a pre-tension.

25 ENERGY STORAGE↗
DOE OSTI2025

Tailoring the Reaction Heterogeneity for Robust Li‐Rich Cathodes

The practical application of Li-rich Mn-based layered oxides (LLO) cathode is hindered by severe capacity and voltage degradation resulting from severe oxygen release and irreversible phase transition. In this work, the reaction heterogeneity, which describes the spatially resolved electrochemical divergence within individual cathode particles, is engineered through compositional gradient design to couple Li + transport kinetics and the anion redox activity between particle interiors and surfaces. It is revealed that Co/Mn concentration gradient within particles creates heterogeneous phase content distribution and structural ordering, inducing surface-bulk reaction heterogeneity that significantly impacts the overall electrochemical performance. Specifically, Li 2 MnO 3 -poor and Co-enriched surface effectively mitigates the oxygen loss and enhances electrochemical reaction kinetics, benefited from the reduced surface redox reactivity and induced highly ordered intra-layered cationic arrangement. Meanwhile, the Li 2 MnO 3 -enriched core with slight Li/Ni intermixing provides high reversible capacity and strong mechanical stability. Consequently, the greatly enhanced anion redox reversibility, Li + diffusion dynamics, and structure stability endow LLO with exceptional electrochemical properties, showing a capacity retention of 86.0% and a reduced voltage decay of 0.518 mV per cycle after 500 cycles at 1 C. This work provides a valuable strategy to tailor the redox chemistry and achieve robust LLO.

25 ENERGY STORAGE↗
DOE OSTI2020

Kinetic pathways of ionic transport in fast-charging lithium titanate

Fast-charging batteries typically use electrodes capable of accommodating lithium continuously by means of solid-solution transformation because they have few kinetic barriers apart from ionic diffusion. One exception is lithium titanate (Li 4 Ti 5 O 12 ), an anode exhibiting extraordinary rate capability apparently inconsistent with its two-phase reaction and slow Li diffusion in both phases. Through real-time tracking of Li+ migration using operando electron energy-loss spectroscopy, we reveal that facile transport in Li 4+x Ti 5 O 12 is enabled by kinetic pathways comprising distorted Li polyhedra in metastable intermediates along two-phase boundaries. Our work demonstrates that high-rate capability may be enabled by accessing the energy landscape above the ground state, which may have fundamentally different kinetic mechanisms from the ground-state macroscopic phases. This insight should present new opportunities in searching for high-rate electrode materials.

25 ENERGY STORAGE↗