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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Advanced Materials Characterization and Processing of Gen II Materials Based Lithium Ion Battery

The purpose of this Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and Dow Kokam, LLC was to investigate the microstructure and materials processing on long-term performance of Dow Kokam’s Gen II anodes and cathodes for lithium ion batteries. The findings were implemented into Dow Kokam’s new U.S. based production line, which has a capacity of 600 MWh/yr in total battery output. A principal need for automotive energy storage applications is the ability of the battery pack to satisfy a 10-15 year calendar life in addition to improved safety, high charge-discharge rate capability, high energy density, and high power density. Current cathode chemistries such as those based on LiNixMnyCo1-x-yO2 (NMC) metal oxides are limited to approximately 1500 cycles (or 5-7 year equivalent automotive calendar life). Dow Kokam Gen II technology has shown a 2× cycle life over conventional NMC based materials, while also improving by similar metrics the charge-discharge limits. The impact of this improvement is significant in terms of launching pure electric vehicles and plug-in hybrid electric vehicles with lifetimes comparable to those of the traditional IC engine. However, in order to scale the technology and achieve substantial market penetration, the electrode structure and processing based on the new Gen II material in comparison to that of the traditional NMC needs to be better understood. As the microstructure and chemistry of the new electrode type have been elucidated by this project, scaling and mass production has become the focus. Electrode dispersion formulations, coating parameters, and methods of energy savings were subsequently investigated. The capabilities of ORNL were implemented to assist in these efforts in terms of quality control, materials characterization, and electrochemical testing. Dow Kokam provided raw materials and electrodes, as well as background IP and technical expertise. The current state-of-the-art for NMC cathode durability is 1500 cycles to 100% depth of discharge (DOD) at 1C/-1C charge/discharge rates. This cycle lifetime only satisfies about half of the lifetime requirement for plug-in hybrid electric vehicles (PHEVs) and electric vehicles (EVs). Dow Kokam’s Gen II modified NMC cathode increases cycle life by 2×, depending on the charge/discharge rates, and will be capable of meeting the full 15 year lifetime once scaled to mass production. This improvement will allow PHEV and EV manufacturers to use only one battery pack per vehicle and will result in approximately 50% reduction in energy required to produce battery packs on a per vehicle basis. This further translates into a significantly reduced cost of ownership for PHEVs and EVs based on lithium ion battery technology. However, the chemical and microstructural changes of the modified Gen II anodes and cathodes during long-term operation are not well understood, as well as the effects of the starting material modifications to anode and cathode active material performance (i.e., nanoscale coatings deposited on the surfaces of graphite and NMC). Effects of processing variables related to mixing and coating of the electrode materials on cell performance and durability were also studied. To supplement these materials characterization and processing variable experiments, thorough electrochemical testing was completed by Dow Kokam.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Structure–Property Relationships of Recycled Lithium-Ion Battery Cathodes: Microstructure Optimization Using Virtual Materials Testing

The increasing demand for sustainable battery technologies requires effective recycling strategies for end-of-life lithium-ion battery cathodes. In this study, virtual materials testing, a well-established framework for modeling conventionally manufactured NMC-based cathodes, is applied to partially recycled cathodes. To this end, virtual cathodes consisting of mixtures of pristine and recycled NMC particles are utilized to systematically analyze structure–property relationships depending on mixing ratios and different spatial arrangement strategies. For this purpose, a stochastic 3D model is developed that is capable of generating virtual cathodes with arbitrary volume fractions of active materials and mixing ratios of pristine and recycled NMC particles. Particularly, the stochastic 3D model can mimic the different size distributions of pristine and recycled particles that are observed in image data. Additionally, the model allows the structuring of pristine and recycled NMC either uniformly mixed or layer-wise arranged, mimicking single- and dual-layer cathodes. Subsequently, a systematic computational analysis is conducted to assess the influence of increasing active material ratios of recycled particles, ranging from 0 % to 100 %, while maintaining a constant overall active material volume fraction. The impact of particle mixing on cathode performance is evaluated by examining transport-relevant geometrical descriptors and effective properties, such as geodesic tortuosity, specific surface area, and tortuosity factor.

25 ENERGY STORAGE↗
DOE OSTI2022

Single-Crystalline Ni-Rich LiNi x Mn y Co 1– x – y O 2 Cathode Materials: A Perspective

To drive electrical vehicles for long-range, the energy density of Li-ion batteries must be further enhanced, which requires high-energy cathode materials. Among them, Ni-rich LiNi x Mn y Co 1–x–y O 2 (x > 0.5, NMC) is one of the most promising candidates. However, traditional poly-crystal (PC) NMC materials, whose particles are secondary clusters consisting of many primary crystalline particles, are susceptible to pulverization along the inter grain/particle boundaries, resulting in poor cycle stability. Recently, single crystal (SC)-NMC cathodes are proposed as they are believed to have several merits such as high structural integrity, lower interface with electrolyte, and potentially better energy storage performance. Nevertheless, several queries, such as the merits of SC structure and the mechanism for their structure degradation, are still controversial and required to be addressed. Here, in this study, the synthesis parameters, properties, energy storage as well as safety of SC- and PC-NMC cathodes with various Ni contents are critically reviewed, for clarifying the merits and drawbacks of SC. Furthermore, the study focuses on the recent advances of insight mechanisms and strategies for stabilizing the structure/interface by doping, morphology engineering, surface coating, and composition tailoring. The remaining challenges, safety concerns, and perspectives to enhance the electrochemical performance of SC-NMC cathodes for electric vehicle application are followed.

25 ENERGY STORAGE↗
DOE OSTI2022

Direct non-oxidative methane coupling on vitreous silica supported iron catalysts

Direct non-oxidative methane coupling (NMC) is one of the promising pathways for methane upgrading into value-added olefin and aromatic hydrocarbons. The silica-supported iron (i.e., Fe/SiO 2 ) catalyst has been reported effective for NMC, but the effects of silica support on the catalyst property and NMC performance have rarely been explored. Here, in this work, we prepared a vitreous silica-supported iron (Fe/SiO 2 -V) catalyst by flame fusion of a mixture of quartz silica and fayalite. The physicochemical properties and NMC performance of the as-prepared catalysts were measured. Compared to crystalline cristobalite support in Fe/SiO 2 catalyst that has been studied previously, vitreous silica support has disordered Si-O bonds and structural defects, enabling better iron dispersion and more vital metal-support interaction. The as-prepared Fe/SiO 2 -V catalyst had a shorter induction period in methane activation and lower coke yield in NMC. The increase in iron concentration in Fe/SiO 2 -V catalysts elongated the catalyst induction period and promoted aromatics and coke formation. The coke type of the spent Fe/SiO 2 -V catalyst is more uniform than the cristobalite-supported iron catalyst.

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

Computation-guided discovery of coating materials to stabilize the interface between lithium garnet solid electrolyte and high-energy cathodes for all-solid-state lithium batteries

All-solid-state batteries with a lithium metal anode, enabled by lithium garnet solid electrolytes such as Li 7 La 3 Zr 2 O 12 (LLZO), are a promising next-generation energy-storage technology. The further development of all-solid-state battery requires the integration of high-energy cathodes such as LiNi 1-x-y Mn x Co y O 2 (NMC) with the garnet solid electrolyte with stable and low-resistance interfaces, which requires a coating layer to stabilize the interface during high-temperature sintering and electrochemical cycling. In order to guide the future development of interfacial coatings, we perform high-throughput thermodynamic analyses based on first-principles computation to investigate the stability of LLZO garnet and high-energy NMC cathodes with a wide range of materials chemistries. Here our study reveals the factors governing the materials stability with LLZO garnet and NMC cathodes, and identifies the mechanisms of good coating layers stable with LLZO and NMC. In addition to classifying known coating layers, our study provides detailed guiding charts and multiple new materials systems as promising coatings for stabilizing LLZO—NMC interfaces to enable high-energy-density garnet-based all-solid-state batteries. Our demonstrated computation scheme and high-throughput analyses are generally applicable to investigate and screen coating materials for stabilizing interfaces in energy-related applications.

25 ENERGY STORAGE↗
DOE OSTI2023

Purification of Lithium-Ion Battery Black Mass through Tailored Alkaline Corrosion

Obtaining high-purity material outputs is crucial to the viability of novel process aimed at direct recycling of lithium-ion batteries. Metallic impurities in recycled cathodes have been shown to inhibit performance, thereby threatening mainstream acceptance of recycled battery products. Thus, shredded black mass (BM) must be purified to remove metallic contaminants, and specifically Al and Cu originating from the electrode current collectors. We herein explore a process to ionize solid copper and aluminum to ionic form based on tailored alkaline chemistry, without incurring damage to the target cathode material (Li(NixMnyCo1-x-y)O2; NMC). Al and Cu corrosion may be enhanced through the addition of chloride salt, elevated temperatures, and the use of ultrasonication - all of which disrupt the formation of passivating films on the metallic surface, and thereby increase corrosion rate. We demonstrate optimized parameters for Al and Cu corrosion both from a kinetic and overall process cost perspective. Further, we analyze the impact of these conditions on the structural (XRD, SEM), chemical (EDS, ICP), and electrochemical (impedance, cycling, dQ/dV) properties of NMC, and suggest that the present purification method does not significantly disrupt NMC performance. Finally, we present preliminary results from a promising bench-scale demonstration of this purification process applied to a simulated black mass.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗
DOE OSTI2015

Tailoring the surface properties of LiNi 0.4 Mn 0.4 Co 0.2 O₂ by titanium substitution for improved high voltage cycling performance

The present research aims to provide insights into the behavior of LiNi0.4Mn0.4Co0.2O2 (NMC442) and LiNi 0.4 Mn 0.4 Co 0.2 O₂ (NMC442-Ti02) cathode materials under galvanostatic cycling to high potentials, in the context of previous work which predicted that Ti-substituted variants should deliver higher capacities and exhibit better cycling stability than the unsubstituted compounds. It is found that NMC cathodes containing Ti show equivalent capacity fading but greater specific capacity than those without Ti in the same potential range. When repeatedly charged to the same degree of delithiation, NMC cathodes containing Ti showed better capacity retention. Soft x-ray absorption spectroscopy (XAS) spectra for Mn and Co indicated increased reduction in these elements for NMC cathodes without Ti, indicating that the substitution of Ti for Co acts to suppress the formation of a high impedance rock salt phase at the surface of NMC cathode particles. The results of this study validate the adoption of a facile change to existing NMC chemistries to improve cathode capacity retention under high voltage cycling conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Accurately constituting robust interfaces for high-performance high-energy lithium metal batteries

High-energy lithium metal batteries (LMBs) have received ever-increasing interest. Among them, coupling lithium metal (Li) with nickel-rich material, LiNi x Mn y Co z O 2 (NMCs, x ≥ 0.6, x + y + z = 1), is promising because Li anodes enable an extremely high capacity (∼3860 mA h g −1 ) and the lowest redox potential (−3.04 V vs. standard hydrogen electrode), while NMCs can achieve a much higher capacity of ∼200 mA h g −1 and lower cost than those of LiCoO 2 . However, the resultant Li‖NMC cells have been hindered from commercialization due to a series of challenges related to the interface stability of both Li anodes and NMC cathodes. Specifically, Li anodes suffer from Li dendritic growth and the formation of solid electrolyte interphase (SEI), while NMC cathodes suffer from the formation of cathode electrolyte interphase (CEI) and other interface-related issues, including transition metal dissolution, oxygen release, cracking, and so on. To tackle these issues, recently, two sister techniques, atomic and molecular layer deposition (ALD and MLD), have emerged and exhibit tremendous capabilities to accurately constitute robust interfaces to achieve high-performance Li‖NMC LMBs. They can uniquely develop uniform and conformal films as surface coatings of LMBs in a precisely controllable mode at the atomic/molecular level, while proceeding with film deposition at low temperatures (e.g., ≤250 °C). In this Feature Article, we review the latest research progress in developing novel surface coatings via ALD and MLD for Li‖NMC LMBs and discuss outcomes for pursuing high performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Application of Neutron Multiplicity Counting Experiments to Optimal Cross-Section Adjustments

This paper presents the first application of model calibration to neutron multiplicity counting (NMC) experiments for cross-section optimization that is informed by adjoint-based sensitivity analysis (SA) and first-order uncertainty quantification (UQ). We summarize previous work on SA applied to NMC and describe notable modifications and additions. We give the procedure for first-order UQ and Bayesian-inference-based parameter estimation (PE). We then discuss model calibration applied to NMC of a 4.5-kg sphere of weapons-grade, alpha-phase plutonium metal (the BeRP ball) with the nPod neutron multiplicity counter. For the BeRP ball in bare and polyethylene-reflected configurations, we discuss the sensitivity of the first- and second-moment detector responses (i.e., first and second moments of the NMC distribution, respectively) to the cross sections. We describe the sources of uncertainty in the measured and simulated responses. Specifically, uncertainty in the measured responses is due to both random and systematic sources. Uncertainty in the simulated responses is due to the cross-section covariances. We describe in detail the adjustment to the cross sections and cross-section covariances due to the optimization. Due to the contribution of systematic uncertainties to the measured response uncertainties, the adjustment to the cross sections is similar in trend but larger in magnitude compared to that recommended by previous work. We compare the measured responses to responses simulated with nominal and optimized cross sections, demonstrating that the best-estimate cross sections produce simulations of NMC experiments that are more accurate with reduced uncertainty.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Atomic-scale constituting stable interface for improved LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes of lithium-ion batteries

Ascribed to their higher capacity and lower cost compared to conventional LiCoO 2 , the Ni-rich layered LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) is now considered as one promising cathode for lithium-ion batteries (LIBs). However, it still suffers from some evident performance degradation, especially under high cutoff voltages (i.e., >4.3 V versus Li/Li + ). The performance degradation typically is exhibited as capacity fading and voltage drop, mainly originating from an instable interface between the NMC622 and electrolyte as well as the evolution of the NMC structure. To improve the interfacial and structural stability of NMC cathodes, herein we deposited an ultrathin layer of Al 2 O 3 coatings (<5 nm) conformally over NMC622 composite electrodes directly using atomic layer deposition (ALD). It was found that, under different upper cutoff voltages (4.3, 4.5, and 4.7 V), the ALD Al 2 O 3 coatings enable enhanced performance of NMC622 cathodes with better cyclability and higher capacity. Particularly, the beneficial effects of the ALD Al 2 O 3 coatings are more remarkable at higher upper cutoff voltages (4.5 and 4.7 V). Furthermore, the ALD coatings can significantly improve the rate capability of NMC622. To this end, we utilized a suite of characterization tools and performed a series of electrochemical tests to clarify the effects of the ALD Al 2 O 3 coatings. This study revealed that the beneficial effects of the Al 2 O 3 ALD coatings are multiple: (i) serving as an artificial layer of solid electrolyte interphase to mitigate undesirable interfacial reactions; (ii) acting as a physical barrier to inhibit metal dissolution of NMC; and (iii) forming a reinforced networked overcoating to boost the mechanical integrity of NMC cathodes. This study is favorable for designing high-performance NMC cathodes.

25 ENERGY STORAGE↗
DOE OSTI2015

Electrochemical Modeling and Performance of a Lithium- and Manganese-Rich Layered Transition-Metal Oxide Positive Electrode

The impedance of a lithium- and manganese-rich layered transition-metal oxide (MR-NMC) positive electrode, specifically Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 , is compared to two other transition-metal layered oxide materials, specifically LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) and Li 1.05 (Ni 1/3 Co 1/3 Mn 1/3 ) 0.95 O 2 (NMC). A more detailed electrochemical impedance spectroscopy (EIS) study is conducted on the LMR-NMC electrode, which includes a range of states-of-charge (SOCs) for both current directions (i.e. charge and discharge) and two relaxation times (i.e. hours and one hundred hours) before the EIS sweep. The LMR-NMC electrode EIS studies are supported by half-cell constant current and galvanostatic intermittent titration technique (GITT) studies. Two types of electrochemical models are utilized to examine the results. The first type is a lithium ion cell electrochemical model for intercalation active material electrodes that includes a complex active material/electrolyte interfacial structure. In conclusion, the other is a lithium ion half-cell electrochemical model that focuses on the unique composite structure of the bulk LMR-NMC materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Optimized purification methods for metallic contaminant removal from directly recycled Li-ion battery cathodes

Metallic contaminants pose a significant challenge to the viability of directly recycling Li-ion batteries. To date, few strategies exist to selectively remove metallic impurities from mixtures of shredded end-of-life material (black mass; BM) without concurrently damaging the structure and electrochemical performance of the target active material. We herein present tailored methods to selectively ionize two major contaminants—Al and Cu—while retaining a representative cathode (LiNi 0.33 Mn 0.33 Co 0.33 O 2 ; NMC-111) intact. This BM purification process is conducted at moderate temperatures in a KOH-based solution matrix. We rationally evaluate approaches to increase both the kinetic corrosion rate and the thermodynamic solubility of Al 0 and Cu 0 , and evaluate the impact of these treatment conditions on the structure, chemistry, and electrochemical performance of NMC. Specifically, we explore the impacts of chloride-based salts, a strong chelating agent, elevated temperature, and sonication on the rate and extent of contaminant corrosion, while concurrently evaluating the effects on NMC. The reported BM purification process is then demonstrated on samples of “simulated BM” containing a practically relevant 1 wt% concentration of Al or Cu. Increasing the kinetic energy of the purifying solution matrix through elevated temperature and sonication accelerates the corrosion of metallic Al and Cu, such that ∼100% corrosion of 75 μm Al and Cu particles is achieved within 2.5 hr. Further, we determine that effective mass transport of ionized species critically impacts the efficacy of Cu corrosion, and that saturated Cl – hinders rather than accelerates Cu corrosion by increasing solution viscosity and introducing competitive pathways for Cu surface passivation. The purification conditions do not induce bulk structural damage to NMC, and electrochemical capacity is maintained in half-cell format. Testing in full cells suggests that a limited quantity of residual surface species are present after treatment, which initially disrupt electrochemical behavior at the graphite anode but are subsequently consumed. Process demonstration on simulated BM suggests that contaminated samples—which prior to treatment show catastrophic electrochemical performance—can be recovered to pristine electrochemical capacity. The reported BM purification method offers a compelling and commercially viable solution to address contamination, particularly in the “fine” fraction of BM where contaminant sizes are on the same order of magnitude as NMC and where traditional separation approaches are unfeasible. Thus, this optimized BM purification technique offers a pathway towards viable direct recycling of BM feedstocks that would otherwise be unusable.

25 ENERGY STORAGE↗
NASA NTRS1986

The atmospheric excitation of earth orientation changes during MERIT

Geodetic estimates of earth orientation variations detected during the MERIT campaign (September 1983-November 1984) are compared with corresponding meteorological data. The geodetic data were obtained using VLBI, lunar laser ranging, and satellite laser ranging and the meteorological data were from the NMC in the U.S. and the European Centre for Medium Range Weather Forecasting (ECMRWF) in the U.K. The effects of changes in pressure, wind, and the inverted barometer ocean response on the excitation of the polar motion and the length of day are examined. The comparison between the meteorological and geodetic data reveals that the equatorial vector component of the atmospheric angular momentum (AAM) has significant annual and semiannual variations. Good correlation is detected between the geodetic polar motion data and the NMC pressure inverted barometer data combined with the ECMRWF wind estimates and semiannual agreement with the NMC pressure data is observed. There is also good correlation between the ECMRWF and NMC polar vector component of the AAM data and the geodetic length of day estimates, and good semiannual agreement with NMC pressure data is noted.

Eubanks, T. M.↗
NASA NTRS1987

Accuracy of atmospheric angular momentum estimates from operational analyses

An attempt is made to assess the accuracy of global atmospheric angular momentum determinations by comparing time series of this quantity derived from both the NMC and ECMWF zonal wind analyses for 1981-85. Over this period, the rms difference betwen the two atmospheric series is comparable to the difference between an atmospheric momentum series and the series that is consistent with observed (nontidal) changes in earth rotation. Most of the difference between the NMC and ECMWF global momentum values comes from the region between 33 deg S and 16 deg N. Differences between NMC and ECMWF regional momentum values become vanishingly small in the high latitudes of the Northern Hemisphere, but they remain large throughout the entire Southern Hemisphere. An annual signal of up to 0.5 m/s exists in the difference between the NMC and ECMWF tropospheric zonal wind fields. Although seemingly small, this signal is vertically coherent and leads to a marked annual component in the NMC-ECMWF difference momentum values in the tropics and also for the Northern Hemisphere as a whole.

Rosen, Richard D.↗
DOE OSTI2020

High accuracy in-situ direct gas analysis of Li-ion batteries

Cycling of lithium-ion batteries containing Ni-rich NMC cathodes at high voltage involves intense gas generation. From the safety standpoint, it is critical to understand how different gas species respond to changes of upper cut-off voltages. In this manuscript, we introduce a novel experimental set up for real-time analysis of gas generation in prismatic pouch cells. In a typical experiment, a lithium-ion pouch cell is directly connected to a quadruple mass spectrometer by glass capillary. Pressure difference helps move the generated gases to the mass spectrometer column for full analysis. The gaseous species are probed during both formation cycle and aging cycles in Li-ion pouch cells comprising NMC811 cathode and graphite anode. The gases are generated upon the creation of the solid electrolyte interphase on graphite during the first formation charge. Besides ethylene gas, C 2 H 4 , whose occurrence is related to the decomposition of ethylene carbonate, a minor solvent decomposition happened at a lower voltage is demonstrated to be associated with residue water on the electrode. For aging cycles, three upper cut-off voltages have been selected to investigate the gas evolution behavior upon charging to 4.2, 4.4 and 4.6 V. Higher upper cut-off voltages do not affect the amount of O 2 measured as a part of the generated oxygen could have reacted with electrolytes. Quite similar and low amounts of O 2 remain in the cells upon charging to the selected cut-off voltages. On the other hand, the generation of CO 2 has been found to be very sensitive to upper cut-off voltage. During similar aging cycles, 6167 nmol $g_{NMC}^{-1}$ of CO 2 is generated at 4.6 V, versus 1650 nmol $g_{NMC}^{-1}$ of CO 2 at 4.4 V, versus 91 nmol $g_{NMC}^{-1}$ of CO 2 at 4.2 V.

25 ENERGY STORAGE↗
DOE OSTI2021

Mesoscale-architecture-based crack evolution dictating cycling stability of advanced lithium ion batteries

The cracking phenomenon of Ni-rich NMC (LiNixMnyCo1-x-yO2, x = 0.6) secondary particles is frequently discovered and believed to be one of critical reasons deteriorating the long-term cycling stability of NMC cathode in lithium ion batteries (LIBs). However, the initiation and evolution of those cracks is still controversial due to the limited quantification especially by in situ monitoring, leading to the challenge of identifying an efficient approach to inhibit the formation of the fractures during repeated cycling. Herein, the irreversible, anisotropic cycling lattice and mesoscale expansion/shrinkage of nano-grain during the first cycle, as revealed by in situ X-ray diffraction (XRD) and in situ atomic force microscopy (AFM), have been quantified and confirmed to be the dominant driving forces of microcracks initiation at the grain boundaries. These microcracks preferentially nucleates at the core region with random oriented nano-grains in early stage. The further growth and aggregation of microcracks into macrocrack eventually results in microfracture propagation radially outward to the periphery region with more uniform nano-grain orientation. This mesoscale nano-grain architecture controlled cracking process highlight the importance of predictive synthesis of cathode materials with controllable multiscale crystalline architecture for high-performance LIBs.

25 ENERGY STORAGE↗