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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

LDRD poster - Identifying the speciation of salt-based actinides in the presence of contaminants

Molten salt reactors (MSRs) are among the most promising Generation IV nuclear reactors. The salts used in these reactors exhibit a high affinity for moisture and oxygen, and heating does not eliminate the oxides that are formed. Additionally, due to the high operating temperatures, reactor parts experience pronounced corrosion, and the resulting corrosion products integrate into the fuel salt system. It is hypothesized that the speciation of f-elements in molten salts would change in the presence of oxides and corrosion products. These changes in local structure can alter the rheological properties, which are critical to the operational and safety parameters of the reactors. Therefore, an in-depth understanding of how corrosion products influence lanthanide/actinide speciation is crucial. To test this hypothesis, lanthanides (as surrogates for actinides) and actinide chlorides were mixed with oxides (such as nickel oxide and lithium oxide) and/or corrosion products (e.g., nickel chloride) and reacted in molten salts. The resulting phases were analyzed using techniques such as powder X-ray diffraction, Raman spectroscopy, UV-Visible spectroscopy, and nuclear magnetic resonance spectroscopy. In the presence of oxides, due to the high oxophilicity of f-elements, these elements capture oxygen from the oxides, forming lanthanide/actinide oxide or oxychloride phases. Specifically, with cerium chloride, the introduction of lithium oxide to the formation of various final products depending on the oxide concentration. At lower oxide concentrations, cerium oxychloride (CeOCl) in the +3 oxidation state was observed, while an increase in the oxide concentration led to the formation of cerium dioxide (CeO2), where cerium is in the +4 oxidation state. In contrast, with nickel oxide, CeOCl formation was consistently observed, regardless of the oxide concentration. This project successfully determined that the speciation of f-elements change in the presence of oxides and different oxides in molten salts result in different final products. When the influence of nickel chloride was examined, changes in f-element speciation were not observed. However, it reacted with lithium chloride to generate a lithium-nickel-chloride (Li6NiCl8) phase, which was also observed when nickel oxide was reacted. Computational models were developed to simulate the phases anticipated under experimental conditions.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2020

Structural Degradation of High Voltage Lithium Nickel Manganese Cobalt Oxide (NMC) Cathodes in Solid-State Batteries and Implications for Next Generation Energy Storage

In this study, we report the stability of the layered high voltage cathode NMC622 with respect to a standard liquid electrolyte and in an all solid-state configuration. NMC622 cathodes with a (104) orientation were found to suffer from degradation at high voltage (4.5 V vs Li/Li + ) due to electrolyte-promoted degradation of the layered structure in a carbonate electrolyte. The lithium phosphorus oxynitride (LiPON) electrolyte was able to suppress the extent of this decomposition in solid-state cells but not totally prevent it from occurring. In the solid-state cells the capacity decreased from 203 to 93 mAh/g in the first cycle and from 93 to 79 mAh/g over the subsequent 99 cycles, whereas, after 20 cycles, the liquid cell charge capacity was dominated by the irreversible electrolyte degradation. Furthermore, the interfacial resistances of the solid-state cells were stable with cycling, suggesting minimal degradation of the NMC622/LiPON interface and incumbent losses due to structural evolution associated with cathode orientation. This data indicates that accessing stable high voltage capacity in NMCs will not be enabled by simply stabilizing the cathode–electrolyte interface. Optimizing cathode crystallographic orientation may be the key to accessing this high voltage regime.

25 ENERGY STORAGE↗
DOE OSTI2021

What is the Role of Nb in Nickel-Rich Layered Oxide Cathodes for Lithium-Ion Batteries?

Nickel-rich layered metal oxide LiNi 1–y–z Mn y Co z O 2 (1 – y – z ≥ 0.8) materials are the most promising cathodes for next-generation lithium-ion batteries in electric vehicles. However, they lose more than 10% of their capacity on the first cycle, and interfacial/structural instability causes capacity fading. Coating and substitution are possible direct and effective solutions to solve these challenges. In this Letter, Nb coating and Nb substitution on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is easily produced through a scalable wet chemistry method followed by sintering from 400 to 800 °C. A Li-free Nb oxide treatment is found to remove surface impurities forming a LiNbO 3 /Li 3 NbO 4 surface coating, to reduce the first capacity loss and to improve the rate performance. Furthermore, Nb substitution stabilizes the structure, as evidenced by less heat evolution on heating, thus providing better long cycling stability with a 93.2% capacity retention after 250 cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Formation of Surface Impurities on Lithium–Nickel–Manganese–Cobalt Oxides in the Presence of CO 2 and H 2 O

Surface impurities involving parasitic reactions and gas evolution contribute to the degradation of high Ni content LiNi x Mn y Co z O 2 (NMC) cathode materials. The transient kinetic technique of Temporal Analysis of Products (TAP), density functional theory, and infrared spectroscopy have been used to study the formation of surface impurities on varying nickel content NMC materials (NMC811, NMC622, NMC532, NMC433, NMC111) in the presence of CO 2 and H 2 O. CO 2 reactivity on a clean surface as characterized by CO 2 conversion rate in the TAP reactor follows the order: NMC811 > NMC622 > NMC532 > NMC433 > NMC111. The capacity of CO 2 uptake follows a different order: NMC532 > NMC433 > NMC622 > NMC811 > NMC111. Moisture pretreatment slows down the direct CO 2 adsorption process and creates additional active sites for CO 2 adsorption. Electronic structure calculations predict that the (012) surface is more reactive than the ($10\bar{1}4$) surface for CO 2 and H 2 O adsorption. CO 2 adsorption leading to carbonate formation is exothermic with formation of ion pairs. The average CO 2 binding energies on the different materials follow the CO 2 reactivity order. Water hydroxylates the (012) surface and surface OH groups favor bicarbonate formation. Water creates more active sites for CO 2 adsorption on the ($10\bar{1}4$) surface due to hydrogen bonding. The composition of surface impurities formed in ambient air exposure is dependent on water concentration and the percentage of different crystal planes. Different surface reactivities suggest that battery performance degradation due to surface impurities can be mitigated by precise control of the dominant surfaces in NMC materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Ceramics↗
DOE OSTI2021

A Cobalt– and Manganese–Free High–Nickel Layered Oxide Cathode for Long–Life, Safer Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 and LiNi 1–x–y Co x Al y O 2 cathodes are receiving growing attention due to the burgeoning demands on high-energy-density lithium-ion batteries. The presence of both cobalt and manganese in them, however, triggers multiple issues, including high cost, high toxicity, rapid surface deterioration, and severe transition-metal dissolution. Herein, a Co- and Mn-free ultrahigh-nickel LiNi 0.93 Al 0.05 Ti 0.01 Mg 0.01 O 2 (NATM) cathode that exhibits 82% capacity retention over 800 deep cycles in full cells, outperforming two representative high-Ni cathodes LiNi 0.94 Co 0.06 O 2 (NC, 52%) and LiNi 0.90 Mn 0.05 Co 0.05 O 2 (NMC, 60%) is presented. It is demonstrated that a titanium-enriched surface along with aluminum and magnesium as the stabilizing ions in NATM not only ameliorates unwanted side reactions with the electrolyte and structural disintegrity, but also mitigates transition-metal dissolution and active lithium loss on the graphite anode. As a result, the graphite anode paired with NATM displays an ultrathin (≈8 nm), monolayer anode-electrolyte interphase architecture after extensive cycling. Furthermore, NATM displays considerably enhanced thermal stability with an elevated exothermic temperature (213 °C for NATM vs 180 and 190 °C for NC and NMC, respectively) and remarkably reduced heat release. This work sheds light on rational compositional design to adopt ultrahigh-Ni cathodes in lithium-based batteries with low cost, long service life, and improved thermal stability.

25 ENERGY STORAGE↗
DOE OSTI2021

Electrolyte Regulating toward Stabilization of Cobalt-Free Ultrahigh-Nickel Layered Oxide Cathode in Lithium-Ion Batteries

Cobalt (Co)-free ultrahigh-nickel (Ni) layered oxides exhibit a double-edged competitive advantages in reducing the cathode cost and boosting the energy density, promising the sustainable development of batteries for electric vehicles. However, the increased Ni content, resultantly more highly oxidative Ni 4+ , potentially induces severe capacity fading due to the aggravated side reactions, limiting the practical applications. Here, we evaluate the compatibility of two localized high-concentration electrolytes (LHCEs) with LiNi 0.96 Mg 0.02 Ti 0.02 O 2 (NMT) cathode under a high charging voltage of 4.4 V in lithium ion batteries. The LHCE with EC additive enables the formation of stable interfacial layers on both NMT cathode and graphite anode, thus realizing a capacity retention of 97.2% over 200 cycles at 25 °C and high reversible capacities of ~180.2 and ~185.8 mAh g -1 , respectively, at 5C charge rate and 5C discharge rate. This study offers a promising approach to enable Co-free ultrahigh-Ni layered oxides for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2024

The Role and Substitution of Cobalt in the Cobalt‐Lean/Free Nickel‐Based Layered Transition Metal Oxides for Lithium Ion Batteries

Here, the Nickel-based layered transition metal oxide cathode represented by NCM (LiNi x Co y Mn z O 2 , x+y+z=1) and NCA (LiNi x Co y Al z O 2 , x+y+z=1) is widely used in the electric vehicle market due to its specific capacity and high working potential, in which Cobalt (Co) plays a huge role in improving the structural stability during the cycle. However, the limited supply of Co, due to its scarcity and the influence of geopolitics, poses a significant constraint on the further advancement of the Nickel-based layered transition metal oxide cathode in the field of energy storage. In this paper, the mechanism of Co in the Nickel-based layered transition metal oxides is reviewed, including its critical role for structural stability such as the inhibition of cationic mixing and the release of lattice oxygen et al. Subsequently, it outlines various strategies to enhance the performance of Co-lean/free materials, such as ion doping, including single-ion doping and multi-ion co-doping, and various surface coating strategies, so as to eliminate the adverse effects of Co loss on materials. Ultimately, this paper offers a glimpse into the promising future of Cobalt-free strategies for high performance of Nickel-based layered transition metal oxides.

25 ENERGY STORAGE↗
DOE OSTI2020

Synthesis of LiNiO 2 at Moderate Oxygen Pressure and Long-Term Cyclability in Lithium-Ion Full Cells

The widespread adoption of electric vehicles necessitates higher-energy-density and longer-life cathode materials for Li-ion batteries. LiNiO 2 offers a higher energy density at a lower cost than other high-Ni-content cathodes containing additional transition-metal ions. However, detrimental phase transformations and impedance growth, resulting from structural defects formed during synthesis, lead to poor cyclability and limit the practical viability of LiNiO 2 . Herein, we demonstrate a considerably improved cycle life for LiNiO 2 by synthesizing it under a pressurized oxygen environment. The capacity retention in pouch-type full cells with a graphite anode after 1000 cycles is increased from 59 to 76% by applying a mere 1.7 atm of oxygen pressure during the synthesis of LiNiO 2 . With iodometric titration and inductively coupled plasma optical emission spectroscopy analysis, we provide clear evidence that oxygen pressure during synthesis reduces the occurrence of lattice oxygen vacancies and increases the content of Ni 3+ in LiNiO 2 , improving its structural integrity and cyclability. Post-mortem analysis of the cycled cathodes provides insights into the sources of degradation occurring during long-term cycling. Here, this work demonstrates a practically viable, synthetic approach combined with doping and coating to achieve improved performance with high-Ni layered oxide materials. Furthermore, this work represents the first report of extended cycling of LiNiO 2 in pouch full cells with graphite anode and will, therefore, serves as an important benchmark for future research on LiNiO 2 .

25 ENERGY STORAGE↗
DOE OSTI2023

Interplay of molten salt and dopants in tuning the performance of single-crystalline LiNiO 2

Single-crystalline layered oxide cathodes have seen great research interest in recent years. Adoption of single-crystal morphology improves mechanical robustness and eliminates intergranular boundaries, improving the chemical stability of the cathode. Furthermore, single-crystal cathodes also suffer from worsened lithium-diffusion kinetics stemming from the significantly increased diffusion path lengths. Sluggish lithiation kinetics induce concentration gradients within the cathode particle during cell operation, resulting in the accumulation of lattice strain, which deteriorates cell performance. Foreign dopants have been shown to greatly improve ion diffusion in many high-Ni layered oxide cathode systems. In particular, we identify Ti and Te as promising dopants to ameliorate the slow diffusion kinetics. We find that doping 1 mol.% Te into single crystal LiNiO 2 greatly improves Li + diffusivity, as determined through galvanostatic intermittent titration technique. Further incorporating 2 mol.% Al and pairing with lithium-metal anode in a localized high concentration electrolyte (LHCE) delivers 206 mA h g -1 at C/3 rate and retains 94% capacity after 100 cycles in Li metal half cells. By addressing kinetically mediated degradation with Te doping, and surface-based degradation with Al and LHCE, the cathode experiences very little polarization and overpotential growth, enabling stable cycling with high accessible capacity.

25 ENERGY STORAGE↗
DOE OSTI2025

The Sensitivity of Nickel Substitution in the Structural Design of Manganese-Based Layered and Lithiated Spinel Electrodes for Li-Ion Batteries

A concerted effort is being made at Argonne National Laboratory to explore and develop high-performance lithium-manganese-nickel-oxide cathode materials for the lithium battery industry. They are both energy- and cost-competitive relative to cobalt- and nickel-rich systems, such as LiCoO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 . The recent discovery of the structural versatility of LiNi 0.5 Mn 0.5 O 2 , has revealed that it can exist in three configurations: lithiated spinel, partially disordered layered, and completely disordered rock salt within a common cubic-close-packed oxygen array. This versatility opens up the possibility of designing structurally integrated electrode components with interlinking 2-D (layered) and 3-D (spinel) channels for Li-ion transport. This paper highlights the sensitivity of Ni substitution and synthesis temperature on the structural and electrochemical properties of LiNi 0.50 Mn 0.50 O 2 , LiNi 0.53 Mn 0.47 O 2 , LiNi 0.47 Mn 0.53 O 2 , and LiNi 0.25 Mn 0.75 O 2 electrodes, as well as a cobalt-containing composition, LiNi 0.333 Mn 0.333 Co 0.333 O 2 , when synthesized at a relatively low temperature of 400 °C.

25 ENERGY STORAGE↗
DOE OSTI2025

Nucleation-promoting and growth-limiting synthesis of disordered rock-salt Li-ion cathode materials

Disordered rock-salt oxides and oxyfluorides are promising positive electrode materials for high-performance lithium-ion batteries free of nickel and cobalt. However, conventional synthesis methods rely on post-synthesis pulverization to achieve cycling-appropriate particle sizes, offering limited control over particle microstructure and crystallinity. This accelerates degradation and complicates secondary particle processing. Here we present a synthesis strategy that enhances nucleation while suppressing particle growth and agglomeration across various disordered rock-salt compositions, including lithium–manganese–titanium oxide, lithium–manganese–niobium oxide, and lithium–nickel–titanium oxide systems. Applied to Li 1.2 Mn 0.4 Ti 0.4 O 2 , this method yields highly crystalline, well-dispersed sub-200 nm particles that form homogeneous electrode films with stable cycling behavior. Tested in cells with lithium metal as the counter electrode, these electrodes deliver ~200 mAh/g with 85% capacity retention relative to the first cycle after 100 cycles (20 mA/g, 1.5–4.8 V), and an average discharge voltage loss of 4.8 mV per cycle, compared to 38.6% retention and 7.5 mV loss per cycle for electrodes derived from pulverized solid-state particles. This approach suggests a route to enhance the performance and durability of disordered rock-salt electrodes for sustainable lithium-ion batteries.

Batteries↗
DOE OSTI2021

Unveiling the Stabilities of Nickel–Based Layered Oxide Cathodes at an Identical Degree of Delithiation in Lithium–Based Batteries

Bulk, surface, and interfacial instabilities that impact the cycle and thermal performances are the major challenges with high-energy-density LiNi 1–x–y Mn x Co y O 2 (NMC) cathodes with high nickel contents. It is generally believed that the instabilities and performance losses become exponentially aggravated as the nickel content increases. Disparate from this prevailing belief, it is herein demonstrated that NMC cathodes with higher Ni contents may imply better overall stability than “lower-Ni” cathodes under an identical degree of delithiation (charging) conditions. With two representative cathodes, LiNi 0.8 Mn 0.1 Co 0.1 O 2 and LiNiO 2 , a systematic investigation into their stabilities with control of the degree of delithiation is presented. Electrochemical tests indicate that LiNiO 2 displays better cyclability than LiNi 0.8 Mn 0.1 Co 0.1 O 2 at the same delithiation state. Comprehensive structural and interphase investigations unveil that the inferior cyclability of LiNi 0.8 Mn 0.1 Co 0.1 O 2 predominantly results from aggravated parasitic reactions, and the interphase stability may be more critical than lattice stability in dictating cyclability. Also, LiNiO 2 delivers similar or better thermal behavior than LiNi 0.8 Mn 0.1 Co 0.1 O 2 . Finally, the findings demonstrate a strong correlation of the stability of NMC cathodes to the degree of delithiation state rather than the Ni content itself, highlighting the importance of reassessing the true implications of Ni content and structural and interphasial tuning on the stabilities of NMC cathodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Stabilizing and understanding the interface between nickel-rich cathode and PEO-based electrolyte by lithium niobium oxide coating for high-performance all-solid-state batteries

The pursuit of high energy density and safe lithium ion batteries (LIBs) is the urgent goal for the development of next-generation electric vehicles (EVs). All-solid-state batteries (ASSBs) with the combination of poly(ethylene oxide) (PEO)-based solid polymer electrolyte (SPE) and Ni-rich lithium nickel manganese cobalt oxide LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode are promising candidates for EVs due to their improved energy density and safety. However, the low electrochemical oxidation window of PEO-based SPE and the instability of NMC811 at the charge/discharge process seriously restrict the battery performance. Herein, a high voltage stable solid-state electrolyte layer lithium niobium oxide (LNO) is coated on the NMC811 electrode surface by atomic layer deposition for stabilizing NMC811-PEO solid polymer batteries. Electrochemical tests show that LNO coating can stabilize the NMC811 active materials and mitigate the decomposition of SPE upon the cycling process, rendering a good performance of NMC811-PEO solid polymer battery. Mechanism studies by SEM, STEM, XAS, and XPS disclose that the uncoated NMC811 suffers from chemomechanical degradations along with oxygen release triggering the decomposition of SPE, which results in unstable cathodic electrolyte interphase. With LNO coating, chemomechanical degradations and oxygen release are inhibited and the decomposition of SPE is mitigated. This paper renders a stable and high-performance high-energy-density SSB for high voltage application, which paves the way toward next-generation solid-state LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Influence of aluminum incorporation and aqueous conditions on metal ion release of high-Ni transition metal oxide nanomaterials

Developing a materials perspective of how to control the degradation and negative impact of complex metal oxides requires an integrated understanding of how these nanomaterials transform in the environment and interact with biological systems. Doping with aluminum is known to stabilize oxide materials, but has not been assessed cohesively from synthesis to environmental fate and biological impact. In the present study, the influence of aluminum doping on metal ion release from transition metal oxides was investigated by comparing aqueous transformations of lithium nickel cobalt aluminum oxide (LiNi 0.82 Co 0.15 Al 0.03 O 2 ; NCA) and lithium nickel cobalt oxide (LiNi 0.80 Co 0.20 O 2 ; NC) nanoparticles and by calculating the energetics of metal release using a density functional theory (DFT) and thermodynamics method. Two model environmental organisms were used to assess biological impact, and metal ion release was compared for NCA and NC nanoparticles incubated in their respective growth media: moderately hard reconstituted water (MHRW) for the freshwater invertebrate Daphnia magna (D. magna) and minimal growth medium for the Gram-negative bacterium Shewanella oneidensis MR-1 (S. oneidensis). Further, the amount of metal ions released was reduced for NCA compared to NC in MHRW, which correlated to changes in the modeled energetics of release upon Al substitution in the lattice. In minimal medium, metal ion release was approximately an order of magnitude higher compared to MHRW and was similar to the stoichiometry of the bulk nanoparticles for both NCA and NC. Interpretation of the release profiles and modeling indicated that the increase in total metal ion release and the reduced influence of Al doping arises from lactate complexation of metal ions in solution. The relative biological impacts of NC and NCA exposure for both S. oneidensis and D. magna were consistent with the metal release trends observed for minimal medium and MHRW, respectively. Together, these results demonstrate how a combined experimental and computational approach provides valuable insight into the aqueous transformations and biological impacts of complex metal oxide nanoparticles.

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

Complementary Effects of Mg and Cu Incorporation in Stabilizing the Cobalt-Free LiNiO 2 Cathode for Lithium-Ion Batteries

Since the discovery of LiNiO 2 several decades ago, a new era of electric vehicles demanding high-energy-density lithium-ion batteries (LIBs) has recently rebooted the interest in this cathode material to eliminate the dependence on expensive and scarcely available cobalt. However, LiNiO 2 has been plagued by cycle instability, thermal instability, and air instability. We present here an exploration of the mutual interaction of magnesium and copper in stabilizing the cobalt-free LiNiO 2 cathode. Although Mg doping is beneficial for the robustness of the bulk structure of LiNiO 2 , surface characterization results of Mg-doped LiNiO 2 implies the need for further surface protection. To that end, we have incorporated Cu in addition to Mg in that Cu stabilizes the surface of Mg-doped LiNiO 2 by forming a protective stable surface layer without harming the bulk. Notable variations of the surface residual lithium composition (Li Li 2 CO 3 /Li LiOH ) along with the incorporation of stabilizers are also discussed. The harmony between Mg and Cu with as little as 0.5 atom % Mg and 0.3 atom % Cu significantly enhances the specific energy and cycle life of LiNiO 2 . Furthermore, this study demonstrates how the co-incorporation of optimal dopants can help stabilize both the bulk and surface and provides new insights toward developing cobalt-free layered oxide cathodes for high-energy-density LIBs.

25 ENERGY STORAGE↗