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At least 397 records · Page 22

Hot-Fire Test Results of an Oxygen/RP-2 Multi-Element Oxidizer-Rich Staged-Combustion Integrated Test Article

As part of the Combustion Stability Tool Development project funded by the Air Force Space and Missile Systems Center, the NASA Marshall Space Flight Center was contracted to assemble and hot-fire test a multi-element integrated test article demonstrating combustion characteristics of an oxygen/hydrocarbon propellant oxidizer-rich staged-combustion engine thrust chamber. Such a test article simulates flow through the main injectors of oxygen/kerosene oxidizer-rich staged combustion engines such as the Russian RD-180 or NK-33 engines, or future U.S.-built engine systems such as the Aerojet-Rocketdyne AR-1 engine or the Hydrocarbon Boost program demonstration engine. For the thrust chamber assembly of the test article, several configurations of new main injectors, using relatively conventional gas-centered swirl coaxial injector elements, were designed and fabricated. The design and fabrication of these main injectors are described in a companion paper at this JANNAF meeting. New ablative combustion chambers were fabricated based on hardware previously used at NASA for testing at similar size and pressure. An existing oxygen/RP-1 oxidizer-rich subscale preburner injector from a previous NASA-funded program, along with existing and new inter-connecting hot gas duct hardware, were used to supply the oxidizer-rich combustion products to the oxidizer circuit of the main injector of the thrust chamber. Results from independent hot-fire tests of the preburner injector in a combustion chamber with a sonic throat are described in companion papers at this JANNAF conference. The resulting integrated test article - which includes the preburner, inter-connecting hot gas duct, main injector, and ablative combustion chamber - was assembled at Test Stand 116 at the East Test Area of the NASA Marshall Space Flight Center. The test article was well instrumented with static and dynamic pressure, temperature, and acceleration sensors to allow the collected data to be used for combustion analysis model development. Hot-fire testing was conducted with main combustion chamber pressures ranging from 1400 to 2100 psia, and main combustion chamber mixture ratios ranging from 2.4 to 2.9. Different levels of fuel film cooling injected from the injector face were examined ranging from none to about 12% of the total fuel flow. This paper presents the hot-fire test results of the integrated test article. Combustion performance, stability, thermal, and compatibility characteristics of both the preburner and the thrust chamber are described. Another companion paper at this JANNAF meeting includes additional and more detailed test data regarding the combustion dynamics and stability characteristics.

Hulka, J. R.↗

A Nucleosynthetic Origin for the Southwestern Fe-rich Structure in Kepler's Supernova Remnant

Chandra X-ray observations of Kepler's supernova remnant indicate the existence of a high-speed Fe-rich ejecta structure in the southwestern region. We report strong K-shell emission from Fe-peak elements (Cr, Mn, Fe, Ni), as well as Ca, in this Fe-rich structure, implying that those elements could be produced in the inner area of the exploding white dwarf. We found Ca/Fe, Cr/Fe, Mn/Fe, and Ni/Fe mass ratios of 1.0%–4.1%, 1.0%–4.6%, 1%–11%, and 2%–30%, respectively. In order to constrain the burning regime that could produce this structure, we compared these observed mass ratios with those in 18 one-dimensional Type Ia nucleosynthesis models (including both near-M Ch and sub-M Ch explosion models). The observed mass ratios agree well with those around the middle layer of incomplete Si burning in Type Ia nucleosynthesis models with a peak temperature of ~(5.0–5.3) × 10(exp 9) K and a high metallicity, Z > 0.0225. Based on our results, we infer the necessity for some mechanism to produce protruding Fe-rich clumps dominated by incomplete Si-burning products during the explosion. We also discuss the future perspectives of X-ray observations of Fe-rich structures in other Type Ia supernova remnants.

Toshiki Sato↗

Sierra Gorda 009: A New Member of the Metal-Rich G Chondrites Grouplet

We investigated the metal-rich chondrite Sierra Gorda (SG) 009, a member of the new G chondrite grouplet (also including NWA 5492, GRO 95551). G chondrites contain 23% metal, very reduced silicates, and rare oxidized mineral phases (Mg-chromite, FeO-rich pyroxene). G chondrites are not related to CH-CB chondrites, based on bulk O, C and N isotopic compositions, mineralogy and geochemistry. G chondrites have no fine-grained matrix or matrix lumps enclosing hydrated material typical for CH-CB chondrites. G chondrites’ average metal compositions are similar to H chondrites. Siderophile and lithophile geochemistry indicate sulfidization and fractionation of the SG 009 metal and silicates, unlike NWA 5492 and GRO 05551. The G chondrites have average O isotopic compositions DELTA 17O >0 ‰ ranging between bulk enstatite (E) and ordinary (O) chondrites. An Al-rich chondrule from SG 009 has DELTA 17O <0 ‰ indicating some heterogeneity in oxygen isotopic composition of G chondrite components. SG 009’s bulk carbon and nitrogen isotopic compositions correspond to E and O chondrites. Neon isotopic composition reflects a mixture of cosmogenic and solar components, and cosmic ray exposure age of SG 009 is typical for O, E, and R chondrites. G chondrites are closely related to O, E, and R chondrites and may represent a unique metal-rich parent asteroid containing primitive and fractionated material from the inner Solar System. Oxidizing and reducing conditions during SG 009 formation may be connected with a chemical micro-environment and possibly could indicate that G chondrites may have formed by a planetesimal collision resulting in the lack of matrix.

chondrite↗

Trace Elemental Abundances in Calcium-Aluminum-Rich Inclusions in CV Chondrites

Introduction: Calcium-aluminum-rich inclusions (CAIs), are the first formed solids that define the age of the Solar System [1,2]. CAIs are thought to have condensed from nebular gas [3,4] within the first <1 Ma of Solar System formation [5,6]. CAIs have experienced numerous early Solar System processes including condensation, evaporation, melting, recrystallization, and aqueous alteration [e.g., 7]. The chemical, mineralogical, and textural diversity among CAIs results from a range of chemical and physical processes recorded during nebular and parent body epoch. This study aims to explore the mineralogical, textural, and chemical compositions of CAIs including the trace elemental abundances in CAI phases to determine the early Solar System processes recorded in them. Samples and Analytical Methods: We analyzed one CAI each from CV3 chondrites Northwest Africa (NWA) 5508 designated as ‘Saguaro’, and Northwest Africa (NWA) 12772 designated as ‘Hoopoe’. Back-scatter electron (BSE) images were collected using a Phenom XL scanning electron microscope (SEM) at the Lunar and Planetary Institute (LPI) and the JEOL JXA-8530F electron probe microanalyzer (EPMA) at Johnson Space Center (JSC)-NASA. Additionally, energy dispersive X-ray spectrometry (EDS) elemental maps of select areas for these samples were collected using a 15.0kV beam energy and a 40µA emission current. Using the EPMA, wavelength-dispersive X-ray spectroscopy (WDS) quantitative data were collected. In-situ trace element measurements for both CAIs were determined at JSC-NASA using a Photon Machines 193nm laser ablation system and a Thermo-Scientific Element-XR inductively coupled plasma mass spectrometer (ICP-MS). Analyses consisted of 30s ablations at 10Hz, spot sizes of 20-25µm, and a fluence of 6.0 J/cm2 for anorthite and melilite, and a 3.5 J/cm2 fluence for all other phases. NIST612 was used to correct for instrument drift, while BHVO-2g was used as a primary calibration standard. BCR-2g and in-house mineral standards were regularly measured as unknowns to ensure accuracy. Results: Saguaro is a coarse-grained CAI, ~11 x 6 mm in dimensions. Saguaro contains spinel, Al-rich pyroxene, anorthite, Mg-rich melilite, and minor perovskite in its interior and is therefore classified as a Type B CAI. Individual melilite grains shows normal compositional zoning with an Ak content ranging from ~24 to 54 with no apparent trend from the core to the edge of the CAI. The spinel appears euhedral and occurs both as clusters and as spinel palisades [8]. Two rim sequences surround most of the sample: the inner rim being a Wark-Lovering (WL) rim (~10-35 µm) containing pyroxene, spinel, and melilite (or anorthite), and the outer rim is a finer-grained, thicker (~100 µm), accretionary rim (Fig. 1). The mineral phases in Saguaro record an overall flat REE pattern with an average negative Eu anomaly in pyroxene, and an average positive Eu anomaly in anorthite and melilite respectively. Anorthite, melilite, and pyroxene have a minor depletion in Tm (Fig. 2). The Hoopoe CAI is a compact, coarse-grained ~6 × 4 mm in size. The major mineralogy includes hibonite, spinel, melilite, anorthite, and perovskite. Therefore, it is classified as a compact transitional type A and B. (?)zoning was observed in some hibonites. Individual melilite grains show both reverse and normal zoning, where the Ak content ranges from ~6- to 28. Melilite shows two distinct textures. One texture consisted of smooth melilite that appeared homogenous, while the second appeared to consist of many fine fractures. The spinel also often appears clustered. The WL-rim sequence surrounding Hoopoe is ~25 µm thick and composed of spinel, perovskite, hibonite, and melilite/anorthite. It is then partially surrounded by an outer accretionary rim (~75µm). Like before, refractory metal nuggets appeared concentrated near the WL rims. Other metal assemblages rich in Fe and Ni were also observed. All major mineral phases in Hoopoe display relatively flat REE patterns, except for varying Eu and Tm between phases (Fig. 2). There is a prominent negative Eu anomaly in perovskite and an average positive Eu anomaly in spinel, anorthite, and hibonite respectively (Fig. 2, 3). The mixed phases along the rim of the CAI also display a negative Eu anomaly, and all phases the CAI were depleted in Pb. Discussion: The CV3 CAIs analyzed in this study were classified based on their mineralogy and textures into Type A versus Type B CAIs [10]. Hibonite appears to be pseudomorphically replacing the spinel, (i.e., is hibonite in composition, but appears in the shape of spinel). Spinel palisades. The presence of spinel palisades present in Saguaro are consistent with the melting and recrystallization experienced by this CAI. Trace elemental analyses. Saguaro and Hoopoe display similar trace element patterns to each other, with both appearing generally flat, with anomalies in Eu, and Tm. Melilite and anorthite display positive Eu anomalies in both CAIs, in addition to the hibonite in Hoopoe (Fig. 2). The phases that are depleted in Eu are pyroxene and perovskite in both Saguaro and Hoopoe, respectively (Fig. 3). Given that Eu is volatile in reducing environments [11], this could possibly indicate reducing conditions at the time anorthite and melilite crystallized, with the gas they formed from containing Eu. As these CAIs continued to form, this gas as a result would become depleted in Eu. This also could be supported by the propensity of anorthite and melilite to take up Eu from its surroundings and incorporate it into their structure [12]. In addition, analyzing the assemblage of the phases in the Saguaro, melilite and anorthite (Eu enriched) often surround the pyroxene (Eu depleted) as they are crystallized. This intergrowth of phases and the proximity of the phases would support that the Eu is being incorporated into some phases, preventing it from incorporating into other. Trace elemental analyses of the CAI rims will be evaluated in more detail, as they are complicated by the transient signal being composed of a mixture of mineral phases. Broadly, however, the patterns in the rims of both CAIs are comparable to each other, and for Hoopoe, to the mixed phase patterns in the core (Fig. 3). Other studies have found that CAI rims can be depleted in Ce and Yb [13], however we did not observe these anomalies in the two CAIs discussed here. Given their similarity, the trace elemental analyses of the mixed interior (i.e. core) and rim phases could be interpreted as forming from similar, if not the same, reservoirs. The REE abundance between the rim and core of Hoopoe are also similar, indicating they may have formed from a gas of the same or similar composition. Acknowledgments: We thank the ASU Center for Meteorite Studies for loaning the samples used in this work and Tabb Prissel for his assistance with the analysis. Mouti Al-Hashimi thanks Sam Crossley and Cyrena Goodrich for their help with the LPI SEM training. This work was supported by the LPI Summer Intern Program in Planetary Science and the LPI Cooperative Agreement. References: [1] Connelly J.N. (2012) Science, 338, 651-655. [2] MacPherson G. J. (2014) Treatise on Geochem., 2, 139-179. [3] Grossman L. (1972) GCA, 36, 597-619. [4] Ebel, D.S. (2006) Meteorites and the Early Solar System II (D. S. Lauretta & H. Y. McSween, Eds.) 253-277. [5] MacPherson G. J. (2012) Earth Planet. Sci. Lett., 331-332, 43-54. [6] MacPherson G.J. (2017) GCA, 201, 65-82. [7] Krot A.N. (1995) Meteoritics & Planet. Sci., 30, 748-775. [8] Wark and Lovering (1982) GCA, 46, 2595-2607. [9] Palme H. and Jones A. (2003) Treatise on Geochemistry (H. D. Holland and K. K. Turekian Eds.), 1, 41-61. [10] Grossman L. (1980) Ann. Rev. Earth Planet. Sci., 8, 559-608. [11] Floss C. et al. (1996) GCA, 60, 1975-1997. [12] Mason B. and Martin P. M. (1974) Earth Planet. Sci. Lett., 22, 141-144. [13] Wark B. and Boynton W. V. (2001) Meteoritics & Planet. Sci., 36, 1135-1166.

X Mouti↗

Solar Activities Associated with 3 He-rich Solar Energetic Particle Events Observed by Solar Orbiter

A series of 3 He-rich solar energetic particle (SEP) events was observed by Solar Orbiter in May 2021 at a radial distance of 0.95 AU. An isolated active region AR 12824 was likely the ultimate source of these SEP events. The period of the enhanced flux of 3He was also a period of frequent type III bursts in the decametric-hectometric range, confirming their close relationship. As in past studies, we try to find the solar activities possibly responsible for 3 He-rich SEP events, using the type III bursts close to the particle injection times estimated from the velocity dispersion. But this exercise is not as straightforward as in many of the past studies since the region produced many more type III bursts and jet-like eruptions than the SEP injections. We may generalize the solar activities for the 3 He-rich SEP events in question as coronal jets, but their appearances do not necessarily conform to classic jets that consist of a footpoint and a spire. Conversely, such jets often did not accompany type III bursts. The areas that produced jet-like eruptions changed within the active region from the first to the second set of 3 He-rich SEP events, which may be related to the extended coronal mass ejection that launched stealthily.

Sun↗

Heavy Ion Acceleration in 3he-Rich Solar Energetic Particle Events: New Insights From Solar Orbiter

We present Solar Orbiter energetic particle observations of two 3 He-rich events with features more clearly observed than in prior studies. The event of 2022 November 9 observed from 0.59 au contained hundreds of ultra-heavy ions (UH, mass >78 amu) whereas previous observations at 1 au have shown only an occasional count or two. The event of 2023 April 8 observed from 0.29 au fortuitously had very low ambient activity, making it possible to observe spectra from the 3 He acceleration mechanism without contamination, revealing extremely low H and 4 He intensities arriving simultaneously with other ions observed in typical 3 He-rich events. Taken together with previous studies we believe these data show that 3 He-rich events have a single acceleration mechanism that is responsible for the unique abundance features of 3 He, heavy ions, and UH ions. Considering the acceleration model of Roth and Temerin (1997) that heats the ions over a broad range of gyrofrequencies away from those damped by H and 4 He, we calculate reasonable fits to the observed abundances O-Fe. A key result is that high values of, e.g., Fe/O typical of such events is not due to preferential Fe heating, but on the contrary is due mainly to the depletion of O which at elevated temperatures has a charge-to-mass ratio in the region of the waves damped by 4He. The model also naturally incorporates features of high ionization states and neutron-rich isotope enhancements that have been long-standing puzzles in observations of this type of flare.

Solar flares↗

Optical Wavelength Guided Self-Supervised Feature Learning For Galaxy Cluster Richness Estimate

Most galaxies in the nearby Universe are gravitationally bound to a cluster or group of galaxies. Their optical contents, such as optical richness, are crucial for understanding the co-evolution of galaxies and large-scale structures in modern astronomy and cosmology. The determination of optical richness can be challenging. We propose a self-supervised approach for estimating optical richness from multi-band optical images. The method uses the data properties of the multi-band optical images for pre-training, which enables learning feature representations from a large but unlabeled dataset. We apply the proposed method to the Sloan Digital Sky Survey. The result shows our estimate of optical richness lowers the mean absolute error and intrinsic scatter by 11.84% and 20.78%, respectively, while reducing the need for labeled training data by up to 60%. We believe the proposed method will benefit astronomy and cosmology, where a large number of unlabeled multi-band images are available, but acquiring image labels is costly.

79 ASTRONOMY AND ASTROPHYSICS↗

Robot Navigation in a Rich Information Map for Inspection in Nuclear Environments - 18596

This paper discusses our approach of using an unmanned ground vehicle (UGV) to perform inspection tasks in nuclear environments. To reduce people's exposure to the environment with elevated radiation levels, our goal is enabling UGV to navigate and perform inspections fully autonomous with no human getting involved. To achieve the full automation, the UGV can take use of a rich information map. In traditional robot navigation, the 2D global cost map used for planning path consists only obstacle locations, while a rich information map also includes location information of interested objects to robot. The UGV can then use a rich information map to perform routine inspection tasks with known object locations. In this paper, we will present our method of generating a rich information map and the usage of this map for International Atomic Energy Agency (IAEA) Robotics Challenge. (authors)

42 ENGINEERING↗

Achieving Thermodynamic Stability of Single-Crystal Co-Free Ni-Rich Cathode Material for High Voltage Lithium-Ion Batteries

Ni-rich layered cathode materials are progressively considered as the standard configuration of high-energy electric vehicles by virtues of their high capacity and eliminated “range anxiety.” However, the poor cyclic stability and severe cobalt supply crisis would restrain their wide commercial applicability. Here, a cost-effective single-crystal Co-free Ni-rich cathode material LiNi 0.8 Mn 0.18 Fe 0.02 O 2 (NMF), which outperforms widely commercial polycrystalline LiNi 0.83 Co 0.11 Mn 0.06 O 2 (MNCM) and single-crystal LiNi 0.83 Co 0.11 Mn 0.06 O 2 (SNCM) is reported. Surprisingly, NMF can compensate for the reversible capacity loss under the designed conditions of high-temperature and elevated-voltage, achieving a competitive energy density compared with conventional MNCM or SNCM. Further, combining operando characterizations and density functional theory calculation, it is revealed that NMF cathode with improved dynamic structure evolution largely alleviates the mechanical strain issue commonly found in Ni-rich cathode, which can reduce the formation of intragranular cracks and improve the safety performance. Consequently, this new Co-free NMF cathode can achieve a perfect equilibrium between material cost and electrochemical performance, which not only reduces the production cost by >15%, but also demonstrates excellent thermal stability and cycling performance.

25 ENERGY STORAGE↗

Hybrid Doping Strategy with High‐Entropy Cu/Fe Surface Modification and Zr Bulk Incorporation for Ni‐Rich Cathodes

A hybrid doping strategy combining Zr 4+ bulk doping with high-entropy Cu 2+ /Fe 3+ surface doping is developed to enhance the structural and interfacial stability of Ni-rich layered oxide cathodes. Cu and Fe are selectively introduced at the particle surface via a surface-selective ion-exchange process, forming a ≈15 nm Fe-rich layer while preserving the layered framework. Compared to the pristine cathode, the hybrid sample exhibits significantly improved electrochemical performance in both half-cell and full-cell configurations. In half-cells, the hybrid retains 88.5% and 90.2% after 100 cycles at 1C under 4.6 and 4.5 V, respectively. During high-voltage full-cell cycling, the hybrid cathode maintains over 80% capacity retention, whereas the pristine counterpart retains less than 10% under identical conditions over the same cycling period. XPS, EELS, and DEMS analyses confirm improved oxygen retention, suppressed gas evolution, and stable surface chemistry, while DFT calculations indicate enhanced Me–O bonding in the selected Fe 0.75 Cu 0.25 (Mn 1/16 Co 2/16 Ni 13/16 )O 2 surface composition, which is identified through DFT-calculated mixing energy reaching a minimum at this ratio, indicating the most thermodynamically favorable configuration. In conclusion, these results demonstrate the effectiveness of this hybrid doping strategy in mitigating coupled degradation pathways in Ni-rich cathodes.

15 GEOTHERMAL ENERGY↗

Understanding the Effects of Bi Modification on the Properties of Ni-Rich Cathodes

With the skyrocketing market demands for energy storage, lithium ions batteries (LIB) with higher energy density are urgently needed. Cathodes play a critical role in determining the energy density of LIB, and the most popular one is Ni-rich cathode due to its high capacity. However, due to the fast structural degradation, Ni-rich cathode materials should be further modified to achieve higher stability. Herein, we introduce bismuth ions in LiNi 0.83 Co 0.11 Mn 0.06 O 2 cathodes by adding Bi 2 O 3 during sintering to optimize the specific capacity and cycle stability. By adding 0.1% mol Bi, the Li + diffusion and structural stability are effectively optimized, leading to improved electrochemical performances. Further, the modified sample delivers much higher specific capacity (222.9 mAhg -1 , 0.05 C) than unmodified sample (204 mAhg -1 , 0.05 C). Meanwhile, the specific capacity of optimized sample after 100 cycles at 0.33 C is 27.75 mAhg -1 higher than that of unmodified sample. Therefore, this work demonstrates that Bi modification can be regarded as a possible solution to optimizing the electrochemical performance of Ni-rich cathodes.

25 ENERGY STORAGE↗

The effects of process parameters on the properties of manganese-rich carbonate precursors: A study of co-precipitation synthesis using semi-batch reactors

The synthesis of precursors for lithium- and manganese-rich xLi 2 MnO 3 ∙ (1-x)LiMO 2 (M = Ni, Mn, Co) (LMR-NMC) materials is generally carried out via co-precipitation using a continuously stirred tank reactor (CSTR) under steady-state conditions. But during the early stages of research (e.g., when screening compositional spaces of interest), using a CSTR in steady-state mode can be time consuming and wasteful. An alternative is to operate the reactor in semi-batch mode, which shortens reaction times and reduces the amount of waste. However, the effect of this mode on the product is not well documented. The present work investigates how several process variables affect the physical properties of Mn-rich NMC carbonate precursors prepared under semi-batch operation of a CSTR. The process variables examined are pH, ammonia concentration of feed solution, process temperature, stirring speed, and reaction time. Overall, the results can help guide research-scale production to support efficient development of Mn-rich carbonates for cathode oxides.

25 ENERGY STORAGE↗

Correlation between long range and local structural changes in Ni-rich layered materials during charge and discharge process

Ni-rich cathode materials can deliver higher energy density with a lower cost compared with other conventional layered oxide materials. However, the cycling performance of Ni-rich materials needs further improvement, and the irreversible phase transformation related to the cell failure is not fully understood yet. Although an H1-H2-H3 structural change process is revealed, a more specific explanation about the difference of these hexagonal phases is needed for deeper comprehension and further targeted modification of Ni-rich materials. In this work, the different phase transformation mechanisms of LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) and LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) are investigated by C X-ray diffraction (XRD) measurement, and the relationship between structural change and capacity degradation is discussed, showing that H3 phase can be harmful for cycling. In addition, Li-6 solid state nuclear magnetic resonance (ss-NMR) experiments are carried out for detecting the Li chemical environment at different state of charge, and the data can be associated with structural change obtained from in operando XRD results. From the analysis mentioned above, a new explanation of H1/H2/H3 is given, and a relationship between long range and local structural change has been put forward for the first time.

36 MATERIALS SCIENCE↗

Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a Li x TM 3-x O 4 -type spinel shell

The poor long-term cycling stability, including the fast capacity fade and the severe voltage decay, has become the main concern hindering the practical application of Li-rich layered oxides, a promising cathode for high- energy-density Li-ion battery. Herein, we design and electrochemically construct a ~10 nm-thick Li x TM 3-x O 4 - type (TM ¼Ni, Co, Mn, 0 3 O 4 -type spinel phase and the good Liþconductivity of LiMn 2 O 4 -type spinel phase. Systemic structural and electrochemical analysis demonstrate that, it slows down the activation rate of Li 2 MnO 3 component and efficiently alleviates the lattice O loss at high voltage (>4.5 V) and Mn dissolution, thereby suppressing the structural degradation from the layered phase to the spinel phase in the bulk, eventually significantly enhancing the long-term cycling stability. This study adds richness into the Mn-based spinel phase system and provides a new heterostructure design strategy to improve the electrochemical performance of Li-rich layered cathodes and beyond.

25 ENERGY STORAGE↗

Fast Charge Induced Phase Evolution and Element Contribution of Nickel-Rich Layered Cathode for Lithium-Ion Batteries

In nickel-rich layered cathode materials, three transition metals (TM = Ni, Co and Mn) play critical roles in Li storage performance. However, rate-dependent phase evolution and elemental contribution of nickel-rich cathode materials are not well understood, but very important for further design and development of these cathodes in high-power applications. Here, the rate-dependent phase evolution and elemental contribution of LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) cathode are investigated thoroughly by using time-resolved synchrotron-based in situ X-ray diffraction and absorption techniques. The increase of Ni content in NMC532 has been found to be the main cause of the complex structural changes, resulting in distortion of TM-O 6 octahedron and strong static vibration between TM and O coordination. It is revealed that the fast charge (10C and 30C) of NMC532 leads to intermediate Li-poor phases, shrinking of H2 phase region, and prolonged O1 phase. During high-rate charging, Co is oxidized easily in low voltage region, while Ni mainly dominates charge compensation in high voltage region. It is found that delithiation-induced local structure distortion transfers from Ni to Co sites in fast kinetic process. In conclusion, these findings provide in-depth understanding for the fast charge behavior of Ni-rich layered cathode materials and help to guide further development of advanced high-power lithium-ion batteries.

25 ENERGY STORAGE↗

First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides

To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO 2 . Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used $R\bar{3}m$ structure for LiNiO 2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, $R\bar{3}m$, C2/m, P2 1 /c, and P2/c, P2/c with charge disproportionation of Ni 2+ and Ni 4+ is the most energetically stable and semiconducting structure of LiNiO 2 . Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO 2 to form Li x Ni y Mn z Co 1-y-z O 2 . In the fully lithiated (x=1.0) high Ni content NMC (y>0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 3+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni 2+ to Ni 3+ , then oxidizing Ni 3+ and Co 3+ , while Mn 4+ remains electrochemically inactive till x=0. Finally, a general relationship for the oxidation state change in each TM as a function of x is derived and shows agreement with both modeling and experimental data.

25 ENERGY STORAGE↗

Novel Ordered Rocksalt-Type Lithium-Rich Li 2 Ru 1–x Ni x O 3-δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential

In this work, a series of ordered rocksalt (OR) type Li-rich Li 2 Ru 1–x Ni x O 3-δ (LRN x O, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN 0.4 O, an ~350 mV decrease of the oxygen oxidation potential compared with Li 2 RuO 3 (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. Additionally, the role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN 0.4 O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.

25 ENERGY STORAGE↗

Accelerated Evolution of Surface Chemistry Determined by Temperature and Cycling History in Nickel-Rich Layered Cathode Materials

Nickel-rich layered cathode materials have the potential to enable cheaper and higher energy lithium ion batteries. However, these materials face major challenges (e.g., surface reconstruction, microcracking, potential oxygen evolution) that can hinder the safety and cycle life of lithium ion batteries. Many studies of nickel-rich materials have focused on ways to improve performance. Understanding the effects of temperature and cycling on the chemical and structural transformations is essential to assess the performance and suitability of these materials for practical battery applications. This study is focused on the spectroscopic analysis of surface changes within a strong performing LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode material. We found that surface chemical and structural transformations (e.g., gradient metal reduction, oxygen loss, reconstruction, dissolution) occurred quicker and deeper than expected at higher temperatures. Even at lower temperatures, the degradation occurred rapidly and eventually matched the degradation at high temperatures. Despite these transformations, our performance results showed that a better performing nickel-rich NMC is possible. Establishing relationships between the atomic, structural, chemical, and physical properties of cathode materials and their behavior during cycling, as we have done here for NMC811, opens the possibility of developing lithium ion batteries with higher performance and longer life. Finally, our study also suggests that a separate, systematic, and elaborate study of surface chemistry is necessary for each NMC composition and electrolyte environment.

25 ENERGY STORAGE↗