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At least 181 records · Page 10

Cost Competitive Process of Battery Grade Oxides Preparation from Aged LIBs

The increasing demand for lithium-ion batteries (LIBs) is driving development of advanced recycling and refining methods. In this project, new cathode active materials are prepared from recycled lithium battery materials and subsequently electrochemically evaluated in coin cells. In detail, scrap LIBs were mechanically processed into a metal rich black mass, then reductive acid leached into an aqueous metal solution, and finally high-purity metal hydroxide precursor materials were prepared by selective electrochemical flow precipitation. Closed-loop LIB recycling into active electrode materials will enable US manufacturers to break their reliance on foreign sources of critical materials. For example, electroextraction process used here has potential to significantly reduce chemical & water use as well as waste production as compared to traditional metallurgic techniques. To this end, electroextracted materials refined from used batteries were collected and processed to be tested as precursor cathode active material (pCAM). For this project, two samples of high purity recycled NMC hydroxide (~1 kg each) were received from N th Cycle’s Ohio demonstration facility. The NMC compositions of the two materials are similar, and the levels of impurities have been confirmed. Indeed, impurities like copper, boron and sodium are present in quantities that could negatively impact battery performance. However, some studies have demonstrated that the control of the quantity of elements like copper or boron may improve the electrochemistry properties of Lithium-NMC batteries. The principal objective is to determine the electrochemical performance of these 2 NMC hydroxide batches and clearly determine the effect of the impurities on the performance.

25 ENERGY STORAGE↗

Tropical Pacific moisture variability

The objectives are to describe synoptic scale variability of moisture over the tropical Pacific Ocean and the systems leading to this variability; implement satellite analysis procedures in support of this effort, and to incorporate additional satellite information into operational analysis forecast systems at the National Meteorological Center (NMC). Composite satellite radiance patterns describe features detectable well before the development of synoptic scale tropical plumes. These typical features were extracted from historical files of Tiros Operational Vertical Sounder (TOVS) radiance observations for a pair of tropical plumes which developed during January 1989. Signals were inserted into the NMC operational medium range forecast model and a suite of model integrations were conducted. Many of the 48 h model errors of the historical forecasts were eliminated by the inclusion of more complete satellite observations. Three studies in satellite radiance analysis progressed. An analysis which blended TOVS moisture channels, OLR observations and European Center for Medium Weather Forecasts (ECMWF) model analysis to generate fields of total precipitable water comparable to those estimated from Scanning Multichannel Microwave Radiometer (SMMR) mu-wave observations. This study demonstrated that a 10 y climatology of precipitable water over the oceans is feasible, using available infrared observations (OLR and TOVS) and model analysis (ECMWF, NMC or similar quality). The estimates are sensitive to model quality and the estimating model must be updated with operational model changes. Coe developed a set of tropical plume and ITCZ composites from TOVS observations, and from NMC and ECMWF analyses which had been passed through a radiative transfer model to simulate TOVS radiances. The composites have been completed as well as many statistical diagnostics of individual TOVS channels. Analysis of the computations is commencing. Chung has initiated a study of the differences between TOVS observed vapor structure during El Nino Southern Oscillation (ENSO) (1983) and non-ENSO (1984) years. Preliminary diagnosis demonstrates gross moisture changes between warm and cold sea surface temperature episodes.

Mcguirk, James P.↗

Construction of surface pressure field from scatterometer wind field

An account of the construction of surface pressure fields from Seasat-A satellite scatterometer (SASS) winds as carried out by different methods, and the comparison of these pressure fields with those derived from in situ ship observations is presented. On the assumption that the pressure adjusts itself instantaneously to the motion field, it may be computed by various methods. One of these makes use of planetary boundary theory, and of the possible techniques in this category a two-layer iterative scheme admitting of the parametrization of diabatic and baroclinic effects and of secondary flow was chosen. A second method involves the assumption of zero two-dimensional divergence, leading to a Laplace's equation (the balance equation) in pressure, with the wind field serving as a forcing function. This method does not accommodate adiabatic or baroclinic effects, and requires a knowledge of the pressure at all boundary points. Two comparison fields are used for validation: the conventional operational analyses of the US National Meteorological Center (NMC), and the special analyses of the Gulf of Alaska Experiment (GOASEX), which were done by hand. The results of the computations were as follows: (1) The pressure fields, as computed from the SASS winds alone, closely approximated the NMC fields in regions where reasonable in situ coverage was available (typically, one or two mb differences over most of the chart, three to four mb in extreme cases); (2) In some cases the SASS-derived pressure fields displayed high-resolution phenomena not detected by the NMC fields, but evident in the GOASEX data; and, (3) As expected, the pressure fields derived from the balance equation were much smoother and less well resolved than the SASS-derived or NMC fields. The divergence as measured from the SASS winds is smaller than, but of the same order of magnitude as, the vorticity.

Wurtele, Morton G.↗

Modelling TOVS radiances of synoptic systems

Two operational analysis models, produced by ECMWF and NMC, are compared against observed satellite radiances by converting the analyzed variables into synthetic radiances using a radiative transfer model (RTM). Observed TOVS satellite radiances are used as a ground truth, since they are the only source of continuous, synoptic-scale resolution observations available over the data-sparse tropical Pacific Ocean. It is assumed that if the analysis models correctly simulate atmospheric conditions, the observed and modelled radiance fields will have similar patterns and magnitudes. In each of seven TOVS channels examined, the mean temperature difference between the models was small, but the differences between the models and the observations were large. The mean temperature difference within each channel was larger than the standard deviation in most cases. The moisture channels of the RTM were sensitive to changes in moisture content, but none of the channels were significantly affected by changes in temperature. Single-day modelled radiance analyses contain synoptic information similar to the satellite observations. ECMWF is often too noisy, producing features not verified by the satellite; NMC is often too smooth. NMC more closely resembles the TOVS contours. Modelled water vapor channel analyses resemble observed monthly and composited observations well, but do not accurately reproduce the highly-variable single-day fields. ECMWF generally has more accurate gradients. Neither model simulates the tropics well. The water vapor channels, especially channel eleven (weighted at 700 mb), most closely resembled the tropical plume composite described by McGuirk and Ulsh. The only plume evidence found in the thermal or microwave channels, in either the observations or the models, was a composite trough situated in the correct location, extending from the mid-latitudes into the subtropics. This feature was not readily discernable until the definition and mature stages. Additional information besides the modelled temperatures would be required to produce an accurate forecast for the tropics. Model patterns more closely resembled the observations in the quiescent atmosphere, though the magnitudes were not any closer. ECMWF simulates the TOVS quiescent state better than NMC. The moisture channels continue to present the most realistic patterns. The models contained more detail in the tropics than was verified by the satellite observations, apparently trying to force an active ITCZ. Lag correlations showed TOVS to be more persistent than the models. TOVS also showed a smoother lag trend, but all products appeared to have adequate ability to react to changes in the atmosphere over time.

Coe, Thomas Eddy↗

Validation of UARS Microwave Limb Sounder Temperature and Pressure Measurements

The accuracy and precision of the Upper Atmosphere Research Satellite (UARS) Microwave Limb Sounder (MLS) atmospheric temperature and tangent-point pressure measurements are described. Temperatures and tangent- point pressure (atmospheric pressure at the tangent height of the field of view boresight) are retrieved from a 15-channel 63-GHz radiometer measuring O2 microwave emissions from the stratosphere and mesosphere. The Version 3 data (first public release) contains scientifically useful temperatures from 22 to 0.46 hPa. Accuracy estimates are based on instrument performance, spectroscopic uncertainty and retrieval numerics, and range from 2.1 K at 22 hPa to 4.8 K at 0.46 hPa for temperature and from 200 m (equivalent log pressure) at 10 hPa to 300 m at 0.1 hPa. Temperature accuracy is limited mainly by uncertainty in instrument characterization, and tangent-point pressure accuracy is limited mainly by the accuracy of spectroscopic parameters. Precisions are around 1 K and 100 m. Comparisons are presented among temperatures from MLS, the National Meteorological Center (NMC) stratospheric analysis and lidar stations at Table Mountain, California, Observatory of Haute Provence (OHP), France, and Goddard Spaceflight Center, Maryland. MLS temperatures tend to be 1-2 K lower than NMC and lidar, but MLS is often 5 - 10 K lower than NMC in the winter at high latitudes, especially within the northern hemisphere vortex. Winter MLS and OHP (44 deg N) lidar temperatures generally agree and tend to be lower than NMC. Problems with Version 3 MLS temperatures and tangent-point pressures are identified, but the high precision of MLS radiances will allow improvements with better algorithms planned for the future.

Fishbein, E. F.↗

Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1– y – z Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy

Direct observations of local lattice aluminum environments have been a major challenge for aluminum -bearing Li ion battery materials, such as LiNi1-y-zCoyAlzO2 Al(NCA) and aluminum-doped LiNixMnyCozO2 (NMC). Al-27 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can qualitatively and quantitatively characterize lattice and nonlattice (i.e., surface, coatings, segregation, secondary phase etc.) aluminum coordination and provide information that helps discern its effect in the lattice. In the present study, we use NMR to gain new insights into transition metal (TM)-O-Al coordination and evolution of lattice aluminum sites upon cycling. With the aid of first-principles DFT calculations, we show direct evidence of lattice Al sites, nonpreferential Ni/Co-O-Al ordering in NCA, and the lack of bulk lattice aluminum in aluminum -"doped" NMC. Aluminum coordination of the paramagnetic (lattice) and diamagnetic (nonlattice) nature is investigated for Al-doped NMC and NCA. For the latter, the evolution of the lattice site(s) upon cycling is also studied. A clear reordering of lattice aluminum environments due to nickel migration is observed in NCA upon extended cycling.

27Al MAS NMR↗

Disintegration of Meatball Electrodes for LiNi x Mn y Co z O 2 Cathode Materials

Mechanical degradation of Li-ion batteries caused by the repetitive swelling and shrinking of electrodes upon electrochemical cycles is now well recognized. Structural disintegration of the state-of-art cathode materials of a hierarchical structure is relatively less studied. In this paper, we track the microstructural evolution of different marked regimes in LiNi x Mn y Co z O 2 (NMC) electrodes after lithiation cycles. Decohesion of primary particles constitutes the major mechanical degradation in the NMC materials, which results in the loss of connectivity of the conductive network and impedance increase. We find that the structural disintegration is largely dependent on the charging rate – slow charging causes more damage, and is relatively insensitive to the cyclic voltage window. We use finite element modeling to study the evolution of Li concentration and stresses in a NMC secondary particle and employ the cohesive zone model to simulate the interfacial fracture between primary particles. Finally, we reveal that microcracks accumulate and propagate during the cyclic lithiation and delithiation at a slow charging rate.

25 ENERGY STORAGE↗

Chemical stability and long-term cell performance of low-cobalt, Ni-Rich cathodes prepared by aqueous processing for high-energy Li-Ion batteries

Cobalt content in Li-ion battery cathodes has become a top concern due to its price volatility and limited source availability. Low-cobalt, Ni-rich active materials are promising candidates for next-generation cathodes due to their high capacities, and water-based processing of these materials can further reduce both cost and environmental impact. We systematically evaluated the water compatibility of four different LiNi x Mn 1-x-y Co y O 2 (NMC) powders with increasing nickel contents. Comprehensive characterization verified there is no major change to their bulk structures, and only slight surface modifications related to the removal of contaminant species. For the first time, we demonstrate that LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC 811) cathodes can be formulated in water and cycled 1000 times in full pouch cells with excellent capacity retention (~70% compared to ~76% for NMP-processed cells). When implemented in future battery production lines, aqueous processing of Ni-rich NMC will simultaneously enable cost reductions and higher cell energy densities.

25 ENERGY STORAGE↗

Modifying the Surface of a High-Voltage Lithium-Ion Cathode

Ni-rich lithium nickel manganese cobalt oxides (LiNi x Mn y Co 1–x–y O 2 , NMCs) suffer from poor cycling stability at potentials above 4.2 V vs Li/Li + . This degraded cyclability at high potentials has been largely ascribed to the parasitic reactions between the delithiated cathode and the nonaqueous electrolyte. In this study, we mitigated the performance degradation of high-voltage NMC 622 by designing a functional interfacial layer that consists of a surface doping by Ti 4+ and a TiO 2 coating at the same time. The doping of Ti 4+ near the surface of NMC can suppress the irreversible phase transformation, while the TiO 2 coating can kinetically reduce the rate of the electron-transfer reaction between the delithiated cathode and the solvent. Furthermore, it is revealed that this interfacial engineering approach significantly enhanced both the cycling stability and the rate performance of NMC 622.

25 ENERGY STORAGE↗

Conformal PEDOT Coating Enables Ultra-High-Voltage and High-Temperature Operation for Single-Crystal Ni-Rich Cathodes

Single-crystal Ni-rich Li[Ni x Mn y Co 1-x-y ]O 2 (SC-NMC) cathodes represent a promising approach to mitigate the cracking issue of conventional polycrystalline cathodes. However, many reported SC-NMC cathodes still suffer from unsatisfactory cycling stability, particularly under high charge cutoff voltage and/or elevated temperature. Herein, we report an ultraconformal and durable poly(3,4-ethylenedioxythiophene) (PEDOT) coating for SC-NMC cathodes using an oxidative chemical vapor deposition (oCVD) technique, which significantly improves their high-voltage (4.6 V) and high-temperature operation resiliency. The PEDOT coated SC LiNi 0.83 Mn 0.1 Co 0.07 O 2 (SC-NMC83) delivers an impressive capacity retention rate of 96.7% and 89.5% after 100 and 200 cycles, respectively. Significantly, even after calendar aging at 45 degrees C and 4.6 V, the coated cathode can still retain 85.3% (in comparison with 59.6% for the bare one) of the initial capacity after 100 cycles at a 0.5 C rate. Synchrotron X-ray experiments and interface characterization collectively reveal that the conformal PEDOT coating not only effectively stabilizes the crystallographic structure and maintains the integrity of the particles but also significantly suppresses the electrolyte's corrosion, resulting in improved electrochemical/thermal stability. Our findings highlight the promise of an oCVD PEDOT coating for single-crystal Ni-rich cathodes to meet the grand challenge of high-energy batteries under extreme conditions.

25 ENERGY STORAGE↗

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↗

Probing the Effect of Electrode Thermodynamics on Reaction Heterogeneity in Thick Battery Electrodes

Thick electrodes present a viable strategy for enhancing energy density and reducing manufacturing costs of lithium-ion batteries. However, reaction heterogeneity during cycling compromises their rate capability and cycle life. While this nonuniformity is commonly attributed to sluggish charge transport, it is demonstrated here that the thermodynamic properties of the electrode material play an equally critical role. Through combined X-ray fluorescence microscopy and absorption near-edge structure spectroscopy, reaction distributions in LiFePO 4 (LFP) and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC) thick electrodes with matched porosity and tortuosity are compared. LFP electrodes develop pronounced depth-oriented state-of-charge (SOC) gradients that worsen with increasing discharge rates, whereas NMC maintains much more uniform SOC distributions under such conditions. This difference originates from their distinct SOC dependence of equilibrium potentials and is quantifiable through a dimensionless “reaction uniformity” number. Intriguingly, LFP thick electrodes also exhibit lateral SOC variations that strengthen during slow discharge. In conclusion, the enhanced reaction uniformity in NMC correlates with better active material utilization and slower capacity fade than LFP, highlighting electrode thermodynamics as a key design consideration for thick electrodes.

36 MATERIALS SCIENCE↗

Direct Observation of Defect‐Aided Structural Evolution in a Nickel‐Rich Layered Cathode

Abstract Ni‐rich LiNi 1− x − y Mn x Co y O 2 (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni‐rich NMC cathode in a solid‐state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock‐salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni‐rich NMC.

Li, Shuang↗

Direct observation of defect-aided structural evolution in Ni-rich layered cathode

Ni-rich LiNi 1-x-y Mn x Co y O 2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.

25 ENERGY STORAGE↗

High-Speed Fabrication of Lithium-Ion Battery Electrodes by UV-Curing

In this study, UV-curing was investigated as an alternative method to provide fast production of composite cathodes and significantly reduce the time and energy required for solvent removal in lithium-ion battery fabrication. To serve our purpose, low-molecular-weight polysiloxane acrylate (PSA) was designed and synthesized from a polysiloxane epoxide precursor. In the presence of the acrylic acid additive LiNi1/ 3Mn1/3Co1/3O2 (NMC), electrode laminates containing 10 wt% PSA binder were successfully fabricated by UVcuring. The cured electrode exhibited good mechanical and electrochemical properties. At current rates up to C/3, the cell performance of the UV-cured NMC electrode was comparable to that of conventional polyvinylidene fluoride (PVDF)-bound NMC electrode. Our initial success in applying high-speed UV-curing in composite electrode fabrication has proved that it is a promising route to substantially reducing the capital and operation costs of lithium-ion battery electrode manufacturing and additionally bringing about important environmental benefits.

binder↗

Synthesis and electrochemical characterization of Cr-doped lithium-rich Li 1.2 Ni 0.16 Mn 0.56 Co 0.08-x Cr x O 2 cathodes

Lithium-rich layer oxide, Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 (NMC), is a possible cathode candidate for high-energy density batteries. Issues such as cycling stability, rate performance, and cost are yet to be overcome before successful commercialization of the material. In this work, we report on the synthesis of Cr-doped lithium-rich phases Li 1.2 Ni 0.16 Mn 0.56 Co 0.08-x Cr x O 2 (where x=0.00, 0.01, and 0.02) (NMC-Cr) by the sol-gel technique. Cr is homogeneously distributed in the crystal structure evidence by elemental mapping measurements. The Cr-doped materials exhibit much better cycling stability with 100% capacity retention versus 44% for the undoped sample after 50 cycles. The Cr-doped samples show excellent electrochemical performance at higher C-rate in comparison with the undoped NMC. The latter shows rapid capacity fading from 220 to 50 mAh g ₋1 at the 0.1 to 1C rates, respectively. Moreover, the Cr-containing materials do not show significant signs of voltage fading during cycling owing to the stabilization of the crystal lattice by Cr. The electrochemical impedance spectroscopy measurements also indicate the stable cell resistance on cycling for the Cr-doped phases compared to the undoped phase.Open image in new window

25 ENERGY STORAGE↗

Boron coated straw-based neutron multiplicity counter for neutron interrogation of TRISO fueled pebbles

Pebble bed reactors (PBRs) can improve the safety and economics of the nuclear energy production. PBRs rely on TRIstructural-ISOtropic (TRISO) fuel pebbles for enhanced fission product retention. Accurate characterization of individual fuel pebbles would enable the validation of computational models, efficient use of TRISO fuel, and improve fuel accountability. Here, we have developed and tested a new neutron multiplicity counter (NMC) based on 192 boron coated straw (BCS) detectors optimized for 235 U assay in TRISO fuel. The new design yielded a singles and doubles neutron detection efficiency of 4.71% and 0.174%, respectively, and a die-away time of 16.7 μs. The NMC has a low intrinsic gamma-ray detection efficiency of 8.71 x 10 –8 at an exposure rate of 80.3 mR/h. In simulation, a high-efficiency version of the NMC encompassing 396 straws was able to estimate the 235 U in a pebble with a relative uncertainty and error both below 2% in 100 s.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tackling issues of lithium metal anodes with a novel polymeric lithicone coating

Lithium metal (Li) has been hindered from as anodes in commercial batteries for over 50 years, due to two main issues: continuous formation of solid electrolyte interphase (SEI) and lithium dendritic growth. In this work, we report a new strategy to tackle these issues, i.e., using molecular layer deposition (MLD) to grow an ionically conducting but electrically insulating polymeric lithicone coating, an Li-containing triethanolamine (LiTEA). Our electrochemical tests revealed that this LiTEA coating could serve as an exceptional protection layer over Li anodes. Consequently, the LiTEA-coated Li electrodes could achieve a superior cyclability of > 10000 Li stripping/plating cycles at a current density of 5 mA cm -2 and a long cyclability of > 5500 cycles at 2 mA cm -2 in Li||Li symmetric cells without failures, under a fixed areal capacity of 1 mAh cm -2 . Characterizations using scanning electron microscopy and X-ray photoelectron microscopy verified that Li + ions could be easily extracted through and deposited under the LiTEA coating during the stripping/plating processes. Consequently, this LiTEA coating significantly inhibited the formation of SEI and Li dendrites. This underlies the long cycling lifetime of the LiTEA-coated Li||Li cells. Coupling with the nickel-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes, more encouragingly, the LiTEA-coated Li anodes could remarkably extend the cyclability and sustainable capacity of the resultant Li||NMC full cells. Finally, we also demonstrated that the performance of Li||NMC cells could be further improved through combining an LiTEA-coated Li anode with an Li 2 S-modified NMC811 via atomic layer deposition (ALD). Thus, this study is inspiring for developing high-energy Li||NMC lithium metal batteries.

25 ENERGY STORAGE↗