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At least 991 records · Page 55

Understanding the Selective Deposition of Li Metal on Nonuniform Electrode Surfaces Using Atomic Force Microscopy

The use of lithium metal in secondary batteries has been impeded by its tendency to form dendrites: branching conductive structures of metal that can lead to capacity loss and, ultimately, internal shorts in the battery. Patterned electrodes, in addition to artificially increasing the current density of cells by increasing the surface area available for reaction, also generate a nonuniform electric field in the vicinity of the electrode surface. This nonuniform electric field, though rapidly screened by the electrolyte, can promote inhomogeneous deposition and Solid Electrolyte Interphase formation. As the consequence of these effects is not theoretically apparent since Solid Electrolyte Interphase volume and conductivity changes can, in principle, offset variations in local current density, we have performed experiments to examine the deposition of Li on nonuniform electrode surfaces using Atomic Force Microscopy. In this work, we measure the local variations in topography, SEI thickness, and composition, and discuss their implications for the formation of dendrites in Li metal.

25 ENERGY STORAGE↗

Operando Measurements of Electrolyte Li-ion Concentration during fast charging with FTIR/ATR

The ability to charge a Li-ion battery at high charging rates is critical for electric vehicle adoption; however, further study of ion transport is required to develop electrolytes suitable for fast charge. Fourier transform infrared spectroscopy (FTIR) used with attenuated total reflection (ATR) enables operando measurements of liquid electrolytes. This research focused on solvation shifting of solvent infrared absorption bands in the presence of lithium ions. Lithium-shifted infrared absorption bands and non-shifted bands of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) were compared to infer ion concentration changes during cycling. Lithium concentrations were calibrated using EC/EMC/LiPF 6 electrolytes with known lithium concentrations. A Li-ion half-cell with a graphite anode and EC/EMC/LiPF 6 electrolyte was observed with FTIR/ATR. The results showed that the magnitude of lithium concentration changes increased with increasing C-rate. During a galvanostatic intermittent titration technique (GITT) test, changes in lithium concentration could be observed. During intercalation, a lithium depletion occurred when a negative current was applied, and a lithium surplus occurred during deintercalation when a positive current was applied. The capability of observing lithium concentration has significant implications for the utility of operando studies and the potential to link lithium movement to battery performance.

25 ENERGY STORAGE↗

In Situ Measurement of Temperature Distributions in a Li-ion Cell during Internal Short Circuit and Thermal Runaway

Here we report in situ measurement of temperature distributions in a 2.5-Ah pouch format Li-ion cell during internal short circuit (ISC) and thermal runaway. The ISC and thermal runaway were triggered by nail penetration. The local temperatures were measured by embedded K type micro thermocouples in the middle layer of the experimental Li-ion cell. Highly non-uniform temperature distributions were observed during ISC and thermal runaway as compared with those during constant current discharging and external short circuit. The in situ measurement also captured details of how thermal runaway started from the ISC location and spread to the entire cell in a few seconds. Moreover, the comparison between ISC without thermal runaway and ISC with thermal runaway suggests that internal short circuit resistance plays a critical role in the risk of thermal runaway.

Huang, Shan↗

Impact of Electrode Thickness and Temperature on the Rate Capability of Li 4 Ti 5 O 12 /LiMn 2 O 4 Cells

Growing demand for stationary energy storage systems requires the development of low cost, long cycle life, safe batteries. Lithium-ion batteries (LiBs) utilizing Li 4 Ti 5 O 12 /LiMn 2 O 4 (LMO) cathode are promising candidates providing critical-material-free chemistry, high power capability, and long lifespan. However, their low energy density is a major drawback. In this work, we evaluate the rate performance of LTO/LMO cells fabricated with electrode loadings from 1.7 to 4.2 mAh cm -2 toward the development of high energy density and low cost LTO/LMO cells. The operating temperature is varied from 30 °C to 55 °C to evaluate the impact of electrode thickness vs temperature limitations on the electrode utilization. In addition, Newman modeling is performed to provide detailed understandings of the cell performance. Combining experimental and simulated results, we show the rate capability of the thicker electrodes is limited by the electrolyte transport. When the cells are discharged by applying pulsed current, Li + ion depletion is mitigated and the discharge capacity increases. Thus, high energy density LTO/LMO cells for BTMS applications can operate more efficiently when intermittent rest is applied. Finally, overcoming electrolyte transport limitations will be the key to enabling the development of high energy density LTO/LMO cells using thick electrodes.

25 ENERGY STORAGE↗

Performance of a Novel In-Situ Converted Additive for High Voltage Li-ion Pouch Cells

In search for new classes of additives for high voltage NMC/graphite lithium-ion cells, the precursor additive bis(trimethylsilyl) malonate (bTMSM) is shown to be activated via a spontaneous reaction with LiPF 6 and LiBF 4 salts in carbonate-based electrolyte to form lithium tetrafluoro(malonato)phosphate (LiTFMP), and lithium difluoro(malonato)borate (LiDFMB), respectively. The reaction schemes and rates were studied via NMR spectroscopy and GCMS. The effects of LiTFMP and LiDFMB on high voltage electrochemical performance were then examined up to 4.5 V in Li[Ni 0.4 Mn 0.4 Co 0.16 ]O 2 (NMC442)/graphite and Li[Ni 0.6 Mn 0.4 Co 0.0 ]O 2 (NMC/640)/graphite pouch cells using aggressive voltage-hold cycling, long-term charge/discharge cycling, storage experiments, electrochemical impedance spectroscopy, and gas evolution measurements. While in situ converted additives suffer from gassing issues due to the presence of trimethylfluorosilane (TMSF) gas, a side product of the in situ reaction of bTMSM with LiPF 6 , the cycling and storage capability for the activated additives under study shows competitive performance and controlled impedance when compared to other well-known high voltage additives. Micro X-ray fluorescence spectroscopy (μXRF) confirmed that LiTFMP successfully minimizes the rate of transition metal deposition on the surface of graphite apparently by forming a protective agent at the cathode surface, hence allowing for improved cycling performance at high voltages.

25 ENERGY STORAGE↗

Isothermal Microcalorimetry Analysis of Li/ β -MnO 2 Discharge

Despite widespread use over several decades, the lithium/manganese dioxide (Li/MnO 2 ) discharge mechanism is not completely understood owing to the structural complexity of the material. However, an improved understanding could lead to broader adoption as a primary and even secondary cathode material. Here, we examine the discharge of single-phaseβ-MnO 2 using isothermal microcalorimetry for the first time. Equilibrium voltage and entropy changes are characterized over the entire discharge range and used to rationalize the results. These measurements are supplemented by electrochemical impedance and X-ray diffraction data that give the clearest picture of theβ-MnO 2 lithiation process to date. We find that the first half of discharge is dominated by a two-phase reaction to form Li 0.5 MnO 2 followed by single-phase insertion to a composition of Li 1.0 MnO 2 , which confirms prior first-principles calculations. The tetragonalβ-MnO 2 lattice undergoes asymmetric expansion from Jahn-Teller distorted Mn 3+ to form an orthorhombic LiMnO 2 phase which retains the 1 × 1 tunnel structure. Microcalorimetry results suggest the presence of parasitic reactions occurring during the second half of discharge, which could arise from decomposition of electrolyte or release and reaction of residual water retained in the structure.

Electrochemistry↗

Detection of a Cobalt-Containing Interphase at the Li 6 PS 5 Cl-NMC111 Interface by In Situ μ XANES and EIS

Sulfide electrolyte all-solid-state lithium batteries (ASLBs) with uncoated Li-Ni x Mn y Co 1–x–y O 2 (NMC) cathodes suffer from a large capacity loss during initial cycling and an increase in cell impedance. Decomposition reactions are known to occur at the Li 6 PS 5 Cl-NMC111 interface due to incompatibility between the two materials. If a stabilizing coating is applied to the NMC, it delivers full capacity during initial charge. However, the loss in capacity during discharge still occurs. The interface was studied by μ XANES and through EIS analysis. A chemically-formed interphase was detected by μ XANES, evident from reduction of Co at an uncoated NMC particle surface. This interphase was produced by decomposition at rest. To study the effect of the interphase on electrochemically active surface area, piecewise in situ EIS was performed and the data was modeled using a transmission line model (TLM). The charge transfer resistance R CT was used to estimate the volume specific active surface area (a act ). The median value for a act was 296 cm –1 , a factor of 7.5 lower than the theoretical value of 2216 cm –1 . This provided evidence of a lower electrochemically active surface area in the ASLB.

36 MATERIALS SCIENCE↗

Impact of Electrolyte Solvent on Li 4 Ti 5 O 12 /LiNi 0.90 Mn 0.05 Co 0.05 O 2 Battery Performance for Behind-the-Meter Storage Applications

Behind-the-Meter Storage (BTMS) systems require dedicated development of battery materials that target long cycle life and low cost at the system level. Pairing Li 4 Ti 5 O 12 (LTO) and LiNi 0.9 Mn 0.05 Co 0.05 O 2 (NMC90-5-5) shows promise to achieve targets for BTMS applications; however, minimal literature is available that discusses electrolyte solvent selection for this pairing. This study explores the role of electrolyte solvent on cycle life in LTO/NMC90-5-5 batteries. Four model electrolytes are evaluated; the baseline, Gen2, is compared with 1M LiPF 6 added to each of three separate solvents: ethylene carbonate (EC), ethyl methyl carbonate (EMC), and fluoroethylene carbonate (FEC). An additional consideration is that NMC90-5-5 undergoes an H2→H3 phase transition that allows for a significant increase to capacity; however, it’s unclear how this phase transition impacts electrolyte stability and cycle life. Therefore, the phase transition is avoided or accessed by cycling to 2.6V or 2.7V, respectively. The cells with Gen2, cycled to 2.6V, show the highest capacity retention due to EC passivating the LTO, EMC improving stability at the NMC90-5-5, and avoiding increased degradation from the 2.7V protocol. Despite having high initial reactivity that causes Li-depletion, FEC was the only solvent to avoid increased degradation when moving to the higher termination voltage.

25 ENERGY STORAGE↗

Capacity Gain in Li-Ion Cells with Silicon-Containing Electrodes

Silicon-containing lithium-ion batteries can exhibit capacity gain early in life, which makes forecasting future cell behavior difficult. We have observed these anomalous trends even in conditions where known mechanisms, such as overhang equalization and excessive electrolyte oxidation, are unlikely to be significant. Here, we combine simulations and experiments to analyze four cases that can produce increased capacity in Si cells. Three of these pathways relate to “break-in” processes, where improved mass and charge transport can lead to increased access to active electrode domains and decreased cell impedance. The fourth case occurs at high levels of prelithiation, when the positive electrode (PE) is completely replenished with Li + at the end of cell discharge. We show that the commonality among these mechanisms is that the underlying transformations change the potentials experienced by electrodes at the end of half-cycles, increasing the Li + inventory available to the cell. A quantitative framework to describe these effects is presented, enabling these ideas to be extended to other battery systems.

25 ENERGY STORAGE↗

Recovery of High Value Anode Materials for a Closed Loop Li-ion Battery Recycling Process (Final Report)

Battery Resourcers’ goal with this Small Business Innovative Research Phase 1 project was to produce high quality and high purity graphite generated from its Li-ion battery recycling technology. Battery Resourcers’ technology recovers cathode material from a broad spectrum of Li-ion battery regardless of size, shape or chemistry. In Battery Resourcers existing model, the graphite is recovered to be used as a reductant and therefore the battery materials cost or recycling cost is not lowered by the recovery of the graphite. Currently, Battery Resourcers is piloting its lithium ion battery recycling process and the recovered LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) or LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC111) cathode materials have shown that they can outperform existing commercial NMC111 cathode materials while being produced at a projected lower cost. Battery Resourcers and its subcontractor WPI have demonstrated the same success with the recovered graphite for anode materials. The success of this award will enable Battery Resourcers offer lowest cost anode materials while reducing the carbon footprint of the battery industry. This will potentially lower the cost of EV by lowering the upfront cost of the battery and the end of life disposal costs. The technical objectives of this Phase 1 research project are to purify the recovered graphite from Battery Resourcers leaching process and demonstrate it is viable to be used in new electric vehicle lithium ion batteries. This project demonstrated that Battery Resourcers can recover graphite with less than 2% impurities. To separate the graphite from other materials Battery Resourcers will employed new filtering techniques and chemical processing methods.

25 ENERGY STORAGE↗

Li Isotope Signatures using Optical Spectroscopies

The primary goal of this work is to investigate the detection capabilities of laser ablation molecular isotopic spectrometry (LAMIS) and Raman spectroscopy for lithium isotopic determination as related to Li enrichment activities. LAMIS is an emerging spectroscopic technique that takes advantage of the fact that molecules exhibit much larger isotopic wavelength shifts in molecular emission spectra than their atomic counterparts. Raman spectroscopy has been shown to exhibit isotopic shifts if a given molecular vibration involves the isotope of interest. Both techniques are comprised of the same basic hardware: a spectrometer, a laser system (pulsed for LAMIS, pulsed or CW for Raman), and an intensified charge-coupled device (ICCD). Shifts in Raman spectra due to lithium isotopes in Li 2 C0 3 and LiOH*H 2 0 were observed. LAMIS measurements of the same compounds have not been successful yet, as no lithium containing molecular emissions have been identified to this point. However, an isotopic shift of the self-reversal of an atomic lithium emission was observed, which is another optical technique used to measure isotopes.

07 ISOTOPE AND RADIATION SOURCES↗

Enabling Extreme Fast Charging through Control of Li Deposition Overpotential on Graphite Electrodes

Currently produced electric vehicles (EVs) rely on the use of lithium ion battery technology due to its high energy and power density. However, a major barrier facing the adoption of electric vehicles is that currently utilized Li-ion batteries take significantly longer to recharge (~ 30 minutes) compared to the time necessary to refuel vehicles powered by internal combustion engines (< 10 minutes). Thus, the need to develop Li-ion batteries which can be charged in approximately 10 minutes (6 C rate) without sacrificing range, cost, or cycle life is critical for the widespread implementation of EVs.

25 ENERGY STORAGE↗

Nanostructured Powders Made from Flame Spray Pyrolysis for Li-Ion Cathode

Flame processes are the most economic ones to produce fine powders and have been used to produce pigment titanium oxide and fused silica in large volumes. In this work a flame spray pyrolysis (FSP) process is used to make positive electrode materials for Li-ion battery, which is made of complex metal oxide powders, such as Li(Ni1/3Mn1/3Co1/3)O2. In particular, the work was focused on making the NMC materials with stoichiometric compositions and desired morphologies. During the pyrolysis process different morphologies can be formed, involving often powders with primary nanoparticles. Such nanostructures were found to have affected the battery performance. Detailed results of the synthesis, characterization, and battery testing of the NMC powder materials will be presented.

25 ENERGY STORAGE↗

Hot Pressing of Reinforced Li-NMC All-Solid State Batteries with Sulfide Glass Electrolyte

The performance of solid-state batteries (SSBs) with sulfide solid-state electrolytes (SSEs) is limited because they are 10 - 30% porous. Porosity limits energy density of the composite cathode and provides a conduit for Li-metal deposits through the separator if operating specifications (e.g. current density, operating temperature, and pressure) are not strictly controlled. This project focused on demonstrating that hot press cell processing and appropriately formulated sulfide glass SSEs can help eliminate porosity to enable SSBs with energy density of ≥ 350 Wh/kg. The objective of the project was to research, develop, and test SSBs capable of achieving program performance metrics by implementing appropriately formulated sulfide glass SSEs and hot press cell processing in a dry room environment. In the composite cathode, hot pressing helps eliminate porosity to increase energy density by enabling thick composite cathodes with high active material loading. In the separator, hot pressing helps eliminate porosity that may otherwise provide a conduit for Li metal deposits to short the cell.

25 ENERGY STORAGE↗

Advanced Anode Manufacturing through Ultra-Thin Li Deposition

During the program's tenure, Applied Materials delivered high-quality (>99.9%) ultra-pure thin lithium metal in sheets and in roll to roll (R2R) formats to program partners for testing, cell builds and evaluation. The thickness range of the deposited Lithium can be controlled between 1-20 μm (<3% nonuniformity). A second R2R tool was commissioned for Li processing and inline CO 2 passivation module was validated. Additionally, S2S deposition tools were used to explore five different surface protection materials for Li-metal. One surface passivation chemistry was down selected for testing and showed improved performance. Key results are summarized in this final report.

25 ENERGY STORAGE↗

Scattering Observables from Few-Body Densities and Compton Scattering on $^6$Li

The dynamics of scattering on light nuclei is numerically expensive using standard methods. Fortunately, recent developments allow one to factor the relevant quantities for a given probe into a convolution of an n -body Transition Density Amplitude (TDA) and the interaction kernel for a given probe. These TDAs depend only on the target, and not the probe; they are calculated once for each set of kinematics and can be used for different interactions.\ % in the same kinematics. The kernels depend only on the probe, and not on the target; they can be reused for different targets and different kinematics. The calculation of TDAs becomes numerically difficult for more than four nucleons, but we discuss a new solution through the use of a Similarity Renormalization Group transformation, and a subsequent back-transformation. This technique allows for extending the TDA method to heavier nuclei such as 6 Li. We present preliminary results for Compton scattering on 6 Li and compare with available data, anticipating an upcoming, more thorough study. We also discuss ongoing extensions to pion-photoproduction and other reactions on light nuclei.

Long, Alexander [George Washington University, Was↗

SPRUCE Surface N2O fluxes measured with LI-7820, 2024

This dataset contains N2O (nitrous oxide) efflux rates measurements from the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experimental site within the Marcell Experimental Forest in northern Minnesota, USA. Measurements were made manually with a LiCor N2O/H2O analyzer (LI-7820) and paired SmartChamber (LI-8200-01S) in June, August, and October (2024-06-24 to 2024-10-22). During each measurement, the SmartChamber was placed on 8” PVC collars that were installed in May 2024. N2O flux was derived from 10-minute flux measurements processed using SoilFluxPro software (v5.3.1) and fit to a linear model. Model slope and R2 are reported along with soil water, soil temperature, and air temperature observations made with SmartChamber sensors. N2O is a gaseous N species formed during the microbial processes of denitrification and ammonia oxidation, and is a powerful greenhouse gas. This dataset contains one data file in comma-separate values (*.csv) format. Additional metadata are provided: one data dictionary and a file-level metadata file in comma-separate values (.csv) format and a user guide in PDF (*.pdf) format.

54 ENVIRONMENTAL SCIENCES↗