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359 records · Page 10

Tailored Solvent Treatment for Optimized Production of Upcycled Anodes from End-Of-Life Li-Ion Batteries

Recycling processes for lithium-ion batteries typically overlook graphite because of its lower market value relative to that of transition-metal-containing cathode materials. However, graphite recovered from cycled lithium-ion batteries holds additional engineered value associated with the solid-electrolyte interphase (SEI). The SEI contributes critical electronic passivation of the graphite surface but becomes highly resistive with extended cycling, yielding poor cell performance. In this work, we apply tailored solvent treatment to end-of-life (EOL) graphite anodes to selectively remove adverse SEI components while retaining beneficially passivating species. We evaluate a series of polar protic solvents to achieve targeted removal of SEI components and control selectivity through rational variation in solvent properties. The physiochemical properties of treatment solvents correlate with both the retained SEI composition and the corresponding electrochemical performance of solvent-treated “upcycled” graphite anodes. Within the initial set of solvents evaluated, top-performing candidates show capacity and Coulombic efficiency nearly equivalent to those of an analogous pristine anode, as well as promising electrochemical performance enhancement with regard to irreversible capacity-loss metrics. This study establishes critical design principles for an optimized anode upcycling method that enhances the value of recycled graphite by retaining and upgrading the SEI.

25 ENERGY STORAGE

Reduced fast-ion transport calculations of m = n = 1 fishbone-like instabilities in MAST-U

Fast-ion transport associated with an m = n = 1 fishbone-like burst in MAST-U discharge 47128 is investigated using a reduced guiding-center-based transport model (ORBIT-Kick) constrained by multi-diagnostic measurements. The two-dimensional beam-emission spectroscopy system provides measurements of the core poloidal mode structure and fluctuation amplitude, while EFIT++ reconstructions constrained by the motional Stark effect diagnostic indicate a flat q-profile with q 0 > 1⁠, indicating the absence of a resonant q = 1 surface and supporting a pressure-driven infernal-mode interpretation. Analytic m = n = 1 displacement profiles consistent with the measured core mode structure and equilibrium constraints are used as the mode structure inputs to ORBIT-Kick. The calculations show that the dominant resonances occur between the mode and co-passing fast ions, producing redistribution localized near the magnetic axis. Synthetic neutron camera signals from TRANSP-Kick recover up to 90% of the experimentally observed neutron deficit at the time of peak mode amplitude, indicating that the measured m = n = 1 mode is a dominant contributor to core fast-ion transport. However, the synthetic neutron signals recover rapidly, whereas the measured neutron emission continues to decrease after the peak amplitude. In conclusion, the remaining discrepancy may arise from contributions not included in the present single-harmonic model, including higher-m and higher-n harmonics, multi-harmonic interactions, and additional transport mechanisms, motivating future diagnostic development and modeling efforts to resolve and incorporate these additional contributions.

Wong, Henry H. [University of California, Los Ange

Concerted Electron-Ion Transport by Polyacrylonitrile Elucidated with Reactive Deep Learning Potentials

Charge transport in polymers, such as polyacrylonitrile (PAN), is crucial for electronics and energy storage. For instance, PAN can transport cations e.g., Li + , by facilitating dynamic cation-nitrile coordination in batteries. However, little is known regarding the underlying role of complex reactive polymer configurations. Herein, we develop a deep-learning potential, trained on ab initio energies and forces of nonequilibrium reactive PAN configurations, to unravel the kinetics of PAN cyclization initiated by a nucleophile (OH – dissociated from LiOH) attacking the terminal nitrile carbon. We find, based on the reaction free-energetics, rates, and charge analysis, that the nucleophile attack producing the first ring is the rate-limiting step, which subsequently triggers Li + -coupled electron transfer along the PAN backbone, causing ∼10 4 times faster sequential ring-formation of the remaining nitriles. PAN’s extended configurations, where dipolar and H-bonding interactions are minimal, enable such rapid kinetics. By validating our computational findings with IR and NMR experiments, we establish a pathway for designing reactive polymers with enhanced charge transport for energy applications.

Chahal-Crockett, Rajni [Oak Ridge National Laborat

Probing the role of local tunnel variations in early-stage lithiation of α-MnO₂ nanowires via in situ TEM

Understanding lithium-ion transport in tunnel-structured manganese oxides is essential for designing high-performance lithium-ion battery electrode materials. Here, we elucidate the early-stage lithiation mechanism of potassium-stabilized α-MnO 2 nanowires using in situ transmission electron microscopy (TEM) coupled with electron energy-loss spectroscopy (EELS), high-resolution TEM (HRTEM), and geometric phase analysis (GPA). Real-time TEM imaging reveals clear volume expansion at the reaction front, while EELS analysis uncovers lithium-ion diffusion far beyond this region, where no visible expansion is observed, indicating fast, defect-assisted transport. GPA and HRTEM analyses show that localized tensile and compressive strain fields, originating from pre-existing local tunnel structural variations, persist after lithiation. The tensile-strained regions enable lithium-ion insertion with minimal lattice distortion, offering additional free volume that facilitates rapid lithium-ion accommodation ahead of the structural transformation. Our results demonstrate a local tunnel variation-mediated fast diffusion pathway that precedes bulk reaction, underscoring the critical role of local strain in enabling early-stage lithium transport. Given the structural versatility of MnO 2 and its ability to accommodate diverse atomic arrangements beyond the well-known tunnel phases (β-, γ-, δ-, λ-, R-phases), our findings highlight the importance of understanding and engineering local structural environments. This work provides fundamental insights into the interplay between defects, strain, and ion dynamics, and presents defect engineering as a promising approach to enhance both rate performance and structural stability in manganese-based cathodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Are There Opportunities To Re-Think How We Manufacture Synthetic Graphite?

This manuscript contributes a Viewpoint article to ACS Sustainable Resource Management and discusses the graphite supply chain, growing mismatch between graphite demand and global manufacturing capacity, current graphite manufacturing technologies, and different feedstocks.

alternative carbon feedstocks

Battery Failure Databank

The Battery Failure Databank contains thermal runaway results gathered from nearly 300 small format fractional thermal runaway calorimetry (S-FTRC) experiments. A majority of these experiments were conducted at synchrotron facilities where high-speed x-ray videography was conducted of the cell while tested inside of the S-FTRC. The databank is a two-component system which consists of a Microsoft ExcelTM spreadsheet which provides S-FTRC results in tabular format and a radiographic video library containing the high-speed x-ray videos. Overall, the databank provides thermal results from S-FTRC experiments conducted on a mixture of commercially available lithium-ion (Li-ion) cells and specialized Li-ion test cells with varying cell format (18650, 21700, and D-cell) and trigger mechanism (heaters, heaters plus internal short circuiting device, and nail penetration). The radiography video component provides insight into the initiation and propagation of TR in the cells, in addition to consequences of TR measured by the FTRC. Fractions of mass ejected for the cell types are separated into regimes based on the different failure modes of the cells, such as purely venting, partial ejection, and total ejection. With knowledge of the rate and characterization of the internal degradation of the cells during TR, and the amounts of mass ejected and unrecovered, the extent of TR, and therefore the mitigation of TR, is revealed relative to cell types and failure modes.

Lithium-ion battery

Transition from Vehicular to Structural Ionic Transport in Electrified Alkali Aqueous Solutions

A molecular understanding of the solvation and dynamics of ions under static electric fields is crucial for modelling a wide range of natural and technological processes. Yet, traditional simulation methods suffer from a trade-off that has to be made between accuracy and statistical convergence. To bridge this gap, herein we extend our recently introduced Perturbed Neural Network Potential Molecular Dynamics (PNNP MD) approach to investigate the solvation structures and ionic transport mechanisms of electrified alkali cationic solutions. We obtain ionic conductivities for Li+, Na+ and Cs+ from the field dependence of the ionic current density in good agreement with experiment. Surprisingly, the migration mechanism is found to be strikingly different for the three ions despite their similar ionic conductivities. While Li+ conducts predominantly through vehicular migration of a stable 4-fold coordinated ion at all field strengths, Cs+ conducts strictly through a structural diffusion mechanism, where 9-12 transient first shell water coordination bonds are broken and renewed. Notably, aqueous Na+ emerges as a “Goldilocks” ion: its ion-water interactions are strong enough to maintain distinct 5-6 fold coordination shells at zero field (unlike Cs+) yet labile enough to be strongly perturbed by electric fields (unlike Li+). As a consequence, we observe an electric field-induced transition from vehicular to structural ionic transport for Na+ that is accompanied by a marked increase in the ionic current density. Our results imply that the conductance mechanism of ions with moderate ion-solvent interactions can be effectively tuned by external electric fields.

Joll, Kit

A Battery Certification Testbed for Small Satellite Missions

A battery pack consisting of standard cylindrical 18650 lithium-ion cells has been chosen for small satellite missions based on previous flight heritage and compliance with NASA battery safety requirements. However, for batteries that transit through the International Space Station (ISS), additional certification tests are required for individual cells as well as the battery packs. In this manuscript, we discuss the development of generalized testbeds for testing and certifying different types of batteries critical to small satellite missions. Test procedures developed and executed for this certification effort include: a detailed physical inspection before and after experiments; electrical cycling characterization at the cell and pack levels; battery-pack overcharge, over-discharge, external short testing; battery-pack vacuum leak and vibration testing. The overall goals of these certification procedures are to conform to requirements set forth by the agency and identify unique safety hazards. The testbeds, procedures, and experimental results are discussed for batteries chosen for small satellite missions to be launched from the ISS.

Certification

Enhancing Battery Safety with Fractional Thermal Runaway Calorimetry

Effective thermal management systems, designed to handle the impacts of thermal runaway (TR) and to prevent cell-to-cell propagation, are key to safe operation of lithium-ion (Li-ion) battery assemblies. Critical factors for optimising these systems include the total energy released during a single cell TR event and the fraction of the total energy that is released through the cell casing versus through the ejecta material. A unique fractional thermal runaway calorimeter (FTRC), designed to characterise said critical factors, was utilised to examine the TR behaviour of Li-ion cells). Delegates will be provided with an in-depth discussion on what fractional thermal runaway calorimetry is and how it benefits the development of safe and optimised battery assemblies that protect against thermal runaway. Delegates will see calorimetry data associated with a variety of Li-ion cells. Data presented is relevant to any industry that utilises high-energy Li-ion cells in closed environments and has a need to focus on safety.

Walker, William

Thermal Data-driven Model Reduction for Enhanced Battery Health Monitoring

Electric aviation faces a major challenge of avoiding potentially catastrophic consequences of the battery’s thermal runaway while keeping the weight of the battery low. Detection of early warning signals of battery failures requires accurate monitoring of the battery’s health throughout its lifespan. However, identifying the parameters of the battery from field data is notoriously difficult. We investigate this problem within the framework of modeling the temperature dynamics of a Li-ion cell during tests simulating loading in electric aircraft flights. It is found that the parameters of a higher-fidelity physics-based thermal model cannot be identified from the simulated flight data. To resolve this issue, we reduce the higher-fidelity thermal model to a model with fewer parameters. The resulting reduced-order model can predict temperature dynamics accurately and is identifiable throughout the cell’s lifespan which allows using the model’s parameters to monitor the state-of-health of the aging cell and detect anomalies in thermal behavior.

Li ion batteries

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.

Yap, Kyra M. K. [University of California, Berkele

Direct Observation of Elusive (DTBM‐SEGPHOS)CuH Monomer Enables Mechanistic Insights Into Hydrocupration, Aggregation, and Dynamics of Alkene Functionalization Catalysis

The bulky diphosphine DTBM-SEGPHOS is widely employed in CuH-catalyzed transformations as it provides remarkably active catalyst systems. The transient (DTBM-SEGPHOS)CuH monomer (LCuH) is the often-invoked active species. However, its instability has prevented spectroscopic characterization and mechanistic elucidation, hindering mechanistic understanding. We report low-temperature NMR spectroscopic characterization of LCuH, enabling quantitative kinetic analysis of the stoichiometric hydrocupration and catalytic hydroboration of cyclopentene, as well as the structural identification of two CuH clusters. LCuH inserts cyclopentene at −43°C, reaffirming its high reactivity toward olefins. LCuH deactivates to form L 2 Cu 3 H 3 and L 2 Cu 4 H 4 clusters, in which LCuH dimerization initiates aggregation. Kinetic analysis of reactions of unactivated alkenes indicates that competing on-cycle alkene hydrocupration and LCuH dimerization impact performance, as catalyst deactivation and turnover occur on comparable timescales. Structure–activity analysis using atomistic simulations shows that the steric profile of DTBM-SEGPHOS increases the CuH dimerization barrier by ∼7.7 kcal mol−1 compared to that of SEGPHOS, rationalizing the unique ability of DTBM-SEGPHOS to stabilize a reactive monomer for hydrocupration of broader alkene substrates. These findings illustrate the fundamental design principle that steric control of aggregation governs CuH catalyst performance, explaining both the exceptional activity of (DTBM-SEGPHOS)CuH and the limitations imposed by competing deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Charm and bottom hadrons in hot hadronic matter

Heavy quarks, and the hadrons containing them, are excellent probes of the QCD medium formed in high-energy heavy-ion collisions, as they provide essential information on the transport properties of the medium and how quarks color-neutralize into hadrons. Large theoretical and phenomenological efforts have been dedicated thus far to assess the diffusion of charm and bottom quarks in the quark–gluon plasma and their subsequent hadronization into heavy-flavor (HF) hadrons. However, the fireball formed in heavy-ion collisions also features an extended hadronic phase, and therefore any quantitative analysis of experimental observables needs to account for the rescattering of charm and bottom hadrons. This is further reinforced by the presence of a QCD cross-over transition and the notion that the interaction strength is maximal in the vicinity of the pseudo-critical temperature. We review existing approaches for evaluating the interactions of open HF hadrons in a hadronic heat bath and the pertinent results for scattering amplitudes, spectral functions and transport coefficients. While most of the work to date has focused on D -mesons, we also discuss excited states as well as HF baryons and the bottom sector. Both the HF hadro-chemistry and bottom observables will play a key role in future experimental measurements. We also conduct a survey of transport calculations in heavy-ion collisions that have included effects of hadronic HF diffusion and assess its impact on various observables.

effective field theories

Analysis of Developing Laminar Flows in Circular Pipes Using a Higher-Order Finite-Difference Technique

A higher-order finite-difference technique is developed to calculate the developing-flow field of steady incompressible laminar flows in the entrance regions of circular pipes. Navier-Stokes equations governing the motion of such a flow field are solved by using this new finite-difference scheme. This new technique can increase the accuracy of the finite-difference approximation, while also providing the option of using unevenly spaced clustered nodes for computation such that relatively fine grids can be adopted for regions with large velocity gradients. The velocity profile at the entrance of the pipe is assumed to be uniform for the computation. The velocity distribution and the surface pressure drop of the developing flow then are calculated and compared to existing experimental measurements reported in the literature. Computational results obtained are found to be in good agreement with existing experimental correlations and therefore, the reliability of the new technique has been successfully tested.

Herbert J Gladden

Asymmetric pathways for lithium extraction and recovery based on the two-phase equilibrium of layered oxides

Electrochemical intercalation offers a promising platform for Li + extraction. However, only limited types of electrode materials have been investigated. The challenge to broaden and tailor materials for electrochemical intercalation-based Li + extraction lies in the lack of understanding of material’s response upon co-intercalation of multiple ions, therefore, paired process design to enable reversible Li + extraction and recovery. Here, we showcase the design of asymmetric ion pathways for Li + extraction and recovery for host material with complex Li + and Na + interaction using layered cobalt oxide as a model material. The two-phase equilibrium of Na 0.48 CoO 2 and Li 0.94 CoO 2 governs Li + selectivity when a high depth of intercalation is achieved (low vacancy level). We show that the relative rate between ion exchange and intercalation is critical to determine the ion pathways. The relationship can be quantitatively compared using the average pseudo ion exchange rate (C pseudoIX ) and the intercalation rate (C inter ). The ion pathways at the three regimes with C pseudoIX > C inter , C pseudoIX ~ C inter , and C pseudoIX < C inter are constructed. By selecting the optimized ion pathway and particle size, we demonstrate 9.7×10 4 Li + selectivity with 99% purity Li + recovery from an initial 1:1000 Li: Na molar ratio solution using 115 mAh/g specific capacity.

electrochemistry

Performance of Li-Ion Cells Under Battery Voltage Charge Control

A study consisting of electrochemical characterization and Low-Earth-Orbit (LEO) cycling of Li-Ion cells from three vendors was initiated in 1999 to determine the cycling performance and to infuse the new technology in the future NASA missions. The 8-cell batteries included in this evaluation are prismatic cells manufactured by Mine Safety Appliances Company (MSA), cylindrical cells manufactured by SAFT and prismatic cells manufactured by Yardney Technical Products, Inc. (YTP). The three batteries were cycle tested in the LEO regime at 40% depth of discharge, and under a charge control technique that consists of battery voltage clamp with a current taper. The initial testing was conducted at 20 C; however, the batteries were cycled also intermittently at low temperatures. YTP 20 Ah cells consisted of mixed-oxide (Co and Ni) positive, graphitic carbon negative, LIPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 32 V. The low temperature cycling tests started after 4575 cycles at 20 C. The cells were not capable of cycling. at low temperature since the charge acceptance at battery level was poor. There was a cell in the battery that showed too high an end-of-charge (EOC) voltage thereby limiting the ability to charge the rest of the cells in the battery. The battery has completed 6714 cycles. SAFT 12 Ah cells consisted of mixed-oxide (Co and NO positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was for 30.8 V. The low temperature cycling tests started after 4594 cycles at 20 C. A cell that showed low end of discharge (EOD) and EOC voltages and three other cells that showed higher EOC voltages limited the charge acceptance at the selected voltage limit during charge. The cells were capable of cycling at 10 C and 0 C but the charge voltage limit had to be increased to 34.3 V (4.3 V per cell). The low temperature cycling may have induced poor chargeability since the voltage had to be increased to achieve the required charge input. The battery has completed 6226 cycles. MSA 10 Ah cells consisted of Co oxide positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 30.8 V. The low temperature cycling tests were started after 2182 cycles at 20 C. The cells were capable of cycling at 10 C and 0 C. Like SAFT, the voltage limit on charge had to be increased to 36 V (4.5 V per cell). There was a cell (cell S/N 13) in the battery that showed poor performance features such as low EOD voltage and high EOC voltage. The battery has completed 3441 cycles. A reconditioning procedure that consisted of C15 charge to a taper current of C/100 and C/20 discharge improved the voltage behavior of SAFT and MSA cells with no significant effect on YTP cells. We have demonstrated that the charge operation with VT clamp at battery rather than at cell level is feasible for onboard Li-Ion battery operation.

Rao, Gopalakrishna M.

Selective Binding and Light-Driven Release of Fluorous PF 6 – and Radioactive 99 TcO 4 – Anions for All-to-Nothing Liquid–Liquid Extraction

The removal of anions from aqueous media using molecular receptors in liquid–liquid extraction is a long-standing strategy to clean up contaminated water sources. Therein, high selectivity is needed to remove specific ions from mixtures of other ions, and high affinity provides extractions at low concentrations. However, the high affinity creates a conundrum by impeding the release of the ions in any stripping steps needed for further processing. To circumvent this problem, light-responsive receptors have been proposed as candidates for turning off the binding, but they are currently untested in liquid–liquid extraction. We tested the feasibility of light-driven release using a cyanostar macrocycle. We demonstrate the selective extraction of PF$^{–}_{6}$ anions over large excesses of competing anions (Cl – , NO$^{–}_{3}$, SO$^{2–}_{4}$) followed by photodriven release for quantitative isolation of the target. Release relies on photoisomerization of the macrocycle’s five stilbenes generating distorted isomers to turn off binding. With modest reversibility, only a single-shot release was demonstrated, akin to photodriven uncaging. These methods were extended to the capture and photodriven release of ReO$^{–}_{4}$ and radioactive 99 TcO$^{–}_{4}$ anions at ∼90% efficiency. Extraction was demonstrated down to the highly dilute 4 ppb levels of the 99 TcO$^{–}_{4}$ anion. Furthermore, this proof-of-concept demonstration verifies the use of a large change in affinity for the all-to-nothing capture and release of target anions between liquid phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH