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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6

Lithium-Ion Battery Life Model with Electrode Cracking and Early-Life Break-in Processes

This paper develops a physically justified reduced-order capacity fade model from accelerated calendar- and cycle-aging data for 32 lithium-ion (Li-ion) graphite/nickel-manganese-cobalt (NMC) cells. The large data set reveals temperature-, charge C-rate-, depth-of-discharge-, and state of charge (SOC)-dependent degradation patterns that would be unobserved in a smaller test matrix. Model structure is informed by incremental capacity analysis that shows loss of lithium inventory and cathode-material loss as the dominant capacity fade mechanisms. The model includes terms attributable to solid-electrolyte interface (SEI) growth, electrode cracking, cycling-driven acceleration of SEI growth, and "break-in" mechanisms that slightly decrease or increase available Li inventory early in life. The study explores what mathematical couplings of these mechanisms best describe calendar aging, cycle aging, and mixed calendar/cycle aging. Various approaches are discussed for extracting relevant stress factors from complex cycling profiles to predict lifetime during real-world battery loads using models trained on constant-current laboratory test results. The complexity of the present human-driven model identification process motivates future work in machine learning to more widely search and statistically discern the optimal model that correctly extrapolates capacity fade based on physical knowledge.

25 ENERGY STORAGE↗

Ion Conducting Polymer Interfaces for Lithium Metal Anodes: Impact on the Electrodeposition Kinetics

Electrochemical cells that utilize metals (e.g., lithium, sodium, zinc) as anodes are under intense investigation as they are projected to replace the current lithium-ion batteries to serve as a more energy-dense option for commercial applications. In addition, metal electrodes provide opportunities for fundamental research of different phenomena, such as ion transport and electrochemical kinetics, in the complex environment of reactive metal-electrodeposition. In this work, computationally and experimentally the competing effects related to transport and kinetics during the metal electrodeposition process are examined. Using Brownian dynamics simulations, it is shown that slower deposition kinetics results in a more compact and uniform Li morphology. This finding is experimentally implemented by designing ion-containing polymeric coatings on the electrodes that simultaneously provide pathways for lithium-ion transport, while impeding the charge transfer (Li + + e - → Li) at heterogeneous surfaces. It is further shown that these ionic polymer interfaces can significantly extend the cell-lifetime of a lithium metal battery in both ether-based and carbonate-based electrolytes. Through theoretical and experimental investigations, it is found that a low kinetic to transport rate ratio is a major factor in influencing the Li plating morphology. The plating morphology can be further fine-tuned by increasing ionic conductivity.

36 MATERIALS SCIENCE↗

Benefits of Fast Battery Formation in a Model System

Lithium-ion battery formation affects battery cost, energy density, and lifetime. An improved understanding of the first cycle of solid-electrolyte interphase (SEI) growth on carbonaceous negative electrodes could aid in the design of optimized formation protocols. In this work, we systematically study SEI growth during the formation of carbon black negative electrodes in a standard carbonate electrolyte. We show that the initial ethylene carbonate (EC) reduction reaction occurs at ~0.5-1.2 V during the first lithiation, except under fast lithiation rates (≥10C). The products of this EC reduction reaction do not passivate the electrode; only the SEI formed at lower potentials affects the second-cycle Coulombic efficiency. Thus, cycling quickly through the voltage regime of this reaction can decrease both formation time and first-cycle capacity loss, without an increase in subsequent-cycle capacity loss. We also show that the capacity consumed by this reaction is minimized at low temperatures and low salt concentrations. Finally, we discuss the mechanism behind our experimental results. This work reveals the fundamental processes underlying initial SEI growth on carbonaceous negative electrodes and provides insights for both optimizing the battery formation process and enabling novel electrolytes.

25 ENERGY STORAGE↗

Identification and characterization of the dominant thermal resistance in lithium-ion batteries using operando 3-omega sensors

Poor thermal transport within lithium-ion batteries fundamentally limits their performance, safety, and lifetime, in spite of external thermal management systems. All prior efforts to understand the origin of batteries' mysteriously high thermal resistance have been confined to ex situ measurements without understanding the impact of battery operation. Here, we develop a frequency-domain technique that employs sensors capable of measuring spatially resolved intrinsic thermal transport properties within a live battery while it is undergoing cycling. Our results reveal that the poor battery thermal transport is due to high thermal contact resistance between the separator and both electrode layers and worsens as a result of formation cycling, degrading total battery thermal transport by up to 70%. We develop a thermal model of these contact resistances to explain their origin. These contacts account for up to 65% of the total thermal resistance inside the battery, leading to far-reaching consequences for the thermal design of batteries. Finally, our technique unlocks new thermal measurement capabilities for future battery research.

25 ENERGY STORAGE↗

Textured Electrodes: Manipulating Built-In Crystallographic Heterogeneity of Metal Electrodes via Severe Plastic Deformation

Control of crystallography of metal electrodeposit films has recently emerged as a key to achieving long operating lifetimes in next-generation batteries. It is reported that the large crystallographic heterogeneity, e.g., broad orientational distribution, that appears characteristic of commercial metal foils, results in rough morphology upon plating/stripping. On this basis, an accumulative roll bonding (ARB) methodology—a severe plastic deformation process—is developed. Zn metal is used as a first example to interrogate the concept. It is demonstrated that the ARB process is highly effective in achieving uniform crystallographic control on macroscopic materials. After the ARB process, the Zn grains exhibit a strong (002) texture (i.e., [002] Zn //ND). The texture transitions from a classical bipolar pattern to a nonclassical unipolar pattern under large nominal strain eliminate the orientational heterogeneity of the foil. The strongly (002)-textured Zn remarkably improves the plating/stripping performance by nearly two orders of magnitude under practical conditions. The performance improvements are readily scaled to achieve pouch-type full batteries that deliver exceptional reversibility. The ARB process can, in principle, be applied to any metal chemistry to achieve similar crystallographic uniformity, provided the appropriate temperature and accumulated strains are employed. Here this concept is evaluated using commercial Li and Na foils, which, unlike Zn (HCP), are BCC crystals. The simple process for creating strong textures in both hexagonal and cubic metals and illustrating the critical role such built-in crystallography plays underscores opportunities for developing highly reversible thin metal anodes (e.g., hexagonal Zn, Mg, and cubic Li, Na, Ca, Al).

36 MATERIALS SCIENCE↗

Probing the Formation of Cathode-Electrolyte Interphase on Lithium Iron Phosphate Cathodes via Operando Mechanical Measurements

Interfacial instabilities in electrodes control the performance and lifetime of Li-ion batteries. While the formation of solid-electrolyte interface (SEI) on anodes has received much attention, there is still lack of understanding about the formation of cathode-electrolyte interface (CEI) on the cathodes. To fill this gap, we report on dynamic deformations on lithium iron phosphate, LiFePO 4 cathodes during charge / discharge by utilizing in-operando digital image correlation, impedance spectroscopy and Cryo X-ray photoelectron spectroscopy. LiFePO4 cathodes were cycled in either LiPF 6 , LiClO 4 or LiTFSI- containing organic liquid electrolytes. Beyond the first cycle, Li-ion intercalation results in a nearly linear correlation between electrochemical strains and the state of (dis)-charge, regardless of the electrolyte chemistry. However, during the first charge in LiPF 6 - containing electrolyte, there is a distinct irreversible positive strain evolution at the onset of anodic current rise as well as current decay at around 4.0V. Impedance studies show the increase in surface resistance in the same potential window, suggesting the formation of CEI layers on the cathode. The chemistry of the CEI layer was characterized by X-ray photoelectron spectroscopy. LiF is detected in CEI layer starting as early as 3.4 V and Li $x$ PO $y$ F $z$ appeared at voltages higher than 4.0 V during the first charge. In conclusion, our approach offers new insights into the formation mechanism of CEI layers on the cathode electrodes, which is crucial for the development of robust cathode and electrolyte chemistries for higher performance batteries.

25 ENERGY STORAGE↗

Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation

The solid–electrolyte interphase (SEI) layer formation is known to play an important role in determining the lifetime of lithium-ion batteries. A thin, stable SEI layer is linked to overall improved battery performance and longevity, however, the factors and mechanisms that lead to optimal SEI morphology and composition are not well understood. Inclusion of electrolyte additives (fluoroethylene carbonate, FEC; and vinylene carbonate, VC) is often necessary for improving SEI characteristics. To understand how these electrolyte additives impact SEI formation, we employed molecular dynamics (MD) and density functional theory (DFT) simulations to study the reaction networks and oligomerization pathways, respectively, for three systems containing ethylene carbonate (EC), a lithium ion, and FEC or VC. MD simulations suggest radical oligomerization pathways analogous to traditional oligomerization with nucleophilic alkoxide species via SN1 reaction mechanisms. Both S N 1 and S N 2 mechanisms were studied for all three systems using DFT. Oligomerization reactions were studied with both a standard alkoxide species and a ring-opened EC radical as the nucleophiles and EC, FEC, and VC as the electrophiles. For all cases, FEC and VC exhibited lower free energy barriers and more stable adducts when compared with EC. We conclude that one of the role of additives is to modify the oligomerization process of EC by introducing branching points (FEC) or termination points (VC).

25 ENERGY STORAGE↗

Generalizable, tunable control of divalent cation solvation structure via mixed anion contact ion pair formation

Multivalent batteries are a promising new technology for energy storage, but they face challenges to developing suitable electrolytes that can support reversible deposition/dissolution at the metal anode and enable compatibility with high voltage oxide cathode materials. Here, in this work, we investigate the solvation behavior of Zn 2+ , Mg 2+ , Ca 2+ and Cu 2+ in mixed anion electrolytes containing TFSI - and Cl - . Raman and nuclear magnetic resonance spectroscopies are utilized to probe the bulk solvation structure of these electrolytes and demonstrate that mixed anion contact ion pairs (CIPs) are formed in all four systems, indicating this behavior is likely general to divalent cations. Furthermore, the relative population of mixed anion CIPs can be tuned by controlling the relative ratio of TFSI : Cl, with significant CIP populations observed even at low relative fractions of Cl - . These findings imply that modifying the anion chemistry can easily adjust the solvation structure of bulk cations, which has important implications for the development of next-generation electrolytes. By understanding the factors that influence the formation of mixed anion CIPs, we can design systems that promote the formation of electrochemically-active solvation structures that can enable multivalent batteries with improved performance and lifetimes.

25 ENERGY STORAGE↗

Bioresorbable Primary Battery Anodes Built on Core–Double-Shell Zinc Microparticle Networks

Bioresorbable implantable electronics require power sources that are also bioresorbable with controllable electrical output and lifetime. In this paper, we report a bioresorbable zinc primary battery anode filament based on a zinc microparticle (MP) network coated with chitosan and Al 2 O 3 double shells. When discharged in 0.9% NaCl saline, a Zn MP filament with a 0.17 × 2 mm 2 cross-sectional area exhibited a stable voltage output of 0.55 V at a current of 0.01 mA. Covered by chitosan and Al 2 O 3 double shells, the zinc MP filament exhibited a directional dissolution behavior with a tunable lifetime approximately linear to its length. A stable 200 h discharging time was achieved with a 15 mm Zn MP filament. The maximum output power was found to be 12 μW at 0.03 mA for one filament. The linearity relationship between the current output and the filament cross-sectional area suggested a facile strategy to raise the power output at constant discharging voltage. The filaments could also be connected in series and in parallel to boost its overall voltage and current output, demonstrating their excellent integration capability. Furthermore, this work presents a promising pathway toward bioresorbable transient batteries with controllable lifetime and power output, demonstrating a great potential for powering transient implantable biomedical devices.

25 ENERGY STORAGE↗

Cost Projections for Utility-Scale Battery Storage: 2021 Update

In this work we describe the development of cost and performance projections for utility-scale lithium-ion battery systems, with a focus on 4-hour duration systems. The projections are developed from an analysis of recent publications that consider utility-scale storage costs. The suite of publications demonstrates varied cost reductions for battery storage over time. Figure ES-1 shows the low, mid, and high cost projections developed in this work (on a normalized basis) relative to the published values. Figure ES-2 shows the overall capital cost for a 4-hour battery system based on those projections, with storage costs of $\$$143/kWh, $\$$198/kWh, and $\$$248/kWh in 2030 and $\$$87/kWh, $\$$149/kWh, and $\$$248/kWh in 2050. Battery variable operations and maintenance costs, lifetimes, and efficiencies are also discussed, with recommended values selected based on the publications surveyed.

25 ENERGY STORAGE↗

Cost Projections for Utility-Scale Battery Storage: 2023 Update

In this work we describe the development of cost and performance projections for utility-scale lithium-ion battery systems, with a focus on 4-hour duration systems. The projections are developed from an analysis of recent publications that include utility-scale storage costs. The suite of publications demonstrates wide variation in projected cost reductions for battery storage over time. We use the recent publications to create low, mid, and high cost projections. Projected storage costs are $245/kWh, $326/kWh, and $403/kWh in 2030 and $159/kWh, $226/kWh, and $348/kWh in 2050. Battery variable operations and maintenance costs, lifetimes, and efficiencies are also discussed, with recommended values selected based on the publications surveyed.

25 ENERGY STORAGE↗

Combined Effects of Uniform Applied Pressure and Electrolyte Additives in Lithium-Metal Batteries

The development of lithium-metal batteries with good performance and long lifetimes requires fundamental insight into the mechanisms underlying performance improvements from individual design strategies and the interactions between multiple improvement approaches. Here, in this work, we investigated the individual and combined effects of applied pressure and a LiAsF 6 electrolyte additive on the performance of anode-free lithium-metal batteries; we employed various pressure application methods, which vary both in magnitude and uniformity. Both approaches individually improve cycling performance of anode-free lithium-metal batteries. Pressure increases the cycling efficiency at both the anode and cathode by promoting improved morphologies, while the LiAsF 6 additive additionally improves performance at the anode by enhancing the solid electrolyte interphase (SEI) properties. The combination of uniform applied pressure and a LiAsF 6 electrolyte additive produces lithium-metal batteries with cycling performance higher than can be achieved with either approach alone. This additional performance improvement is able to be realized due to the complementary rather than competitive nature of the mechanisms underlying applied pressure (lithium morphology) and electrolyte additives (SEI properties). Our results highlight the importance of moving beyond the investigation of isolated design strategies and demonstrate that superior cycling can be achieved by combining multiple approaches.

25 ENERGY STORAGE↗

Investigation of Active Life Balancing to Recondition Li-ion Battery Packs for 2nd Life

An investigation is presented into the application of active life balancing battery management systems to recondition inhomogeneous Li-ion battery packs and achieve homogeneity in capacity for second life. This paper proposes a life balancing objective map, which controls the state of charge references for each cell in a battery pack based on its capacity relative to other cells. The impacts of life balancing objective maps on the reconditioning time and overall pack capacity fade are considered. Moreover, the proposed approach accounts for various load and environmental effects, including depth-of-discharge, battery pack temperature, number of cycles per day, and cells’ resting time at various states of charge. The study results in a battery pack with convergent capacities achieved in minimal time, while curtailing overall capacity fade. Simulation results for a battery pack with sixteen series connected 75 Ah Kokam NMC cells with 3.6% initial capacity imbalance are presented, indicating a reconditioning time of 1.34 months with a final capacity imbalance of 0.1% and an overall capacity fade of 0.005%.

47 OTHER INSTRUMENTATION↗

Cost Projections for Utility-Scale Battery Storage: 2025 Update

In this work we describe the development of cost and performance projections for utility-scale lithium-ion battery systems, with a focus on 4-hour duration systems. The projections are developed from an analysis of recent publications that include utility-scale storage costs. The suite of publications demonstrates wide variation in projected cost reductions for battery storage over time. We present the suite of projected cost reductions collected from the literature as well as the low, mid, and high cost projections developed in this work. Storage cost projections are $\$$152/kWh, $\$$247/kWh, and $\$$349/kWh in 2035 and $\$$111/kWh, $\$$184/kWh, and $\$$333/kWh in 2050 for the low, mid, and high cases respectively. Battery variable operations and maintenance costs, lifetimes, and efficiencies are also discussed, with recommended values selected based on the publications surveyed.

25 ENERGY STORAGE↗

Predicting battery capacity from impedance at varying temperature and state of charge using machine learning

Prediction of battery health from electrochemical impedance spectroscopy (EIS) data can enable rapid measurement of battery state in real-world applications without using additional sensors or time-consuming performance measurements. However, deconvoluting the effect of capacity, state of charge, and temperature on EIS response is complicated analytically. Here, various machine-learning models, such as linear, Gaussian process, random forest, and artificial neural network regression, are utilized to predict capacity from EIS using hundreds of capacity, direct current (DC) resistance, and EIS measurements recorded under varying conditions of health, temperature, and state of charge (SOC). Several feature extraction and selection methods from traditional electrochemical analysis and statistical modeling are explored using machine-learning pipelines. EIS data from just two frequencies can accurately predict capacity, and interrogation shows that the optimal set of frequencies is not usually intuitive. Best results are achieved with an ensemble model, which predicts battery capacity with a mean absolute error of 1.9% on data from unobserved cells.

25 ENERGY STORAGE↗

Feasibility of Prelithiation in LiFePO 4

Lithium iron phosphate (LiFePO 4 ) is widely applied as the cathode material for the energy storage Li-ion batteries due to its low cost and high cycling stability. However, the low theoretical specific capacity of LiFePO 4 makes its initial capacity loss more concerning. Therefore, lithium compensation by way of prelithiation and applications of sacrificial Li-rich additives in LiFePO 4 is imminent in elevating the energy density and/or prolonging the lifetime of the LiFePO 4 -based Li-ion batteries (LIBs). Prelithiation in LiFePO 4 is herein carried out by electrochemical and chemical methods and its feasibility is proved on the basis of the electrochemical evaluations such as the initial charge capacity and the cycling stability. In addition, the site of the pre-intercalated Li-ions is found via comprehensive physical characterizations and the density functional theory (DFT) calculations. Furthermore, these findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high-energy-density batteries.

36 MATERIALS SCIENCE↗

Non-destructive electrochemical diagnosis of failure mechanisms in aqueous zinc batteries

The early detection of secondary reactions that affect the life and performance of zinc manganese oxide batteries requires a shift from conventional time-consuming and often destructive procedures to rapid lifetime-predictive techniques. In this work, an electrochemical approach is employed to elucidate independent signatures for four common types of failure mechanisms in zinc manganese dioxide (Zn||MnO2) batteries—namely, the loss of zinc inventory, the loss of active material at the cathode, electrolyte depletion, and increased cell impedance. Our findings, specific to coin cell configurations, reveal that each induced failure mechanism can be distinctively modeled and identified based on responses from the rest voltage and columbic-efficiency data for prompt detection. For instance, electrolyte depletion response manifests a distinctive abrupt (>80 %) decrease in columbic efficiency (CE) and charge-rest voltage (Vc) while the discharge-rest voltage remained constant at ~1.3 V. Furthermore, electrolyte rejuvenation of the cell increased the CE to >95 % and restored Vc from ~0.3 to >1.7 V. Recovery experiments and reference performance tests demonstrated consistency between electrochemical descriptors and their associated failure mechanisms. Further, the outcomes of this work provide valuable insights and data models for some of the dominant failure mechanisms present in zinc manganese battery chemistries, which are beneficial to accelerated early-lifetime diagnosis and advancement of Zn batteries development.

25 ENERGY STORAGE↗