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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Quantification of Dead Lithium on Graphite Anode under Fast Charging Conditions

A series of computational and experimental studies were conducted to understand the onset of lithium plating and subsequent quantification of dead lithium on graphite electrodes in the design of fast charging batteries. The experiments include titration and relaxation studies for detecting initiation of lithium metal plating for various SOC and C-rates, which are compared against the thermodynamically consistent phase field computational results. The collaborative study on "model graphite electrode" with 2.18 mAh cm-2 nominal capacity at 25 degrees C demonstrates: (1) the macroscopic voltage response during relaxation studies indicate the reintercalation of plated lithium into the graphite anode; (2) for SOC below 60% and low C-Rates, there is no dead lithium; (3) for SOC between 60% to 80%, and C-Rates in the range of 4C-6C show dead lithium both in experiments and simulations; (4) at 100% SOC and 4C-6C rates, large amounts of dead lithium are observed. The study presented here allows us to evaluate the effects of the physical properties of the electrochemical system on plating and stripping kinetics and the amount of dead lithium on graphite electrodes, which determines the cell capacity loss under fast charge.

batteries↗
DOE OSTI2023

Large Local Currents in a Lithium-Ion Battery during Rest after Fast Charging

Increasing electric vehicle (EV) adoption requires lithium-ion batteries that can be charged quickly and safely. Some EV batteries have caught on fire despite being neither charged nor discharged. While the lithium that plates on graphite during fast charging affects battery safety, so do the internal ionic currents that can occur when the battery is at rest after charging. These currents are difficult to quantify; the external current that can readily be measured is zero. Here we study a graphite electrode at rest after 6C fast charging using operando X-ray microtomography. We quantify spatially resolved current density distributions that originate at plated lithium and end in underlithiated graphite particles. The average current densities decrease from 1.5 to 0.5 mA cm -2 in about 20 min after charging is stopped. Surprisingly, the range of the stripping current density is independent of time, with outliers above 20 mA cm -2 . In conclusion, the persistence of outliers provides a clue as to the origin of catastrophic failure in batteries at rest.

25 ENERGY STORAGE↗
DOE OSTI2020

Fast Charge-Driven Li Plating on Anode and Structural Degradation of Cathode

Enabling fast charging in lithium ion batteries (LIBs) is a key factor to make electric vehicles drive just like gasoline-powered vehicles when the time comes to refuel. However, fast charging to current LIBs (LiNi x Mn y Co 1–z O 2 /graphite) is limited by lithium plating, which is barely reversible and causes LIBs to lose capacity over time. Thus, research to quantify the lithium plating in LIB cells is extremely important in improving our fundamental understanding of lithium plating behavior and enabling fast charging for LIBs. Here, we precisely quantified the amount of fast-charge-driven lithium plating in a coin-cell composed of LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532)/graphite. We found that the amount of lithium plating gradually increases with the cycle count and reaches 25.59 μmole (26.80 mAh g –1 cathode ) by the 100th cycle. The study also reveals that the NMC532 has lost 19% of its original lithium content after 100 fast-charging cycles; this, correspondingly, causes a lattice volumetric strain of 0.59%.

25 ENERGY STORAGE↗
DOE OSTI2020

Correlating capacity fade with film resistance loss in fast charging of lithium-ion battery

Fast charging of lithium-ion (Li-ion) batteries makes it susceptible to lithium plating. Here, we report the correlation between capacity loss and cell impedance changes in the battery due to lithium electrodeposition. Li-ion pouch cells with nickel-manganese-cobalt cathode and graphite anode were charged at rates varying from 0.5C to 6C. The cell voltage evolution immediately after charging was monitored to identify the C-rates that result in lithium plating. Electrochemical impedance spectroscopy (EIS) was used to monitor the cell impedance evolution. The impedance of battery cells at C-rates lower than 1C and no lithium plating showed minimal changes from their baseline values in the period immediately after charging. However, the impedance of battery cells undergoing lithium plating and C-rates higher than 3C showed a substantial reduction immediately after charging, with recovery back to baseline values after 30 min of relaxation. These observations suggest that lithium plating causes damage to the solid electrolyte interface (SEI) layer on the anode particles during the charging period, followed by the reformation of the SEI during the relaxation period. The measured capacity loss has a linear correlation with observed impedance change. The linear relationship suggests that impedance monitoring may be used for prognostication of the state-of-health of Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Electrochemical-driven green recovery of lithium, graphite and cathode from lithium-ion batteries using water

The expected exponential increase in consumption of lithium-ion batteries (LIBs) would pose a unique challenge to the availability of near-critical resources like lithium and graphite in the upcoming decade. In this work, we present a lithium recovery process that utilizes a degradation mechanism, i.e., lithium plating, as a tool to concentrate metallic lithium at the anode/separator interface for convenient extraction at room temperature – using only water. Electrochemical characterization of fast charged (1–6 C) LIBs yielded a maximum capacity fade of 50% over ten cycles. The lithium plating was confirmed via voltage plateau analysis, coulombic efficiency, and DC resistance measurements. A maximum lithium plating condition was observed to exist between 4C and 5C, thereby limiting the energy consumption in the extraction process. Post-mortem film thickness measurement showed an incrementing film deposition with a maximum of 35 µm thickness. SEM and XPS analysis confirmed increasing concentration of a dense dendritic metallic lithium deposition on the anode/separator interface with C-rate. A green recovery process was adopted to extract the concentrated metallic lithium using distilled water. The lithium from the plated film, solid/electrolyte interface (SEI), electrolyte, anode, and cathode, was extracted as salts. A 37% improvement in lithium recoverability was achieved with fast charging under ambient conditions. XPS analysis showed ~92% of lithium yield with no residual lithium in the graphite. In addition, the battery-grade graphite was recovered with 97% purity after heat treatment of the washed anode film, and concentrated transition metals oxides in the cathode to 93% purity for convenient extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

High-throughput Li plating quantification for fast-charging battery design

Fast charging of most commercial lithium-ion batteries is limited due to fear of lithium plating on the graphite anode, which is difficult to detect and poses considerable safety risk. In this report we demonstrate the power of simple, accessible and high-throughput cycling techniques to quantify irreversible Li plating spanning data from over 200 cells. We first observe the effects of energy density, charge rate, temperature and state of charge on lithium plating, use the results to refine a mature physics-based electrochemical model and provide an interpretable empirical equation for predicting the plating onset state of charge. We then explore the reversibility of lithium plating and its connection to electrolyte design for preventing irreversible Li accumulation. Finally, we design a method to quantify in situ Li plating for commercially relevant graphite|LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC) cells and compare with results from the experimentally convenient Li|graphite configuration. The hypotheses and abundant data herein were generated primarily with equipment universal to the battery researcher, encouraging further development of innovative testing methods and data processing that enable rapid battery engineering.

25 ENERGY STORAGE↗
DOE OSTI2021

Ultrafast charging of energy-dense lithium-ion batteries for urban air mobility

Urban air mobility (UAM) demands batteries with high energy density, long cycle life, and fast rechargeability. In this paper, we demonstrate an energy-dense lithium-ion battery (LiB) with ultralong cycle life under ultrafast charging. By using the asymmetric temperature modulation (ATM) method, i.e., charging at an elevated temperature and discharging around the ambient temperature, it is experimentally shown that the 209 Wh/kg LiB is charged to 88% state of charge (SOC) in ~5 min under UAM cycling while retaining 97.7% capacity after 1,000 cycles. Moreover, an experimentally validated electrochemical-thermal (ECT) model is developed to elucidate the fast charging process and the degradation mode of UAM batteries, quantitatively capturing lithium plating during fast charging. We find that the LiBs for UAM applications are most prone to lithium plating due to their higher initial SOC required as the reserve for safety; nevertheless, the ATM method is effective in minimizing or preventing lithium plating in the high SOC range of 30-90%. In addition to slowing down capacity fade, the ATM method also raises the usable capacity by 10%, which boosts the battery energy density and ensures the battery to perform full UAM cycles even at the end of life.

25 ENERGY STORAGE↗
DOE OSTI2020

Performance degradation due to anodic failure mechanisms in lithium-ion batteries

Here, we report a mechano-chemical model for anodic degradation during fast-charging of nickel-manganese-cobalt (NMC)/graphite (C) cell due to SEI growth, lithium plating/stripping, dead lithium storage, and film fracture of composite SEI and plated lithium film. Degradation of the battery is analyzed for a range of charging rates from 1 to 6 C-rates, and the influence of plating mechanisms – lithium plating and dead lithium deposition and recovery during stripping – on the film resistance of the anode are accounted for in the model. Dynamic evolution of the interfacial properties is modeled using rule-of-mixture approach. Model predictions of plating associated stress fields are used to compute critical energy release rate for film cracking. The results indicate an increased tendency of fracture for thinner SEI film with lithium plating at higher charging rates. The process of reforming the cracked film absorbs a significant portion of the electrode current thereby reducing the cell capacity and plating efficiency. The mechano-chemical model provides an extensive analytical framework for understanding the synergistic coupling of anodic degradation mechanisms, prognosticating conditions of SEI failure, and evaluating the capacity fade and efficiency of lithium-ion battery.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrode scale and electrolyte transport effects on extreme fast charging of lithium-ion cells

A combination of cell testing and electrochemical modeling is used to investigate extreme fast charging (XFC) performance for cells with a low loading of 1.5 mAh.cm -2 and moderate loading of 2.5 mAh.cm -2 . Cells with a low loading of 1.5 mAh.cm -2 withstand XFC performance remarkably well even up to 9C CC charging with high charge acceptance and very little lithium plating. For a moderate loading of 2.5 mAh.cm -2 , the 6C CC charge capacity is poor with significant amounts of lithium plating. Insufficient electrolyte transport properties are shown to be a major limitation for XFC performance of moderate and high loading cells. Charging at elevated temperature is shown to be an effective strategy for moderate loading cells enabling good 10-minute charge acceptance and mitigating lithium plating. Finally, the electrochemical model is used to investigate strategies for enabling 4-6C CC charging for cells with a loading of 3-4 mAh.cm -2 . A combination of elevated temperature, reduced tortuosity, and electrolytes with improved transport are likely needed to enable XFC for high energy density cells.

25 ENERGY STORAGE↗
DOE OSTI2022

Lithium metal stripping mechanisms revealed through electrochemical liquid cell electron microscopy

An understanding of lithium stripping is as important as that of lithium plating to achieve significant advances in using lithium metal anodes for high-energy rechargeable batteries. However, there have been limited studies on lithium stripping compared to lithium plating. Here we report the lithium stripping mechanisms revealed through in-situ electrochemical liquid cell transmission electron microscopy (TEM). We directly observe and compare the stripping behavior of the in-situ grown lithium dendrites and lithium nanograins covered by a lithium fluoride-rich solid-electrolyte interphase (SEI). Furthermore, we find the sporadic lithium stripping behavior and three important modes that can describe the stripping of individual lithium deposits, regardless of their morphology: (i) symmetric stripping, (ii) surface-preferred asymmetric stripping, and (iii) interface-preferred asymmetric stripping. In addition, SEI chemical mapping with high spatial resolution shows a remarkable SEI loss at the end of the lithium metal stripping, which illustrates the importance of SEI protection in the subsequent cycles.

25 ENERGY STORAGE↗
DOE OSTI2023

Rational designs to enable 10-min fast charging and long cycle life in lithium-ion batteries

A daunting challenge in the design of lithium ion batteries (LiBs) is enabling 10-min extreme fast charging (XFC) while achieving appreciable charge acceptance and cycle life. This desirable outcome requires both a comprehensive understanding of LiB operation and aging behavior at different length scales and careful optimization. Lithium plating has been a critical bottleneck because, at XFC rates, it consumes cyclable lithium causing distinct aging and safety concerns even in moderate-loading LiBs. Here, we propose combining multiple solutions, including materials-to-electrode design-to-charging protocols, that are intended to overcome limitations in lithium-ion transport in the electrolyte phase, thus enabling 10-min XFC in LiBs. Some implemented strategies include cathode chemistry, optimized carbon binder domain in the cathode, dual layer anode design, improved separator and advanced electrolyte. Further, innovative charging protocols in moderately loading (~3 mAh/cm 2 anode/2.7 mAh/cm 2 cathode) single-layer pouch cells are proposed, together with demonstrated 10-min XFC with higher charge acceptance between 87.3 and 92.1% (or 2–2.1 mAh/cm 2 ) for 600 cycles without lithium plating. This methodical study with well-defined cells shows promise in combining multiple solution strategies to enable 10-min XFC, charting a pathway to achieve XFC in higher-loading energy-optimized LiBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Parametric analysis of anodic degradation mechanisms for fast charging lithium batteries with graphite anode

In this work, we report the impact of the temperature-driven synergistically-coupled anodic degradation mechanisms on the electrochemical performance of lithium batteries with graphite anode over multiple cycles. Temperature dependence of electrochemical reactions and damage mechanisms, such as solid electrolyte interface (SEI) growth, lithium plating/stripping, dead lithium storage/dissolution, and film cracking are incorporated into the degradation model. Results of a parametric analysis are presented, evaluating the effects of charging rates (1–6 C), operating temperatures (-15 – 45°C) and electrode design parameters, on the relative performance fade in the lithium-ion battery. Thermo-electrochemical process maps are developed to provide insights into the relationship between electrode performance and failure mechanisms. The simulation results predict a severe capacity loss due to lithium plating at low temperatures, which is further aggravated at high charging rates. A common strategy for mitigating lithium plating, through charging at high temperatures, also results in rapid capacity loss due to accelerated SEI formation. Simulation results are used to identify the combination of operating conditions and electrode design parameters that improve the electrochemical performance of the battery. These results demonstrate an opportunity to design safe and high-performance lithium-ion batteries, guided by anodic degradation models.

Battery design↗
DOE OSTI2023

Voltage-Based Strategies for Preventing Battery Degradation under Diverse Fast-Charging Conditions

Maintaining safe operating conditions is a key challenge for high-performance lithium-ion battery applications. The lithium-plating reaction remains a risk during charging, but limited studies consider the highly variable charging conditions possible in commercial cells. Here we combine pseudo-2D electrochemical modeling with data visualization methods to reveal important relationships between the measurable cell voltage and difficult-to-predict Li-plating onset criteria. An extensively validated model is used to compute Li plating for thousands of multistep charging conditions spanning diverse rates, temperatures, states-of-charge, and cell aging. Here we observe an empirical cell operating voltage limit below which plating does not occur across all conditions, and this limit varies with the battery state-of-charge and aging. A model sensitivity analysis also indicates that, when comparing two charging voltage profiles, the capacity difference at 4.0 V correlates well with the difference in the plating onset capacity. These results encourage simple strategies for Li-plating prevention that are complementary to existing battery controls.

25 ENERGY STORAGE↗
DOE OSTI2025

Microstructure Scale Lithium-Ion Battery Modeling: Part I. On Through-Plane Heterogeneity, Impact of Mesh Representation, and Differences between Macro- and Microscale Models

Li-ion battery performance and degradation are strongly correlated with the electrode microstructures and can be modeled at different scales, each with their own limitations. Herein, we compare predictions achieved with a macro- and a micro-scale model, that is, respectively, neglecting or considering the microstructural heterogeneity of the composite electrodes, on virtual numerically generated and real microstructures. While both models are in relative agreement at the low charge rates, differences arise for fast charging scenarios and especially for the real, highly heterogenous, microstructures. The microscale model predicts that electrolyte concentration saturation and depletion, respectively, at the back of the cathode and of the anode are exacerbated, and that lithium plating occurs earlier for real microstructures. The present work also indicates that the mesh representation significantly impacts the microscale model predictions, and consequently that microscale models should add surface area as a parameter to consider explicitly surface roughness. This article is the first of a series, with subsequent entries further investigating in-plane heterogeneities, lithium plating, and the impact of microstructure representativity on model predictions.

25 ENERGY STORAGE↗
DOE OSTI2025

Depth-Resolved Lithiated Gradients in Pristine and Laser-Ablated Anodes During Fast Charging

Laser ablating 3D electrode microstructures is a technique to improve Li-ion battery fast-charge performance. This technique has been theoretically proposed and electrochemically validated previously in the literature. The fundamental principle underlying laser ablation is that the ablated features reduce Li-ion transport pathways, improving access to the electrode active material near the current collector. This, in turn, promotes more homogeneous electrode utilization. The present study seeks to directly affirm the physics attributed to laser ablation using operando high-speed synchrotron X-ray diffraction. In this study, depth-resolved graphite lithiation gradients are measured operando during high-rate (15 min) charging. The depth-resolved lithiation dynamics of both ablated and non-ablated anodes are compared. The results highlight that the laser-ablated graphite electrode has notably more homogeneous utilization as compared to the non-ablated electrode. Additionally, the ablated electrode has a significant delay in reaching the maximum graphite lithiation at the separator, indicating less propensity for lithium plating. During low rate delithiation/discharge (2 hr), the two cells' lithiation gradients converge. Notably, a calibrated physics-based electrochemical model accurately reflects experimental findings, suggesting the potential to use pseudo-4D models not only to optimize laser ablation parameters in fast-charge capable electrodes but also to guide fast charging protocols that avoid lithium plating.

25 ENERGY STORAGE↗
DOE OSTI2024

Understanding particle size effect on fast-charging behavior of graphite anode using ultra-thin-layer electrodes

Extreme fast charging (≤ 15 min) of lithium-ion batteries is highly desirable to accelerate mass-market adoption of electric vehicles. However, significant capacity fading, as well as safety issues due to the lithium plating caused by the fast charging rate, limit its implementation. In this study, we investigated the fast-charging capability of graphite materials with various particle sizes. To eliminate the Li + ion concentration gradient effect across the thickness of the electrode, ultra-thin-layer graphite electrodes were developed to investigate the "real" fast-charging capability of graphite at the particle level. Electrochemical assessments as well as microscopic characterizations revealed that smaller particles exhibited superior fast-charging performance, featuring enhanced capacity reversibility, faster charging rate, and less lithium plating under the same fast-charging conditions. It is shown that small-particle graphite (mean radius of 3.3 μm) could withstand a 4C charge (to 80 % state-of-charge) without plating, with minimal plating occurring at 6C. Thicker particles exhibited plating at lower C-rates. Since the experimental data could not directly explain whether intra-particle diffusion limitations or interfacial reaction limitations dominated the plating mechanism, the pseudo-2-dimensional model was used to evaluate the most likely plating mechanism. The model suggested that particle-level diffusion is the dominant mechanism contributing to plating at high rates. Finally, this work provides comprehensive insights into the particle size effects on fast-charging capability, offering a better understanding of fast-charging behavior and valuable guidance for designing optimal electrode architecture for high-rate lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Developing extreme fast charge battery protocols – A review spanning materials to systems

Extreme fast charging (XFC) has become a focal research point in the lithium-battery community over the last several years. As adoption of electric vehicles increases, fast charging has become a key driver in enhancing consumer recharge experience. Recently, the research community has made significant improvements in developing charge protocols to support XFC. New charge protocol designs derived using a combination of advanced, physically derived models, and electrochemical and secondary characterization methods, increase charge acceptance and decrease aging. By coordinating these methods and modifying protocols to account for different material constraints, including lithium plating and cathode particle degradation, novel charge protocols have increased the energy accepted during charging by over 25% in 10 min and increased the charge acceptance prior to a constant-voltage step by approximately 3x. Here, we review several charge-protocol advances, aging factors which are enhanced by XFC and advances which will enable adoption of XFC capable vehicles. These advances include implementing machine learning and other detection algorithms to reduce and classify lithium plating, which is known to significantly degrade cell performance and reduce cell life. The review concludes by discussing full-system fast charge requirements, including electric vehicle service equipment needs for implementing XFC protocols.

25 ENERGY STORAGE↗