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At least 19 records

Combining Fractional Calorimetry with Statistical Methods to Characterize Thermal Runaway

Fractional thermal runaway calorimetry (FTRC) techniques were introduced to examine thermal runaway (TR) behavior of lithium-ion (Li-ion) cells. Specifically, FTRC considers the total energy released vs. the fraction of the total energy that is released through the cell casing vs. through the ejecta material. This device has been expanded to universally support FTRC testing of additional cell types including 21700-format, D-Cell format, and large prismatic format Li-ion cells. The TR behavior as influenced by cell format, manufacturer, chemistry, capacity, and in situ safety features are described in this presentation.

Walker, William↗

Combining Fractional Calorimetry with Statistical Methods to Characterize Thermal Runaway

Thermal management systems designed to handle the impacts of thermal runaway (TR) are key to safe operation of lithium-ion (Li-ion) batteries. Critical factors for optimizing these systems include the total energy released and the fraction of the total energy that is released through the cell casing versus through the ejecta material. A unique calorimeter, designed to characterize said factors, was utilized to examine the TR behavior of a variety of 18650-format Li-ion cells. Statistical methods were implemented to interpret the data.

Walker, William↗

Comparative Analysis of Thermal Runaway Heat Output as a Function of Trigger Mechanism and Cell Format

High demand for energy storage systems across many fields drives the need for safe and reliable Li-ion batteries. In order to assess the risk of using such batteries in various applications, many types of abuse tests have been developed to push battery cells to their limits and learn how they fail. In this work, internal short circuit (ISC) tests, nail penetration tests, and thermal tests were used to trigger thermal runaway in D-cell, 18650, and 21700 Li-ion cells. High-speed radiography was used to gain insight to the propagation of thermal runaway throughout the cell, while calorimetric and thermal data were recorded in real time. Post-test disassembly of the calorimeter allowed for any mass ejected from the cell to be analyzed and the distribution of mass through the calorimeter to be determined. The impact of cell geometry and trigger mechanism on post-test mass distribution, thermal runaway propagation and internal cell temperature are discussed.

Lithium-ion battery; thermal runaway; calorimetry;↗

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↗

Coupling Fractional Thermal Runaway Calorimetry (FTRC) Results with Statistical Analysis Methods

Important factors to consider when optimizing Lithium-ion (Li-ion) battery thermal management systems, from a battery safety perspective, include the total energy released during a single cell thermal runaway (TR) event and the fraction of the total energy that is released through the cell casing versus through the ejecta material. A fractional thermal runaway calorimeter (FTRC) was used to examine the TR behavior of the following 18650-format Li-ion cells: (1) Molicel 18650-J, (2) LG 18650-HG2, (3) Samsung 18650-30Q, (4) 3.35 Ah LG 18650 test cell, (5) Sony 18650-VC7, and (6) LG 18650-MJ1. These cells were intentionally selected to represent a variety of manufacturers, chemistries, capacities, and safety features. Because of the large number of random and non-random variables associated with the FTRC results, a linear regression model, developed using engineering statistical methods, was utilized to provide final interpretation of the TR behavior for each cell type and design variable combination.

Walker, William↗

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↗

Development and Application of a Novel Calorimetry Technique for the Study of Lithium-Ion Cell Thermal Runaway

Lithium-ion battery technology is widely used and is attractive due to demonstrated specific energies in the 200-300 W-hr/kg range. The excellent, mass-efficient energy storage capability of lithium-ion batteries has led to their use on many aerospace platforms. However, lithium-ion batteries can exhibit thermal runaway behavior wherein stored electrochemical energy is released rapidly as a result of thermal or mechanical failure, electrochemical abuse, internal or external short circuiting. A single cell undergoing thermal runaway within a battery has the potential to induce thermal runaway in adjacent cells if heat dissipation is not properly managed and can result in a catastrophic failure of the battery. Designing batteries that are resistant to thermal runaway propagation requires an understanding of, not only, total energy yield but also the means by which that energy is liberated from the cell. While Accelerating Rate Calorimetry and other techniques provide total thermal runaway energy yield, they do not provide the fractional breakdown of energy liberated via conduction through the cell casing from that which is vented from the cell as hot gases and effluents. Such data are needed to inform battery thermal design and analysis. To measure the total energy yield, the fraction conducted through the cell casing, and the fraction lost due to gases and effluents, NASA developed Fractional Thermal Runaway Calorimetry (FTRC). Two calorimeters have been developed and demonstrated, the Small-format- and Large-format Fractional Thermal Runaway Calorimeters (S-FTRC and L-FTRC, respectively). The technique has been successfully applied to small- and large-format cells (2.4-3.5 Ah and >100 Ah capacity, respectively) and has given new insights into Li-ion cell thermal runaway. Development of the calorimeters is discussed and results from the initial thermal runaway testing campaigns are presented.

Lithium-Ion Cell↗

The Effect of Cell Geometry and Trigger Method on the Risks Associated with Thermal Runaway of Lithium-Ion Batteries

Consideration of thermal runaway heat output variability is paramount for the development of safe lithium-ion battery assemblies. This study utilizes data gathered from fractional thermal runaway calorimetry (FTRC) experiments to conduct a comparative analysis of thermal runaway heat output for three cell formats (18650, 21700, and 33600) as a function of trigger method (heaters, internal short-circuiting device, and nail penetration). The analysis is based on comparisons for the calculated total energy yield, fractional energy yield, heat rate, and heat flux. This study reveals that nail penetration tends to result in higher thermal runaway heat output for larger cells (21700 & 33600); these experiments also tended to result in higher fractions of the total energy being released through the cell body. The smaller cells (18650) did not appear to have significant variation in heat output as a function of trigger method. This finding suggests that, for this cell type, worst-case scenario heat output could be achievable in assembly level testing regardless of the utilized trigger method. This study also demonstrates successful translation of FTRC results, as recorded in the Battery Failure Databank, into meaningful analysis that breaks down the influence of specific conditions on thermal runaway heat output.

calorimetry↗

Correlative acoustic time-of-flight spectroscopy and X-ray imaging to investigate gas-induced delamination in lithium-ion pouch cells during thermal runaway

It remains difficult to detect internal mechanical deformation and gas-induced degradation in lithium-ion batteries, especially outside specialized diagnostics laboratories. In this work, we demonstrate that electrochemical acoustic time-of-flight (EA-ToF) spectroscopy can be used as an insightful and field-deployable diagnostic/prognostic technique to sense the onset of failure. A 210 mAh commercial lithium-ion cell undergoing thermal abuse testing is probed with in situ and operando EA-ToF spectroscopy, together with simultaneous fractional thermal runaway calorimetry (FTRC) and synchrotron X-ray imaging. The combination of X-ray imaging and EA-ToF analysis provides new understanding into the through-plane mechanical deformation in lithium-ion batteries through direct visualisation and the acoustic ToF response. Internal structural changes, such as gas-induced delamination, are identified using EA-ToF spectroscopy due to variations in the attenuation and signal peak shifts. This is corroborated using X-ray imaging, demonstrating EA-ToF spectroscopy as a promising technique for detecting onset of battery failure.

25 ENERGY STORAGE↗

Thermal Runaway of Li-Ion Cells: How Internal Dynamics, Mass Ejection, and Heat Vary with Cell Geometry and Abuse Type

Thermal runaway of lithium-ion batteries can involve various types of failure mechanisms each with their own unique characteristics. Using fractional thermal runaway calorimetry and high-speed radiography, the response of three different geometries of cylindrical cell (18650, 21700, and D-cell) to different abuse mechanisms (thermal, internal short circuiting, and nail penetration) are quantified and statistically examined. Correlations between the geometry of cells and their thermal behavior are identified, such as increasing heat output per amp-hour (kJ Ah −1 ) of cells with increasing cell diameter during nail penetration. High-speed radiography reveals that the rate of thermal runaway propagation within cells is generally highest for nail penetration where there is a relative increase in rate of propagation with increasing diameter, compared to thermal or internal short-circuiting abuse. For a given cell model tested under the same conditions, a distribution of heat output is observed with a trend of increasing heat output with increased mass ejection. Finally, internal temperature measurements using thermocouples embedded in the penetrating nail are shown to be unreliable thus demonstrating the need for care when using thermocouples where the temperature is rapidly changing. All data used in this manuscript are open access through the NREL and NASA Battery Failure Databank.

25 ENERGY STORAGE↗

The effects of zinc addition on the environmental stability of Al-Li alloys

It was found that relatively small addition of Zn can improve the stress corrosion cracking (SCC) resistance of Al-Li alloys. However, the mechanism by which this is accomplished is unclear. The role that Zn plays in altering the behavior of Alloy 8090 is investigated. Early results suggest that Zn additions increase the volume fraction of delta(Al3Li) precipitation and differential scanning calorimetry (DSC) on these alloys confirms this. The four alloys studied each had initial compositions lying in the 8090 window and had varying amounts of Zn added to them. Alloy 8090, like other Al-Li alloys, displays a delta' precipitate free zone (PFZ) upon artificial aging along the grain and subgrain boundaries. However Zn additions greatly decreased or eliminated a delta' PFZ after 100 hours at 160 C. This implies that the subgrain boundary precipitation kinetics are being altered and suppressed. Furthermore, there appears to be a window of Zn concentration above which a delta ' PFZ can reappear with the nucleation and growth of a currently unidentified precipitate on the boundaries. Polarization experiments were performed and the results presented. The experiments were performed in deaerated 3.5 w/o NaCl in both as received (T3) condition and at peak aging of 100 hours at 160 C. The aging profile was determined via Vickers Hardness tests.

Kilmer, Raymond J.↗

Estimation of the nucleation rate by differential scanning calorimetry

A realistic computer model is presented for calculating the time-dependent volume fraction transformed during the devitrification of glasses, assuming the classical theory of nucleation and continuous growth. Time- and cluster-dependent nucleation rates are calculated by modeling directly the evolving cluster distribution. Statistical overlap in the volume fraction transformed is taken into account using the standard Johnson-Mehl-Avrami formalism. Devitrification behavior under isothermal and nonisothermal conditions is described. The model is used to demonstrate that the recent suggestion by Ray and Day (1990) that nonisothermal DSC studies can be used to determine the temperature for the peak nucleation rate, is qualitatively correct for lithium disilicate, the glass investigated.

Kelton, Kenneth F.↗

Aging mechanisms of filled cross-linked polyethylene (XLPE) cable insulation material exposed to simultaneous thermal and gamma radiation

Thermal and simultaneous thermal and gamma radiation aging experiments were conducted on an industry grade cross-linked polyethylene (XLPE) cable insulation material, which is a composite material with XLPE as polymer matrix and various additives and fillers. Reverse engineering was conducted to identify and quantify the material composition given that this information was not revealed by the cable manufacture. Samples were then aged at temperatures of 60, 90, and 115 °C, exposed to gamma radiation for total doses of 0 to 324 kGy, and at dose rates of 0 to 540 Gy/h. Aging mechanisms were studied using various materials characterization techniques including pyrolysis gas chromatography mass spectrometry (Py-GCMS), differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy (NMR), and gel-fraction tests. Results show that the flame-retardant components were decomposed into smaller molecules when the material was exposed to gamma radiation, while no changes were observed when the samples were aged thermally without gamma radiation. With exposure to gamma radiation, the crystalline phase of the XLPE were damaged by gamma radiation introducing defects in the crystals, resulting in smaller and less perfect crystals. The dominance of chain scission or chain reformation process largely depends on the chain mobility, which is decided by the aging temperature. Chain scission was seen to dominate when the material was exposed to gamma radiation at 60 °C. Chain cross-linking slightly dominated when the material was exposed to gamma radiation at 90 °C and became more dominant with exposure to gamma radiation at 115 °C. No significant change to the XLPE polymer matrix was observed when the samples were exposed to thermal aging without gamma radiation. Finally, antioxidant is more effective in protecting the XLPE polymer matrix under thermal aging, but less effective with sample exposure to gamma radiation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Hard-to-soft transition-enhanced piezoelectricity in poly(vinylidene fluoride) via relaxor-like secondary crystals activated by high-power ultrasonication

We report although high piezoelectric coefficients have recently been observed in poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] random copolymers, they have low Curie temperatures, which makes their piezoelectricity thermally unstable. It has been challenging to achieve high piezoelectric performance from the more thermally stable PVDF homopolymer. In this report, we describe how high-power ultrasonic processing was used to induce a hard-to-soft piezoelectric transition and improve the piezoelectric coefficient d 31 in neat PVDF. After high-power ultrasonication for 20 min, a uniaxially stretched and poled PVDF film exhibited a high d 31 of 50.2 ± 1.7 pm V -1 at room temperature. Upon heating to 65 °C, the d 31 increased to a maximum value of 76.2 ± 1.2 pm V -1 , and the high piezoelectric performance persisted up to 110 °C. The enhanced piezoelectricity was attributed to the relaxor-like secondary crystals in the oriented amorphous fraction, broken off from the primary crystals by ultrasonication, as suggested by differential scanning calorimetry and broadband dielectric spectroscopy studies.

relaxor-like secondary crystals↗

Predicting the heat release variability of Li-ion cells under thermal runaway with few or no calorimetry data

Accurate measurement of the variability of thermal runaway behavior of lithium-ion cells is critical for designing safe battery systems. However, experimentally determining such variability is challenging, expensive, and time-consuming. Here, we utilize a transfer learning approach to accurately estimate the variability of heat output during thermal runaway using only ejected mass measurements and cell metadata, leveraging 139 calorimetry measurements on commercial lithium-ion cells available from the open-access Battery Failure Databank. We show that the distribution of heat output, including outliers, can be predicted accurately and with high confidence for new cell types using just 0 to 5 calorimetry measurements by leveraging behaviors learned from the Battery Failure Databank. Fractional heat ejection from the positive vent, cell body, and negative vent are also accurately predicted. We demonstrate that by using low cost and fast measurements, we can predict the variability in thermal behaviors of cells, thus accelerating critical safety characterization efforts.

25 ENERGY STORAGE↗