Electrochemical, Thermal, and Safety Properties of Lithium and Post-Li Materials and Cells II

A special issue of Batteries (ISSN 2313-0105). This special issue belongs to the section "Battery Performance, Ageing, Reliability and Safety".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 50040

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Guest Editor
Group Leader Batteries—Calorimetry and Safety, Institute for Applied Materials-Applied Materials Physics (IAM-AWP), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Interests: lithium and post-lithium-ion batteries; battery calorimetry; thermal characterization of materials/cells/batteries; safety testing; thermal management; multiscale electric, electrochemical, and thermal modeling of cells and batteries
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Special Issue Information

Dear Colleagues,

New cheaper, safer, and more sustainable battery materials and technology concepts are urgently required for the decarbonization of the energy system and an extensive market penetration of electric vehicles and stationary storage systems. So-called post-lithium batteries based on, e.g., Na or Mg ions, which no longer rely on Li are promising alternatives that offer a huge potential. Therefore, characterization of electrochemical, thermal, and safety properties of the cells and their individual active and passive materials is required to obtain quantitative and reliable data, which are necessary to improve the current understanding in order to design and develop better materials and cells. This Special Issue addresses all techniques, which are necessary for a holistic assessment from materials to cell level. I warmly invite you to publish your original research paper or a review paper in this Special Issue.

Potential topics include but are not limited to:

  • Electrochemical characterization techniques (galvanostatic cycling, PITT, GITT, CIT, CV, EIS, entropymetry);
  • Thermal characterization techniques (DSC, DTA, TG, drop solution calorimetry, battery calorimetry, laser flash, hot-plate, thermography, etc.) for materials and cells;
  • Determination of heat generation of cells under normal use;
  • Safety testing (mechanical, electrical, thermal abuse) combined with pressure measurement and gas analytics;
  • Cell aging studies;
  • Thermal propagation mitigation;
  • Development of safer materials and cell designs;
  • Development of more sustainable materials;
  • Thermodynamic modeling of battery materials (CALPHAD, kinetic modeling) and database generation;
  • Electrical, thermal, and electrochemical modeling.

Share your results to get a deeper understanding of the electrochemical and thermal processes under both normal use and abuse conditions. This will be an important milestone to increase their safety and to exploit their full potential.

Dr. Carlos Ziebert
Guest Editor

Manuscript Submission Information

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Keywords

  • post-lithium batteries
  • electrochemical and thermal characterization
  • battery calorimetry, safety testing, and gas analytics
  • cell aging studies
  • thermal propagation mitigation
  • development of safer and more sustainable materials
  • thermodynamic modelling
  • electrical, thermal, and electrochemical modelling

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Published Papers (10 papers)

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Research

10 pages, 993 KiB  
Article
On the Theory of the Arrhenius-Normal Model with Applications to the Life Distribution of Lithium-Ion Batteries
by Omar Kittaneh
Batteries 2023, 9(1), 55; https://doi.org/10.3390/batteries9010055 - 12 Jan 2023
Cited by 5 | Viewed by 2671
Abstract
Typically, in accelerated life testing analysis, only probability distributions possessing shape parameters are used to fit the experimental data, and many distributions with no shape parameters have been excluded, including the fundamental ones like the normal distribution, even when they are good fitters [...] Read more.
Typically, in accelerated life testing analysis, only probability distributions possessing shape parameters are used to fit the experimental data, and many distributions with no shape parameters have been excluded, including the fundamental ones like the normal distribution, even when they are good fitters to the data. This work shows that the coefficient of variation is a replacement for the shape parameter and allows using normal distributions in this context. The work focuses on the Arrhenius-normal model as a life-stress relationship for lithium-ion (Li-ion) batteries and precisely derives the estimating equations of its accelerating parameters. Real and simulated lives of Li-ion batteries are used to validate our results. Full article
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20 pages, 5682 KiB  
Article
Simulation, Set-Up, and Thermal Characterization of a Water-Cooled Li-Ion Battery System
by Max Feinauer, Nils Uhlmann, Carlos Ziebert and Thomas Blank
Batteries 2022, 8(10), 177; https://doi.org/10.3390/batteries8100177 - 12 Oct 2022
Cited by 5 | Viewed by 4332
Abstract
A constant and homogenous temperature control of Li-ion batteries is essential for a good performance, a safe operation, and a low aging rate. Especially when operating a battery with high loads in dense battery systems, a cooling system is required to keep the [...] Read more.
A constant and homogenous temperature control of Li-ion batteries is essential for a good performance, a safe operation, and a low aging rate. Especially when operating a battery with high loads in dense battery systems, a cooling system is required to keep the cell in a controlled temperature range. Therefore, an existing battery module is set up with a water-based liquid cooling system with aluminum cooling plates. A finite-element simulation is used to optimize the design and arrangement of the cooling plates regarding power consumption, cooling efficiency, and temperature homogeneity. The heat generation of an operating Li-ion battery is described by the lumped battery model, which is integrated into COMSOL Multiphysics. As the results show, a small set of non-destructively determined parameters of the lumped battery model is sufficient to estimate heat generation. The simulated temperature distribution within the battery pack confirmed adequate cooling and good temperature homogeneity as measured by an integrated temperature sensor array. Furthermore, the simulation reveals sufficient cooling of the batteries by using only one cooling plate per two pouch cells while continuously discharging at up to 3 C. Full article
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Graphical abstract

16 pages, 766 KiB  
Article
Identifying Anode and Cathode Contributions in Li-Ion Full-Cell Impedance Spectra
by Marco Heinrich, Nicolas Wolff, Steffen Seitz and Ulrike Krewer
Batteries 2022, 8(5), 40; https://doi.org/10.3390/batteries8050040 - 27 Apr 2022
Cited by 2 | Viewed by 4095
Abstract
Measured impedance spectra of Li-ion battery cells are often reproduced with equivalent circuits or physical models to determine losses due to charge transfer processes at the electrodes. The identified model parameters can usually not readily or unambiguously be assigned to the anode and [...] Read more.
Measured impedance spectra of Li-ion battery cells are often reproduced with equivalent circuits or physical models to determine losses due to charge transfer processes at the electrodes. The identified model parameters can usually not readily or unambiguously be assigned to the anode and the cathode. A new measurement method is presented that enables the assignment of features of impedance spectra of full cells to single electrodes. To this end, temperature gradients are imprinted perpendicular to the electrode layers of a single-layered Li-ion battery cell while impedance spectra are measured. The method exploits different dependences of the charge transfer processes at the electrodes on temperature. An equivalent circuit model of RC-elements and the effect of temperature on the related electrode properties is discussed to demonstrate the feasibility of the method. A reliable assignment of the change of impedance spectra to the electrode processes is shown to be possible. The assignment can be used to identify if changes in an impedance spectrum originate from the anode or the cathode. Full article
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20 pages, 9428 KiB  
Article
Radial Thermal Conductivity Measurements of Cylindrical Lithium-Ion Batteries—An Uncertainty Study of the Pipe Method
by Markus Koller, Johanna Unterkofler, Gregor Glanz, Daniel Lager, Alexander Bergmann and Hartmut Popp
Batteries 2022, 8(2), 16; https://doi.org/10.3390/batteries8020016 - 11 Feb 2022
Cited by 4 | Viewed by 5080
Abstract
A typical method for measuring the radial thermal conductivity of cylindrical objects is the pipe method. This method introduces a heating wire in combination with standard thermocouples and optical Fiber Bragg grating temperature sensors into the core of a cell. This experimental method [...] Read more.
A typical method for measuring the radial thermal conductivity of cylindrical objects is the pipe method. This method introduces a heating wire in combination with standard thermocouples and optical Fiber Bragg grating temperature sensors into the core of a cell. This experimental method can lead to high uncertainties due to the slightly varying setup for each measurement and the non-homogenous structure of the cell. Due to the lack of equipment on the market, researchers have to resort to such experimental methods. To verify the measurement uncertainties and to show the possible range of results, an additional method is introduced. In this second method the cell is disassembled, and the thermal conductivity of each cell component is calculated based on measurements with the laser flash method and differential scanning calorimetry. Those results are used to numerically calculate thermal conductivity and to parameterize a finite element model. With this model, the uncertainties and problems inherent in the pipe method for cylindrical cells were shown. The surprising result was that uncertainties of up to 25% arise, just from incorrect assumption about the sensor position. Furthermore, the change in radial thermal conductivity at different states of charge (SOC) was measured with fully functional cells using the pipe method. Full article
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14 pages, 4089 KiB  
Article
Combined Thermal Runaway Investigation of Coin Cells with an Accelerating Rate Calorimeter and a Tian-Calvet Calorimeter
by Wenjiao Zhao, Magnus Rohde, Ijaz Ul Mohsin, Carlos Ziebert, Yong Du and Hans J. Seifert
Batteries 2022, 8(2), 15; https://doi.org/10.3390/batteries8020015 - 11 Feb 2022
Cited by 6 | Viewed by 3579
Abstract
Commercial coin cells with LiNi0.6Mn0.2Co0.2O2 positive electrode material were investigated using an accelerating rate calorimeter and a Tian-Calvet calorimeter. After cycling and charging to the selected states of charge (SOCs), the cells were studied under thermal [...] Read more.
Commercial coin cells with LiNi0.6Mn0.2Co0.2O2 positive electrode material were investigated using an accelerating rate calorimeter and a Tian-Calvet calorimeter. After cycling and charging to the selected states of charge (SOCs), the cells were studied under thermal abuse conditions using the heat-wait-seek (HWS) method with the heating step of 5 K and a threshold for self-heating detection of 0.02 K/min. The onset temperature and the rate of the temperature rise, i.e., the self-heating rate for thermal runaway events, were determined. The morphology of the positive electrode, negative electrode and the separator of fresh and tested cells were compared and investigated with scanning electron microscopy (SEM). Furthermore, the microstructure and the chemical compositions of the individual components were investigated by X-ray diffraction (XRD) and inductively coupled plasma with optical emission spectrometry (ICP-OES), respectively. In the Tian-Calvet calorimeter, the coin cells with the selected SOCs and the individual components (positive electrode, negative electrode and separator) were heated up with a constant heating rate of 0.1 °C/min (ramp heating mode). Simultaneously, the heat flow signals were recorded to analyze the heat generation. The combination of the three different methods—the HWS method using the ES-ARC, ramp heating mode on both cells and the individual components using the Tian-Calvet calorimeter—together with a post-mortem analysis, give us a complete picture of the processes leading to thermal runaway. Full article
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12 pages, 3638 KiB  
Article
Effects of State-of-Charge and Penetration Location on Variations in Temperature and Terminal Voltage of a Lithium-Ion Battery Cell during Penetration Tests
by Yiqun Liu, Yitian Li, Y. Gene Liao and Ming-Chia Lai
Batteries 2021, 7(4), 81; https://doi.org/10.3390/batteries7040081 - 1 Dec 2021
Cited by 9 | Viewed by 5129
Abstract
The nail penetration test has been widely adopted as a battery safety test for reproducing internal short-circuits. In this paper, the effects of cell initial State-of-Charge (SOC) and penetration location on variations in cell temperature and terminal voltage during penetration tests are investigated. [...] Read more.
The nail penetration test has been widely adopted as a battery safety test for reproducing internal short-circuits. In this paper, the effects of cell initial State-of-Charge (SOC) and penetration location on variations in cell temperature and terminal voltage during penetration tests are investigated. Three different initial SOCs (10%, 50%, and 90%) and three different penetration locations (one is at the center of the cell, the other two are close to the edge of the cell) are used in the tests. Once the steel cone starts to penetrate the cell, the cell terminal voltage starts to drop due to the internal short-circuit. The penetration tests with higher initial cell SOCs have larger cell surface temperature increases during the tests. Also, the penetration location always has the highest temperature increment during all penetration tests, which means the heat source is always at the penetration location. The absolute temperature increment at the penetration location is always higher when the penetration is close to the edge of the cell, compared to when the penetration is at the center of the cell. The heat generated at the edges of the cell is more difficult to dissipate. Additionally, a battery cell internal short-circuit model with different penetration locations is built in ANSYS Fluent, based on the specifications and experimental data of the tested battery cells. The model is validated with an acceptable discrepancy range by using the experimental data. Simulated data shows that the temperature gradually reduces from penetration locations to their surroundings. The gradients of the temperature distributions are much larger closer to the penetration locations. Overall, this paper provides detailed information on the temperature and terminal voltage variations of a lithium-ion polymer battery cell with large capacity and high power under penetration tests. The presented information can be used for assessing the safety of the onboard battery pack of electric vehicles. Full article
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9 pages, 2223 KiB  
Article
Layered Iron Vanadate as a High-Capacity Cathode Material for Nonaqueous Calcium-Ion Batteries
by Munseok S. Chae, Dedy Setiawan, Hyojeong J. Kim and Seung-Tae Hong
Batteries 2021, 7(3), 54; https://doi.org/10.3390/batteries7030054 - 9 Aug 2021
Cited by 24 | Viewed by 5067
Abstract
Calcium-ion batteries represent a promising alternative to the current lithium-ion batteries. Nevertheless, calcium-ion intercalating materials in nonaqueous electrolytes are scarce, probably due to the difficulties in finding suitable host materials. Considering that research into calcium-ion batteries is in its infancy, discovering and characterizing [...] Read more.
Calcium-ion batteries represent a promising alternative to the current lithium-ion batteries. Nevertheless, calcium-ion intercalating materials in nonaqueous electrolytes are scarce, probably due to the difficulties in finding suitable host materials. Considering that research into calcium-ion batteries is in its infancy, discovering and characterizing new host materials would be critical to further development. Here, we demonstrate FeV3O9∙1.2H2O as a high-performance calcium-ion battery cathode material that delivers a reversible discharge capacity of 303 mAh g−1 with a good cycling stability and an average discharge voltage of ~2.6 V (vs. Ca/Ca2+). The material was synthesized via a facile co-precipitation method. Its reversible capacity is the highest among calcium-ion battery materials, and it is the first example of a material with a capacity much larger than that of conventional lithium-ion battery cathode materials. Bulk intercalation of calcium into the host lattice contributed predominantly to the total capacity at a lower rate, but became comparable to that due to surface adsorption at a higher rate. This stimulating discovery will lead to the development of new strategies for obtaining high energy density calcium-ion batteries. Full article
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18 pages, 7849 KiB  
Article
Analysis and Investigation of Thermal Runaway Propagation for a Mechanically Constrained Lithium-Ion Pouch Cell Module
by Luigi Aiello, Ilie Hanzu, Gregor Gstrein, Eduard Ewert, Christian Ellersdorfer and Wolfgang Sinz
Batteries 2021, 7(3), 49; https://doi.org/10.3390/batteries7030049 - 19 Jul 2021
Cited by 12 | Viewed by 7948
Abstract
In this paper, tests and analysis of thermal runaway propagation for commercial modules consisting of four 41 Ah Li-ion pouch cells are presented. Module samples were tested at 100% state-of-charge and mechanically constrained between two steel plates to provide thermal and mechanical contact [...] Read more.
In this paper, tests and analysis of thermal runaway propagation for commercial modules consisting of four 41 Ah Li-ion pouch cells are presented. Module samples were tested at 100% state-of-charge and mechanically constrained between two steel plates to provide thermal and mechanical contact between the parts. Voltage and temperature of each cell were monitored during the whole experiment. The triggering of the exothermal reactions was obtained by overheating one cell of the stack with a flat steel heater. In preliminary studies, the melting temperature of the separator was measured (from an extracted sample) with differential scanning calorimetry and thermogravimetric analysis techniques, revealing a tri-layers separator with two melting points (≈135 °C and ≈170 °C). The tests on module level revealed 8 distinct phases observed and analyzed in the respective temperature ranges, including smoking, venting, sparkling, and massive, short circuit condition. The triggering temperature of the cells resulted to be close to the melting temperature of the separator obtained in preliminary tests, confirming that the violent exothermal reactions of thermal runaway are caused by the internal separator failure. Postmortem inspections of the modules revealed the internal electrical failure path in one cell and the propagation of the internal short circuit in its active material volume, suggesting that the expansion of the electrolyte plays a role in the short circuit propagation at the single cell level. The complete thermal runaway propagation process was repeated on 5 modules and ended on average 60 s after the first thermal runaway triggered cell reached a top temperature of 1100 °C. Full article
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16 pages, 6274 KiB  
Article
Investigation into the Lithium-Ion Battery Fire Resistance Testing Procedure for Commercial Use
by Daniel Darnikowski and Magdalena Mieloszyk
Batteries 2021, 7(3), 44; https://doi.org/10.3390/batteries7030044 - 30 Jun 2021
Cited by 5 | Viewed by 4375
Abstract
Lithium-ion batteries (LIBs) have many advantages (e.g., high voltage and long-life cycle) in comparison to other energy storage technologies (e.g., lead acid), resulting in their applicability in a wide variety of structures. Simultaneously, the thermal stability of LIBs is relatively poor and can [...] Read more.
Lithium-ion batteries (LIBs) have many advantages (e.g., high voltage and long-life cycle) in comparison to other energy storage technologies (e.g., lead acid), resulting in their applicability in a wide variety of structures. Simultaneously, the thermal stability of LIBs is relatively poor and can be damaged by exposure to fire. This paper presents an investigation into a fire resistance safety test for LIBs and the use of thermal sensors to evaluate exposure conditions and estimate the temperatures to which cells are subjected. Temperature distribution data and statistical analysis show significant differences of over 200 C, indicating the stochastic nature of the heating curve despite following the testing procedure requirements. We concluded that the current testing procedure is inadequate for the reliable testing of LIBs, leaving an alarming loophole in the fire safety evaluation. The observed instability is mostly related to wind speed and direction, and fire source size. Full article
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12 pages, 2369 KiB  
Article
Thermophysical Characterization of a Layered P2 Type Structure Na0.53MnO2 Cathode Material for Sodium Ion Batteries
by Ijaz Ul Mohsin, Carlos Ziebert, Magnus Rohde and Hans Jürgen Seifert
Batteries 2021, 7(1), 16; https://doi.org/10.3390/batteries7010016 - 1 Mar 2021
Cited by 8 | Viewed by 5667
Abstract
Over the last decade, the demand for safer batteries with excellent performance and lower costs has been intensively increasing. The abundantly available precursors and environmental friendliness are generating more and more interest in sodium ion batteries (SIBs), especially because of the lower material [...] Read more.
Over the last decade, the demand for safer batteries with excellent performance and lower costs has been intensively increasing. The abundantly available precursors and environmental friendliness are generating more and more interest in sodium ion batteries (SIBs), especially because of the lower material costs compared to Li-ion batteries. Therefore, significant efforts are being dedicated to investigating new cathode materials for SIBs. Since the thermal characterization of cathode materials is one of the key factors for designing safe batteries, the thermophysical properties of a commercial layered P2 type structure Na0.53MnO2 cathode material in powder form were measured in the temperature range between −20 and 1200 °C by differential scanning calorimetry (DSC), laser flash analysis (LFA), and thermogravimetry (TG). The thermogravimetry (TG) was combined with mass spectrometry (MS) to study the thermal decomposition of the cathode material with respect to the evolved gas analysis (EGA) and was performed from room temperature up to 1200 °C. The specific heat (Cp) and the thermal diffusivity (α) were measured up to 400 °C because beyond this temperature, the cathode material starts to decompose. The thermal conductivity (λ) as a function of temperature was calculated from the thermal diffusivity, the specific heat capacity, and the density. Such thermophysical data are highly relevant and important for thermal simulation studies, thermal management, and the mitigation of thermal runaway. Full article
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