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(a) Comparison of fully charged states at 1C and 2C; (b) Comparison of fully discharged states at 1C and 2C; (c) Comparison of fully charged and fully discharged states at 2C; (d) Comparison of fully charged and fully discharged states at 1C; (e) Radiographic image of the discharged battery normalized to fully charged state and details of the area vertically averaged and depicted in (a-d).
Source publication
We report an operando neutron imaging study of a commercial ICR 10440 Li ion battery during charge and discharge. The cylindrical battery with a spiral configuration is composed of a multiphase layered oxide cathode and graphite anode. In spite of a two-dimensional nature of the projection data of this time-resolved study, structural and functional...
Contexts in source publication
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... and their Li exchange can be resolved (compare Fig. 2a). This provides a rich qualitative information about the process and local differences, while at this stage a precise quantification of the Li redistribution is hindered because of a lack of the sufficient amount of data, and further measurements and simulations need to be performed. Fig. 3. (a-d) shows the line profile comparison of the battery at fully charged and discharged states at 1C and 2C, in the marked region (e). Fig. 3a demonstrates that the structure of the layers did not alter in the given area during the charge/discharge processes at different C rates, as there is no change in the corresponding fringes position. ...
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... while at this stage a precise quantification of the Li redistribution is hindered because of a lack of the sufficient amount of data, and further measurements and simulations need to be performed. Fig. 3. (a-d) shows the line profile comparison of the battery at fully charged and discharged states at 1C and 2C, in the marked region (e). Fig. 3a demonstrates that the structure of the layers did not alter in the given area during the charge/discharge processes at different C rates, as there is no change in the corresponding fringes position. Even their relative behaviour, i.e. the ratio between the subsequent maxima seems unaltered in the final discharged state. As the position ...
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... of the battery and the relative positions of the battery layers remain unchanged. However, the offset of the intensity modulation, which can be attributed to a significant contribution of the change in Δt e well agreed with the findings of the initial investigation of the electrolyte redistribution during charge and discharge. It can be seen from Fig. 3c and d, that the mean neutron transmission is lower at the electrode windings in the fully discharged states, due to the highest volumetric concentration on Li in the layered oxide cathode (as compared to anode and electrolyte) which becomes saturated by Li. Furthermore, the amount of electrolyte in the electrodes, separator and a buffer ...
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... fully discharged states, due to the highest volumetric concentration on Li in the layered oxide cathode (as compared to anode and electrolyte) which becomes saturated by Li. Furthermore, the amount of electrolyte in the electrodes, separator and a buffer volume changes as related to the applied current density, 1C or 2C, as is evident from the Fig. ...
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... of a real macroscopic expansion and the accuracy of the collected neutron imaging data concludes that it is not possible to resolve the real expansion with the given resolution. Nevertheless, the periodicity of the fringes appears to be constant while the distance between the fringes fits the interlayer dimensions in the battery as seen in Fig. 3 and is constant, independent of the state of the battery (charged/discharged) and a rate of the electrochemical processes -1C or 2C. These distances are too large to cause any modulations during the cycling as the design of the battery interior can easily accommodate a marginal expansion occurring in the ...
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... and their Li exchange can be resolved (compare Fig. 2a). This provides a rich qualitative information about the process and local differences, while at this stage a precise quantification of the Li redistribution is hindered because of a lack of the sufficient amount of data, and further measurements and simulations need to be performed. Fig. 3. (a-d) shows the line profile comparison of the battery at fully charged and discharged states at 1C and 2C, in the marked region (e). Fig. 3a demonstrates that the structure of the layers did not alter in the given area during the charge/discharge processes at different C rates, as there is no change in the corresponding fringes position. ...
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... while at this stage a precise quantification of the Li redistribution is hindered because of a lack of the sufficient amount of data, and further measurements and simulations need to be performed. Fig. 3. (a-d) shows the line profile comparison of the battery at fully charged and discharged states at 1C and 2C, in the marked region (e). Fig. 3a demonstrates that the structure of the layers did not alter in the given area during the charge/discharge processes at different C rates, as there is no change in the corresponding fringes position. Even their relative behaviour, i.e. the ratio between the subsequent maxima seems unaltered in the final discharged state. As the position ...
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... of the battery and the relative positions of the battery layers remain unchanged. However, the offset of the intensity modulation, which can be attributed to a significant contribution of the change in Δt e well agreed with the findings of the initial investigation of the electrolyte redistribution during charge and discharge. It can be seen from Fig. 3c and d, that the mean neutron transmission is lower at the electrode windings in the fully discharged states, due to the highest volumetric concentration on Li in the layered oxide cathode (as compared to anode and electrolyte) which becomes saturated by Li. Furthermore, the amount of electrolyte in the electrodes, separator and a buffer ...
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... fully discharged states, due to the highest volumetric concentration on Li in the layered oxide cathode (as compared to anode and electrolyte) which becomes saturated by Li. Furthermore, the amount of electrolyte in the electrodes, separator and a buffer volume changes as related to the applied current density, 1C or 2C, as is evident from the Fig. ...
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... of a real macroscopic expansion and the accuracy of the collected neutron imaging data concludes that it is not possible to resolve the real expansion with the given resolution. Nevertheless, the periodicity of the fringes appears to be constant while the distance between the fringes fits the interlayer dimensions in the battery as seen in Fig. 3 and is constant, independent of the state of the battery (charged/discharged) and a rate of the electrochemical processes -1C or 2C. These distances are too large to cause any modulations during the cycling as the design of the battery interior can easily accommodate a marginal expansion occurring in the ...
Citations
... Previous studies have applied neutron imaging to monitor the movement of Li + ions in batteries [9][10][11] and during CDI by ordered mesoporous carbon electrodes with approximately 10 nm pore size [12][13][14][15]. The first two of the CDI studies employed Gd nitrate solutions [12,13], whereas the latter two imaged 6 Li ( a = 940 barn) from concentrated LiCl solutions [14,15]. ...
Neutron imaging was employed to track the uptake of Gd3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^{3+}$$\end{document} ions by the sub 2 nm micropores of charged activated carbon cloth electrodes from an aqueous Gd(NO3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_3$$\end{document})3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_3$$\end{document} solution. The transmitted neutron intensity evinces the persistent presence of Gd3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^{3+}$$\end{document} in the micropores during the discharge cycle, which is caused by the adsorption of oppositely charged ions. The charge efficiency of the activated carbon cloth system was determined by direct comparison with the imaged Gd3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^{3+}$$\end{document} concentration changes, with which the influence of ion swapping and resistive losses on capacitive deionization cells can be ascertained.
... For TiNi 0.8 Cu 0.2 electrode, structural transformations were observed to change on cycling (Fig. 41a,b). On the first charge at C/10 Reprinted from an open access article [151]. Distributed under the Creative Commons Attribution license (http://creativecommons.org/licenses/by/4.0/). ...
... x Cu x (0 ≤ x ≤ 0.5) alloys showed that the change of the reaction mechanism with Cu substitution results from Cu-induced destabilization of β-hydride [51]. [150,151] The structural evolution of the electrode materials in an ICR 10440 commercial cylindrical lithium-ion battery, which has a discharge capacity of 360 mAh and a nominal voltage of 3.7 V has been studied using in situ neutron diffraction. A three-phase mixture of Li (Ni,Mn,Co)O 2 , LiCoO 2 and LiMn 2 O 4 was identified as the active material of the cathode, with graphite acting as the anode material. ...
The paper presents an overview of advanced in situ diffraction studies as a highly valuable tool to probe the structure and reacting mechanisms of hydrogen and energy storage materials. These studies offer benefits from the use of a high flux diffraction beam in combination with high resolution measurements, and allow, even when using very small samples, establishing the mechanism of the phase-structural transformations and their kinetics based on a rapid data collection for the various charge-discharge states at variable test conditions. The applied conditions include a broad range of hydrogen/deuterium pressures, from vacuum to high pressures reaching 1000 bar H 2 /D 2 , and temperatures, from cryocooling (2 K) to as high as 1273 K (1000 °C). Simultaneously, various state-of-charge and discharge are probed when studying metal-H/D systems for hydrogen/deuterium gas storage and as anode electrodes of metal hydride batteries. The range of the studied systems includes but is not limited to the AB 5 , AB 2 Laves type, AB, equiatomic ternary ABC intermetallics and Mg-containing layered AB 3 structures and composites. Prospects on Li-ion full cells are considered as well. Interrelations between the structure and hydrogen storage performance, including maximum and reversible H storage capacity, hysteresis of hydrogen absorption and desorption, H 2 absorption and desorption in dynamic equilibrium conditions, are considered and related to the ultimate goal of optimisation of the H storage behaviours of the advanced H storage materials. Numerous contributions of Dr. Michel Latroche to the field are highlighted, particularly in in situ studies during electrochemical transformations.
... The core is 2 to 3 mm in diameter. Nazer et al. 3 used operando neutron imaging to study the motion of electrolyte within 360 mAh cylindrical 10440 cells. Figure 1c in Ref. 3 shows the electrolyte level in the core of the cell increasing during charge (as electrolyte is forced out of the electrode winding) and decreasing during discharge (as electrolyte re-infiltrates the electrode winding). ...
... Nazer et al. 3 used operando neutron imaging to study the motion of electrolyte within 360 mAh cylindrical 10440 cells. Figure 1c in Ref. 3 shows the electrolyte level in the core of the cell increasing during charge (as electrolyte is forced out of the electrode winding) and decreasing during discharge (as electrolyte re-infiltrates the electrode winding). The work in Refs. 2 and 3 requires access to a neutron beam facility and hence is not readily accessible. ...
High-energy-density cylindrical Li-ion cells are densely packed with active materials, inactive materials, and electrolyte. When such cells are charged, the overall volume of the electrode materials increases and therefore some electrolyte is pushed under hydrostatic pressure to the spaces outside the electrode winding at the ends of the cylindrical can and also possibly into the hollow core of the cylindrical electrode winding. During discharge this electrolyte re-enters the pore spaces of the electrodes as electrode particles contract. Therefore, the moment of inertia of the cell about an axis perpendicular to the axis of the cylindrical can change as the cell is charged and discharged. We have built a torsional oscillator that can measure the resonant frequency, and hence the moment of inertia, of a cylindrical Li-ion cell as it is charged and discharged. Because the moment of inertia of the cell depends on the electrolyte distribution, we can “watch” the electrolyte move within the cell. The design and operation of the instrument is described here as well as experiments that demonstrate the electrolyte motion that occurs in cylindrical cells. Consequences of this electrolyte motion are discussed.
Crystallographic features of battery active particles impose an inherent limitation on their electrochemical figures of merit namely capacity, roundtrip efficiency, longevity, safety, and recyclability. Therefore, crystallographic properties of these particles are increasingly measured not only to clarify the principal pathways by which they store and release charge but to realize the full potential of batteries. Here, state‐of‐the‐art advances in Li⁺, K⁺, and Na⁺ chemistries are reviewed to reiterate the links between crystallography variations and battery electrochemical trends. These manifest at different length scales and are accompanied by a multiplicity of processes such as doping, cation disorder, directional crystal growth and extra redox. In light of this, an emphasis is placed on the need for more accurate correlations between crystallographic structure and battery electrochemistry in order to harness crystallographic beneficiation into electrode material design and manufacture, translating into high‐performance and safe energy storage solutions.
The lithium-ion battery is currently the preferred power source for applications ranging from smart phones to electric vehicles. Imaging the chemical reactions governing its function as they happen, with nanoscale spatial resolution and chemical specificity, is a long-standing open problem. Here, we demonstrate operando spectrum imaging of a Li-ion battery anode over multiple charge-discharge cycles using electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Using ultrathin Li-ion cells, we acquire reference EELS spectra for the various constituents of the solid-electrolyte interphase (SEI) layer and then apply these "chemical fingerprints" to high-resolution, real-space mapping of the corresponding physical structures. We observe the growth of Li and LiH dendrites in the SEI and fingerprint the SEI itself. High spatial- and spectral-resolution operando imaging of the air-sensitive liquid chemistries of the Li-ion cell opens a direct route to understanding the complex, dynamic mechanisms that affect battery safety, capacity, and lifetime.
Solid-state lithium batteries (SSLBs) have made significant progress in recent decades in response to increasing demands for improved safety and higher energy density. Nonetheless, the current state SSLBs are not suitable for wide commercial applications. The low ionic conductivity, lithium dendrites growth, and unstable interfaces between solid electrodes and electrolytes are some of the challenges that need to be overcome. Therefore, it is critical to fully comprehend the structural information of SSLBs at a nanometer scale. Neutron-based techniques (NBTs) are sensitive to light elements (H, Li, B, N, O, etc.) and can distinguish heavy metals (e.g., Mn, Fe, Co, Ni, etc.) containing close atomic numbers or even isotopes (e.g., 1H and 2H). Therefore, NBTs are important and powerful structural and analytical tools for SSLB research and have substantially improved our understanding of these processes. To provide real-time monitoring, researchers have explored many sophisticated in situ NBTs to investigate the underlying mechanisms of SSLBs. This minireview article is primarily dedicated to the investigation of SSLBs using in situ NBTs. In addition, it illustrates the capabilities of different in situ NBTs on SSLBs by illustrating the capabilities of different techniques in recently published works. Ultimately, some perspectives for the next evolution of in situ NBTs in SSLBs are highlighted.
