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Winter 2018

Catching a Battery in the Act

Lithium-ion battery operation revealed in real time by scientists at NECCES

Zachary Lebens-Higgins

Rechargeable lithium-ion batteries can only run so long, and extended use shortens this life. But what causes this lifetime to decline? Scientists at the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center, are working to answer this question by taking a look inside a battery while it is operating. These experiments focus on commonly used positive electrodes to understand just how these materials work.

In a battery, the positive and negative electrodes are essential to storing and delivering energy. When storing energy in a battery (charging), lithium ions are transported from the positive to the negative electrode. By reversing this process (discharging), the stored energy can be used to run everyday devices. The positive electrode, usually referred to as the cathode, plays a key role in these processes.

One type of commonly tested battery design is the coin cell, in which the battery components are stacked inside a button-like casing. The cathode is just one of the many parts in a typical battery. NECCES scientists use X-rays to selectively look at the cathode. X-rays provide sensitivity to different types of materials. In medical X-rays, for example, denser bones absorb more X-rays, distinguishing them from skin and tissues. By choosing the desired X-ray wavelength and experimental conditions, NECCES scientists can probe a range of information, from individual atoms to groups of particles within the cathode.

Probing the battery during operation requires modification to the coin cell design. The button-like casing is too thick for X-rays to penetrate. Adding windows to the top and bottom of the casing allows X-rays to transmit through. However, the windows can alter how the battery performs. To overcome this issue, a team of NECCES researchers, led by Karena Chapman, helped develop a specialized cell, known as the AMPIX cell, in 2012. They continue to use it today. This modified cell performs like a typical coin cell so reliable measurements can be made.

“Drilling a hole in a coin cell to let X-rays through will alter the pressure and create inhomogeneities in the cathode. The AMPIX was especially designed to avoid this issue,” says Antonin Grenier, a researcher in Chapman’s group.

Taking advantage of the AMPIX cell, these scientists investigate the nature of lithium storage in the cathode material. As lithium moves out of the cathode, the crystal structure of the material, related to the local arrangement of atoms, will change to accommodate this loss. X-ray diffraction is used to correlate changes in lithium content to changes in the crystal structure.

Looking at the cathode during the first cycle, these researchers identified non-uniform structural changes when lithium is removed. This non-uniformity occurred for particles stored in air, before they were used in the battery. During storage in air, these particles can form a surface layer like the process of rust forming on a car. When these particles were used as the cathode, lithium was not evenly removed from all particles. Instead, some particles lagged behind, which led to non-uniform structural changes. This non-uniformity was removed when the particles were kept in inert storage conditions such as argon.

A surface layer forms on the cathode during air exposure. This layer causes lithium to be “stuck” in the particle during the start of the charge. Storing in better conditions prevents the formation of this layer, leading to uniform structural changes during the first cycle.

While the first cycle is often looked at for the basics of how the cathode material works in the battery, long-term cycling provides insight into battery failure. Crystal structure changes of the cathode material were compared over long-term cycling using the AMPIX cell. Over this long-term cycling, 20 percent of the cathode’s storage capacity was lost.

During the first cycle, the cathode structure changed uniformly when removing and inserting lithium. This is similar to when food coloring is added to water: All the water changes to the new color. But on the 93rd cycle, a fraction of the cathode material did not fully participate in the cycling process. Microscopy images revealed cracks forming between groups of particles. Cracking leads to the isolation of individual particles, and they become less active during battery operation.

Cathode particles stick together in groups. For the first cycle, these groups are well connected, but cracks form between particles with further cycling. Battery performance drops when isolated particles don’t fully participate in charge and discharge.

Hao Liu, the lead author for this study, explains, “With the optimized AMPIX cell, we looked at how capacity fading related to crack development over the period of a few months.” Looking at how the battery operated during the 93rd cycle revealed the culprit for capacity fade.

Diffraction experiments provide just one type of video of lithium motion into the cathode. Another NECCES group, led by Jordi Cabana, combines spectroscopy with microscopy to visualize particles’ shapes and chemical states. Spectroscopy uses X-rays to excite atoms that can be used to distinguish the chemical state of the atom. In the cathode, an atom’s chemical state changes when lithium ions move into the system or can change from undesirable reactions. By combining spectroscopy with microscopy (referred to as spectromicroscopy), these chemical states can be mapped across a range of particles.

A spectromicroscopy image of groups of cathode particles. These are 2-D projections of 3-D cathode particles. By changing the photon energy, chemical states are determined at each pixel.

Using spectromicroscopy, with a similarly modified coin cell, these researchers obtain a video of the particle shape and local chemical environments. Yet, for current specialized coin cells, these videos are only 2-D projections of the whole particle.

Mark Wolf, a graduate researcher in Cabana’s group, said, “Since they’re transmission techniques, you can’t tell where in the depth of the particle a certain signal originates.” As part of NECCES, he is developing a specialized cell to overcome some of the limitations of coin cells and these 2-D projections.

These various X-ray measurements during battery operation shine a new light on a range of long-standing problems. Rather than snapshots of the endpoints, these operation experiments provide a time-lapse video of battery operation. As batteries are vital for everyday devices, these time-lapse measurements provide insight into making the best and most reliable battery.

More Information

Borkiewicz OJ, B Shyam, KM Wiaderek, C Kurtz, PJ Chupas, and KW Chapman. 2012. “The AMPIX Electrochemical Cell: A Versatile Apparatus for In Situ X-ray Scattering and Spectroscopic Measurements.Journal of Applied Crystallography 45:1261-1269. DOI: 10.1107/S0021889812042720

Grenier A, H Liu, KM Wiaderek, ZW Lebens-Higgins, OJ Borkiewicz, LFJ Piper, PJ Chupas, and KW Chapman. 2017. “Reaction Heterogeneity in LiNi0.8Co0.15Al0.05O2 Induced by Surface Layer.Chemistry of Materials 29(17):7345-7352. DOI: 10.1021/acs.chemmater.7b02236

Liu H, M Wolf, K Karki, YS Yu, EA Stach, J Cabana, KW Chapman, and PJ Chupas. 2017. “Intergranular Cracking as a Major Cause of Long-Term Capacity Fading of Layered Cathodes.Nano Letters 17(6):3452-3457. DOI: 10.1021/acs.nanolett.7b00379

Wolf M, BM May, and J Cabana. 2017. “Visualization of Electrochemical Reactions in Battery Materials with X-ray Microscopy and Mapping.Chemistry of Materials 29(8):3347-3362. DOI: 10.1021/acs.chemmater.6b05114

Acknowledgments

Borkiewicz et al. Work done at Argonne National Laboratory and use of the Advanced Photon Source, a Department of Energy (DOE) Office of Science user facility operated by Argonne National Laboratory was supported by DOE. The authors acknowledge support as part of the NorthEast Center for Chemical Energy Storage, an Energy Frontier Research Center funded by DOE, Office of Science, Basic Energy Sciences.

Grenier et al. This work was supported as part of the NorthEast Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES). Research at the Advanced Photon Source was supported by DOE, Office of Science, BES. The authors thank Diamond Light Source for access to beamline I09 that contributed to the results.

Liu et al. This research was supported as part of the NorthEast Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the Department of Energy (DOE), Office of Science, Basic Energy Sciences. Y.S.Y. also acknowledges support from an Advanced Light Source Collaborative Postdoctoral Fellowship. This research used resources of the Advanced Photon Source, a DOE Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by DOE, Office of Science, Basic Energy Sciences. Scanning electron microscopy was performed at the Center for Functional Nanomaterials, which is a DOE Office of Science user facility, at Brookhaven National Laboratory.

Wolf et al. This work was supported as part of the NorthEast Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the Department of Energy (DOE), Office of Science, Basic Energy Sciences.

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More Information

Borkiewicz OJ, B Shyam, KM Wiaderek, C Kurtz, PJ Chupas, and KW Chapman. 2012. “The AMPIX Electrochemical Cell: A Versatile Apparatus for In Situ X-ray Scattering and Spectroscopic Measurements.Journal of Applied Crystallography 45:1261-1269. DOI: 10.1107/S0021889812042720

Grenier A, H Liu, KM Wiaderek, ZW Lebens-Higgins, OJ Borkiewicz, LFJ Piper, PJ Chupas, and KW Chapman. 2017. “Reaction Heterogeneity in LiNi0.8Co0.15Al0.05O2 Induced by Surface Layer.Chemistry of Materials 29(17):7345-7352. DOI: 10.1021/acs.chemmater.7b02236

Liu H, M Wolf, K Karki, YS Yu, EA Stach, J Cabana, KW Chapman, and PJ Chupas. 2017. “Intergranular Cracking as a Major Cause of Long-Term Capacity Fading of Layered Cathodes.Nano Letters 17(6):3452-3457. DOI: 10.1021/acs.nanolett.7b00379

Wolf M, BM May, and J Cabana. 2017. “Visualization of Electrochemical Reactions in Battery Materials with X-ray Microscopy and Mapping.Chemistry of Materials 29(8):3347-3362. DOI: 10.1021/acs.chemmater.6b05114

Disclaimer: The opinions in this newsletter are those of the individual authors and do not represent the views or position of the Department of Energy.