(Energy Technology Division Graduate Student Award sponsored by BioLogic) In-Situ, Non-Destructive, 3D Neutron Imaging of Lithium Plating Following Extreme Fast-Charging of Full-Cell Lithium-Ion Batteries
Authors: Yusuf Maha , Kaestner Anders , Zhang Yuxuan , LaManna Jacob Michael , Wied Markus , Vo Nghia , Bilheux Jean-Christophe , Strobl Markus , Wood Vanessa , Toney Michael F , Weker Johanna Nelson 
Published: August 2024

One of the primary challenges impeding extreme fast-charging (XFC) of current lithium-ion batteries (LIBs) for electric vehicles (EVs) within 10–15 minutes is the deposition of Li metal on graphite known as “Li plating”.1-2 After Li plates, it either re-intercalates into the graphite electrode or is stripped off during battery discharging to form “active Li”or becomes electronically disconnected resulting in “dead Li.” Previous studies have indicated that dead Li is the main contributor to the XFC-related capacity loss of LIBs. However, mechanistic understanding of the 3D morphological behavior and spatial heterogeneities of dead Li; and how they differ from those of plated and active Li during the XFC is not well understood.3-4

Here, we present an in-situ, non-destructive 3D characterization of the morphological behavior and spatial heterogeneities of plated, dead, and active Li on graphite electrodes in full-cell LIBs using high-resolution neutron micro-computed tomography. We performed neutron µCT5 (pixel size: ~ 5.74 µm; effective spatial resolution: ~10-15 µm) at the ICON beamline6 at the Swiss Spallation Neutron Source at the Paul Scherrer Institute. We imaged two batteries in the charged and discharged states: (1) after 4 cycles of 1C charging and (2) after 6 cycles of 6C charging.
Our results show that Li plates at and around the edges of the graphite electrodes, indicating that graphite edges and the areas around these edges are the most susceptible to Li plating. However, certain edges and areas around these edges formed dead Li whereas others formed active Li, suggesting 3D spatial heterogeneities in the formation of dead and active Li at both 1C and 6C. Mainly, we discuss these heterogeneities at four regions: (1) near the Cu CC, (2) in the middle of the graphite electrode, (3) near the graphite-separator interface, and (4) in the separator. Specifically, we found that Li near the Cu CC remains active whereas most of the plated Li at the graphite-separator interface and in the separator becomes dead at both 1C and 6C.
Morphologically, we observed porous nature of plated and dead Li at both 1C and 6C. Our 3D visualizations noticeably show nodules of varying densities of metallic Li. However, we observed different 3D behavior of Li plating at 1C and 6C. For example, tip-like Li deposits were seen laterally closer to the center of the graphite electrode, near the graphite-separator interface, and into the separator at 6C. In contrast, at 1C, no tip-like Li deposits were observed near the graphite-separator interface and into the separator. Based on our findings, we concluded that higher XFC-charging rate and cycling number (6 cycles of 6C charging) cause the formation of tip-like Li deposits as compared to the relatively slower XFC-charging rate and cycling number (4 cycles of 1C charging). We believe that insights derived from this work will guide the design of thick graphite electrodes with minimized-plating for fast-charged EVs.

References:

Liu et al. (2019). Challenges and opportunities towards fast-charging battery materials. Nature Energy, 1.

Tomaszewska, A., Chu, Z., Feng, X., O'kane, S., Liu, X., Chen, J., ... & Wu, B. (2019). Lithium-ion battery fast charging: A review. ETransportation, 1, 100011.

Liu et al. (2016). Understanding undesirable anode lithium plating issues in lithium-ion batteries. RSC advances, 6(91), 88683-88700.

Paul et al. (2021). A Review of Existing and Emerging Methods for Lithium Detection and Characterization in Li‐Ion and Li‐Metal Batteries. Advanced Energy Materials, 11(17), 2100372.

Morgano et al. (2018). Unlocking high spatial resolution in neutron imaging through an add-on fibre optics taper. Optics Express, 26(2), 1809-1816.

Kaestner et al. (2011). The ICON beamline–A facility for cold neutron imaging at SINQ. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 659(1), 387-393.

Keywords: Plated Lithium; Dead lithium; Active lithium; Neutron imaging; Extreme Fast Charging (XFC).