Fast-Charging Li4Ti5O12 Anode Driven By Light
Authors: Ma Yuanyuan , Shen Yaxin , Jeong Heonjae , Lipton Jason , Wang Hang , Maclean Stephen A. , Rohr Jason A. , Johnson Christopher S. , Taylor Andre 
Published: December 2024

The development of fast-charging lithium-ion batteries (LIBs) is crucial for achieving significant market adoption of electric vehicles (EVs). The successful achievement of fast-charging LIBs depends on efficient charge transfer and the diffusivity of lithium ions. The photo-assisted battery system exhibits promising fast-charging properties. Previous research has shown that direct exposure to white light can induce a more oxidized center in a spinel LiMn2O4 (LMO) cathode, accelerating its charging rate.[
1] Recently, our group found that illumination with red light on an operating LMO cathode induces an Mn d-d electron excitation, simultaneously shrinks the Mn-Mn lattice, and facilitates faster delithiation of the LMO cathode.[
2] Consequently, the charging time of the battery decreases. This encourages us to consider whether the photon energy from a specific wavelength of light can also enhance the lithiation process on the anode side. Spinel Li4Ti5O12 (LTO) is a promising material for faster-charging anodes due to its small volume charge and high-rate capability in lithium intercalation. However, the system displays slow lithium diffusivity due to poor bulk ionic conductivity. To examine the photon effect of light on these anodes, we demonstrate the photo-accelerated fast-charging (lithiation process) mechanism with an LTO spinel anode.

The thin film LTO's energy band gap (Eg), approximately 3.4 eV, was determined through intense UV-visible (UV-Vis) absorption spectrum analysis, assessed in a transmission mode employing Tauc’s Law. This indicates that an LED light with photon energy around 3.4 eV might trigger rapid charging by exciting electron transfer to the T-t2g band. To explore the impact of light on the fast-charging behavior of the LTO electrode, current was measured while applying a constant voltage of 1.2 V. During the 20-minute chronoamperometry experiment, utilizing the 3.4 eV UV LED to illuminate the cell resulted in a progressive increase in current. This current increase peaked at approximately 200s, leading to a maximum average capacity increase of 13 mA h g-1. This suggests that UV illumination accelerates the lithiation process compared to the dark state, particularly favoring the early lithiation stage. Subsequently, a red LED emitting 2 eV photon energy was used to illuminate the same cell, resulting in no discernible change in current levels compared to the dark state. Electrochemical impedance spectroscopy (EIS) further revealed a significant reduction in charge transfer resistance of the window cell when illuminated with UV light compared to both the dark state and red illumination. This alteration in electrode reaction kinetics at the interface suggests a distinct influence of different light wavelengths on the charging process.

In addition to assessing charge transfer at the electrode interface, galvanostatic intermittent titration technique (GITT) analysis was conducted at a 2 C rate to further elucidate diffusion within the LTO electrode. The GITT curves reveal that the diffusion of Li+ ions was approximately 1.3 times faster when the cell was illuminated by UV light compared to dark conditions. Consequently, we deduce that photo-accelerated fast charging can also occur during the lithiation process (reduction reaction) of anode materials, driven by optical forces.

To delve into the underlying mechanisms, we conducted first-principles density functional theory (DFT) calculations. The outcomes revealed that the generation of additional electrons in LTO results in a reduction in the bandgap and shifts the Fermi level above the conduction band minimum, effectively transforming LTO into an active conductor of electricity. These calculations indicate that UV light illumination has the capability to surmount the bandgap of LTO, generating electron-hole pairs and thereby facilitating charge transfer and lithium-ion diffusion.

In conclusion, our study showcased that UV light illumination on the LTO anode can lead to a faster charging speed of approximately 17% compared to dark conditions. We posit that the observed phenomenon of photo-accelerated fast charging in LTO is linked to the formation of electron-hole pairs in intrinsically wide-bandgap insulators or semiconducting materials. This discovery holds considerable implications for the advancement of fast charging technologies for lithium-ion batteries, potentially mitigating range anxiety concerns and facilitating the widespread adoption of electric vehicles.

Acknowledgments: This work was supported by funding from Royal Dutch Shell plc. Argonne National Laboratory operates under contract no. DE-AC02-06CH11357 with the U.S. Department of Energy Office of Science. We gratefully acknowledge use of the Bebop or Swing or Blues cluster in the Laboratory Computing Resource Center at Argonne National Laboratory and supported by the U.S. Department of Energy Office of Science.

Reference

[1] A. Lee et al., Nat. Commun., 10, 4946 (2019).

[2] J. Lipton et al., Cell Reports Physical Science, 3, 101051 (2022).