Titanium Carboxylate Molecular Layer Deposited Hybrid Films As Protective Coatings for Lithium-Ion Batteries
Authors: Vandenbroucke Sofie S. T. , Henderick Lowie , De Taeye Louis T. , Li Jin , Jans Karolien , Vereecken Philippe M. , Dendooven Jolien , Detavernier Christophe 
Published: November 2022

Thirty years after the release of the first commercial lithium-ion battery, capacity fading due to complex ageing mechanisms remains one of the major concerns in lithium-ion battery research. Lithium-ion battery cathodes age due to phenomena as transition metal dissolution, electrolyte oxidation and volume expansions.[1] To suppress these effects, a protective coating can be applied to the cathode’s surface to avoid direct contact with the liquid electrolyte. Many studies exist in literature, showing the protective effect of conformal and pinhole-free Atomical Layer Deposited (ALD) coatings. However, the inorganic coatings deposited by ALD are rigid and will crack upon volume expansion of the cathode.[2]
Molecular Layer Deposition (MLD) offers the same benefits as ALD but can be used to deposit hybrid inorganic/organic flexible films that can accommodate potential volume expansions of the cathode. To our knowledge, apart from ‘metalcones’ i.e. MLD films grown using a metal containing precursor and an alcohol, MLD films remain to be explored as protective and flexible coatings for lithium-ion batteries.[3] In this work, hybrid MLD titanium carboxylate thin films are deposited using tetrakis(dimethylamido)titanium (TDMAT) and various dicarboxylic acid precursors: oxalic acid, malonic acid, succinic acid, glutaric acid and 3,6-dioxaoctanedioic acid. The latter containing two ethylene oxide units per molecule, potentially increasing the lithium-ion conductivity.[4]
The growth of the titanium carboxylate MLD processes is studied using in situ ellipsometry at a substrate temperature of 100 °C and 160 °C. Only the TDMAT/oxalic acid process is found to display good saturation behavior, while a parasitic CVD component is present during the TDMAT pulse for the other processes. The structure of the as-deposited films is physically characterized using Fourier Transform IR spectroscopy (FTIR) and X-Ray Photoelectron Spectroscopy (XPS), confirming the successful deposition of titanium carboxylate films. The films are found to be stable in air up to 50 days as shown by FTIR. This is in contrast to many metalcone MLD films which are considered to be air sensitive as the organic backbone degrades upon air exposure. In addition, FTIR, X-Ray Reflectivity (XRR) and X-Ray Fluorescence (XRF) measurements show that the titanium carboxylate films remain intact upon immersion into a solution of 1 M LiClO4 in propylene carbonate, the liquid electrolyte used for electrochemical characterization.
The electrochemical properties of a 5 nm TDMAT/oxalic acid, TDMAT/3,6-dioxaoctanedioic acid and TDMAT/glycerol film (conventional titanicone film [5]) are tested on top of three ideal electrode systems: anatase TiO2, TiN and LiMnO2 (LMO). The titanium carboxylate films are observed to have little to no effect on the lithium-ion kinetics of the TiO2 electrode system compared to the uncoated electrode. This is in contrast to the titanicone film displaying a detrimental effect on the kinetics. All films are observed to effectively suppress electrolyte oxidation when exposing the TiN electrode system to elevated potentials. On the LMO electrode an activation step is necessary for all films, after which a good lithium-ion mobility through the titanium carboxylate films is observed without the severe irreversible reactions detected in the potential profile for the titanicone films. Overall, the explorative tests on thin film electrodes in this work indicate that the electrochemical properties of the titanium carboxylate films seem promising candidates as protective and flexible coating of lithium-ion battery cathodes.
[1] Vetter, J., Novák, P., Wagner, M. R., Veit, C., Möller, K. C., Besenhard, J. O., ... & Hammouche, A. (2005). Ageing mechanisms in lithium-ion batteries. Journal of power sources, 147(1-2), 269-281.
[2] Ban, C., & George, S. M. (2016). Molecular layer deposition for surface modification of lithium‐ion battery electrodes. Advanced Materials Interfaces, 3(21), 1600762.
[3] Zhao, Y., Zhang, L., Liu, J., Adair, K., Zhao, F., Sun, Y., ... & Sun, X. (2021). Atomic/molecular layer deposition for energy storage and conversion. Chemical Society Reviews, 50(6), 3889-3956.
[4] Xue, Z., He, D., & Xie, X. (2015). Poly (ethylene oxide)-based electrolytes for lithium-ion batteries. Journal of Materials Chemistry A, 3(38), 19218-19253.
[5] Van de Kerckhove, K., Mattelaer, F., Deduytsche, D., Vereecken, P. M., Dendooven, J., & Detavernier, C. (2016). Molecular layer deposition of “titanicone”, a titanium-based hybrid material, as an electrode for lithium-ion batteries. Dalton Transactions, 45(3), 1176-1184.