Vertically Aligned Nanocomposite Thin Films Incorporating 3D-Architectures for Micro-Battery Applications
Authors: Lovett Adam J , Daramalla Venkateswarlu , Nayak Debasis , Sayed Farheen , Mahadevegowda Amoghavarsha , Ducati Caterina , Spencer Ben , Dutton Sian , Grey Clare P. , Driscoll Judith L. 
Published: February 2024

Vertically aligned nanocomposite (VAN) thin films have shown strong potential in oxide nanoionics but are yet to be explored in detail in solid-state battery systems [1,2]. VANs, typically grown by pulsed laser deposition (PLD), are chessboard-like structures comprised of pillars of one phase embedded in a matrix the second phase. They form by solid-state thermodynamic self-assembly, allowing the spontaneous formation of interdigitated battery components in a single deposition without additional processing steps such as etching. Their 3D architectures are attractive because they may allow enhancements in capacity, current and power densities [3]. Furthermore, VAN films grow with a preferential orientation, allowing for selective growth of the optimum crystallographic orientation for high performance by altering the substrate phase and/or orientation. Also, owing to their large interfacial surface areas, VAN could serve as models to study interfaces and solid-electrolyte interphase formation during cycling due to their high interfacial surface areas.
In this poster, first we present highly crystalline and epitaxial vertically aligned nanocomposite PLD films comprised of a LixLa0.32±0.05(Nb0.7±0.1Ti0.32±0.05)O3±δ-Ti0.8±0.1Nb0.17±0.03O2±δ-anatase (LL(Nb,Ti)O-(Ti,Nb)O2) electrolyte/anode system, the first anode VAN battery system reported (Figure 1) [4]. This system exhibits an order of magnitude increased Li+ ionic conductivity over that in bulk Li3xLa1/3-xNbO3 (LLNO) and is comparable with the best available Li3xLa2/3-xTiO3 (LLTO) pulsed laser deposition films. Then, we will highlight the considerations and challenges that VANs pose, and how to overcome them [5]. Finally, we will also present our recently submitted work on VAN based cathodes [6]. Our carefully selected materials combination exhibits remarkable high-rate performance, achieving discharge capacities > 70 mAh g-1 up to ~200 C with clear redox behavior of the cathode-of-choice. The enhanced electrochemical performance is enabled by the 3D VAN architecture. Interestingly, we elucidate the relationship between pillar morphology and electrochemical performance, namely there is an optimum size and orientation of cathodic nanopillars such that high discharge capacity under high-rate regimes is possible. These works open up the possibility of incorporating VAN films into an all solid-state battery, either as electrodes or electrolytes, by the pairing of suitable materials.
References
[1] S. Lee, J.L. MacManus-Driscoll, APL Mater. 5 (2017) 042304.
[2] D.M. Cunha, C.M Vos, T.A. Hendriks, D.P. Singh, M. Huijben. ACS Appl. Mater. Interfaces. 11 (2019) 44444-44450.
[3] J. F. M. Oudenhoven, L. Baggetto and P. H. L. Notten, Adv. Energy Mater. 1(2011) 10–33.
[4] A.L Lovett, A. Kursumovic, S.E. Dutton, Z. Qi, Z He, H. Wang, J.L. MacManus-Driscoll. APL Mater. 10 (2022) 051102.
[5] A.J. Lovett, A. Kursumovic, and J.L. MacManus-Driscoll. Under Review
[6] A.J. Lovett, V. Daramalla, D. Nayak, F. N. Sayed, A. Mahadevegowda, C. Ducati, B. F. Spencer, S E. Dutton, C.P. Grey, J.L. MacManus-Driscoll. Under Review
Figure Caption
Figure 1: (a) & (b) Cross-sectional TEM images of a nanocomposite thin film composed of pillars of (Ti,Nb)O2 embedded in a LL(Nb,Ti)O matrix with red line/arrow marking clear interface between phases (c) Arrhenius plot displaying high Li+ ionic conductivity of VAN film. Reproduced with Permission from Ref. [4].

Figure 1