Atomic Layer Deposition of SnO2-Based Composite Anodes for Thin-Film Lithium-Ion Batteries

Abstract

Transition metal oxides are promising anode materials for lithium-ion batteries thanks to their good electrochemical reversibility, high theoretical capacities, high abundance, and low cost. The mechanism of lithium insertion or deintercalation into or from these metal oxides can be different depending upon their lattice structure or chemical nature. Synergistic effects obtained from mixing different metal oxides with (dis)similar lithiation/delithiation mechanisms (intercalation, conversion and alloying) can significantly improve the device performances. In this research, we systematically investigate the impact on electrochemical properties of SnO2 thin-films upon mixing with TiO2, Fe2O3 and ZnO. In these pure thin-films, SnO2 displays conversion- as well as alloying-type lithiation and serves as the host material, whereas TiO2 represents an intercalation-type anode material, Fe2O3 exhibits conversion reactions and ZnO expresses alloying during lithiation-delithiation processes. Importantly, all the composite thin-films have an intermixed structure at the atomic scale, as they are precisely prepared by the atomic layer deposition method. The electrochemical properties demonstrate that the composite thin-films show better performance, either higher capacities or better cycling retentions, than the individual constituent material (SnO2, TiO2, Fe2O3 or ZnO). Overall cycling stability improves to a great extent along with a slight increase in capacity with the addition of TiO2. The supplement of Fe2O3 in the SnO2–Fe2O3 composite thin-films moderately improves both capacity and retention, while the SnO2–ZnO composite electrodes demonstrate a good cyclability and stabilize at a relatively high capacity. The systematic investigation of synergistic effects on the different types (intercalation, conversion and alloying) of metal oxide composites is expected to provide guidance towards the development of composite anode materials for lithium-ion batteries.

Ultrathin Tin-Doped Titanium Oxide by Atomic Layer Deposition on a Mesoporous Substrate: Physical/Electronic Structure, Spectroelectrochemistry, and Interfacial Charge Transfer

“…While this report is narrowly focused on comparisons of Sn-doped TiO 2 to SnO 2 /TiO 2 core/shell materials, broader implications, interest, and influence can be derived from the work presented. SnO 2 –TiO 2 mixed oxides and interfaces are ubiquitous in a number of fields including dye-sensitized solar cells and DSPECs, ,− perovskite solar cells, batteries, , photocatalysis, ,− and gas-sensing technologies. , The TiO 2 interface with fluorine-doped tin oxide is especially prevalent in the aforementioned areas of study. The diffusion of Sn into TiO 2 has been demonstrated to occur from heat treatments during normal sample processing, − and thin interfacial mixed tin–titanium oxides should be of interest to researchers assessing charge transfer and separation at any general SnO 2 –TiO 2 interface.…”

An overview of the application of atomic layer deposition process for lithium‐ion based batteries

“…In another study, Zhao et al 149 examined an ALD of SnO 2 composite anodes for thin films in LIBs. This study exhaustively investigated the influence on electrochemical characteristics of thin films of SnO 2 when mixed with Fe 2 O 3 , TiO 2 , and ZnO.…”

High-performance Ti-doped ZnS thin film anode for lithium-ion batteries

“…The anode materials based on lithium storage mechanisms of conversion reaction or alloying reaction generally exhibit higher theoretical special capacities due to multielectron transfer during electrochemical reactions, which can be promising thin film anodes applied in lithium-ion microbatteries. Up till now, most of the reported papers focus on various metal oxide and Si-based thin film anodes, such as Cr 2 O 3 [3], MnO [4], WO 3 [5], Cu x O-TiO 2 (x=1, 2) [6], MoO 2 [7], SnO 2 [8], multilayer C/Si [9,10], sandwich-like Ti/Si/Ti [11], Ni-Si [12], Si (1−x) Ge x [13] and composite Si-O-C [14] thin films. However, for the dense thin film anodes with high specific capacity, the huge stress and the significant volume strain originated from repeated insertion/extraction of large amounts of Li + ions are difficult to mitigate without obvious change in electrode structure.…”