posted on 2022-12-21, 16:04authored byValentin Sallaz, Sylvain Poulet, Jouhaiz Rouchou, Jean-Marc Boissel, Isabelle Chevalier, Frédéric Voiron, Yann Lamy, Sami Oukassi
In this work, nanometric (6–21 nm thick) amorphous
TiO2 films have been elaborated and characterized in liquid-
and
solid-state electrolyte (LiPON) half-cell architectures. For all considered
configurations, the volumetric capacity extracted from cyclic voltammetry
and galvanostatic cycling within the 0.5–3 V potential range
almost corresponds to the theoretical value expected for the LixTiO2 (x ∼
1) phase at low current density. Interestingly, TiO2 films
after LiPON deposition exhibited a thickness-independent constant
initial amount of intercalated lithium ions and did not require a
first activation process, in comparison to the liquid electrolyte
configuration. Furthermore, the cooperative effects of high Li+ intercalation kinetics and low interfacial charge transfer
resistance for a 6 nm TiO2 electrode led to an outstanding
surface capacity of 0.7 μAh cm–2 at 1 μA
cm–2 and high rate performance with 60% capacity
holding ratio at 1 mA cm–2, thus highlighting the
extrinsic pseudocapacitive behavior of our sub-10 nm TiO2 electrodes. A LixTiO2 6 nm/LiPON
100 nm/Pt hybrid micro-supercapacitor has been successfully fabricated,
achieving an operating voltage window of 3 V and a surface capacitance
of 94 μF cm–2 at 50 mV s–1. In addition, the device also exhibited 97% coulombic efficiency
upon cycling for 10,000 continuous charge–discharge cycles.
This work proposes an approach that allows us to adjust the Li-ion
storage properties of TiO2 by nanoengineering and gives
insights into the electrochemical performance enhancement by taking
advantage of the pseudocapacitance-assisted lithium storage mechanism.