posted on 2022-01-26, 18:04authored bySheng Liu, Hongliang Zhang, Xin Zhang, Qiang Wang, Chengli Zhang, Ran Jiang, Junhua Gao, Lingyan Liang, Hongtao Cao
Multivalent chemistry has drawn extensive
research interests because
it provides intriguing benefits to develop beyond-lithium-ion electrochromic
and energy storage technologies. Among the multivalent candidates,
the aluminum (Al)-based electrolyte offers an attractive high capacity
for designing multivalent-ion electrochromic batteries and devices.
However, the understanding of complex electrochemical and mechanical
interactions of the electrode/electrolyte
interface during cycling is extremely limited. Herein, we develop
an Al3+-based half-cell that consisted of a WO3 thin film cathode, Al(ClO4)3-PC electrolyte,
and Au counter electrode. Electrochemical quartz crystal microbalance
(EQCM) observations suggest that there is a link between the interfacial
degradation of WO3/electrolyte and the formation of chelate-like
compounds in a high-concentration electrolyte environment. The intercalation/de-intercalation
of the Al3+ cations in WO3 electrodes was directly
evaluated through in situ real-time EQCM. As indicated by the results
of EQCM, the formation of chelate-like compounds leads to the irreversible
process of intercalation and de-intercalation in the WO3 thin film electrode and the instability of the solid electrolyte
interphase. The validated EQCM-based analysis provides a correlation
between solution concentration and cycle stability, which would be
expected to reveal new insights into the electrochemical and electrochromic
behavior in many other multivalent systems.