The swelling mechanism is widely used to explain the response of ionic liquids (ILs) or poly(ionic liquid)s (PILs) to moisture. While a fairly broad consensus has been attained, there are still some phenomena that are not well explained. As a complement to the swelling mechanism, we systematically studied the free volume theory in the rapid response and recovery of PIL humidity performance. We chose poly(1-ethyl-3-vinylimidazolium bromide) (PIL-Br), poly(1-ethyl-3-vinylimidazolium tetrafluoroborate) (PIL-BF4) and poly(1-ethyl-3-vinylimidazolium bis(trifluoromethane sulfonimide)) (PIL-TFSI) as model materials and investigated the impact of PIL structure including anion type, film thickness and affinity to moisture on performance to obtain the humidity sensing mechanism for PILs based on free volume theory. Hence, we can combine free volume theory with the designed PIL structures and their affinity with moisture to obtain a high concentration of free ions in PIL sensing films. Furthermore, the PIL humidity sensors also show fast, substantial impedance changes with changing humidity for real-time monitoring of the human respiratory rate due to a fast response and recovery performance. Therefore, our findings develop a new perspective to understand the humidity performance of PILs based on free volume theory, resulting in fast response and recovery properties realized by the rational design of PIL sensing films.
Keywords: fast response and recovery; free-ion concentration; humidity sensing; poly(ionic liquid)s; respiratory rate monitoring.