In addition, the thermodynamics of the RDS with organic cations is unfavorable (Fig. ), i.e., the overpotential with organic cations is lower at a given electrode potential compared to those of alkali metal cations. were obtained for AEI-functionalized Au electrodes (denoted as M-P and M-Q for Au modified by PiperIon and QAPPT, respectively, with alkali metal cation M in Fig. ). The influence of hydration free energy in AEI-functionalized systems is attributed to both alkali cations in electrolytes and piperidinium cations of AEIs, which is defined as the equivalent ∆𝐺 /0& of mixed alkali and AEI systems calculated from 𝐸 * * (Fig. ) and 𝜆 !" ! 44 (Fig. ) and the results are summarized in Table . Importantly, the values of 𝐸 * * , 𝜆 and 𝑗 '%( in M-P and M-Q systems fit well on the 𝑗 '%( vs. |𝜎| # 𝑒𝑥𝑝(-0.38[∆𝐺 /0& [) and 𝐸 * * vs. 𝜆 plots (Fig. and Fig. ) based on alkali metal and organic cations (Fig. and Fig. ), suggesting that the mechanistic framework established with free cations remains valid in complex systems involving AEI and a mixture of multiple types of cations. |𝜎| and ∆𝐺 /0& of M-AEI systems generally are in between values of the alkali cations and quaternary ammonium cations (Fig. ). This is reasonable because the both PiperIon and QAPPT share the piperidinium cation, whose structure resembles those of tetraalkyl ammoniums. Among all M-AEI systems, K-Q exhibits the optimal 𝑗 !" (Fig. ), which could be attributed to the favorable tradeoff between |𝜎| and ∆𝐺 /0& .