The ratio of hydration numbers from bulk to pore could serves as an indicator of ion hydration/desolvation ability at varying concentrations. For micropores, the ratios were 14.66, 12.93, 12.25, 8.39, and 6.20, while for mesopores, they were 5.27, 4.57, 2.94, 1.83, and 1.20 at 0.5, 1, 5, 10, 15, and 20 mol•kg⁻¹, respectively. The monotonic decline in these values indicates that with increasing concentration, ion pairs stabilize partially dehydrated states, as ions bound in pairs are less likely to disrupt their hydration shells (Scheme 1b). Consequently, the extent of ion desolvation is governed by the strength and type of ion pairing, with stronger pair interactions promoting reduced solvation and limiting further desolvation within pores. As a result, electrosorption dynamics shift, with high concentrations leading to less structured ion sorption and potentially reduced charge storage efficiency. The strong hydration and structuring effects of cosmotropic Li⁺ ions are counteracted by the chaotropic nature of TFSI⁻ ions, leading to a complex interplay that influences the overall performance of the electrolyte in electrochemical capacitors. Hence, moderate concentrations, such as 5 and 10 mol•kg⁻¹, demonstrated better charge screening performance. Except for CEDL from 𝜎 𝑏𝑢𝑙𝑘 ′′ , the Debye length minima, CEDL from 𝜎 pore ′′ , differential capacitance from CVs, and other theoretical CEDL values were higher at 10 mol•kg⁻¹. This is attributable to the higher desolvation number compared to 5 mol•kg⁻¹. In other words, up to 10 mol•kg⁻¹, the decreasing Debye length suggests strong hydration shells around Li⁺ ions, facilitating effective charge screening and enhancing electrosorption efficiency. Above 10 mol•kg⁻¹, the coexistence of intimate and aggregated ion pairs results in Bjerrum lengths of 2.5 and 3.5 nm for 15 and 20 mol•kg⁻¹, respectively, which are larger than the micropores (≤ 2 nm) (Figure ). This results in a smaller diffuse layer thickness in porous carbon, as shown in Figure , derived from the loss tangent plot (Method S9). To correlate the ion pairing and desolvation phenomena with the EDL charging rate, we derived the time-constant (𝜏 EDL ) from the characteristic frequency positions at the maximum 𝜎 bulk ′′ and 𝜎 pore ′′ using equation 18, as shown in Figure and listed in Table . describe the ion diffusivity ratio from bulk to in-pore as ion transport resistance. Similarly, the 𝜏 EDL ratio of porous to non-porous electrodes can be considered as an indicator of EDL charging readiness. The peak 𝜏 EDL porous/𝜏 EDL non-porous at 10 mol•kg⁻¹ suggests the highest charge accumulation, signifying the formation of a compact and efficient EDL at this concentration. These findings indicate that a 10 mol•kg⁻¹ concentration is better suited for maximizing EDL capacitance and achieving higher energy density. Conversely, the timeconstants derived from the maximum imaginary conductivity, capacitance, power, and loss tangent (Table ) suggest that a 5 mol•kg⁻¹ concentration may be more favorable for faster EDL charge/discharge rates, resulting in higher power density (Method S10 and Figures S13).