After establishing that solvent exchange was successful, the electrochemical performance of LFP/Li metal cells containing the various gels was compared against each other and to the corresponding liquid systems. When comparing the liquid electrolyte cells (Figure ), a high cycle stability is found for all three electrolytes (~0.15% loss per cycle). As expected, the best rate capability is found for the PC electrolyte as the higher viscosity and/or lower lithium transference number of the DOL/DME and ILE electrolytes hinders ion conduction, lowering the system conductivity (Figure ). At lower currents, a worse columbic efficiency is identified, for the ILE cell, not seen for other electrolytes, which likely stems from the ILE instability with lithium metal. Depending on the trapped electrolyte, the performance of the gels can vary widely (Figure ). For the ionogel, a significant decrease in the rate capability is identified (Figure ). This likely stems from the ionic liquid interaction with charged species on the silica wall , essentially narrowing the pore for Li + transport. A similar decrease in the rate capability has been identified in other silica-based ionogel systems. However, comparing the PC gel to the neat liquid, an almost identical electrochemical response is identified (Figure ), indicating the silica matrix does not significantly hinder lithium transport in the carbonate-based system. The DOL/DME system shows similar results as the liquid, though a significant decrease in the cycle stability at 1C occurs that is not seen in the liquid system (Figure ). This instability could stem from the identified poly-DOL species that may hinder Li + movement at higher rates by obstructing the structure, making it inaccessible to further Li + transport. This could explain the increased capacity loss seen even after reducing the current. The electrochemical performance of the different gels correlates well to the initial polarization and cell impedance, where the gel resistance decreases as the liquid component transitions from ILE to DOL/DME or PC (Figure ). This decrease in the gel resistance follows the measured conductivity trend and correlates to the expected solvents interaction with the silica matrix walls, as determined by the degree of hydrogen bonding. Similar to ionogels, we expect many of the exchanged systems fundamental characteristics, such as the Li + transference number, electrochemical stabilility window, and SEI products, to be the same as the base liquid systems. Further study is required into the impact entrappment in the silica matrix has on the formation and growth of Li dendrites for these systems. To further illustrate the advantages of our solvent exchange process, the electrochemical performance was evaluated at different temperatures and in AM architectures. While ionogels are known to be hindered by their lower conductivity and transference number, their high thermal and electrochemical stability aligns well to high temperature applications. To showcase this high-temperature performance, electrochemical cycling of a LFP/Ionogel/Li cell was performed at 100 o C. Typically, these temperatures are unobtainable for most liquid or polymer-based electrolytes due to the safety hazards associated with solvent flammability. By increasing the temperature, the electrolytic and charge transfer resistance notably decreases (Figure ), which enables achievement of stable capacities over 160 mAh g -1 at 1C, six-times higher than the room temperature performance (Figure ). Further, use of the ionogel improved the columbic efficiency of the cell, in comparison to the liquid cell (Figure ), likely by suppressing adverse reactions at the lithium anode. While able to be cycled to high temperatures, the propensity for ionic liquids to solidify at temperatures close to 0 o C make them incompatible for many low temperature applications (Figure ). As such, the DOL/DME system, which has shown some success at low temperatures , was explored at -40 o C to evaluate the low temperature performance of an exchanged gel. Figure demonstrates reasonable capacities (95 mAh g -1 ) for the DOL/DME systems at low rates (C/20), with similar performance maintained between the gel and liquid cycled at higher currents (~60 mAh g -1 at C/5, Figure ). The multiple, identifiable plateaus in the liquid DOL/DME system likely stem from the electrolyte being frozen to different degrees. While the DOL/DME system has not been optimized for low temperature applications, it still demonstrates adequate performance especially when incorporated into the silica matrix. Further low-temperature improvement could be achieved through use of designer electrolytes, such as the all-fluorinated systems, which should be facilely incorporated into the silica matrix due to the affinity of fluorine to silica . In addition to its potential utility in traditional cast cells, the novelty of the electrolyte exchange is best exemplified in additively manufactured (AM) systems that cannot be readily fabricated with current solid electrolyte processes. To this end, a cell made using direct-inkwrite printing (Figure ), composed of an LFP/Ionogel/LTO AM stack, was exchanged with the 1M LiClO4 PC electrolyte and compared to the ionogel. An exemplary image of AM process of the IG electrolyte over a large area is shown in Figure . Exploring the electrochemical performance, Figure demonstrates that while reasonable capacities can be achieved for the carbonate gel (118 mAh g -1 at C/4), the ionogel system is severely limited (41 mAh g -1 at C/4) due to its low conduction and transference number. As with the cast electrodes, similar behavior is maintained between the base PC liquid and PC gel at lower rates while the ionogel behaved significantly worse than the base ILE. The loss of capacity over the extended cycling and lower capacity at higher rates for the gels in comparison to the base liquids likely stems from heterogeneity in the gel introduced by the unoptimized AM process. While the gels have a higher impedance than the base liquids (Figure ), the performance of the different AM cells correlate closer to the polarization displayed in the GVs (Figure ). The complete AM fabrication presents a route to create unique architectural and composition solid-state cells that are impractical with current methods while maintaining the properties dictated by the exchanged electrolyte. Noteworthy of ionogels, by controlling the assembly process, the preliminary solid electrolytes can be uniformly incorporated throughout each AM electrode before joining of the full cell, ensuring uniform access.