Bicontinuous solid–liquid electrolytes can combine
high
ionic conduction with high mechanical performance and provide an opportunity
to realize laminated structural batteries. Polymerization-induced
phase separation is a facile one pot reaction to make these electrolytes.
It is a versatile method but requires control over the complex interaction
of various parameters to tune the morphologies and properties of biphasic
electrolytes as it is highly system dependent. This study examines
the effects of thiol–ene chemistry and parameters such as porogen
type and content, thiol content, and salt concentration in the liquid
electrolyte, linking these factors to their curing behavior, morphology,
and multifunctional properties. We present a toolbox showing how different
morphologies and properties can be reached by changing these parameters.
The porogen type and a 10% increase in the porogen content affected
ionic conductivity by an order of magnitude. Thiol–ene chemistry
accelerates the curing process but reduces mechanical properties while
slightly increasing the ionic conductivities for small amounts of
thiol. The best negative structural electrode, containing carbon fibers
as negative electrode, showed increased rate capability compared to
previous work and a discharge capacity of 219 mA h g–1 at a current density of 18 mA g–1 (∼0.08C).
The results also indicate the potential of applying the concept of
highly concentrated electrolytes in structural electrodes to improve
safety and capacity retention while maintaining high specific capacities
and good rate capability. Interestingly, the increased ionic conductivity
of the electrolyte does not always imply an improved electrochemical
performance of the structural electrode.