Enthalpic and Entropic Contributions to Fast Lithium Ion Conduction in Solid-State Aqueous Polymer Electrolytes

Solid-state aqueous polymer electrolytes (SAPEs), a mixture of hydrophilic polymers and an appropriate amount of water, can produce high Li-ion conductivity while maintaining a solid state. Also, they can overcome the limitations of normal solid electrolytes. This study reports that the very high SAPE ionic conductivity (∼10 mS/cm at T = 298.15 K) originates from a low energy barrier (∼0.28 eV) closely correlated with water-filled ion passages in the medium. The low energy barrier is ascribed to a considerable reduction of the enthalpic barrier due to water addition despite a growth of the entropic barrier incurred by the negative nature of entropy change across water tubes. The extremely high ionic conductivity, coupled with an exceptionally low energy barrier, provides a unique advantage to SAPEs over conventional solid electrolytes

Enthalpic and Entropic Contributions to Fast Lithium Ion Conduction in Solid-State Aqueous Polymer Electrolytes

Solid-state aqueous polymer electrolytes (SAPEs), a mixture of hydrophilic polymers and an appropriate amount of water, can produce high Li-ion conductivity while maintaining a solid state. Also, they can overcome the limitations of normal solid electrolytes. This study reports that the very high SAPE ionic conductivity (∼10 mS/cm at T = 298.15 K) originates from a low energy barrier (∼0.28 eV) closely correlated with water-filled ion passages in the medium. The low energy barrier is ascribed to a considerable reduction of the enthalpic barrier due to water addition despite a growth of the entropic barrier incurred by the negative nature of entropy change across water tubes. The extremely high ionic conductivity, coupled with an exceptionally low energy barrier, provides a unique advantage to SAPEs over conventional solid electrolytes

Electrochemistry at the Edge of a Single Graphene Layer in a Nanopore

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al₂O₃ dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to a unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 10⁴ A/cm². The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices