Design and Sintering of All-Solid-State Composite Cathodes with Tunable Mixed Conduction Properties via the Cold Sintering Process

Abstract

Electrodes for solid-state batteries require the conduction of both ions and electrons for extraction of the energy from the active material. In this study, we apply cold sintering to a model composite cathode system to study how low-temperature densification enables a degree of control over the mixed conducting properties of such systems. The model system contains the NASICON-structured Na₃V₂(PO₄)₃ (NVP) active material, NASICON-structured solid electrolyte (Na₃Zr₂Si₂PO₁₂, NZSP), and electron-conducting carbon nanofiber (CNF). Pellets of varying weight fractions of components were cold-sintered to greater than 90% of the theoretical density at 350-375 °C, a 360 MPa uniaxial pressure, and with a 3 h dwell time using sodium hydroxide as the transient sintering aid. The bulk conductivity of the diphasic composites was measured with impedance spectroscopy; the total conductivities of the composites are increased from 3.8 × 10^-8 S·cm^-1 (pure NVP) to 5.81 × 10^-6 S·cm^-1 (60 wt % NZSP) and 1.31 × 10^-5 S·cm^-1 (5 wt % CNF). Complimentary direct current polarization experiments demonstrate a rational modulation in transference number (τ) of the composites; τ of pure NVP = 0.966, 60 wt % NZSP = 0.995, and 5 wt % CNF = 0.116. Finally, all three materials are combined into triphasic composites to serve as solid-state cathodes in a half-cell configuration with a liquid electrolyte. Electrochemical activity of the active material is maintained, and the capacity/energy density is comparable to prior work.