Keeyoung Jung

Sodium Ion Diffusion in Nasicon (Na3Zr2Si2PO12) Solid Electrolytes: Effects of Excess Sodium

The Na superionic conductor (aka Nasicon, Na1+xZr2SixP3-xO12, where 0 ≤ x ≤ 3) is one of the promising solid electrolyte materials used in advanced molten Na-based secondary batteries that typically operate at high temperature (over ∼270 °C). Nasicon provides a 3D diffusion network allowing the transport of the active Na-ion species (i.e., ionic conductor) while blocking the conduction of electrons (i.e., electronic insulator) between the anode and cathode compartments of cells. In this work, the standard Nasicon (Na3Zr2Si2PO12, bare sample) and 10 at% Na-excess Nasicon (Na3.3Zr2Si2PO12, Na-excess sample) solid electrolytes were synthesized using a solid-state sintering technique to elucidate the Na diffusion mechanism (i.e., grain diffusion or grain boundary diffusion) and the impacts of adding excess Na at relatively low and high temperatures. The structural, thermal, and ionic transport characterizations were conducted using various experimental tools including X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). In addition, an ab initio atomistic modeling study was carried out to computationally examine the detailed microstructures of Nasicon materials, as well as to support the experimental observations. Through this combination work comprising experimental and computational investigations, we show that the predominant mechanisms of Na-ion transport in the Nasicon structure are the grain boundary and the grain diffusion at low and high temperatures, respectively. Also, it was found that adding 10 at% excess Na could give rise to a substantial increase in the total conductivity (e.g., ∼1.2 × 10-1 S/cm at 300 °C) of Nasicon electrolytes resulting from the enlargement of the bottleneck areas in the Na diffusion channels of polycrystalline grains.

Kinetics aspects of initial stage thin γ-Al2O3 film formation on single crystalline β-NiAl (110)

The growth kinetics and mechanisms of thermally-grown thin γ-Al2O3 film at 650 °C in air on single-crystalline β-NiAl (110) was characterized via transmission electron microscopy, X-ray diffractometry, and thermo-gravimetric analyses. The oxidation kinetics as a function of thickness was gradually changing from an inverse-logarithmic to parabolic behavior across the “intermediate thickness regime” as the oxide thickness increases. To define the boundaries of the three thickness regimes, the high field approximation (x1) and Debye-Huckel length (LD) were determined using the existing theoretical kinetics models combined with experimentally measured data. All the relevant constants for each rate law at the three thickness regimes were also experimentally determined to quantitatively describe the initial stage growth kinetics.

Advanced Na-NiCl2 Battery Using Nickel-Coated Graphite with Core–Shell Microarchitecture

Stationary electric energy storage devices (rechargeable batteries) have gained increasing prominence due to great market needs, such as smoothing the fluctuation of renewable energy resources and supporting the reliability of the electric grid. With regard to raw materials availability, sodium-based batteries are better positioned than lithium batteries due to the abundant resource of sodium in Earths crust. However, the sodium-nickel chloride (Na-NiCl2) battery, one of the most attractive stationary battery technologies, is hindered from further market penetration by its high material cost (Ni cost) and fast material degradation at its high operating temperature. Here, we demonstrate the design of a core-shell microarchitecture, nickel-coated graphite, with a graphite core to maintain electrochemically active surface area and structural integrity of the electron percolation pathway while using 40% less Ni than conventional Na-NiCl2 batteries. An initial energy density of 133 Wh/kg (at ∼C/4) and energy efficiency of 94% are achieved at an intermediate temperature of 190 °C.

Effects of Ni particle morphology on cell performance of Na/NiCl 2 battery

Electrochemical reaction of Ni particle, one of active cathode materials in the Na/NiCl2 battery, occurs on the particle surface. The NiCl2 layer formed on the Ni particle surface during charging can disconnect the electron conduction path through Ni particles because the NiCl2 layer has very low conductivity. The morphology and size of Ni particles, therefore, need to be controlled to obtain high charge capacity and excellent cyclic retention. Effects of the Ni particle size on the cell performance were investigated using spherical Ni particles with diameters of 0.5 μm, 6 μm, and 50 μm. The charge capacities of the cells with spherical Ni particles increased when the Ni particle size becomes smaller because of their higher surface area but their charge capacities were significantly decreased with increasing cyclic tests owing to the disconnection of electron conduction path. The inferior cyclic retention of charge capacity was improved using reticular Ni particles which maintained the reliable connection for the electron conduction in the Na/NiCl2 battery. The charge capacity of the cell with the reticular Ni particles was higher than the cell with the small-sized spherical Ni particles approximately by 26% at 30th cycle.

Decorating β′′-alumina solid-state electrolytes with micron Pb spherical particles for improving Na wettability at lower temperatures

Overcoming poor physical contact is one of the most critical hurdles for batteries using solid-state electrolytes. In particular, overpotential from the liquid–solid interface between molten sodium and a β′′-alumina solid-state electrolyte (BASE) in a sodium–metal halide (Na–MH) battery could be enormous at lower operating temperatures (<200 °C) due to intrinsically poor Na wetting on the BASE surface. In this work, we describe how surface modification with lead acetate trihydrate (LAT) at different temperatures affects Na wetting on BASEs. LAT treatment conducted at a temperature of 400 °C (under a nitrogen gas atmosphere) shows significantly better Na wettability and battery performance than treatments at lower temperatures. The formation of a unique morphology—micron-sized Pb spherical particles—is observed on the surface of the BASE LAT treated at 400 °C. We also observed evolution of the Na wetting configuration from a Cassie drop, to a Wenzel drop, and finally to a sunny-side-up drop, which is clearly different from the Young–Dupre relation, with increasing the contact-angle measurement temperature. We conclude that formation of a thin Na penetrating film (sunny-side-up shape) on Pb-decorated BASEs is crucial for achieving good battery performance at lower operating temperatures. The new observations and fundamental understanding of Na wetting reported here will provide excellent guidance for improving cell performance in general and will further promote development of practical Na–MH battery technologies for large-scale energy storage applications.