Engineering Papers⌕ Search

Engineering topics

Kozen, Alexander C.

Publications and source records attributed to Kozen, Alexander C..

Chemical and Electrochemical Characterization of Hot–Pressed Li 6 PS 5 Cl Solid State Electrolyte: Operating Pressure–Invariant High Ionic Conductivity

Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li 6 PS 5 X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10 –2 S cm –1 ) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250°C. Furthermore, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa.

25 ENERGY STORAGE↗

Nanoscale Li, Na, and K ion-conducting polyphosphazenes by atomic layer deposition

A key trailblazer in the development of thin-film solid-state electrolytes has been lithium phosphorous oxynitride (LiPON), the success of which has led to recent progress in thin-film ion conductors. Here we compare the structural, electrochemical, and processing parameters between previously published LiPON and NaPON ALD processes with a novel ALD process for the K analogue potassium phosphorous oxynitride (KPON). In each ALD process, alkali tert-butoxides and diethylphosphoramidate are used as precursors. To understand the ALD surface reactions, this work proposes a reaction mechanism determined by in-operando mass spectrometry for the LiPON process as key to understanding the characteristics of the APON (A = Li, Na, K) family. As expected, NaPON and LiPON share similar reaction mechanisms as their structures are strikingly similar. KPON, however, exhibits similar ALD process parameters but the resulting film composition is quite different, showing little nitrogen incorporation and more closely resembling a phosphate glass. Due to the profound difference in structure, KPON likely undergoes an entirely different reaction mechanism. Furthermore, this paper presents a comprehensive summary of ALD ion conducting APON films as well as a perspective that highlights the versatility of ALD chemistries as a tool for the development of novel thin film ion-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Room temperature plasma-etching and surface passivation of far-ultraviolet Al mirrors using electron beam generated plasmas

The development of optical systems operating in the far ultraviolet range (FUV, λ=100-200 nm) is limited by the efficiency of passivated aluminum (Al) mirrors. Although it is presently possible to obtain high-reflectivity FUV mirrors through physical vapor deposition, the process involves deposition with substrates at high temperatures, which is technically challenging for large optical elements. A novel passivation procedure for bare Al mirrors is reported. The treatment consisted of using a low-temperature electron-beam generated plasma produced in a gas mixture of Ar and SF6 to etch away the native oxide layer from the Al film, while simultaneously promoting the generation of a thin aluminum tri-fluoride (AlF3) layer on the Al surface. In the first section we analyze the effect of varying both ion energy and SF6 concentration on the FUV reflectance, thickness, composition, and surface morphology of the resulting AlF3 protective layers. In the second section, the reflectivity of samples is optimized at selected important FUV wavelengths for astronomical observations. Notably, samples attained state-of-the-art reflectances of 75% at 108.5 nm (He Lyman γ), 91% at 121.6 nm (H Lyman α), 90% at 130.4 nm (OI), and of 95% at 155.0 nm (C IV). The stability over time of these passivated mirrors is also investigated.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Protection layers for metal anodes

A protection layer is formed on a highly-reactive substantially-pure metal anode to a thickness of between 1 nm and 200 nm, inclusive, using atomic layer deposition (ALD). The ALD protection layer allows the conduction of ions of the metal of the anode therethrough but suppresses electron transport therethrough. The ALD protection layer may also be effective to inhibit passage of air and/or water therethrough. The ALD protection layer can allow more relaxed purity requirements for subsequent battery assembly, electrolyte specifications, and/or cathode gas purity. Fabrication methods for the protection layers, protected metal anodes, and systems and devices incorporating such protected metal anodes are also disclosed herein.

Kozen, Alexander C.↗

E-Beam Generated Plasma Etching for Developing High-Reflectance Mirrors for Far-Ultraviolet Astronomical Instrument Applications

Astronomical space telescopes to study astrophysical phenomena from the far-ultraviolet (FUV) to the near infrared (NIR) will require mirror coatings with high reflectance over this entire spectral region. While coatings for the optical and NIR part of the spectrum are fairly well developed with proven performance, the FUV presents significant challenges. The U.S. Naval Research Laboratory (NRL) has developed a processing system based on an electron beam-generated plasma that provides for controlled fluorination and/or etching of surfaces with near monolayer precision and minimal changes to surface morphology. In this paper, we report recent results of samples treated in the NRL Large Area Plasma Processing System (LAPPS) where restoration of the high intrinsic reflectance in the FUV spectral range have been observed of aluminum (Al) mirrors protected with a magnesium di-fluoride (MgF2) overcoat. This paper will also extend these studies to other Al mirrors protected with aluminum tri-fluoride (AlF3) in order to realize the high intrinsic reflectance Al down to FUV wavelengths (100−200 nm), while still maintaining the high reflectance in the optical and NIR spectral regions. Laboratory test data and optical diagnostic techniques used to verify surface scattering and durability of selected coatings will be presented. Finally, we will discuss the scalability of the LAPPS etching process in order to realize these high-reflectivity coatings on mirror segments as large as those proposed for the Large Ultraviolet, Optical, and Infrared (LUVOIR) astronomical telescope system (1+meter class).

LUVOIR↗