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DOE OSTI2019

Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries

Enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against sulfide solid electrolytes. While protective oxide coating layers such as LiNbO 3 (LNO) have been proposed, its precise working mechanisms are still not fully understood. Existing literature attributes reductions in interfacial impedance growth to the coating's ability to prevent interfacial reactions. However, its true nature is more complex, with cathode interfacial reactions and electrolyte electrochemical decomposition occurring simultaneously, making it difficult to decouple each effect. Herein, we utilized various advanced characterization tools and first-principles calculations to probe the interfacial phenomenon between solid electrolyte Li6PS5Cl (LPSCl) and high-voltage cathode LiNi 0.85 Co 0.1 Al 0.05 O 2 (NCA). We segregated the effects of spontaneous reaction between LPSCl and NCA at the interface and quantified the intrinsic electrochemical decomposition of LPSCl during cell cycling. We report both experimental and computational results demonstrated improved thermodynamic stability between NCA and LPSCl after incorporation of the LNO coating. Additionally, we revealed the in situ passivation effect of LPSCl electrochemical decomposition. When combined, both these phenomena occurring at the first charge cycle result in a stabilized interface, enabling long cyclability of all-solid-state batteries.

25 ENERGY STORAGE↗

NASA NTRS2004

Whispering-Gallery-Mode Tunable Narrow-Band-Pass Filter

An experimental tunable, narrow-band-pass electro-optical filter is based on a whispering-gallery resonator. This device is a prototype of tunable filters needed for the further development of reconfigurable networking wavelength-division multiplexers and communication systems that utilize radio-frequency (more specifically, microwave) subcarrier signals on optical carrier signals. The characteristics of whispering-gallery resonators that make them attractive for such applications include high tuning speed, compactness, wide tuning range, low power consumption, and compatibility with single-mode optical fibers. In addition, relative to Fabry-Perot resonators, these devices offer advantages of greater robustness and lower cost. As described in several prior NASA Tech Briefs articles, a whispering-gallery resonator is a spheroidal, disk-like, or toroidal body made of a highly transparent material. It is so named because it is designed to exploit whispering-gallery electromagnetic modes, which are waveguide modes that propagate circumferentially and are concentrated in a narrow toroidal region centered on the equatorial plane and located near the outermost edge. The experimental whispering-gallery tunable filter (see figure) is made from a disk of Z-cut LiNbO3 of 4.8-mm diameter and 0.17-mm thickness. The perimeter of the disk is rounded to a radius of curvature of 100 m. Metal coats on the flat faces of the disk serve as electrodes for exploiting the electro-optical effect in LiNbO3 for tuning. There is no metal coat on the rounded perimeter region, where the whispering-gallery modes propagate. Light is coupled from an input optical fiber into the whispering-gallery modes by means of a diamond prism. Another diamond prism is used to couple light from the whispering-gallery modes to an output optical fiber. This device is designed and operated to exploit transverse magnetic (TM) whispering- gallery modes, rather than transverse electric (TE) modes because the resonance quality factors (Q values) of the TM modes are higher. If Q values were not of major concern, it would be better to use the TE modes because the electro-optical shifts of the TE modes are 3 times those of the TM modes.

Savchenkov, Anatoliy↗

NASA NTRS2006

Tunable Filter Made From Three Coupled WGM Resonators

A tunable third-order band-pass optical filter has been constructed as an assembly of three coupled, tunable, whispering-gallery-mode resonators similar to the one described in Whispering-Gallery-Mode Tunable Narrow-Band-Pass Filter (NPO-30896), NASA Tech Briefs, Vol. 28, No. 4 (April 2004), page 5a. This filter offers a combination of four characteristics that are desirable for potential applications in photonics: (1) wide real-time tunability accompanied by a high-order filter function, (2) narrowness of the passband, (3) relatively low loss between input and output coupling optical fibers, and (4) a sparse spectrum. In contrast, prior tunable band-pass optical filters have exhibited, at most, two of these four characteristics. As described in several prior NASA Tech Briefs articles, a whispering-gallery-mode (WGM) resonator is a spheroidal, disklike, or toroidal body made of a highly transparent material. It is so named because it is designed to exploit whispering-gallery electromagnetic modes, which are waveguide modes that propagate circumferentially and are concentrated in a narrow toroidal region centered on the equatorial plane and located near the outermost edge. Figure 1 depicts the optical layout of the present filter comprising an assembly of three coupled, tunable WGM resonators. Each WGM resonator is made from a disk of Z-cut LiNbO3 of 3.3-mm diameter and 50-m thickness. The perimeter of the disk is polished and rounded to a radius of curvature of 40 microns. The free spectral range of each WGM resonator is about 13.3 GHz. Gold coats on the flat faces of the disk serve as electrodes for exploiting the electro-optical effect in LiNbO3 for tuning. There is no metal coat on the rounded perimeter region, where the whispering-gallery modes propagate. Light is coupled from an input optical fiber into the whispering-gallery-modes of the first WGM resonator by means of a diamond prism. Another diamond prism is used to couple light from the whispering-gallery-modes of the third WGM resonator to an output optical fiber. The filter operates at a nominal wavelength of 1,550 nm and can be tuned over a frequency range of plus or minus 12 GHz by applying a potential in the range of plus or minus 150 V to the electrodes. The insertion loss (the loss between the input and output coupling optical fibers) was found to be repeatable at 6 dB. The resonance quality factor (Q) of the main sequence of resonator modes was found to be 5 x 10(exp 6), which corresponds to a bandwidth of 30 MHz. The filter can be shifted from one operating frequency to another within a tuning time less than or equal to 30 micro seconds. The transmission curve of the filter at frequencies near the middle of the passband closely approximates a theoretical third-order Butterworth filter profile, as shown in Figure 2.

Savchenkov, Anatoliy↗

NASA NTRS2001

All-Optical Micro Motors Based on Moving Gratings in Photosensitive Media

An all-optical micromotor with a rotor driven by a traveling wave of surface deformation of a stator being in contact with the rotor is being studied. Instead of an ultrasonic wave produced by an electrically driven piezoelectric actuator as in ultrasonic motors, the wave is a result of a photo-induced surface deformation of a photosensitive material produced by an incident radiation. A thin piezoelectric polymer will deform more easily LiNbO3 or metal when irradiated with light. The type of photosensitive material studied are piezoelectric polymers with and without coatings for connecting electrodes. In order to be considered as a possible candidate for micromotors, the material should exhibit surface deformation produced by a laser beam of the order of 10 microns. This is compared to the deformations produced by static holographic gratings studied in photorefractive crystals of LiNbO3 using high vertical resolution surface profilometer Dektak 3 and surface interferometer WYKO. An experimental setup showing the oscillations has been developed. The setup uses a chopped beam from an Argon ion laser to produce the deformation while a probe beam is reflected by the thin film into a fiber which is then detected on an oscilloscope. A ramp voltage signal generator will drive the piezoelectric film in another experiment to determine the resonance of the film. A current is generated when light is incident upon the film and this current can be measured. The reverse process has already been demonstrated in other piezoelectric actuators. Changing voltage, polarity, and frequency of the signal can easily generate vibrations similar to those when light is incident on the film. This can be compared to the effects of laser interaction with light absorbing fluids such as solutions of 2,9,16,23-Tetrakis(phenylthio)-29H, 31 H-phthalocyanine in chlorobenzene in capillary tubes, The possibility of using a liquid with the piezoelectric film would be a novel idea for a micromotor since the interaction of a single low power focused laser beam at 633 nm with such fluid produced an intensive circular motion.

Curley, M.↗