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Nguyen, Han

Publications and source records attributed to Nguyen, Han.

Lithium and sodium superionic conductors

Presented are new, earth-abundant lithium superionic conductors, Li 3 Y(PS 4 ) 2 and Li 5 PS 4 Cl 2 , that emerged from a comprehensive screening of the Li—P—S and Li-M-P—S chemical spaces. Both candidates are derived from the relatively unexplored quaternary silver thiophosphates. One key enabler of this discovery is the development of a first-of-its-kind high-throughput first principles screening approach that can exclude candidates unlikely to satisfy the stringent Li+ conductivity requirements using a minimum of computational resources. Both candidates are predicted to be synthesizable, and are electronically insulating. Systems and methods according to present principles enable new, all-solid-state rechargeable lithium-ion batteries.

Zhu, Zhuoying↗

A free-standing lithium phosphorus oxynitride thin film electrolyte promotes uniformly dense lithium metal deposition with no external pressure

Lithium phosphorus oxynitride (LiPON) is an amorphous solid electrolyte that has been extensively studied over the last three decades. Despite the promise of pairing it with various electrode materials, LiPON’s rigidity and air sensitivity set limitations to understanding its intrinsic properties. We report a methodology to synthesize LiPON in a free-standing form that manifests remarkable flexibility and a Young’s modulus of ∼33 GPa. We use solid-state nuclear magnetic resonance and differential scanning calorimetry to quantitatively reveal the chemistry of the Li/LiPON interface and the presence of a well-defined LiPON glass-transition temperature of 207 °C. Combining interfacial stress and a gold seeding layer, our free-standing LiPON shows a uniformly dense deposition of lithium metal without the aid of external pressure. This free-standing LiPON film offers opportunities to study fundamental properties of LiPON for interface engineering for solid-state batteries.

25 ENERGY STORAGE↗

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na 3-x Y 1-x Zr x Cl 6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na + ) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10 –5 S cm –1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl 6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO 2 + NYZC composite cathode, Na 3 PS 4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room emperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.

99 GENERAL AND MISCELLANEOUS↗

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↗

Elucidating Reversible Electrochemical Redox of Li 6 PS 5 Cl Solid Electrolyte

Sulfide-based solid electrolytes are promising candidates for all solid-state batteries (ASSBs) due to their high ionic conductivity and ease of processability. However, their narrow electrochemical stability window causes undesirable electrolyte decomposition. Existing literature on Li-ion ASSBs report an irreversible nature of such decompositions, while Li–S ASSBs show evidence of some reversibility. Here, we explain these observations by investigating the redox mechanism of argyrodite Li 6 PS 5 Cl at various chemical potentials. We found that Li–In | Li 6 PS 5 Cl | Li 6 PS 5 Cl–C half-cells can be cycled reversibly, delivering capacities of 965 mAh g –1 for the electrolyte itself. During charging, Li 6 PS 5 Cl forms oxidized products of sulfur (S) and phosphorus pentasulfide (P 2 S 5 ), while during discharge, these products are first reduced to a Li 3 PS 4 intermediate before forming lithium sulfide (Li 2 S) and lithium phosphide (Li 3 P). Lastly, we quantified the relative contributions of the products toward cell impedance and proposed a strategy to reduce electrolyte decomposition and increase cell Coulombic efficiency.

25 ENERGY STORAGE↗

Correction to Insights into the Performance Limits of the Li 7 P 3 S 11 Superionic Conductor: A Combined First-Principles and Experimental Study

Page 7847. The authors express regret that one mistake was made in their paper. In Figure 4b, the “Endo-Exo” direction was supposed to be reversed. When the orientation is corrected, T g is assigned an endothermic process and T c is assigned an exothermic process. A corrected Figure 4b (along with its original caption) is provided. Although the error was present, it does not affect the interpretation and conclusions of the manuscript as a whole. The authors apologize for any inconvenience this may have caused the readers.

36 MATERIALS SCIENCE↗

Development and Validation of a Pressurization System Model for a Crossfeed Subscale Water Test Article

A pressurization system model was developed for a crossfeed subscale water test article using the EASY5 modeling software. The model consisted of an integrated tank pressurization and pressurization line model. The tank model was developed using the general purpose library, while the line model was assembled from the gas dynamic library. The pressurization system model was correlated to water test data obtained from nine test runs conducted on the crossfeed subscale test article. The model was first correlated to a representative test run and frozen. The correlated model was then used to predict the tank pressures and compared with the test data for eight other runs. The model prediction showed excellent agreement with the test data, allowing it to be used in a later study to analyze the pressurization system performance of a full-scale bimese vehicle with cryogenic propellants.

Nguyen, Han↗

Pressurization System Modeling for a Generic Bimese Two- Stage-to-Orbit Reusable Launch Vehicle

A pressurization system model was developed for a generic bimese Two-Stage-to-orbit Reusable Launch Vehicle using a cross-feed system and operating with densified propellants. The model was based on the pressurization system model for a crossfeed subscale water test article and was validated with test data obtained from the test article. The model consists of the liquid oxygen and liquid hydrogen pressurization models, each made up of two submodels, Booster and Orbiter tank pressurization models. The tanks are controlled within a 0.2-psi band and pressurized on the ground with ambient helium and autogenously in flight with gaseous oxygen and gaseous hydrogen. A 15-psi pressure difference is maintained between the Booster and Orbiter tanks to ensure crossfeed check valve closure before Booster separation. The analysis uses an ascent trajectory generated for a generic bimese vehicle and a tank configuration based on the Space Shuttle External Tank. It determines the flow rates required to pressurize the tanks on the ground and in flight, and demonstrates the model's capability to analyze the pressurization system performance of a full-scale bimese vehicle with densified propellants.

Mazurkivich, Pete↗

Testing of a Spray-Bar Zero Gravity Cryogenic Vent System for Upper Stages

The capability to vent in zero gravity without resettling is a fundamental technology need that involves practically all uses of subcritical cryogenics in space. Venting without resettling would extend cryogenic orbital transfer vehicle capabilities. However, the lack of definition regarding liquid/ullage orientation coupled with the somewhat random nature of the thermal stratification and resulting pressure rise rates, lead to significant technical challenges. Typically a zero gravity vent concept, termed a thermodynamic vent system (TVS), consists of a tank mixer to destratify the propellant, combined with a Joule- Thomson (J-T) valve to extract then-nal energy from the propellant. In a cooperative effort, Marshall Space Flight Center's (MSFC's) Multipurpose Hydrogen Test Bed (N4HTB) was used to test a unique "spray bar" TVS system developed by Boeing. A schematic of this system is included in Figure 1. The system consists of a recirculation pump, a parallel flow concentric tube, heat exchanger, and a spray bar positioned close to the longitudinal axis of the tank. In the mixing mode, the recirculation pump withdraws liquid from the tank and sprays it radially into the tank liquid, ullage, and exposed tank surfaces. When energy extraction is required, a small portion of the recirculated liquid is passed sequentially through the J-T expansion valve, the spray bar heat exchanger element, and is vented overboard. The vented vapor cools the circulated bulk fluid, thereby removing thermal energy and reducing tank pressure. Figure 2 is a plot of ullage pressure (P4) and liquid vapor pressure (PSAI) versus time. The pump operates alone, cycling on and off, to destratify the tank liquid and ullage until the liquid vapor pressure reaches the lower set point. At that point, the J-T valve begins to cycle on and off with the pump. Thus, for short duration missions, only the mixer may operate, thus minimizing or even eliminating boil-off losses. The primary advantage of the spray bar configuration is that pressure reduction is achieved independent of liquid and vapor location, thereby enhancing the applicability of normal gravity test data to zero gravity conditions. The in-tank components are minimized with the proposed TVS design. Because the recirculation pump is external to the tank, no electrical power penetration of the tank is required for pump or valve operation. This is especially desirable for L02 tanks since the presence of an electrical ignition source in oxygen represents a critical failure mode. Also, since the critical components (pump, motor, valve, orifice) are external to the tank, system checkout and ground servicing/replacement are easier. For zero-g operation, component replacement external to the tank may be a significant benefit. In addition to satisfying the zero g TVS design objectives, the TVS concept tested offers additional benefits to the integrated subcritical cryogenic storage and launch system.

Lak, Tibor↗

Zero-G Thermodynamic Venting System (TVS) Performance Prediction Program

This report documents the Zero-g Thermodynamic Venting System (TVS) performance prediction computer program. The zero-g TVS is a device that destratifies and rejects environmentally induced zero-g thermal gradients in the LH2 storage transfer system. A recirculation pump and spray injection manifold recirculates liquid throughout the length of the tank thereby destratifying both the ullage gas and liquid bulk. Heat rejection is accomplished by the opening of the TVS control valve which allows a small flow rate to expand to a low pressure thereby producing a low temperature heat sink which is used to absorb heat from the recirculating liquid flow. The program was written in FORTRAN 77 language on the HP-9000 and IBM PC computers. It can be run on various platforms with a FORTRAN compiler.

Nguyen, Han↗

Design and integrated operation of an innovative thermodynamic vent system concept

A unique zero-g thermodynamic vent system (TVS) is being developed by NASA's Marshall Space Flight Center (MSFC) and Rockwell International to meet cryogenic propellant management requirements for future space missions. The design is highly innovative in that it integrates the functions of a spray-bar tank mixer and a TVS. This concept not only satisfies the requirement for efficient tank mixing and zero-g venting but also accommodates thermal conditioning requirements for other components (e.g., engine feed lines, turbopumps, and liquid acquisition devices). In addition, operations can be extended to accomplish tank chill-down, no-vent fill, and emergency venting during zero-g propellant transfer. This paper describes the system performance characterization and future test activities that are part of MSFC's Multipurpose Hydrogen Test Bed (MHTB) program. The testing will demonstrate the feasibility and merit of the design, and serve as a proof-of-concept development activity.

Fazah, Michel M.↗