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NASA NTRS2018

Integrated Computational-Experimental Development of Lithium-Air Batteries for Electric Aircraft

The primary obstacle to enable NASA's vision of Green Aviation is the extraordinary energy storage requirements for electric aircraft. Significant advances in high energy, rechargeable, safe batteries are required to enable electric aviation. Boeing's SUGAR and NASA studies have identified 400 Wh/kg as the threshold energy density for general aviation and 750 Wh/kg for commercial regional air service. State of the Art Lithium Ion Battery (LIB) technology currently has a density of 200 Wh/kg and is expected to plateau at 300 Wh/kg due to fundamental chemistry limitations making it unsuitable for future electric aircraft. Additional demanding requirements include high power, rechargeability, and high safety. Such battery technology does not currently exist. The recent considerable activity in battery research (DOE, Tesla Gigafactory, etc) overwhelmingly has been geared towards reducing cost and improving safety of LIB technology in order to promote the adoption of electric automobiles; and thus it is expected to have little impact on electric aviation development. New battery materials will be needed for the "Beyond Li Ion" (BLI) technologies required for high energy, safe electric aviation. Li-Air batteries have the highest known theoretical energy density (3400 Wh/kg) and therefore and if realized promises to transform the global transportation system. These high energy batteries have the potential to meet the energy storage challenges of current and future NASA aeronautics and space missions in addition to many terrestrial transportation applications as well. However, this technology requires significant components development and integration, as it is currently unable to achieve aircraft requirements. The objective of this project is to leverage modern computational materials methods combined with battery multiphysics tools to develop radically advanced compatible cathode and electrolyte materials, build several Li-Air cells, and flight-demonstrate the corresponding Li-Air battery packs. A significant problem for current Lithium-Air batteries is large scale decomposition of the battery electrolyte during operation leading to battery failure after a handful of charge/discharge cycles. Therefore, development of large scale, ultra-high energy, rechargeable, and safe Lithium-Air batteries require highly stable electrolytes that are resistant to decomposition under operating conditions. A NASA-based cross-organizational "dream team" of high-powered experts combined integrated supercomputer modeling, fundamental chemistry analysis, advanced material science, and battery cell development to tackle this very challenging, multidisciplinary problem. The ultimate goal for the team is to develop an integrated experimental/computational infrastructure to produce a reliable predictive capability for the selection of optimal components, their fabrication parameters, and "design rules" of novel cell components for advanced ultra-high energy batteries that can meet energy storage challenges of NASA missions and many terrestrial transportation applications.

Li-air battery↗

NASA NTRS2015

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

cathodes↗

NASA NTRS2018

Exploring Li-Air Batteries for High Specific Energy and High Power Applications: A Simulation Study

Commercialization of lithium-air batteries face many challenges, such as electrolyte decomposition, short cycle life, low energy efficiency, low power density, etc. However, commercialization of Li-air batteries for mass sensitive applications such as electric vehicles, portable power source, and drones is more challenging due to additional constraints of safety, electrolyte evaporation, high specific energy requirements, and reliable discharge times. In this presentation, we will present our finite element simulation results comparing Li-O2 and Li-air batteries using power density, energy density, specific power, and discharge times as metrics to evaluate different electrolytes and electrode geometry to reduce total mass and maximize discharge current. We use a finite element model and a discharge product model developed in which is based on porous electrode and concentrated electrolyte theories and the discharge product is modeled using quantum tunneling; for reaction kinetics and oxygen diffusion, an improved model was used. The electrolyte properties such as ion conductivity and ion diffusion were obtained from Molecular Dynamics (MD) simulations while the other parameters for the finite element model were calibrated to match experiments at high discharge current densities (>1.5 mA/cm2). The mass densities of different electrolytes were computed using MD simulations as well. For this presentation, we examine the practical electrochemical mass of a system at different current ratings, the sensitivity of mass to the use of ambient air as compared to pure oxygen as well as the electrolyte, which affects maximum current density and the total mass associated with the electrolyte (which includes the mass of additional components), and, the optimization of battery geometry for total discharge time, average discharge voltage, maximum discharge current, and minimum electrochemical mass.

Mehta, M.↗

NASA NTRS2019

A Multi-Physics Study on High-Specific Power Li-O2 Batteries for Electric Aircraft

Commercialization of lithium-air batteries faces many challenges, such as electrolyte decomposition, short cycle life, low energy and power density, etc. However, commercialization of Li-O2 batteries for aeronautics is much more challenging due to additional safety constraints on cyclability and performance (high specific power and specific energy). For this presentation, we will discuss inter-related aspects of physics-based modeling of a pack: cell and battery model calibration. In addition, we will evaluate and present optimal battery designs for high discharge current density, high discharge time, and low battery mass using simulation-based optimization.The Finite Element Model (FEM) used to simulate a Li-O2 cell is based on the work of Bevara [1]. The different aspects of the model are based on: porous electrode theory and concentrated electrolyte theory; quantum tunneling model for the resistance of conformal layer of discharge product (Li2O2) [1]; Butler-Volmer kinetics for electrochemical reaction; Fick's diffusion for oxygen transport; and an oxygen dissolution model is applied at the air/electrolyte interface [2]. The electrolyte properties such as ion conductivity, ion diffusion, oxygen diffusion, and mass density of the electrolyte were taken from Molecular Dynamics (MD) simulations [3]; while the other model parameters, which includes mass of cell components, were calibrated to match experiments at high discharge current densities. The cell mass includes the anode, cathode, separator, electrolyte, and other components (such as current collector). This calibrated model is used to perform parametric studies on cathode thickness, porosity, tortuosity, carbon particle size, electrolyte transport and material properties, partial pressure of oxygen, discharge time, and discharge current density to study optimal designs for high specific power and energy. References:1. Bevara, V. & Andrei, P. (2014), J. Electrochem. Soc. 161 (14), A2068-A2079.2.Mehta, M. & Andrei, P. (2015), J. Power Sources. 286, 299-308.3.Liyana-Arachchi, T.; Haskins, J.; Burke, C.; Diederichsen, K.; McCloskey, B.; & Lawson, J. (2018), J. Phys. Chem. B. 122 (36), 8548 - 8559.4.Choi, W.; Kikumoto, H.; Choudhary, R. & Ooka, R. (2018), Applied Energy, 209, 306-321.

Mehta, Mohit↗

NASA NTRSDate not supplied

Probing Model Sensitivity in Discharge Characteristics for a Li-O2 Battery using Uncertainty Quantification

For this presentation, we looked into using uncertainty quantification to understand the uncertainty in model parameters in predicting voltage and time response of a lithium-air battery.

Lithium-air↗

NASA NTRS2019

Novel Electrolytes for Use in Li-Air Batteries for NASA Electric Aircraft

Li-Air batteries are a unique fit for electric aircraft due to their high theoretical energy densities and their potential to leverage on-board oxygen systems. The electrolyte and cathode are the limiting factors for advancing this technology. We are investigating novel "electrolyte and cathode engineering" concepts to enable Li-Air batteries with high practical energy densities, rechargeability and safety. New stable electrolytes and cathodes are being designed and fabricated for Li-Air batteries. An array of various electrolytes were screened and analyzed using NMR and DEMS analysis techniques to understand the fundamental decomposition mechanisms at the cathode surface and within the porous polymer separator. (NMR) spectroscopy has yielded mechanistic insight into decomposition pathway, which is vital to the development of future stable electrolyte candidates. Thus far, five new electrolytes have been screened with 2 showing promising results.

Li-Air↗

NASA NTRS2003

Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

Future NASA and Air Force missions require reliable and safe sources of energy with high specific energy and energy density that can provide thousands of charge-discharge cycles at more than 40% depth- of-discharge and that can operate at low temperatures. All solid-state batteries have substantial advantages with respect to stability, energy density, storage fife and cyclability. Among all solid-state batteries, those with flexible polymer electrolytes offer substantial advantages in cell dimensionality and commensurability, low temperature operation and thin film design. The above considerations suggest that lithium-polymer electrolyte systems are promising for high energy density batteries and should be the systems of choice for NASA and US Air Force applications. Polyelectrolytes (single ion conductors) are among most promising avenues for achieving a major breakthrough 'in the applicability of polymer- based electrolyte systems. Their major advantages include unit transference number for the cation, reduced cell polarization, minimal salt precipitation, and favorable electrolyte stability at interfaces. Our research is focused on synthesis, modeling and cell testing of single ion carriers, polyelectrolytes. During the first year of this project we attempted the synthesis of two polyelectrolytes. The synthesis of the first one, the poly(ethyleneoxide methoxy acrylateco-lithium 1,1,2-trifluorobutanesulfonate acrylate, was attempted few times and it was unsuccessful. We followed the synthetic route described by Cowie and Spence. The yield was extremely low and the final product could not be separated from the impurities. The synthesis of this polyelectrolyte is not described in this report. The second polyelectrolyte, comb polysiloxane polyelectrolyte containing oligoether and perfluoroether sidechains, was synthesized in sufficient quantity to study the range of properties such as thermal stability, Li- ion- conductivity and stability toward lithium metal. Also, the batteries containing this polyelectrolyte were assembled and tested. The results are detailed below. The synthesis of another polyelectrolyte similar to polysiloxane polyelectrolyte has been started, however, the synthesis was not completed due to termination of the project.

Shriver, D. F.↗

NASA NTRS2014

Lithium-Air Cell Development

Lithium-air (Li-air) primary batteries have a theoretical specific capacity of 11,400 Wh/kg, the highest of any common metal-air system. NASA is developing Li-air technology for a Mobile Oxygen Concentrator for Spacecraft Emergencies, an application which requires an extremely lightweight primary battery that can discharge over 24 hours continuously. Several vendors were funded through the NASA SBIR program to develop Li-air technology to fulfill the requirements of this application. New catalysts and carbon cathode structures were developed to enhance the oxygen reduction reaction and increase surface area to improve cell performance. Techniques to stabilize the lithium metal anode surface were explored. Experimental results for prototype laboratory cells are given. Projections are made for the performance of hypothetical cells constructed from the materials that were developed.

Lithium-air↗

NASA NTRS2000

Prototype Lithium-Ion Battery Developed for Mars 2001 Lander

In fiscal year 1997, NASA, the Jet Propulsion Laboratory, and the U.S. Air Force established a joint program to competitively develop high-power, rechargeable lithium-ion battery technology for aerospace applications. The goal was to address Department of Defense and NASA requirements not met by commercial battery developments. Under this program, contracts have been awarded to Yardney Technical Products, Eagle- Picher Technologies, LLC, BlueStar Advanced Technology Corporation, and SAFT America, Inc., to develop cylindrical and prismatic cell and battery systems for a variety of NASA and U.S. Air Force applications. The battery systems being developed range from low-capacity (7 to 20 A-hr) and low-voltage (14 to 28 V) systems for planetary landers and rovers to systems for aircraft that require up to 270 V and for Unmanned Aerial Vehicles that require capacities up to 200 A-hr. Low-Earth-orbit and geosynchronousorbit spacecraft pose additional challenges to system operation with long cycle life (>30,000 cycles) and long calendar life (>10 years), respectively.

Manzo, Michelle A.↗

NASA NTRS2019

LiON: Lithium Oxygen Batteries for NASA Electric Aircraft

Li-Air batteries are a unique fit for electric aircraft due to their high theoretical energy densities and their potential to leverage on-board oxygen systems. Electrolytes are the limiting factor for advancing this technology. We will investigate novel "electrolyte engineering" concepts to enable Li-Air batteries with high practical energy densities, rechargeability and safety. New stable electrolytes will be designed and fabricated for Li-Air batteries and tested in an electric flight. An unprecedented "Dream Team" of experts from NASA, DOE, academia and industry will tackle this problem.

Lawson, John↗

NASA NTRS1992

The NASA space power technology program

NASA has a broad technology program in the field of space power. This paper describes that program, including the roles and responsibilities of the various NASA field centers and major contractors. In the power source area, the paper discusses the SP-100 Space Nuclear Power Project, which has been under way for about seven years and is making substantial progress toward development of components for a 100-kilowatt power system that can be scaled to other sizes. This system is a candidate power source for nuclear electric propulsion, as well as for a power plant for a lunar base. In the energy storage area, the paper describes NASA's battery- and fuel-cell development programs. NASA is actively working on NiCd, NiH2, and lithium batteries. A status update is also given on a U.S. Air Force-sponsored program to develop a large (150 ampere-hour) lithium-thionyl chloride battery for the Centaur upper-stage launch vehicle. Finally, the area of power management and distribution (PMAD) is addressed, including power system components such as solid-state switches and power integrated circuits. Automated load management and other computer-controlled functions offer considerable payoffs. The state of the art in space power is described, along with NASA's medium- and long-term goals in the area.

Stephenson, R. Rhoads↗

NASA NTRS1968

Lithium anode

Lithium anodes for metal-air batteries

Toni, J.↗

NASA NTRS2007

The NASA "PERS" Program: Solid Polymer Electrolyte Development for Advanced Lithium-Based Batteries

In fiscal year 2000, The National Aeronautics and Space Administration (NASA) and the Air Force Research Laboratory (AFRL) established a collaborative effort to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The ultimate objective of this development program, which was referred to as the Polymer Energy Rechargeable System (PERS), was to establish a world-class technology capability and U.S. leadership in polymer-based battery technology for aerospace applications. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. Out of a total of 38 proposals received in response to a NASA Research Announcement (NRA) solicitation, 18 proposals (13 contracts and 5 grants) were selected for initial award to address these technical challenges. Brief summaries of technical approaches, results and accomplishments of the PERS Program development efforts are presented. With Agency support provided through FY 2004, the PERS Program efforts were concluded in 2005, as internal reorganizations and funding cuts resulted in shifting programmatic priorities within NASA. Technically, the PERS Program participants explored, to various degrees over the lifetime of the formal program, a variety of conceptual approaches for developing and demonstrating performance of a viable advanced solid polymer electrolyte possessing the desired attributes, as well as several participants addressing all components of an integrated cell configuration. Programmatically, the NASA PERS Program was very successful, even though the very challenging technical goals for achieving a viable solid polymer electrolyte material or the overall envisioned long-term, program objectives were not met due to funding reductions. The NASA PERS Program provided research opportunities and generated and disseminated a wealth of new scientific knowledge and technical competencies within the polymer electrolyte area.

Baldwin, Richard S.↗

NASA NTRS2021

Parametric Study of State-of-Charge for an Electric Aircraft in Urban Air Mobility

The envisioned concept of urban air mobility is anticipated to support passenger transportation, cargo delivery, and emergency services in major metropolitan areas with increasing autonomy levels in the future. Distributed electric propulsion powered electric vertical takeoff and landing aircraft are expected to enable urban air mobility. However, the low specific energy of onboard lithium-ion polymer batteries and wind conditions impose constraints on flight endurance. Therefore, to enable autonomous urban air mobility operations using electric aircraft, one of the critical steps from a safety and efficiency perspective is to understand how various operational and environmental conditions impact the state-of-charge of the onboard lithium-ion polymer batteries. This research performs a parametric study of the state-of-charge for a NASA-proposed conceptual multirotor aircraft flight in the urban environment. The parameters considered for the parametric analysis are cruise airspeed, cruise altitude, climb and descent profiles, wind conditions (wind magnitude, wind direction relative to the route, and wind magnitude uncertainty), and required time of arrival.

Urban Air Mobility↗

NASA NTRS2021

Parametric Study of State of Charge for an Electric Aircraft in Urban Air Mobility

Urban Air Mobility↗

NASA NTRS1990

The NASA research and technology program on batteries

The NASA research and technology program on batteries is being carried out within the Propulsion, Power and Energy Division (Code RP) of NASA's Office of Aeronautics, Exploration and Technology (OAET). The program includes development of high-performance, long-life, cost-effective primary and secondary (rechargeable) batteries. The NASA OAET battery program is being carried out at Lewis Research Center (LeRC) and the Jet Propulsion Laboratory (JPL). LeRC is focusing primarily on nickel-hydrogen batteries (both individual pressure vessel or IPV and bipolar). LeRC is also involved in a planned flight experiment to test a sodium-sulfur battery design. JPL is focusing primarily on lithium rechargeable batteries, having successfully transferred its lithium primary battery technology to the U.S. Air Force for use on the Centaur upper stage. Both LeRC and JPL are studying advanced battery concepts that offer even higher specific energies. The long-term goal is to achieve 100 Wh/kg.

Bennett, Gary L.↗

NASA NTRSDate not supplied

Ultrahigh Areal Capacity Holey Graphene Air Cathodes for Li-O2 and Li-CO2 Batteries

Advanced lithium (Li) batteries using gaseous cathode reactants such as oxygen (O2) and carbon dioxide (CO2)are attractive energy storage platforms because the gases are obtained externally and thus not accounted for in the total battery weight when fully charged.The discharge products at the cathode, typically Li2O2 for Li-O2 batteries and Li2CO3 for Li-CO2 batteries, are insoluble in the electrolyte.Therefore, in order for such batteries to function properly, an “air cathode”,which is a conductive scaffold within the battery cell,is required as a physical location for cathode electrochemical reactions to occur. Prior research has identified many carbon nanomaterials such as carbon nanotubes and graphene as viable choices for air cathode scaffold, while various metallic and metal-free catalytic systems integrated onto carbon-based air cathodes have been developed to improve the sluggish discharge and charge reactions. For future practical applications, the air cathode must exhibit a usable capacity per unit electrode area, or areal capacity, a critical parameter that has been largely overlooked so far in this field. In order to achieve high areal capacity, the air cathode must exhibit a sufficient amount of accessible void volume per unit electrode area while maintaining the conductive scaffold integrity during the entire electrochemical process. Here we present an ultrathick,holey graphene-based air cathode platform fabricated from a facile dry compression process that exhibits remarkable areal capacity values. Holey graphene is a carbon nanomaterial derived from graphene, but with nanometer sized holes through the nanosheet thickness.The presence of these holes enhances mass transport through electrode thickness and also enables the unique dry-press fabrication process that is not achievable using other carbon scaffold materials.The dry-pressed holey graphene air cathode platform is not only compatible with catalyst incorporation to improve battery reaction kinetics, but also allows for novel engineering of electrode architectures that is not achievable using conventional electrode fabrication approaches.The applications of such highly versatile, ultrahigh areal capacity air cathode platforms to both Li-O2 and Li-CO2 battery chemistries will be discussed.

Li-O2 batteries, Li-CO2 batteries, holey graphene,↗

NASA NTRSDate not supplied

Computationally Guided Development of Components for High Energy Density Solid-State Lithium-Sulfur Batteries

All electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The most challenging of these technical barriers to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria1. The performance metrics for eVTOL craft, such as specific energy, specific power, and safety, exceed those of electric automobiles by a factor of two to four. Current state-of-the-art (SOA) lithium-ion batteries are incapable of meeting the key performance criteria of energy and safety for eVTOL. Therefore, next generation advanced chemistries and designs must be developed to meet required performance metrics for electric aviation2. Beyond lithium-ion chemistries, such as lithium-sulfur, show promise in their high energy, while limitations exist in their power and cyclability due to low electrical conductivity and high intermediate solubility in organic liquid electrolytes. Several strategies to overcome the low electrical conductivity involve the use of selenium as a dopant in the active sulfur material, along with the incorporation of 2-dimensional electron-conducting holey-graphene to improve the composite cathodes electronic conductivity. Furthermore, combining this chemistry with a solid-electrolyte avoids the components’ dissolution issues3. However, the development of composite solid-state cathodes is non-trivial as several components must be intimately mixed so that the active component has sufficient access to both electrons and lithium ions to undergo full electrochemical conversion. Mathematical modeling of battery components can assist experimental design through a robust and rigorous combination of computational modeling techniques covering multiple length scales. The objective is to leverage modern computational materials methods combined with battery multiphysics tools to develop radically advanced compatible cathode and electrolyte materials, build and test solid state lithium-sulfur cells and packs. A NASA-based cross-organizational team of high-powered experts combined integrated computational predictive modeling, fundamental chemistry analysis, advanced material science, and battery cell development to tackle this very challenging, multidisciplinary problem. This presentation will show a multiscale computational modeling approach that has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM modeling targets the 1-10 µm scale structures and provides electromechanical and grain interactions for predictive design guidelines for the manufacturing of solid-state components. Parameters such as particle size and volume fraction of the constituent materials were modeled and experimentally fabricated to optimize electrochemical performance through improved microstructure design. Experimental feedback was provided through ionic and electronic conductivity assessment and structural analysis of developed materials and cell components.

battery↗