Cycling mechanism of Li2MnO3: Li–CO2 batteries and commonality on oxygen redox in cathode materials
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25 ENERGY STORAGE↗
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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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A KMnO 4 -Generated Colloidal Electrolyte for Redox Mediation and Anode Protection in a Li–Air Battery
The rechargeable lithium-oxygen (Li-O 2 ) battery has the highest theoretical specific energy density of any rechargeable batteries and could transform energy storage systems if a practical device could be attained. However, among numerous challenges, which are all interconnected, are polarization due to sluggish kinetics, low cycle life, small capacity, and slow rates. Here, in this study, we report on use of KMnO 4 to generate a colloidal electrolyte made up of MnO 2 nanoparticles. The resulting electrolyte provides a redox mediator for reducing the charge potential and lithium anode protection to increase cycle life. This electrolyte in combination with a stable binary transition metal dichalcogenide alloy, Nb 0.5 Ta 0.5 S 2 , as the cathode enables the operation of a Li-O 2 battery at a current density of 1 mA center dot cm -2 and specific capacity ranging from 1000 to 10000 mA center dot h center dot g -1 (corresponding to 0.1-1 mA center dot h center dot cm -2 ) in a dry air environment with a cycle life of up to 150. This colloidal electrolyte provides a robust approach for advancing Li-air batteries.
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Mechanistic Study of the Li–Air Battery with a Co 3 O 4 Cathode and Dimethyl Sulfoxide Electrolyte
The lithium–air battery, a powerful competitor to replace the traditional lithium-ion battery, has attracted increasing attention due to its extremely high theoretical energy density. However, its development is limited by the cathode and electrolyte properties, which should include high stability, conductivity, and electrocatalytic properties in oxygen-rich environments. Here, we employ a systematic first-principles study of Li–O 2 discharge and charge reactions on the Co 3 O 4 -based cathode with the assistance of dimethyl sulfoxide (DMSO) electrolyte. The structure, stability, and electronic properties of different surface reconstructions of the Co 3 O 4 (100) facet are investigated. In addition, the mechanisms and thermodynamic overpotentials of multi-step reactions between Li + /e – and O 2 are provided, where lithium suboxide products (Li 2 O 2 or Li 3 O 2 ) are formed on the different Co 3 O 4 (100) terminations. The solvation shell of Li + components in explicit DMSO solvent is investigated through ab initio molecular dynamics simulations. In general, we find that the Co 3 O 4 (100)-O (oxidized) surface is the most stable one under standard conditions, and the stable Li + solvation structure is found in a tetrahedral Li(DMSO) 4 + shell in the DMSO-based electrolyte. Moreover, in the system of the Co 3 O 4 (100)-O cathode and DMSO electrolyte, the solution model pathway is energetically favorable for the Li–O 2 discharge reaction. It provides a low constant overpotential of 0.17 V during a long-term discharging process, thus causing the final toroid Li 2 O 2 formation on the cathode. During the charging process, an overpotential of 0.36 V is required to rapidly decompose Li 2 O 2 .
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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↗
Lithium superoxide encapsulated in a benzoquinone anion matrix
Lithium peroxide is the crucial storage material in lithium–air batteries. Understanding the redox properties of this salt is paramount toward improving the performance of this class of batteries. Lithium peroxide, upon exposure to p –benzoquinone (p–C 6 H 4 O 2 ) vapor, develops a deep blue color. This blue powder can be formally described as [Li 2 O 2 ] 0.3 • [LiO 2 ] 0.7 • {Li[p–C 6 H 4 O 2 ]} 0.7 , though spectroscopic characterization indicates a more nuanced structural speciation. Infrared, Raman, electron paramagnetic resonance, diffuse-reflectance ultraviolet-visible and X-ray absorption spectroscopy reveal that the lithium salt of the benzoquinone radical anion forms on the surface of the lithium peroxide, indicating the occurrence of electron and lithium ion transfer in the solid state. As a result, obligate lithium superoxide is formed and encapsulated in a shell of Li[p–C 6 H 4 O 2 ] with a core of Li 2 O 2 . Lithium superoxide has been proposed as a critical intermediate in the charge/discharge cycle of Li–air batteries, but has yet to be isolated, owing to instability. The results reported herein provide a snapshot of lithium peroxide/superoxide chemistry in the solid state with redox mediation.
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Computational Approaches for Li-O2 Battery Design
Threshold energy densities for general aviation electric aircraft are 400 Wh/kg with more ambitious air vehicles having significantly higher requirements. Li-O2 batteries, with the highest theoretical capacity, are one of the few “beyond Li-ion” chemistries that might satisfy the extraordinary specific capacity as well as specific power requirements of electric aircraft. However, side reactions at interfaces, in particular at the cathode, over the charge-discharge cycles result in very short cycle-life and dramatic reduction of capacity. Addressing these issues, in addition to others, are crucial for realizing practical, high performance Li-O2 batteries. In this talk, we discuss atomistic computational work to understand and mitigate some of the issues, including those at interfaces, that affect the Li-O2 electrochemistry. To start, we discuss the deposition mechanisms, both surface and solution based, of Li2O2 and their dependence on external potential. Next, we explore molten salt electrolytes as a stable alternative to organic electrolytes and approaches taken to develop new practical molten salt eutectic mixtures. Finally, we address the issue of reactive carbon-cathodes and possible cathode-candidates that were identified throughput high-throughput computations.
Li-Air battery↗
Energy Storage Technologies and U.S. Department of War Requirements
This report offers an overarching primer the energy storage market and assessment of each technology’s suitability for U.S. Department of War applications. We find that battery energy storage is the most promising technology for energy storage applications in terms of energy density and cost. While commercial and advanced Li-ion can satisfy certain electric mobility (e.g., cars, midsized vehicles) and electric flight application (e.g. drones) needs of DoW, next generation technologies like Li metal solid-state batteries, and conversion chemistries (Li-air, Li-CFx) are needed for heavy duty applications like armored vehicles, tanks, airplanes, jets. Batteries should also be supplemented with technologies such as supercapacitors and next-generation flywheels to provide short bursts of high energy for high power needs. Thermal energy storage solutions (sensible and latent heat) and fuel cells (PEMFC and SOFC) are good alternatives for supporting energy storage applications in terms of energy density and cost. Gravity-based energy storage promises the least energy density with high cost and should only be used for niche DoW applications. Of the different gravity energy storage technologies reviewed, pumped-hydro, flywheel, and compressed air energy storage are promising, while solid gravity energy storage appears the least attractive. Military facilities requiring 14 days of energy storage can benefit from flow batteries, especially commercial VFRBs and next generation iron-air systems. While VFRBs are expensive, iron-air batteries have the coupled benefits of low cost and good energy density promising 100+ hours of storage.
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Continuum-Scale Battery Modeling for Space Applications
Discussing detailed modeling of Li-air and suggesting possible solutions for space.
Li-CO2↗
Composite Solid Ion Conductor with Engineered Lithium Interface
Successful widespread commercialization of electric vehicles is contingent upon development of safe high energy density batteries capable of long cycle life. Lithium metal affords the highest theoretical capacity (3,860 mAh/g) and lowest electrochemical potential (-3.04V vs SHE), which offers the highest specific energy density of anode materials today. While Li-ion batteries are capable of delivering energy densities of 400-600 Wh/kg, the development of lithium metal batteries such as Li-S and Li-air may boost this number up to 650 and 950 Wh/kg, respectively. However, significant progress towards the passivation of lithium metal must occur before the energy density benefit can be realized. Issues with lithium dendrite formation, anode volume expansion, and continuous solid electrolyte interphase (SEI) build-up often result in significant safety concerns, high cell resistance, and poor cycle life. The intrinsic high reactivity between lithium metal with conventional lithium ion electrolytes (organic carbonate-based solvents) makes it extremely difficult to overcome these problems. In this project, Wildcat performed focused, fundamental research and development on composite polymer/ceramic electrolytes and protected lithium metal anodes to develop an all solid state lithium metal battery targeting the DOE requirements to enable commercialization. Wildcat successfully leveraged its high throughput battery platform and explored a broad composite electrolyte compositional space. Additionally, Wildcat screened large numbers of inorganic and organic coatings for lithium metal protection using in situ liquid methods and translated the best results to all solid cells. The proposed composite polymer/ceramic electrolyte and a protected lithium metal anode enabled a solid-state lithium metal battery. The ultimate targets from this effort will deliver a safe all solid-state lithium metal pouch cell with over 350 Wh/kg and over 1,000 cycles (C/3) with the cost estimate below $100/kWh. During the course of the project, we demonstrated stable cycling of 10’s of cycles with the composite SSE and our protected lithium. The work has continued after the conclusion of the DOE funding, demonstrating further improvements in catholyte composition and thinner composite solid electrolytes.
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Understanding the complexities of Li metal for solid-state Li-metal batteries
Li-metal anodes are a key enabling technology for next-generation high-energy batteries, including Li–S, Li-air, and high-voltage cathodes. While most research enabling Li metal focuses on electrolyte design, especially in the solid state, the nature of the Li metal itself has a significant impact on the performance of both solid- and liquid-based batteries. This has historically been understudied, but recent work has highlighted the importance of tailoring the Li metal to optimize high-performance batteries. This article focuses on the key aspects of Li metal that impact performance, including the method of synthesis, microstructure, surfaces, impurities, mechanics, and alloying strategies to optimize Li anode performance. Finally, the article will also briefly look at the impact of long-term cycling on the evolution of Li-metal anodes in solid-state batteries and highlight key areas of needed research.
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Development of lithium ion conducting interface between lithium metal and a lithium ion conducting ceramic using block polymers
The lithium-air (Li-air) technology developed by EDF uses an air electrode which works with an aqueous electrolyte, which prevent the use of unprotected lithium metal electrode. A Li+ ionic conductor glass ceramic is used to separate the aqueous electrolyte compartment from the negative lithium electrode. However, this glass-ceramic is not stable in contact with lithium, it is thus necessary to add a protective buffer layer. In another hand, this protection should ideally resist to lithium dendritic growth. It is in this context that this research project which has as goal the development of a protective buffer layer based on block copolymer electrolytes (BCE) between the lithium metal and the lithium ionic conductor ceramic, for lithium-air battery. In a first part, the BCE is studied in lithium-lithium symmetric cells, in order to determine their electrochemical properties such as ionic conductivity, steady state transference number, and finally their resistance to dendritic growth during cycling. Several characterization techniques were employed and especially hard X-ray micro-tomography to analyze the lithium morphology before and after cycling. For single-ion BCE, we expect to suppress dendritic growth, however, we report here for the first time, the visualization of a homogeneous growth of lithium but the formation of dense lithium objects. In another part, the composite BCE-ceramic is studied by electrochemical impedance spectroscopy (EIS). The cycling of lithium-composite-lithium symmetric cells and the analysis of the EIS measurement after each cycle permit to determine if the dendrites have cross the protective layer and are in contact with the ceramic. Besides, the quantification of the polarization loss at the interface polymer-ceramic is evaluated by polarization experiments. This contribution is found to be small.
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