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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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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

MoS 2 -Decorated Graphene@porous Carbon Nanofiber Anodes via Centrifugal Spinning

Sodium-ion batteries (SIBs) are promising alternatives to lithium-ion batteries as green energy storage devices because of their similar working principles and the abundance of low-cost sodium resources. Nanostructured carbon materials are attracting great interest as high-performance anodes for SIBs. Herein, a simple and fast technique to prepare carbon nanofibers (CNFs) is presented, and the effects of carbonization conditions on the morphology and electrochemical properties of CNF anodes in Li- and Na-ion batteries are investigated. Porous CNFs containing graphene were fabricated via centrifugal spinning, and MoS 2 were decorated on graphene-included porous CNFs via hydrothermal synthesis. The effect of MoS 2 on the morphology and the electrode performance was examined in detail. The results showed that the combination of centrifugal spinning, hydrothermal synthesis, and heat treatment is an efficient way to fabricate high-performance electrodes for rechargeable batteries. Furthermore, CNFs fabricated at a carbonization temperature of 800 °C delivered the highest capacity, and the addition of MoS 2 improved the reversible capacity up to 860 mAh/g and 455 mAh/g for Li- and Na-ion batteries, respectively. A specific capacity of over 380 mAh/g was observed even at a high current density of 1 A/g. Centrifugal spinning and hydrothermal synthesis allowed for the fabrication of high-performance electrodes for sodium ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

A Single‐Ion Conducting Borate Network Polymer as a Viable Quasi‐Solid Electrolyte for Lithium Metal Batteries

Abstract Lithium‐ion batteries have remained a state‐of‐the‐art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high‐voltage cathodes represent promising candidates for next‐generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high‐performing single‐ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room‐temperature conductivity of 1.5 × 10 −4 S cm −1 , and exceptional selectivity for Li‐ion conduction ( t Li+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi‐solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.

Shin, Dong‐Myeong↗
DOE OSTI2021

Effects of Plasticizer Content and Ceramic Addition on Electrochemical Properties of Cross-Linked Polymer Electrolyte

The development of a safe electrolyte is the key to improving energy density for next generation lithium batteries. In this work, UV-crosslinked poly(ethylene oxide) (PEO) -based polymer and composite electrolytes are systematically investigated on their ionic conductivity, mechanical and electrochemical properties. The polymer electrolytes are plasticized with non-flammable linear short-chain PEO. In the composite electrolytes, a doped lithium aluminum titanium phosphate (LATP) ceramic, LICGC™, is used as the ceramic filler. It is found that the addition of the plasticizer leads to a tradeoff between ion transport and mechanical properties. In contrast, the addition of ceramic fillers improves both the ionic conductivity and mechanical properties. The sample with 20 wt% of LICGC™ shows a conductivity of ~0.6 mS cm –1 at 50 °C. This sample also demonstrates much longer cycle life than the neat polymer electrolyte in Li platting/stripping test with a capacity of 1 mAh cm –2 . Further, a full cell made with this composite electrolyte against Li metal anode and high voltage LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode shows 94% capacity retention after 30 cycles, compared to 58% capacity retention with the neat polymer electrolyte. These results demonstrate that a hybrid of polymer/ceramic/non-flammable plasticizer is a promising path to high energy density, high voltage lithium batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Challenges in Lithium Metal Anodes for Solid-State Batteries

In this Perspective, we highlight recent progress and challenges related to the integration of lithium metal anodes in solid-state batteries. While prior reports have suggested that solid electrolytes may be impermeable to lithium metal, this hypothesis has been disproven under a variety of electrolyte compositions and cycling conditions. Herein, we describe the mechanistic origins and importance of lithium filament growth and interphase formation in inorganic and organic solid electrolytes. Multimodal techniques that combine real and reciprocal space imaging and modeling will be necessary to fully understand nonequilibrium dynamics at these buried interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in symmetric Li–Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell experiments are necessary. Lastly, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure, geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we highlight the need for detailed reporting of experimental conditions and standardization of protocols across the community.

25 ENERGY STORAGE↗
DOE OSTI2024

Custom-form iron trifluoride Li-batteries using material extrusion and electrolyte exchanged ionogels

Custom-form factor batteries fabricated in non-conventional shapes can maximize the overall energy density of the systems they power, particularly when used in conjunction with energy dense materials (e.g., Li metal anodes and conversion cathodes). Additive manufacturing (AM), and specifically material extrusion (ME), have been shown as effective methods for producing custom-form cell components, particularly electrodes. However, the AM of several promising energy dense materials (conversion electrodes such as iron trifluoride) have yet to be demonstrated or optimized. Furthermore, the integration of multiple AM produced cell components, such as electrodes and separators, along with a custom package remains largely unexplored. In this work, iron trifluoride (FeF 3 ) and ionogel (IG) separators are conformally printed using ME onto non-planar surfaces to enable the fabrication of custom-form Li-FeF 3 batteries. Further, to demonstrate printing on non-planar surfaces, cathodes and separators were deposited onto cylindrical rods using a 5-axis ME printer. ME printed FeF 3 was shown to have performance commensurate with FeF 3 cast using conventional means, both in coin cell and cylindrical rod formats, with capacities exceeding 700 mAh/g on the first cycle and ranging between 600 and 400 mAh/g over the next 50 cycles. Additionally, a ME process for printing polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) based IGs directly onto FeF 3 is developed and enabled using an electrolyte exchange process. In coin cells, this process is shown to produce cells with similar capacity to cells built with Celgard separators out to 50 cycles, with the exception that cycling instabilities are observed during cycles 8–20. When using printed and exchanged IGs in a custom cylindrical cell package, 6 stable high-capacity cycles are achieved. Overall, this work demonstrates approaches for producing high-energy-density Li-FeF 3 cells in coin and cylindrical rod formats, which are translatable to customized, arbitrary geometries compatible with ME printing and electrolyte exchange.

25 ENERGY STORAGE↗
DOE OSTI2025

Designing Moderately‐Solvating Electrolytes for High‐Performance Lithium–Sulfur Batteries

New electrolytes are critical for high‐energy lithium (Li)–sulfur (S) batteries (LSBs) to ensure their stability against Li metal anode and polysulfides (PSs) shuttling which hinder the large‐scale application of LSBs. In this study, the design principle of moderately solvating electrolytes (MSEs) for LSBs is demonstrated by using a multiple‐solvent system comprising of a highly solvating solvent, a weakly solvating solvent, and a non‐solvating solvent to create a well‐balanced electrolyte system. This resulting electrolyte significantly improves the cycle life of LSBs, achieving 300 cycles, which is twice as long as that of similar cells with the conventional electrolyte and it also ensures stable calendar life for at least seven months. The optimal MSE forms robust passivation layers enhancing the structural integrity of both S and Li metal electrodes after cycling. These virtues effectively hinder parasitic side reactions and self‐discharge behavior of LSBs. This electrolyte design principle is versatile and can be applied to other battery chemistries, providing a potential path toward the development of a more efficient and stable battery system. By addressing key challenges such as the instability of electrodes and shuttling of polysulfides, this electrolyte approach offers promising solutions for advancing LSB technology.

25 ENERGY STORAGE↗
DOE OSTI2023

Localized high-concentration electrolytes get more localized through micelle-like structures

Liquid electrolytes in batteries are typically treated as macroscopically homogeneous ionic transport media despite having a complex chemical composition and atomistic solvation structures, leaving a knowledge gap of the microstructural characteristics. Here, we reveal a unique micelle-like structure in a localized high-concentration electrolyte, in which the solvent acts as a surfactant between an insoluble salt in a diluent. The miscibility of the solvent with the diluent and simultaneous solubility of the salt results in a micelle-like structure with a smeared interface and an increased salt concentration at the centre of the salt–solvent clusters that extends the salt solubility. These intermingling miscibility effects have temperature dependencies, wherein a typical localized high-concentration electrolyte peaks in localized cluster salt concentration near room temperature and is used to form a stable solid–electrolyte interphase on a Li metal anode. Importantly, these findings serve as a guide to predicting a stable ternary phase diagram and connecting the electrolyte microstructure with electrolyte formulation and formation protocols of solid–electrolyte interphases for enhanced battery cyclability.

25 ENERGY STORAGE↗
DOE OSTI2021

Achieving Highly Reproducible Results in Graphite-based Li-ion Full Coin Cells

Electrode materials, cathodes or anodes, are mostly evaluated in half coin cells where lithium (Li) metal is used. However, due to the instability nature of Li metal, the cycling performances of the half cells is more likely reflecting Li anode stability instead of the coupled electrodes, questioning the conclusions. Full coin cells utilizing graphite as the anode effectively assesses materials. But the key factors of preparing full coin cells with reproducible performances have rarely been discussed and overlooked leading to many inconsistent results. This work discusses the scientific gap between cell preparation and observed electrochemical performances to unveil the key parameters for achieving consistent and reliable results in full coin cells, critical for effective evaluation of any new materials tested under relevant conditions. The knowledge from this work is broadly applicable in other full cells systems such as Si-based full cells or Na-ion batteries.

Hu, Jiangtao↗
DOE OSTI2020

Electro-chemo-mechanical evolution of sulfide solid electrolyte/Li metal interfaces: operando analysis and ALD interlayer effects

Sulfide solid electrolytes (SE) show promise for high-performance solid-state batteries because of their high ionic conductivity and ease of processing. However, sulfide electrolytes have suffered from chemical and electrochemical instability against Li metal anodes. In this paper, we use a suite of in situ/operando microscopy and spectroscopy techniques to demonstrate that Al 2 O 3 interlayers deposited using atomic layer deposition (ALD) delay degradation at the Li/LGPS interface by modifying the solid electrolyte interphase (SEI) chemistry and morphology. Optical and scanning electron microscopy are used to rationalize the electrochemical response of the system, which is attributed to a delayed onset of mechanical degradation at the interface when ALD interlayers are used. Operando X-ray photoelectron spectroscopy demonstrates that the dynamic evolution of SEI chemistry is impacted by the presence of the ALD interlayer. In situ Auger spectroscopy and operando optical microscopy provide visual evidence of spatial heterogeneity of Li plating, which is attributed to the chemo-mechanical degradation of the ALD interphase. The implications of these observations provide valuable insights toward the development of robust interlayers for solid-state batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Towards extreme fast charging of 4.6V LiCoO 2 via mitigating high-voltage kinetic hindrance

High-voltage LiCoO 2 (LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries (LIBs) in the 3C markets. However, the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability. Herein, combining experiments with density functional theory (DFT) calculations, we demonstrate that the kinetic limitations can be mitigated by a facial Mg 2+ +Gd 3+ co-doping method. The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage, making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process. The homogeneity enables the structural stability of LCO at a high-rate current density, inhibiting stress accumulation and irreversible phase transition. When used in combination with a Li metal anode, the doped LCO shows an extreme fast charging (XFC) capability, with a superior high capacity of 193.1 mAhg -1 even at the current density of 20C and high-rate capacity retention of 91.3% after 100 cycles at 5C. In conclusion, this work provides a new insight to prepare XFC high-voltage LCO cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Efficient diffusion of superdense lithium via atomic channels for dendrite-free lithium–metal batteries

The non-uniform aggregation of fast-diffused Li on an anode surface would aggravate its tip-effect-induced nucleation/growth, leading to the notorious dendrite growth in Li metal batteries (LMBs). Tuning the Li diffusion on the anode surface has been regarded previously as a mainstream method to induce its uniform deposition, while the diffusion of Li in the anode bulk is usually ignored. In this study, conceptually different from the classic surface modification, we propose a molecular tunnelling strategy to construct atomic channels in graphite bulk, which enables the fast diffusion of superdense Li. Density functional theory calculations and ab initio molecular dynamics simulations prove that the bulk diffusion through atomic channels could become a new and dominating path. Its reversible and efficient diffusion has been further visualized by in situ transmission electron microscopy. As a result, when coupled with high-loading LiFePO 4 cathodes (20 mg cm –2 ), a high areal capacity and 100% capacity retention are achieved over 370 cycles. Through this work a new strategy is developed based on the bulk-diffusion of superdense Li for dendrite-free LMBs, which can be pervasive in other high-performance energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2022

Identification of efficient and stable solid-solid electrochemical interfaces for Li-S batteries. Final Report

The objective of this work is to develop a better understanding of the interactions between battery components that drive the observed battery performance. Using computational tools at the atomistic level, we elucidate molecular, crystal, and amorphous structures, interfacial structures and reactions, and electrochemical behavior. We focus on Li metal anodes, liquid electrolytes, solid electrolytes, S cathodes, and metal-oxide cathodes, and their corresponding interfaces. Within liquid electrolytes, we study their bulk structure and dynamics, as a function of salt concentration. The analysis allows to understand the formation of localized high concentrated regions as the solvent is substituted by a weakly interacting diluent species. Analysis of the electron distribution yields the reactive behavior at interfaces. Moreover, we employ tools that allow the characterization of ion and electron transport at interfaces, during the processes of solvation and desolvation occurring while cycling. For Sulfur cathodes we elucidate synthesis processes and the role of carbon-sulfur and nitrogen-sulfur interactions not only to provide electronic conductivity but also to define alternative reaction pathways during discharge of Li-S batteries. Full-cell simulations offer new insights regarding the integration of all the battery components. Our studies also include solid electrolytes and their interfaces with Li metal, S-C, and metal-oxide electrodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Two-layer cathode architecture for high-energy density and high-power density solid state batteries

Solid state batteries with high-energy density and high-power density require the development of thick and energy dense cathodes. Structured cathode electrodes with a double-layer configuration were enabled using a freeze tape casting technique. A bottom dense layer was utilized to enhance the energy density whereas a top porous layer with vertically aligned walls was utilized to enhance the power density. The porous structure of the power layer was achieved by ice templating this layer on top of the densified energy layer of the cathode. This configuration was found to better utilize the active material of the cathodes and was optimized using numerical simulation and computer modeling. Cells with Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) at approximately 5 and 20 mg/cm 2 were cycled at 70 °C at different C-rates. Poly(ethylene oxide) (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) was used for the catholyte and the solid-state electrolyte. The structured cathodes exhibited more than double capacity values as well as better Coulombic efficiency compared to non-structured (single-layer) thick cathodes. In conclusion, synchrotron X-ray tomography and scanning electron microscopy were used to characterize the microstructure of the cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Effects of Salt Aggregation in Perfluoroether Electrolytes

Electrolytes comprised of polymers mixed with salts have great potential for enabling the use of Li metal anodes in batteries for increased safety. Ionic conductivity is one of the key performance metrics of these polymer electrolytes and achieving high room-temperature conductivity remains a challenge to date. For a bottom-up design of the polymer electrolytes, we must first understand how the structure of polyelectrolytes on a molecular level determines their properties. Here, we use classical molecular dynamics to study the solvation structure and ion diffusion in electrolytes composed of a short-chain perfluoroether with LiFSI or LiTFSI salts. Density functional theory is also used to provide some insights into the structures and energies of the salt interactions with the perfluoroether. We observe the formation of aggregates of salts in the fluorinated systems even at low salt concentrations. The fluorine-fluorine attraction in the solvent is the governing factor for creating the salt aggregates. The aggregates’ size and lifetime change with concentration and anion. These simulations provide an insight into the structure and dynamics of perfluoroether based electrolytes that can be used to improve Li-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Dual Function Solid State Battery with Self-Forming Self-Healing Electrolyte and Separator (Final Scientific/Technical Report)

Over the course of this program, we have demonstrated an improved rechargeable Li/I2 battery with reduced impedance, improved cyclability, improved Coulombic Efficiency, and the ability to “self-heal” during shorting events. Multi-year efforts have led to the development and improvements in the composition, fabrication, and preparation of the solid state electrolyte, the role of the interface, and design of appropriate test conditions. These investigations have led to significant improvements in Coulombic efficiency. By systematic development of a composite solid state electrolyte, this system is able to self-form upon charge, thus lending itself to long shelf life before use. The initial project objective was to demonstrate a solid-state rechargeable battery based on a Li-metal anode and iodine cathode with a self-forming, self-healing electrolyte and separator with high gravimetric and volumetric energy density. The final deliverables of this project build on a multi-year effort beginning with materials development and design to generate a suitable solid state electrolyte composite with demonstrated higher ionic conductivity compared to the baseline (LiI). Development in cell design and interface modification leading to the generation of rechargeable solid electrolyte cells with Coulombic efficiency improvements of ~3X over initial tests, as well as demonstration of self-healing behavior, where the cells retained their ability to continue extended cycling after shorting events. The hypothesis put forward as part of the initial concept for the project was that the cell chemistry would be self-healing. For example, if a lithium dendrite formed during charge of the cell and reached the iodine cathode, the reaction of the lithium dendrite with the iodine would consume the tip of the dendrite to form lithium iodide, more of the solid electrolyte. The formation of the solid electrolyte would allow the cell to recover and continue to function. This type of self-healing during cycling has been demonstrated and has the potential to improve on safety considerations that stem from shorting events in other Li- containing systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Safe, Low-Cost, High Energy-Density, Solid-State Li-Ion Batteries

We developed intrinsically safe, robust, low-cost, high-energy-density solid-state Li-ion batteries, by integrating high conductivity garnet-type solid Li ion electrolytes and several different cathodes in tailored microstructures, fabricated by low-cost supported thin-film ceramic techniques, to overcome the primary technological barriers to next generation battery technology. In this ARPA-E project we employed Li-garnet solid-state electrolytes pioneered by one of the co-investigators (Thangadurai) which has room temperature (RT) conductivity of ~10 -3 S cm -1 . The highly stable garnet SSE allowed the use of S, NMC, and other cathodes with Li metal anodes without stability or flammability concerns. We studied the garnet’s stability when exposed to CO 2 and humidity (with or without an ALD coating) and showed that the material can be processed in ambient air for most steps prior to battery assembly, significantly reducing production costs. We extensively studied and scaled up the synthesis of the powder and explored external suppliers of garnet to determine the best pathway for commercial success. We used low-cost and scalable tapecasting fabrication methods to create porous-dense-porous “trilayer” solid electrolyte microstructures with a ~20 μm separating dense layer, and >70% porosity porous layers to host the electrodes. These scalable multilayer ceramic fabrication techniques, without need for dry rooms or vacuum equipment, also provide for dramatically reduced manufacturing costs. The tailored microstructured electrode supports (scaffold) increased interfacial area ~50x, overcoming the high impedance typical of planar geometry SSLiBs, resulting in record-setting 10 mA/cm 2 lithium cycling in a symmetric cell. We expanded our tapecasting ability and showed tapes >25m in length by the end of the project. We demonstrated the ability to sinter garnet without the use of a garnet powderbed, which could have been a major obstacle and waste of material at scale. At the same time, we expanded the size of our trilayers from coin cells (0.7 cm 2 ) to the full format design (30 cm 2 ). To develop full cells, we demonstrated 250 Wh/kg at room temperature with commercial NMC electrode films in a bilayer configuration. Similarly, we demonstrated 280 Wh/kg trilayer Li-S cells at room temperature with >90% capacity retention over 300 cycles. At 90°C we demonstrated 350 Wh/kg with a Li-S trilayer. The high thermal stability of the garnet electrolyte also enabled extended cycling (400 cycles) of a Li-TiS 2 cell at 150 °C, showcasing the exceptional safety and nonflammability of the solid-state trilayer batteries. Ion Storage Systems has taken this technology and knowledge to produce trilayer garnet electrolytes and is building out facilities to commercialize high performance solid state batteries. ISS has hired a strong staff, identified and communicated with a large number of potential partners, and successfully secured follow-on funding.

25 ENERGY STORAGE↗
DOE OSTI2025

Mechanistic Study of Functional Electrolyte Solvents for High-Voltage Lithium Batteries

The pervasive use of Ni-rich cathode active materials, e.g., LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), for high-energy-density Li-ion batteries (LIBs) has been hindered by rapid battery capacity decay when cycled with high charge cutoff voltages due to electrolyte decomposition in the conventional carbonate solvent-based electrolytes, oxidative parasitic side reactions at the electrolyte/cathode interface, and irreversible phase changes in the cathode active materials leading to dissolution of transition metals into the electrolytes. Various functional electrolyte solvents have been studied to tackle the above technical challenges, yet the roles of individual solvents in the performance of LIBs remain poorly understood. Here, in this study, we systematically investigate electrochemical performance mechanisms of fluorinated and organosilicon single solvents and cosolvents, for the first time, in high-voltage Li/NMC811 batteries, using electrochemical and analytical characterizations and density functional theory modeling. We observe that some unique combinations of the functional solvents can lead to exceptionally stable high-voltage cycle performance in the Ni-rich cathode-based LIBs. Our mechanistic study reveals that the synergistic effect of solvents plays a vital role in enabling electrochemical stability at both the Ni-rich cathode and the Li metal anode. Understanding the electrochemical performance mechanisms of functional solvents can greatly help in designing and formulating advanced electrolytes that enable the development of high-voltage, high-energy-density, long-cycle-life lithium batteries.

density functional theory modeling↗