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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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NASA has interest in secondary energy storage batteries that display high specific energy, high energy density, long life characteristics, and perform well over a wide range of temperatures, in order to enable a number of future applications.
The drastic environmental and economic costs of global warming have driven the necessity to reduce, if not eliminate, a dependency on oil and gas for energy applications. Alternative clean energy reliance has been initiated as a global investment for a more sustainable future. Part of this transitional effort is focused on energy storage via a rechargeable battery. High energy density storage is necessary for utilizing non-dispatchable green energy technologies, as well in the electric transition of our vehicle fleet. Further, understanding methods of extracting, manufacturing, and recycling lithium is necessary to lessen environmental impact. Lithium metal is often considered the “Holy Grail” of battery technology, due to its high theoretical capacity (3,860 mAh/g) and low electrochemical potential (-3.04 V vs. SHE). However, parasitic reactions lead to rapid and dangerous battery failure. Therefore, determining methods of stabilizing lithium metal is paramount for the transition to a greener future.
A new optimized LiFSI–LiPF6 dual-salt controlled-solvation electrolyte (E-DS) is demonstrated to enable practical graphite||LiNi0.8Mn0.1Co0.1O2 cells (˜4.0 mAh cm?²) to achieve exceptional performance and safety under extreme conditions. By optimizing anion coordination with the smaller, more dissociating FSI? anion, the E-DS forms ultrathin, dense, and inorganic-rich electrode/electrolyte interphases that dramatically suppress solvent decomposition, transition-metal dissolution, and surface reconstruction compared to the conventional LiPF6/carbonate electrolyte. Consequently, E-DS cells deliver >78% capacity retention after 300 cycles at 60 °C, retain fast discharging capacity at 30 °C, and operate effectively at -20 °C. Most strikingly, fully charged full cells with E-DS, even under overcharging to 4.8 V, show a lower heat evolution in stable formulations — transforming a traditionally unstable high-voltage/high-temperature configuration into an intrinsically safe state. This work establishes a new benchmark for carbonate-containing electrolytes, simultaneously achieving high energy density, fast-discharging capability, wide-temperature operation (-20 to 60 °C), and outstanding thermal safety in nickel-rich lithium-ion batteries.
Solid polymer electrolytes have yet to achieve the desired ionic conductivity (>1 mS/cm) near room temperature required for many applications. This target implies the need to reduce the effective energy barriers for ion transport in polymer electrolytes to around 20 kJ/mol. In this work, we combine information extracted from existing experimental results with theoretical calculations to provide insights into ion transport in single-ion conductors (SICs) with a focus on lithium ion SICs. Through the analysis of temperature-dependent ionic conductivity data obtained from the literature, we evaluate different methods of extracting energy barriers for lithium transport. The traditional Arrhenius fit to the temperature-dependent ionic conductivity data indicates that the Meyer–Neldel rule holds for SICs. However, the values of the fitting parameters remain unphysical. Our modified approach based on recent work (Macromolecules 2023, 56, 15, 6051), which incorporates a fixed pre-exponential factor, reveals that the energy barriers exhibit temperature dependence over a wide range of temperatures. Using this approach, we identify anions leading to the energy barriers <30 kJ/mol, which include trifluoromethane sulfonimide (TFSI), fluoromethane sulfonimide (FSI), and boron-based organic anions. In our efforts to design the next generation of anions, which can exhibit the energy barriers <20 kJ/mol, we have performed density functional theory (DFT) based calculations to connect the chemical structures of boron-based anions via the binding energy of cation (lithium)-anion pairs with the experimentally derived effective energy barriers for ion hopping. Not only have we identified a correlation between the binding energy and the energy barriers, but we also propose a strategy to design new boron-based anions by using the correlation. This combined approach involving experiments and theoretical calculations is capable of facilitating the identification of promising new anions, which can exhibit ionic conductivity >1 mS/cm near room temperature, thereby expediting the development of novel superionic single-ion conducting polymer electrolytes.
Current density has been perceived to play a critical rule for controlling Li deposition morphology and solid electrolyte interphase (SEI). However, the atomic level mechanism of current density on Li deposition and the SEI remains unclear. In this work, based on cryogenic transmission electron microscopy imaging combined with energy dispersive X-ray spectroscopy and electron energy loss spectroscopy electronic structure analyses, we reveal the atomic level correlation of Li deposition morphology and SEI with current density. We discover that increasing current density leads to increased overpotential for Li nucleation and growth, leading to the transition from growth-limited to nucleation-limited mode for Li dendrite. Independence of current density, the electrochemically deposited Li metal (EDLi) exhibits crystalline whisker-like morphology. The SEI formed at low current density (0.1 mA cm -2 ) is monolithic amorphous; while, a current density of above 2 mA cm -2 leads to a mosaic structured SEI, featuring an amorphous matrix with Li 2 O and LiF dispersoids, and the thickness of the SEI increases with the increase of current density. Uniquely, the Li 2 O particles is spatially located at the top surface of the SEI, while LiF is spatially adjacent to the Li-SEI interface. These results highlight the possible tuning of crucial structural and chemical features of EDLi and SEI through altering deposit conditions and consequently direct correlation with electrochemical performance.
Uniform size of Si nanowires (NWs) is highly desirable to enhance the performance of Si NW-based lithium-ion batteries.
Batteries keep devices working by utilizing high energy density, however, they can run down and take tens of minutes to hours to recharge. For rapid power delivery and recharging, high-power density devices, i.e., supercapacitors, are used. The electrochemical processes which occur in batteries and supercapacitors give rise to different charge-storage properties. In lithium ion (Li+) batteries, the insertion of Li+, which enables redox reactions in bulk electrode materials, is diffusion controlled and can be slow. Supercapacitor devices, also known as electrical double-layer capacitors (EDLCs) store charge by adsorption of electrolyte ions onto the surface of electrode materials. No redox reactions are necessary, so the response to changes in potential without diffusion limitations is rapid and leads to high power. However, the charge in EDLCs is confined to the surface, so the energy density is lower than that of batteries.
The practical deployment of lithium–sulfur batteries (LSBs) is hindered by fundamental limitations in conventional slurry-cast cathodes, including poor sulfur utilization, sluggish ion transport, and low areal capacity, particularly in thick electrodes required for high energy density. To address these challenges, we present direct ink writing (DIW) as an additive manufacturing strategy to fabricate advanced current-collector-free, 3D-printed sulfur cathodes (3DP S@CoNi-DSACs/NC) with hierarchically porous architectures that enhance lithium-ion diffusion, promote electrolyte penetration, and reduce interfacial resistance. The synergistic effects of Co/Ni dual-atom sites accelerate redox kinetics and mitigate polysulfide shuttling. As a result, the optimized 3DP cathode with a sulfur loading of 5.4 mg cm −2 demonstrated excellent rate capability, delivering a high reversible capacity of 1041.4 mAh g −1 at 1C with 85.5% capacity retention after 1000 cycles, significantly outperforming its cast counterpart. Remarkably, even at a higher sulfur loading of 8.1 mg cm −2 , the 3DP cathode maintains outstanding performance, achieving a discharge capacity of 1538.4 mAh g −1 and an areal capacity of 12.5 mAh cm −2 at 0.1C. This study not only demonstrates the functional integration of catalytically active materials into 3D printable sulfur cathode architectures but also offers a scalable and transformative platform for building high-performance LSBs beyond conventional electrode manufacturing methods.
Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.
Binders play a crucial role in binding electrodes, current collectors, and conductive agents during battery manufacturing. The selection of the binders and their blends considerably affect various properties such as mechanical durability, adhesion performance, ionic/electronic conductivities, and solid electrolyte interface stability for lithium-ion batteries. In this work, polyvinylidene di-fluoride (PVDF), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP), and lithiated polyacrylic acid (Li-PAA) were selected as the model binders, and their blends were studied on graphene surfaces. Further, among them, PVDF is hardly soluble in water unlike the other binders, so in practice, the blend of PVP:PVDF is not thought to be a proper combination. However, the PVP:PVDF binder has also been included because the purpose of this work is to calculate several electronic properties such as binding energies, intermolecular interaction energies, bond critical points, electron density, and the Laplacian of electron density at critical bonding regions of all these blends at the molecular level via density functional theory (DFT) simulations in order to evaluate and compare how is the interaction strength and bonding type of three different lithium-ion batteries (LIBs) binder blends on graphene surfaces. Most stable binder pairs and their binding mechanisms on graphene surfaces were studied. The delocalization of lithium in Li-PAA was studied with the presence of water.
The rapid rise of AI has exposed significant limitations in conventional Von Neumann computing architecture, particularly in regard to speed and energy efficiency. To address these challenges, researchers are exploring a brain-inspired neuromorphic architecture that mimics biological neural networks, enabling massive parallel processing with reduced power consumption for complex AI computational demands. Recent interest has focused on utilizing battery electrodes and solid electrolyte materials for their resistive switching properties in developing a neuromorphic architecture. These properties are precisely tuned through local- and bulk-level chemical composition modifications via voltage bias stimuli. In this study, we demonstrate fabricating a three-terminal lithium-ion electrochemical transistor based on lithium titanium oxide (Li 4 Ti 5 O 12 ), a popular lithium-ion battery anode material. We deposited and characterized LTO thin films using RF sputtering, demonstrating a 6 orders of magnitude increase in electronic conductivity upon lithiation, with conductivity plateauing after 20% lithiation. Density functional theory calculations revealed transformation from the insulating to conducting state, supported by experimental characterization through X-Ray Photoelectron Spectroscopy (XPS) and Direct Current (DC) polarization analyses. The fabricated transistor consisted of LTO as the channel layer, gold as source/drain terminals, lithium phosphorus oxynitride (LiPON) as the lithium-ion conductor, and copper as the gate terminal. The device exhibited clear hysteresis in transfer characteristics due to lithium insertion/extraction processes. Long-term potentiation (LTP) and long-term depression (LTD) measurements showed an asymmetric ratio of 1.425 and maximum/minimum conductance ratio of 7.83. When implemented in a deep neural network (DNN) for MNIST handwritten digit recognition, the device achieved 92.03% accuracy over 20 training epochs. Detailed transport mechanism analysis revealed the crucial role of oxygen vacancies and interface effects in device operation. Our preliminary findings establish LTO-based lithium-ion electrochemical transistors as promising candidates for energy-efficient neuromorphic computing applications, offering potential solutions to traditional Von Neumann architecture limitations.
Liquid electrolyte engineering plays a critical role in modern lithium-ion batteries. However, the existing electrolytes fall short when used with some trending battery chemistries such as high-voltage and high-energy-density electrodes. Fluorination of electrolyte solvents has been identified as an effective approach for improved cyclability, but few works systematically studied the effects of fluorination extent of carbonate solvents on battery performance. Here we design and synthesize a family of fluorinated ethyl methyl carbonates. Different numbers of F atoms are finely tuned to yield monofluoroethyl methyl carbonate (F1EMC), difluoroethyl methyl carbonate (F2EMC) and trifluoroethyl methyl carbonate (F3EMC). The cycling behavior of several types of lithium-ion pouch cells, including graphite (Gr)/single-crystalline LiNi 0.8 Mn 0.1 Co 0.1 O 2 (SC-NMC811), Gr-SiO x /LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), high-voltage Gr/LiNi 0.5 Mn 1.5 O 4 (LNMO), Gr/layered Li-rich Mn-based oxide (LLMO) and fast-charging Gr/NMC622, were systematically investigated to understand the impact of fluorination degree. Compared to the commercially available F3EMC, we found that the partially-fluorinated F1EMC and F2EMC in some cases showed improved cycling stability, which we attribute to their locally-polar –CH 2 F and –CHF 2 groups and thus fast ion conduction than –CF 3 . This work suggests that highly or fully fluorinated solvents are not necessarily desirable; instead, fluorination degree needs to be rationally and finely tuned for optimized lithium-ion cell performance.
Around 20% of the total primary energy in the United States is consumed for thermal demands of buildings such as space cooling, dehumidification, and space heating (EIA 2018). Low-temperature geothermal energy is abundant and can effectively satisfy buildings’ thermal demands. However, low-temperature geothermal energy is underutilized because the energy density of geothermal fluid is too low to justify the costs associated with transporting it between existing geothermal resources and buildings. The mobile sorption-based thermal battery (MSTB) system has been developed using three-phase (i.e., vapor–liquid, solution–solid, crystal) sorption technology to harvest low-temperature heat and store it with a much higher energy density than the geothermal fluid. The energy density of salt crystals is over six times higher than geothermal fluid, which makes long-distance transportation of salt crystals economically feasible. Salt crystals can be used to dehumidify air or provide space cooling in buildings, which alleviates peak demand on the electricity grid by offsetting electricity use for these end uses. This helps improve the grid’s stability and resilience. High-energy storage density, fast crystallization, and dissolution of salt crystals are all critical to the viability and performance of the MSTB system. Therefore, the design and operation of MSTB systems need to ensure effective generation and dissolution of salt crystals inside the MSTB. To achieve this target, this seedling project developed an experimental apparatus for characterizing the crystallization and dissolution processes. The energy density and potential latent cooling capacity of the MSTB are also evaluated based on lab test results. The crystallization results showed that the generated lithium chloride hydrate crystals are fluffy, the crystallization process lasts about 50 min, and the maximum crystal fraction (i.e., the ratio of crystal mass to the mass in the MSTB) can be up to 51.1% of the total mass in the MSTB at a solution flow rate of 1.58 g/s. The dissolution results show that the salt crystals in the MSTB can be fully dissolved within 15–28 min, based on different test conditions. Reducing solution flow rate and cooling water temperature can achieve increased energy storage density and crystal fraction. While the increase in the discharge rate (i.e., latent cooling capacity for dehumidifying air) is achieved by increasing flow rate and temperature of inlet diluted solution, as well as by using a pump for internal solution circulation, the discharge rate increases by 38%, from 0.95 kW to 1.31 kW. Compared with increasing the inlet solution flow rate, power consumption of salt solution transportation can be reduced by using a pump for internal solution circulation. The crystallization test results also showed that the maximum energy storage density is 981.8 kJ/kg, and the maximum discharge rate of the dissolution tests is ≤1.79 kW. Both are above the target values of 900 kJ/kg and 1.75 kW) for this project. The work reported here proves the feasibility and advancement of the MSTB system, which is helpful to the further study and improvement of the MSTB system.
Electrochemical characteristics of lithium in various electrolytes and magnesium in aluminum chloride-acetonitrile studied by voltammetric sweep method
Li-ion battery degradation and safety events are often attributed to undesirable metallic lithium plating. Since their release, Li-ion battery electrodes have been made progressively thicker to provide a higher energy density. However, the propensity for plating in these thicker pairings is not well understood. Herein, we combine an experimental plating-prone condition with robust mesoscale modeling to examine electrode pairings with capacities ranging from 2.5 to 6 mAh/cm 2 and negative to positive (N/P) electrode areal capacity ratio from 0.9 to 1.8 without the need for extensive aging tests. Using both experimentation and a mesoscale model, we identify a shift from conventional high state-of-charge (SOC) type plating to high overpotential (OP) type plating as electrode thickness increases. Further, these two plating modes have distinct morphologies, identified by optical microscopy and electrochemical signatures. We demonstrate that under operating conditions where these plating modes converge, a high propensity of plating exists, revealing the importance of predicting and avoiding this overlap for a given electrode pairing. Further, we identify that thicker electrodes, beyond a capacity of 3 mAh/cm 2 or thickness >75 μm, are prone to high OP, limiting negative electrode (NE) utilization and preventing cross-sectional oversizing the NE from mitigating plating. Here, it simply contributes to added mass and volume. The experimental thermal gradient and mesoscale model either combined or independently provide techniques capable of probing performance and safety implications of mild changes to electrode design features.
This article reports the synergy between ceramic nanofibers and a polymer, and the enhanced interfacial Li-ion transport along the nanofiber/polymer interface in a solid-state ceramic/polymer composite electrolyte, in which a three-dimensional (3D) electrospun aluminum-doped Li 0.33 La 0.557 TiO 3 (LLTO) nanofiber network is embedded in a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) matrix. Strong chemical interaction occurs between the nanofibers and the polymer matrix. Addition of the ceramic nanofibers into the polymer matrix results in the dehydrofluorination of the PVDF chains, deprotonation of the –CH 2 moiety and amorphization of the polymer matrix. Solid-state nuclear magnetic resonance (NMR) spectra reveal that lithium ions transport via three pathways: (i) intra-polymer transport, (ii) intra-nanofiber transport, and (iii) interfacial polymer/nanofiber transport. In addition, lithium phosphate is coated on the LLTO nanofiber surface before the nanofibers are embedded into the polymer matrix. The presence of lithium phosphate at the LLTO/polymer interface further enhances the chemical interaction between the nanofibers and the polymer, which promotes the lithium ion transport along the polymer/nanofiber interface. This in turn improves the ionic conductivity and electrochemical cycling stability of the nanofiber/polymer composite. As a result, the flexible LLTO/Li 3 PO 4 /polymer composite electrolyte membrane exhibits an ionic conductivity of 5.1 × 10 -4 S cm -1 at room temperature and an electrochemical stability window of 5.0 V vs. Li/Li + . A symmetric Li|electrolyte|Li half-cell shows a low overpotential of 50 mV at a constant current density of 0.5 mA cm -2 for more than 800 h. In addition, a full cell is constructed by sandwiching the composite electrolyte between a lithium metal anode and a LiFePO 4 -based cathode. Such an all-solid-state lithium metal battery exhibits excellent cycling performance and rate capability.
Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.
The Super LightWeight Tank (SLWT) team was tasked with a daunting challenge from the outset: boost the payload capability of the Shuttle System by safely removing 7500 lbs. from the existing 65,400 lb. External Tank (ET). Tools they had to work with included a promising new Aluminum Lithium alloy, the concept of a more efficient structural configuration for the Liquid Hydrogen (LH2) tank, and a highly successful, mature Light Weight Tank (LWT) program. The 44 month schedule which the SLWT team was given for the task was ambitious by any measure. During this time the team had to not only design, build, and verify the new tank, but they also had to move a material from the early stages of development to maturity. The aluminum lithium alloy showed great promise, with an approximately 29% increase in yield strength, 15% increase in ultimate strength, 5 deg/O increase in modulus and 5 deg/O decrease in density when compared to the current 2219 alloy. But processes had to be developed and brought under control, manufacturing techniques perfected, properties characterized, and design allowable generated. Because of the schedule constraint, this material development activity had to occur in parallel with design and manufacturing. Initial design was performed using design allowable believed to be achievable with the Aluminum Lithium alloy system, but based on limited test data. Preliminary structural development tests were performed with material still in the process of iteration. This parallel path approach posed obvious challenges and risks, but also allowed a unique opportunity for interaction between the structures and materials disciplines in the formulation of the material.