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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Semi-solid alkali metal electrodes enabling high critical current densities in solid electrolyte batteries

The need for higher energy density rechargeable batteries has generated interest in alkali metal electrodes paired with solid electrolytes. However, metal penetration and electrolyte fracture at low current densities have emerged as fundamental barriers. Here, we show that for pure metals in the Li-Na-K system, the critical current densities scale inversely to mechanical deformation resistance. Furthermore, we demonstrate two electrode architectures in which the presence of a liquid phase enables high current densities while preserving the shape retention and packaging advantages of solid electrodes. First, biphasic Na-K alloys show K + critical current densities (with K-β*-Al 2 O 3 electrolyte) that exceed 15 mA∙cm -2 . Second, introducing a wetting interfacial film of Na-K liquid between Li metal and Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO) solid electrolyte doubles the critical current density and permits cycling at areal capacities exceeding 3.5 mAh∙cm -2 . These design approaches hold promise for overcoming electro-chemo-mechanical stability issues that have heretofore limited performance of solid-state metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Characterization of the structure and chemistry of the solid–electrolyte interface by cryo-EM leads to high-performance solid-state Li-metal batteries

Solid-state lithium-metal (Li 0 ) batteries are gaining traction for electric vehicle applications because they replace flammable liquid electrolytes with a safer, solid-form electrolyte that also offers higher energy density and better resistance against Li dendrite formation. Solid polymer electrolytes (SPEs) are highly promising candidates because of their tunable mechanical properties and easy manufacturability; however, their electrochemical instability against lithium metal (Li 0 ), mediocre conductivity, and poorly understood Li 0 /SPE interphases have prevented extensive application in real batteries. In particular, the origin of the low Coulombic efficiency (CE) associated with SPEs remains elusive, as the debate continues as to whether it originates from unfavored interfacial reactions or lithium dendritic growth and dead lithium formation. In this work, we use state-of-the-art cryo-electromicroscopy (cryoEM) imaging and spectroscopic techniques to characterize the structure and chemistry of the interface between Li 0 and a polyacrylate-based SPE. Contradicting the conventional knowledge, we find that no protective interphase forms, owing to the sustained reactions between deposited Li dendrites and polyacrylic backbones and succinonitrile plasticizer. Due to the reaction induced volume change, large amounts of cracks form inside the Li dendrites with a stress corrosion-cracking behavior, indicating that Li0cannot be passivated in this SPE system. Based on this observation, we then introduce additive engineering leveraging on the knowledge of liquid electrolytes, and demonstrate that the Li 0 surface can be effectively protected against corrosion using fluoroethylene carbonate (FEC), leading to densely packed Li 0 domes with conformal and stable solid-electrolyte interphases (SEIs) films. Owing to the high room temperature ionic conductivity of 1.01 mS/cm -1 , the high transference number of 0.57 and the stabilized lithium electrolyte interface, this improved new SPE delivers an excellent lithium plating/stripping CE of 99% and 1800 hours of stable cycling in Li||Li symmetric cells (0.2 mA/cm -2 , 1mAh/cm -2 ). Furthermore, this improved cathodic stability along with the high anodic stability enables record high cycle life of >2000 cycles for Li||LiFePO 4 and >400 cycles for Li||LiCoO 2 full cells.

25 ENERGY STORAGE↗
DOE OSTI2020

DFT modelling of explicit solid–solid interfaces in batteries: methods and challenges

Density Functional Theory (DFT) calculations of electrode material properties in high energy density storage devices like lithium batteries have been standard practice for decades. By contrast, DFT modelling of explicit interfaces in batteries arguably lacks universally adopted methodology and needs further conceptual development. In this paper, we focus on solid–solid interfaces, which are ubiquitous not just in all-solid state batteries; liquid-electrolyte-based batteries often rely on thin, solid passivating films on electrode surfaces to function. We use metal anode calculations to illustrate that explicit interface models are critical for elucidating contact potentials, electric fields at interfaces, and kinetic stability with respect to parasitic reactions. The examples emphasize three key challenges: (1) the “dirty” nature of most battery electrode surfaces; (2) voltage calibration and control; and (3) the fact that interfacial structures are governed by kinetics, not thermodynamics. To meet these challenges, developing new computational techniques and importing insights from other electrochemical disciplines will be beneficial.

25 ENERGY STORAGE↗
DOE OSTI2021

All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries

Solid-state batteries (SSBs) could significantly improve the safety and energy density over conventional liquid cells. One key enabling technology is the use of solid electrolytes. NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) is a very attractive solid-state electrolyte for the cathode side due to its high oxidation potential and high ionic conductivity. The usage, however, is limited by its large interfacial resistance against most of the cathode materials as well as the thermodynamic instability during high temperature sintering needed to achieve high mass density. Here we construct thin, percolative, and mixed conductive interphases through in situ low-melting-point liquid sintering. These mixed conductive interphases drastically improve the kinetics, leading to high-loading solid LATP/LiCoO 2 cathodes achieving capacity loading of up to ~6 mA h cm –2 . The technique is also applicable to Ni-rich cathode materials, achieving up to ~10 mAh cm –2 , which can lead to more than 400 W h kg –1 cells in SSBs. Furthermore, our composite cathodes show a ten-times and three-times area capacity improvement over the state-of-the-art cathodes using oxide and sulfide SSEs, respectively.

25 ENERGY STORAGE↗
DOE OSTI2021

Materials design of sodium chloride solid electrolytes Na3MCl6 for all-solid-state sodium-ion batteries

All-solid-state sodium-ion batteries have attracted increasing attention owing to the low cost of sodium and the enhanced safety compared to conventional Li-ion batteries. Recently, halides have been considered as promising solid electrolytes (SEs) due to their favorable combination of high ionic conductivity and chemical stability against high-voltage cathode materials. Although a wide variety of lithium chloride SEs, Li 3 MCl 6 , have been developed for high-voltage all-solid-state batteries, only a limited number of sodium chloride SEs have been reported. This study aims to offer a material design insight for the development of sodium chloride SEs through systematic assessment of the phase stability, electrochemical stability, and transport properties of novel Na 3 MCl 6 SEs. Structural calculations indicate that Na 3 MCl 6 exhibits trigonal $P\bar{3}$1c, monoclinic P2 1 /n, and trigonal $R\bar{3}$ phases, and the stable phase of Na 3 MCl 6 is dependent on the type and ionic radius of M. Na 3 MCl 6 typically exhibits a high oxidation potential, demonstrating good electrochemical stability against cathodes. The bond-valence site energy and ab initio molecular dynamics calculations revealed that Na 3 MCl 6 with P2 1 /n and $R\bar{3}$ phases showed low ionic conductivity, while the $P\bar{3}$1c phase slightly improved the ionic conductivity of Na 3 MCl 6 . The formation of Na vacancies by aliovalent substitution considerably increased the ionic conductivity up to four orders of magnitude for pristine Na 3 MCl 6 , exhibiting ~10 –5 S cm –1 for trigonal $P\bar{3}$1c and $R\bar{3}$ phases. The formation of defects could further enhance the ionic conductivity of Na 3 MCl 6 , and the optimization of defect type and ratio can be helpful in developing superionic Na chloride SEs. The material design of Na 3 MCl 6 in this study will provide fundamental guidelines for the development of novel sodium halide SEs for all-solid-state sodium-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Beyond conventional batteries: a review on semi-solid and redox targeting flow batteries-LiFePO{sub 4} as a case study.

Clean and sustainable energy is becoming increasingly crucial to tackle the current energy crisis. However, the intermittent nature of renewable energy sources presents a challenge for their effective implementation. Redox flow batteries (RFBs) have emerged as a promising solution to this problem, as they can help enhance the stability of grid networks and promote the use of renewable energy sources. RFBs are highly modular and scalable systems that can be customized to meet the power and energy requirements of different renewable energy plants. Moreover, they offer several advantages over conventional battery technologies, including cost and safety concerns. However, conventional RFBs have limited energy densities due to the low solubility of their active species in electrolyte. To overcome this limitation, semi-solid (SSRFBs) and redox targeting (RTFBs) flow batteries have been proposed. These systems feature high concentrations of active species and impressive energy densities, making them highly attractive for renewable energy applications. LiFePO4 (LFP) is a highly promising active material for semi-solid and targeting flow batteries. One of the key advantages of LFP is its low raw materials cost, as it is composed of Earth-abundant elements such as iron and phosphorus. This makes it an attractive option for large-scale battery production. The recent developments in SSRFBs and RTFBs using LFP as catholyte hold great promise for the future of sustainable energy storage. The combination of LFP's low cost, safety, durability, and high energy density with the modularity and scalability of flow battery systems make for a compelling solution to the challenges of intermittent renewable energy sources. Ongoing research and development in this area will likely yield even further improvements in the performance and efficiency of LFP-based flow batteries, opening exciting new possibilities for sustainable energy storage.

El Halya, Nabil↗
DOE OSTI2023

Method for concentrating solids and removing solids from a filter medium

Disclosed are methods for concentrating solids and removing solids from a filter medium. The method includes the step of concentrating first particles of a first solid by removing a fluid stream through a filter medium in a filter. At least some of the first particles become blocking particles that block pores of the filter medium. The method also includes the step of inserting second particles of a second solid into the filter. These second particles scrape, vibrate, agglomerate, or a combination thereof along the filter medium, thus dislodging at least a portion of the blocking particles.

Frankman, David↗
DOE OSTI2025

Design of Sodium Chalcohalide Solid Electrolytes with Mixed Anions for All‐Solid‐State Sodium‐Ion Batteries

Solid-state sodium-ion batteries (SSNIBs) have emerged as a promising alternative to lithium-ion systems for grid-scale energy storage, owing to sodium's abundance and the improved safety of solid-state designs. Among various solid-state electrolytes (SSEs), halide-based Na + SSEs offer high electrochemical stability but are limited by low ionic conductivity and poor thermal stability. Herein, a novel class of sodium hafnium chalcohalide SSEs is reported with a dual-anion (S 2− /Cl − ) framework, with a high ionic conductivity of 4.5 × 10 −4 S cm −1 . The incorporation of sulfur enhances Na⁺ mobility by reducing the migration barrier through increased anion polarizability and expanded diffusion pathways. Additionally, S 2− contributes to stronger interatomic bonding, leading to higher cohesive energy density, improved thermal stability, and mechanical robustness. These SSEs exhibit minimal sulfur oxidation and excellent chemical/electrochemical interface stability with different cathode materials, such as O3-layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 , and Na 3 V 2 (PO 4 ) 3 cathodes. As a result, SSNIBs with P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 employing the sodium hafnium chalcohalide SSEs demonstrate outstanding cycling performance, achieving a capacity retention of 88.5% after 200 cycles at 0.1 C. This study establishes a new design strategy for high-performance SSEs, demonstrating that mixed-anion frameworks offer a viable route to overcome the intrinsic limitations of single-anion electrolytes in next-generation SSNIBs.

DFT calculation↗
DOE OSTI2023

Multifunctional Coatings on Sulfide‐Based Solid Electrolyte Powders with Enhanced Processability, Stability, and Performance for Solid‐State Batteries

Abstract Sulfide‐based solid‐state electrolytes (SSEs) exhibit many tantalizing properties including high ionic conductivity and favorable mechanical properties for next‐generation solid‐state batteries. Widespread adoption of these materials is hindered by their intrinsic instability under ambient conditions, which makes them difficult to process at scale, and instability at the Li||SSE and cathode||SSE interfaces, which limits cell performance and lifetime. Atomic layer deposition is leveraged to grow thin Al 2 O 3 coatings on Li 6 PS 5 Cl powders to address both issues simultaneously. These coatings can be directly grown onto Li 6 PS 5 Cl particles with negligible chemical modification of the underlying material and enable exposure of powders to pure and H 2 O‐saturated oxygen environments for ≥4 h with minimal reactivity, compared with significant degradation of the uncoated powder. Pellets fabricated from coated powders exhibit ionic conductivities up to 2× higher than those made from uncoated material, with a simultaneous decrease in electronic conductivity and significant suppression of chemical reactivity at the Li‐SSE interface. These benefits result in significantly improved room temperature cycle life at high capacity and current density. It is hypothesized that this enhanced performance derives from improved intergranular properties and improved Li metal adhesion. This work points to a completely new framework for designing active, stable, and scalable materials for next‐generation solid‐state batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2021

New Cost-Effective Halide Solid Electrolytes for All-Solid-State Batteries: Mechanochemically Prepared Fe 3+ -Substituted Li 2 ZrCl 6

Owing to the combined advantages of sulfide and oxide solid electrolytes (SEs), that is, mechanical sinterability and excellent (electro)chemical stability, recently emerging halide SEs such as Li 3 YCl 6 are considered to be a game changer for the development of all-solid-state batteries. However, the use of expensive central metals hinders their practical applicability. In this study, a new halide superionic conductors are reported that are free of rare-earth metals: hexagonal close-packed (hcp) Li 2 ZrCl 6 and Fe 3+ -substituted Li 2 ZrCl 6 , derived via a mechanochemical method. Conventional heat treatment yields cubic close-packed monoclinic Li 2 ZrCl 6 with a low Li + conductivity of 5.7 × 10 –6 S cm –1 at 30 °C. In contrast, hcp Li 2 ZrCl 6 with a high Li + conductivity of 4.0 × 10 –4 S cm –1 is derived via ball-milling. More importantly, the aliovalent substitution of Li 2 ZrCl 6 with Fe 3+ , which is probed by complementary analyses using X-ray diffraction, pair distribution function, X-ray absorption spectroscopy, and Raman spectroscopy measurements, drastically enhances the Li + conductivity up to ≈1 mS cm –1 for Li 2.25 Zr 0.75 Fe 0.25 Cl 6 . The superior interfacial stability when using Li 2+ x Zr 1– x Fe x Cl 6 , as compared to that when using conventional Li 6 PS 5 Cl, is proved. Furthermore, an excellent electrochemical performance of the all-solid-state batteries is achieved via the combination of Li 2 ZrCl 6 and single-crystalline LiNi 0.88 Co 0.11 Al 0.01 O 2 .

25 ENERGY STORAGE↗
DOE OSTI2023

Polycarbonate‐Based Solid‐Polymer Electrolytes for Solid‐State Sodium Batteries

Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1 mS cm −1 at 80 °C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83 mA h g −1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60 °C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. In conclusion, these results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.

25 ENERGY STORAGE↗
DOE OSTI2024

Development of Thin, Robust, Lithium-Impenetrable, HighConductivity, Electrochemically Stable, Scalable, and Low-Cost Glassy Solid Electrolytes for Solid State Lithium Batteries (Final Report)

Solid-state electrolytes (SSEs) must have thicknesses of < 50 microns in order to be competitive with current state-of-the-art organic liquid electrolyte batteries. Mixed oxy-sulfide-nitride (MOSN) glassy solid electrolytes (GSEs) can be drawn into thin ribbons using the glass redraw process, to form glasses with superior performance in a safe, lower-cost, monolithic glass film. It is expected that these new GSEs in solid-state lithium batteries (SSLBs) increase the energy density (anode basis) from ~300 mAh/g to ~ 4000 mAh/g. This project is focused on the development of candidate MOS GSE compositions, and optimization of the thin film drawing process to generate thin film glass ribbons for use in SSLBs.

25 ENERGY STORAGE↗
DOE OSTI2021

F and N Rich Solid Electrolyte for Stable All-Solid-State Battery

We report the instability of sulfide solid electrolytes to Li anode and high-voltage LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes limits the cyclic performance of all-solid-state lithium battery (ASSLB). Herein, the stability of Li 6 PS 5 Cl against Li anode is enhanced by mixing a small amount (0.32 wt%) of CuF 2 -LiNO 3 (CL) into Li 6 PS 5 Cl electrolyte layer to in-situ form a mixed-conductive-lithiophobic and self-healing LiF-Li 3 N-Cu solid electrolyte interphase (SEI) at Li 6 PS 5 Cl-CL/Li interface. The critical current density (CCD) of Li 6 PS 5 Cl-CuF 2 -LiNO 3 increases to 1.4 mA cm –2 /1.4 mAh cm –2 at room temperature, which is much higher than that of pristine Li 6 PS 5 Cl (0.4 mA cm –2 /0.4 mAh cm –2 ) even though mixing 0.32 wt% CL into Li 6 PS 5 Cl slightly reduces the ionic conductivity from 2.9 × 10 –3 to 1.5 × 10 –3 S cm –1 . The compatibility of Li 6 PS 5 Cl-CL electrolyte to single-crystalline NMC811 (S-NMC811) is further enhanced by adding a small amount (0.02 wt%) of AlF 3 into Li 6 PS 5 Cl-CL forming Li 6 PS 5 Cl-CuF 2- LiNO 3 -AlF 3 (Li 6 >PS 5 Cl-CLA) as a cathode electrolyte and by doing Cl – on S-NMC811 (Cl@S-NMC811) surface. The Cl@S-NMC811-Li 6 PS 5 Cl-CLA|Li 6 PS 5 Cl-CL|Li cells with areal capacity of 2.55 mAh cm -2 achieve a capacity retention of 69.4% after 100 cycles at 1C (1C = 200 mAh g -1 ). Adding a small amount of SEI and cathode/electrolyte interphase (CEI) former into the sulfide electrolytes with minimal reduction (48.3%) of ionic conductivity is an effective method to enhance the performance of ASSLB.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A conservative discontinuous-Galerkin-in-time (DGiT) multirate time integration framework for interface-coupled problems with applications to solid–solid interaction and air–sea models

In this paper we extend the DGiT multirate framework, developed in Connors and Sockwell (2022) for scalar transmission problems, to a solid–solid interaction (SSI) problem involving two coupled elastic solids and a coupled air–sea model with the rotating, thermal shallow water equations. In so doing we aim to demonstrate the broad applicability of the mathematical theory and governing principles established in Connors and Sockwell (2022) to coupled problems characterized by subproblems evolving at different temporal scales. Further, multirate time integration algorithms employing different time steps, optimized for the dynamics of each subproblem, can significantly improve simulation efficiency for such coupled problems. However, development of multirate algorithms is a highly non-trivial task due to the coupling, which can impact accuracy, stability or other desired properties such as preservation of system invariants. DGiT provides a general template for multirate time integration that can achieve these properties. To elucidate the manner in which DGiT accomplishes this task, we fully detail each step in the application of the framework to the SSI and air–sea coupled problems. Numerical examples illustrate key properties of the resulting multirate schemes for both problems.

42 ENGINEERING↗
DOE OSTI2021

Proton-detected 15 N- 1 H dipolar coupling/ 1 H chemical shift correlation experiment for the measurement of NH distances in biological solids under fast MAS solid-state NMR

Measurement of distances from dipolar couplings is essential for structural characterization, refinement and validation using the solid-state nuclear magnetic resonance (ssNMR) spectroscopy. Particularly, knowledge about NH dipolar interactions in biological solids is important for understanding the hydrogen (H)-bonding interactions, molecular geometry and spin dynamics. In this regard, we have proposed a proton-detected two-dimensional (2D) 15 N- 1 H dipolar coupling/ 1 H chemical shift correlation experiment using the C-symmetry based windowless recoupling of chemical shift anisotropy (ROCSA) in combination with the DIPSHIFT pulse-based method for the measurement of short NH distances in the isotopically labeled and naturally abundant biological solids at fast magic angle spinning (MAS) rates (40–70 kHz). Our proposed method results in undistorted recoupled 15 N- 1 H dipolar coupling powder lineshapes that are free from the recoupled 1 H CSA contributions under the 15 N evolution, a feature that is essential for the measurement of NH distances with improved accuracy (± 500 Hz in terms of the NH dipolar couplings). The pulse sequence developed in the present study is also insensitive to the 1H–1H homonuclear dipolar interactions, relaxation effects owing to its constant-time implementation, and t1-noise from the fluctuations in the MAS.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Operando X-Ray Tomography Imaging of Solid-State Electrolyte Response to Li Evolution under Realistic Operating Conditions

Solid-state Li-ion conductors are a next-generation battery technology that are particularly promising for electric vehicles, offering the capacitive benefits of Li metal anodes with nonflammable electrolytes. Microstructural evolution in these solid-state batteries, especially the Li anode, requires deeper understanding of the conditions under which certain undesired behaviors are more likely to occur. This study utilizes operando X-ray computed tomography to visualize the behavior of lithium in response to device operation, considering variables that are relevant to a realistic battery: stack pressure, microscale defects such as pores, and temperature. This work demonstrates that experimental and operational conditions, especially temperature, affect the fundamental driving forces of realistic solid electrolyte systems and provides visual insight into possible mechanisms of Li migration. In particular, the effect of these variables on Li propagation from the anode through pre-existing defects and Li nucleation within the imperfectly electron-insulating electrolyte is highlighted.

battery↗
DOE OSTI2021

Solvent-Cast Solid Electrolyte Membranes Based on a Charged Rigid-Rod Polymer and Ionic Liquids

Solid-state electrolytes are attractive for use in electrochemical devices because they remove the need for a flammable liquid electrolyte while contributing to the structural integrity of the device. We have recently developed a class of solid electrolytes, termed molecular ionic composites (MICs), composed of ionic liquids (ILs) and a rigid-rod polyelectrolyte, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT). MIC materials, originally obtained through an ion-exchange process between IL and PBDT aqueous solution, possess an unprecedented combination of high ionic conductivity, high thermal stability, low flammability and widely tunable tensile storage moduli. Here we present a facile solvent casting method for preparing MIC membranes. These membranes are uniform, flexible, and tough, with tunable composition and thickness (≥ 40 μm). Unlike the previous ion-exchange method, which only allowed incorporation of hydrophilic ILs, we can now incorporate hydrophobic ILs to prepare MIC membranes for, e.g. battery electrolytes. A sodium (Na) metal symmetric cell constructed with a PBDT-Pyr 14 TFSI membrane as the solid electrolyte shows long-term stable cycling (> 500 h.) at 60 °C. Furthermore, the ability to prepare MICs using both hydrophilic and hydrophobic ILs initiates a wider range of MIC materials and broadens the array of applications accessible by MIC membranes.

25 ENERGY STORAGE↗