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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 163 records · Page 9

Rational Electrolyte Formulation for Sodium Metal Batteries Operating in Extremely Cold Environments

Sodium metal batteries have shown considerable potential when operated at ambient temperatures. However, their performance in cold environments is constrained by increased electrolyte resistance with decreasing temperature and dendritic sodium plating associated with unstable solid electrolyte interphase (SEI), which are primarily influenced by the electrolyte composition. In this study, we present an electrolyte formulation that remains thermally stable down to −150 °C, which not only facilitates low internal resistance but also contributes to the formation of a protective SEI under cryogenic conditions. When cycled at −40 °C at 1 mA cm −2 , the sodium metal electrode exhibits a low overpotential of only 16 mV over 750 h; even at an ultra-low temperature of −80 °C, the electrode demonstrates remarkable long-term stability with a low overpotential of 54 mV sustained over 1500 h at 0.5 mA cm −2 . Furthermore, full cell evaluations when paring with Na 3 V 2 (PO 4 ) 3 cathode reveal a high average Coulombic efficiency exceeding 99.1% and a capacity retention over 83% after 100 cycles at both −40 °C and −80 °C.

Electrolyte↗

Efficient Low-Temperature Direct Lithium Extraction from Chloride Brines Enabled by High-Capacity Sorbent

The demand for lithium, a key component in rechargeable batteries for electric vehicles and renewable energy storage systems, has surged in recent years. Meeting this demand requires efficient extraction methods that are both environmentally friendly and economically viable. This study investigates the utilization of the high-capacity sorbent amorphous aluminum hydroxide for enabling efficient direct lithium extraction at low temperatures. Traditional extraction methods often involve acid-leaching and energy-intensive processes that are not only expensive but also environmentally taxing. In contrast, our approach leverages the exceptional sorption properties of amorphous aluminum hydroxide to facilitate lithium extraction directly from brine, achieving extraction efficiencies of 94.4% in case 1 and 96.2% in case 2 at low temperatures. Kinetic modeling using the Avrami–Erofe’ev framework reveals a nucleation-growth mechanism ( n = 0.71, k = 0.131 h –1 ), providing quantitative insights into the solid-state phase transformation process. This method significantly reduces energy consumption and minimizes the environmental footprint. Through systematic experimentation and optimization, we demonstrate the effectiveness and scalability of our approach, highlighting its potential to revolutionize lithium extraction processes. Our findings highlight the potential of high-capacity sorbents, particularly amorphous aluminum hydroxide toward sustainable lithium production, contributing to the advancement of clean-energy technologies.

anions↗

Stable metal anodes enabled by a labile organic molecule bonded to a reduced graphene oxide aerogel

Significance Rechargeable batteries based on metal anodes are highly desirable due to their high energy density. However, the electrochemical interface is generally not favorable for metal deposition, resulting in dendritic metal growth and an unstable solid–electrolyte interphase (SEI). We altered the interface using a labile organic molecule, benzenesulfonyl fluoride. This molecule was bonded to the surface of a reduced graphene oxide aerogel, which not only guides uniform metal deposition but also enables formation of a stable SEI layer. The lithium metal batteries showed stable cycling and excellent tolerance to low-temperature operation. Stable sodium and zinc anodes were also realized, demonstrating the versatility of this concept.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Electrolytes for Lithium-Ion Batteries in Wide Temperature Range Applications (Abstract)

The purpose of the proposed project is to improve the performances of Farasis’ commercial high-energy lithium ion batteries in a wide temperature range. PNNL has developed intellectual property about electrolyte additives and electrolyte formulations to greatly improve the low temperature discharge performance and the long-term cycling stability at room temperature and elevated temperatures of lithium ion batteries.

25 ENERGY STORAGE↗

Humins-Derived Hard Carbon as a Low-Cost Material for Sodium-Ion Battery Anodes

The growing demand for sodium-ion batteries (SIBs) in grid storage underscores the need for electrode materials that balance performance and cost, including sustainable and robust carbon sources. The equitable and abundant distribution of materials for SIBs, along with their superior low-temperature performance, safety, and fast-charging capability, further distinguishes them from lithium-ion batteries (LIBs). Hard carbon (HC) is the state-of-the-art anode for SIBs, but current commercial HC production is localized mostly to one region of the world, raising concerns about supply chain vulnerability, critical material dependency, and environmental aspects. Here, the first demonstration of humins, an abundant biorefinery byproduct, as a precursor for HC anodes for sodium-ion storage is reported. Humins were carbonized at 1100 degrees C-1300 degrees C, and the resulting materials were subjected to comprehensive materials and electrochemical characterization. Among the temperatures studied, humins-derived hard carbon synthesized at 1200 degrees C delivers an initial reversible capacity 270mA h g-1 , with stable cycling performance up to 500 cycles and excellent rate capability, representing the optimal performance. This study establishes humins as a promising and low-cost carbon source that provides a route to mitigate supply chain risks and valorizes an underutilized biorefinery waste stream for high-performance SIB anodes.

25 ENERGY STORAGE↗

Low-temperature paddlewheel effect in glassy solid electrolytes

Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic conductivity remain poorly understood. Here, ab initio molecular dynamics is used to characterize migration processes in the prototype glass, 75Li2S–25P2S5. Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS4 3- anions. This latter effect, known as the ‘paddlewheel’ mechanism, is typically observed in high temperature crystalline polymorphs. In contrast to the behavior of crystalline materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temperature. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable crystalline analogue, γ-Li3PS4, where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses containing complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temperature. Consequently, these systems may be fertile ground in the search for new solid electrolytes.

36 MATERIALS SCIENCE↗

Low-temperature synthesis process of making MgzMxOy, where M is Mn, V or Fe, for manufacture of electrode materials for group II cation-based batteries

Preparation, characterization, and an electrochemical study of Mg 0.1 V 2 O 5 prepared by a novel sol-gel method with no high-temperature post-processing are disclosed. Cyclic voltammetry showed the material to be quasi-reversible, with improved kinetics in an acetonitrile-, relative to a carbonate-, based electrolyte. Galvanostatic test data under a C/10 discharge showed a delivered capacity >250 mAh/g over several cycles. Based on these results, a magnesium anode battery, as disclosed, would yield an average operating voltage ˜3.2 Volts with an energy density ˜800 mWh/g for the cathode material, making the newly synthesized material a viable cathode material for secondary magnesium batteries.

25 ENERGY STORAGE↗

Highly disordered amorphous Li-battery electrolytes

"Medium-entropy" highly disordered amorphous Li garnets, with ≥4 unique local bonding units (LBUs), hold promise for use as solid-state electrolytes in hybrid or all-solid-state batteries owing to their grain-boundary-free nature and low-temperature synthesis requirement. Through this work, we resolved the local structure of amorphous Li garnet and understood their implication for Li dynamics. These medium-entropy amorphous structures possess unique characteristics with edge- and face-sharing LBUs, not conforming to the classic Zachariasen glass formation rules, and can be synthesized in a wide but processing-friendly temperature range (<680°C). Within these amorphous structures, Li and Zr are identified as the network formers and La as network modifier, with maxima in Li dynamics observed for smaller Li-O and Zr-O coordination; this structure understanding serves as a baseline for identifying additional network formers to further modulate Li transport. In conclusion, our insight provides fundamental guidelines for the structure and phase design for amorphous Li garnets and paves the way for their integration in next-generation batteries.

25 ENERGY STORAGE↗

Controlled Dy-doping to nickel-rich cathode materials in high temperature aerosol synthesis

Layered nickel-rich materials are promising next-generation cathode materials for lithium ion batteries due to their high capacity and low cost. However, the poor thermal stability and longtime cycling performance hinders the commercial applications of high nickel materials. Doping with heteroatoms has been an effective approach for improving electrochemical performance of cathode materials. Controlling doping concentration and geometrical distribution is desired for optimal electrochemical performance, but it is challenging in traditional co-precipitation methods. In this work, controlled dysprosium (Dy) doping to NCM811 was studied in an aerosol synthesis method by controlling the precursor concentrations and heating parameters. The obtained materials were characterized by SEM, XRD, and XPS, and their electrochemical properties and thermal stability were evaluated. By controlling the doping concentration (1.5%), Dy-doped NCM811 was improved simultaneously in long-term cycling and high-rate performance. Here, the thermal-chemical stability of the Dy-doped cathode materials was examined in a microflow reactor with a mass spectrometer. The results showed that Dy-doping shifted the O 2 onset temperature to a higher temperature and reduced O 2 release by 80%, thus dramatically increasing the thermal-chemical stability and improving the fire safety of cathode materials. Since high temperature aerosol synthesis is a low-cost and scalable method, the findings in this work have broad implications for commercial synthesis of novel materials with controlled doping modification to achieve high electrochemical performance and safety in lithium ion batteries.

25 ENERGY STORAGE↗

Cool rooms for indoor heat resilience: Evaluating affordable cooling strategies in heat-stressed California homes

Extreme heat conditions pose significant indoor survivability challenges for resource-constrained communities, which often lack access to cooling, have poorly insulated homes, and face compounding socioeconomic vulnerabilities. Moreover, concurrent power outages worsen health risks and heat-related illnesses. It is therefore crucial to develop innovative and affordable cooling approaches to protect vulnerable populations. This study assesses the efficacy of “cool rooms”– a designated space within a home equipped with passive and low-power active cooling measures to maintain safe indoor temperatures during extreme heat events and power disruptions. Using a physics-based building energy modeling approach, we evaluate the efficacy of various retrofit packages in maintaining thermal safety within the cool room under recent extreme heat conditions. The results indicate that passive measures can reduce 64% of hours with unmet standard effective temperatures, while the combination of passive and low-power active measures with built-in batteries further cuts this to 86%. Nevertheless, these strategies remain insufficient to maintain indoor thermal safety during extended outages. In contrast, integrating a solar-powered mini-split heat pump, whose technical potential was evaluated in this study, reduces indoor air temperatures below the 28 °C overheating threshold and significantly improves indoor habitability. The localized cool room strategy also offers potential for grid resilience by reducing peak electricity demand by up to 70% compared to whole house cooling during heat waves. The findings can inform the development of actionable heat mitigation plans and retrofit policies for residential communities with relatively low adoption of air conditioning such as warm marine climates.

Cool room↗

Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered Oxides

Layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-nickel (Ni) systems are attractive because of their high capacity. For practical use, synthetic control of stoichiometry and structural ordering is crucial but has been nontrivial due to the complexity inherent to synthesis reactions, which often proceed via nonequilibrium pathways. In this paper, we report here a combined in situ synchrotron X-ray diffraction and ab initio study of solid-state synthesis of layered oxides starting from acetate precursors for LiCoO 2 and LiNiO 2 and their solid solution LiNi 0.8 Co 0.2 O 2 . While all three systems ultimately evolve into the same thermodynamically stable layered phase ($R\overline{3}m$), each chemistry involves distinct metastable intermediates. We explain the phase progressions using a structural template model, demonstrating that during the synthesis of LiCoO 2 , the formed metastable spinel polymorph (Li 2 Co 2 O 4 ; $Fd\overline{3}m$) is a kinetically facile lithiation product of spinel Co 3 O 4 —the low-temperature (LT) intermediate from the decomposed Co-acetate. Similarly, in the Ni-based systems, the acetate decomposition products, rocksalts (Ni,Co)O, topotactically template the kinetic pathways of forming disordered rocksalts (Li x (Ni,Co) 2–x O 2 ; $Fm\overline{3}m$), consequently leading to off-stoichiometric Li x (Ni,Co)O 2 with undesired high Li/Ni mixing. These findings highlight new opportunities for engineering precursors to form LT intermediates that template the synthesis of target phases and structural properties.

36 MATERIALS SCIENCE↗

Investigating the Effects of Lithium Deposition on the Abuse Response of Lithium-Ion Batteries

Li deposition at the graphitic anode is widely reported in literature as one of the leading causes of capacity fade in lithium-ion batteries (LIBs). Previous literature has linked Li deposition resulting from low-temperature ageing to diminished safety characteristics, however no current research has probed the effects of Li deposition on the abuse response of well-characterized cells. Using overtemperature testing, a relationship between increased concentrations of Li deposition and exacerbated abuse response in 1 Ah pouch cells has been established. A novel Li deposition technique is also investigated, where cells with n:p < 1 (anode-limiting) have been cycled at a high rate to exploit Li + diffusion limitations at the anode. Scanning Electron Microscopy of harvested anodes indicates substantial Li deposition in low n:p cells after 20 cycles, with intricate networks of Li(s) deposits which hinder Li + intercalation/deintercalation. Peak broadening and decreased amplitude of differential capacity plots further validates a loss of lithium inventory to Li + dissolution, and Powder X-ray Diffraction indicates Li + intercalation with staging in anode interstitial sites as the extent of Li deposition increases. A cradle-to-grave approach is leveraged on cell fabrication and testing to eliminate uncertainty involving the effects of cell additives on Li deposition and other degradation mechanisms.

25 ENERGY STORAGE↗

Scale-up Production of Graphene Monoxide for Next-Generation LIB Anodes (AMMTO Final Report)

COnovate, LLC has developed a patented material called graphene monoxide and demonstrated that its unique chemical and crystal structure enables lithium-ion batteries (LIB) with greater specific capacity, safer and faster charging, and better low temperature performance than the industry standard. The current capability gap with COnovate’s technology is to scale up this new active anode material, developing processing technology to commercially relevant levels. This project will develop the means for progressive scale-up to 100g, 1kg, and 10kg levels, incorporating industrial synthesis and processing technologies, and deliver an industrial procedure/batch record draft for use by potential full-scale manufacturers to develop metric-ton production levels. The project goals of 10kg production and industrial procedure for full-scale production are necessary for COnovate’s customers to adequately evaluate and adopt their technology, and to pursue purchase orders for tons of material. MERF will confirm material analytics and performance in half cell tests during scaling and deliver materials to COnovate for QA/QC testing during the iterative scale up efforts. The final product batches will be delivered to COnovate for battery assembly and lifetime testing.

25 ENERGY STORAGE↗

Scalable, Ultrathin, and High-Temperature-Resistant Solid Polymer Electrolytes for Energy-Dense Lithium Metal Batteries

We report all-solid-state batteries (ASSBs) demonstrate great promise, offering high energy density, good thermal stability, and safe operation compared with traditional Li-ion batteries. Among various solid-state electrolytes (SSEs), solid polymer electrolytes (SPEs) offer an attractive choice due to their thinness, low density, and good manufacturability. However, ultrathin SPEs that work with practical current densities or at high temperatures remain challenging, limiting applicable conditions of SPE-based batteries. Here, the authors report a novel scalable, ultrathin, and high-temperature-resistant SPE for ASSBs. This design includes an electrospun polyacrylonitrile (PAN) matrix and polyethylene oxide (PEO)/Li salt ionic conductor, which offers a stable LiF and Li 3 N containing SSE/Li interface. The unique interface—as well as the good mechanical strength—inhibits lithium dendrites and prevents short circuiting. As a result, symmetrical Li-Li cells deliver more than 300 h cyclability at 0.5 mA cm -2 . ASSBs fabricated with only 5 µm-thickness PAN-PEO/lithium bis(trifluoromethanesulfonyl)imide reach 300 cycles at 0.3 C rate at 60 °C. The excellent thermal stability of PAN also results in safer SPEs at high temperatures. The design extends battery operation up to temperatures of 120 and 150 °C, where it achieves 500 cycles at C/2 rate and 100 cycles at 2C rate, respectively.

25 ENERGY STORAGE↗

Molten Salt Assisted Low-Temperature Electro-Catalytic Graphitization of Coal Chars

A great effort has been centered around developing clean energy technologies (energy storage devices) to curtail burning fossil fuels' deleterious environmental effects. Rechargeable batteries [lithium-ion batteries (LIBs)] are among the most invested and investigated storage devices showing potential to transform fossil fuel-powered mobility to next-generation safe electromobility. However, LIBs powered electric vehicles (EV) are expensive due to the high-cost graphite anode associated with LIBs. Herein, the synthesis of low-cost, highly crystalline nano-graphite with a tunable microstructural architecture has been demonstrated via molten salt assisted low-temperature electro-catalytic graphitization of coal chars, traditionally non-graphitizable carbon. Thus, graphite derived from coal chars exhibited nanoflake architecture and delivered high reversible capacity, stable long cycle life, and excellent electrochemical performance under fast charging/discharging conditions (5C, ~12 min charge/discharge time). This finding paves the way to manufacture cost-effective high-energy-density batteries using as-synthesized graphite from readily available coal sources that could propel the EVs to the next level.

25 ENERGY STORAGE↗

A Cross‐Linked Flexible Metaferroelectrolyte Regulated by 2D/2D Perovskite Heterostructures for High‐Performance Compact Solid‐State Sodium Batteries

Abstract To address the issues of limited ionic conductivity and poor interface stability at room and low temperatures in solid‐state electrolytes, a robust intrinsic ferroelectrolyte or nanoferroelectrolyte strategy for engineering solid‐state flexible ferroelectric composite electrolytes utilizing strongly coupled intrinsic ion conducting 2D/2D sodium‐rich anti‐perovskite (NaRAP)/ferroelectric perovskite heterostructures is introduced. Herein, highly scalable PVDF‐based metaferroelectrolytes with Na 2.99 Ba 0.005 OCl/Ca 2 Na 2 Nb 5 O 16 − (CNNO − ) nanosheets into a ferroelectric poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) matrix, through an in situ cross‐linking and spontaneous bridging method, for compact solid‐state sodium batteries (SSBs), are reported. Benefiting from unique well‐dispersed 3D ferroelectric coupled network and the Na 2.99 Ba 0.005 OCl/CNNO − ‐induced PVDF‐HFP ferroelectric β phase, the Na + flux is regulated, thereby inhibiting Na dendrite growth at the interface. Notably, the optimized PH‐5% NC metaferroelectrolyte exhibits rapid ion transport (1.11 × 10 −4 S cm −1 at 25 °C), a wide electrochemical window (> 4.8V), superior conformal mechanical compatibility, improved flexibility, good elasticity and flame retardancy. The solid‐state Na 3 V 2 (PO 4 ) 3 /PH‐5% NC/Na batteries present a stable cycling performance (remaining 56.4 mAh g −1 after 500 cycles at 1 C) even at 0 °C, potential for cost‐effective, safe, stable and compact SSB energy storage over 600 Wh L −1 , vastly surpassing 365 Wh L −1 of the current commercial sodium‐ion liquid‐electrolyte batteries.

Chemistry↗

Electrolytic recovery of metals from lithium battery cathodes in moisture-tolerant molten hydroxide salt

Lithium-ion battery recycling offers an opportunity to develop innovative technologies to close the loop on the battery materials cycle and increase the resilience of the battery supply chain. Here, in this study, we demonstrate a two-step pyroelectrochemical method for producing mixed-metals from lithium-ion cathodes in a molten hydroxide salt. Mixed metal oxides in the form of insoluble lithium-ion cathode materials of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and spent lithium-ion battery materials (black mass) were electrochemically reduced to a soluble form and dissolved into a molten hydroxide salt bath. Electrochemical characterization of the process salt indicated accumulation of dissolved transition metals in the salt. A separate cathode was used to produce alloys of Ni, Mn, and Co electrochemically from the dissolved lithium-ion cathode materials. Characterization by scanning electron microscopy fitted with an energy dispersive X-ray spectrometer showed transition metals present in the cathode materials were recovered at the separate cathode. This approach represents a scalable, low temperature pyroelectrochemical process that can potentially reduce the cost and close the loop of battery cathode recycling.

25 ENERGY STORAGE↗

Molten Sodium Penetration in NaSICON Electrolytes at 0.1 A cm –2

High-conductivity solid electrolytes, such as the Na superionic conductor, NaSICON, are poised to play an increasingly important role in safe, reliable battery-based energy storage, enabling advanced sodium-based batteries. Coupled demands of increased current density (≥0.1 A cm –2 ) and low-temperature (<200 °C) operation, combined with increased discharge times for long-duration storage (>12 h), challenge the limitations of solid electrolytes. Here, we explore the penetration of molten sodium into NaSICON at high current densities. Previous studies of β"-alumina proposed that Poiseuille pressure-driven cracking (mode I) and recombination of ions and electrons within the solid electrolyte (mode II) are the two main mechanisms for Na penetration, but a comprehensive study of Na penetration in NaSICON is necessary, particularly at high current density. To further understand these modes, this work employs unidirectional galvanostatic testing of Na|NaSICON|Na symmetric cells at 0.1 A cm –2 over 23 h at 110 °C. Further, while galvanostatic testing shows a relatively constant yet increasingly noisy voltage profile, electrochemical impedance spectroscopy (EIS) reveals a significant decrease in cell impedance correlated with significant sodium penetration, as observed in scanning electron microscopy (SEM). Further SEM analysis of sodium accumulation within NaSICON suggests that mode II failure may be far more prevalent than previously considered. Further, these findings suggest that total (dis)charge density (mAh cm –2 ), as opposed to current density (mA cm –2 ), may be a more critical parameter when examining solid electrolyte failure, highlighting the challenge of achieving long discharge times in batteries using solid electrolytes. Together, these results provide a better understanding of the limitations of NaSICON solid electrolytes under high current and emphasize the need for improved electrode–electrolyte interfaces.

25 ENERGY STORAGE↗