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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Beyond Volume Variation: Anisotropic and Protrusive Lithiation in Bismuth Nanowire

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. Here, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li–Bi alloying process exhibits a two-step transition, that is, Bi–Li 1 Bi and Li 1 Bi–Li 3 Bi. Interestingly, the Bi–Li 1 Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li 1 Bi nanograins as a result of anisotropic Li–Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li 1 Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li 1 Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li 1 Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Revolutionizing Lithium Storage Capabilities in TiO 2 by Expanding the Redox Range

TiO 2 is a widely recognized intercalation anode material for lithium-ion batteries (LIBs), yet its practical capacity is kinetically constrained due to sluggish lithium-ion diffusion, leading to a lithiation number of less than 1.0 Li + (336 mAh g -1 ). Here, the growth of TiO 2 crystallites is restrained by integrating Si into the TiO 2 framework, thereby enhancing the charge transfer and creating additional active sites potentially residing at grain boundaries for Li + storage. This strategy is corroborated by the expanded redox range of Ti, as thoroughly demonstrated via synchrotron radiation-based X-ray spectroscopy and Cs-corrected electron microscopy. Consequently, when deployed for lithium storage, the tailored material achieves an extraordinarily high reversible capacity of 559 mAh g -1 , 116% of the theoretical maximum of 483 mAh g -1 calculated based on all active species, while simultaneously retaining superior rate capability and robust cycling stability. Further, this work offers fresh perspectives on the revitalization of traditional electrode materials to achieve enhanced capacities.

25 ENERGY STORAGE↗
DOE OSTI2020

Systematic Study of Al Impurity for NCM622 Cathode Materials

Many recycling processes have been developed for spent Li-ion batteries (LIBs), such as pyrometallurgy, hydrometallurgy, and direct recycling. For all the recycling methods, however, impurities are always introduced from the current collectors or casing materials, especially aluminum (Al), which might lead to negative effects on recovered electrode materials. Therefore, it is significant to determine the impacts of Al impurity on recovered materials. Here, the influence of the Al impurity for the synthesized LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) precursor and cathode is systematically studied. The cell with 0.2 at % Al impurity displays the highest reversible capacities (145.2, 130.5, and 100.3 mAh g -1 from 2, 3, and 5 C, respectively) and striking cycling capability at 2 C after 100 cycles with the highest retention capacity of 138.5 mAh g -1 . Meanwhile, the excess Al ions (5 at %) lead to the Li/Mn superlattice structure and deteriorate electrochemical performance of the synthesized NCM622 cathode.

25 ENERGY STORAGE↗
DOE OSTI2021

Life Cycle Assessment and Techno-Economic Assessment of Lithium Recovery from Geothermal Brine

Lithium-ion batteries (LIB) play an essential role in the electrification of the transportation sector, and battery demand for lithium compounds will see a significant increase in the coming decades. This has raised concerns on the supply of lithium, and as a result, technologies are being developed to process unconventional lithium sources. One promising technology is to extract lithium from geothermal brine using lithium-aluminum-layered double hydroxide chloride (LDH) sorbent and forward osmosis. A combined life cycle assessment (LCA) and techno-economic assessment (TEA) is conducted to evaluate the environmental and economic performance of this technology. It is assumed that the lithium extraction unit is an add-on to a 50 MW geothermal power plant located in California. The analysis is based on lab-scale experimental data and stoichiometry while considering the economy of scale for an industrial system. LCA results suggest that, compared with conventional LiOH and Li 2 CO 3 production pathways, the new technology achieves 1–95% reduction in environmental impacts. Even higher reduction can be achieved for LiOH produced via electrolysis. This add-on unit for lithium extraction could achieve a payback period of less than 1 year and reach net present values of $454M and $315M and internal rates of return of 792 and 1130% for LiOH and Li 2 CO 3 production pathways, respectively. The favorable environmental and economic performance suggests that LDH sorption coupled with forward osmosis has great potential to enable the domestic production of battery lithium compounds and that further development should be carried out.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Versatile Graphitized Carbon Nanofibers in Energy Applications

Graphitized carbon nanofibers (CNFs) are the allotropic forms of carbon that offer exceptional electrical conductivity, high aspect ratio, large surface-to-volume ratio, flexibility, mechanical robustness, and structural stability. These properties render CNFs as useful materials in energy applications, including water electrocatalysis and electrochemical energy storage devices (EESDs). Graphitized CNFs manifest huge versatility in EESDs and have been employed as electrode materials, as supports for other electrode materials, and conductive additives. This perspective summarizes the production methods, structural aspects, and energy applications of graphitized CNFs. Different design strategies have been employed to produce CNFs with diverse and distinct morphologies and structures. Their fabrication methods, along with precursors and dopants or cocatalysts, impact the overall structural, functional, and topographical properties. Recent developments on the state-of-the-art interests of graphitic CNFs in lithium-ion batteries (LIBs), lithium–sulfur (Li–S) batteries, vanadium redox flow batteries (VRFBs), supercapacitors, and water splitting have explored the many possibilities in energy sectors. Finally, the assembly and functioning of CNFs in water splitting and EESDs as well as primary challenges are discussed in this perspective.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Transforming CO 2 to Porous Carbon as a High-Performing Sodium-Ion Battery Anode via Electrochemical Reduction in Molten Carbonates

The prevalence of sodium over lithium prompts exploration of sodium-ion batteries (SIBs) as a viable alternative to lithium-ion batteries (LIBs). Hard carbon has emerged as a promising anode material for SIBs, yet its synthesis poses sustainability challenges and emits pollutants. Here, in this study, we introduce CO 2 -derived porous carbon (graphitic and amorphous) as an anode for SIBs via electrochemical reduction of CO 2 in a molten eutectic carbonate salt at a lower temperature that yields materials with controlled microstructure, morphology, and porosity conducive to energy storage. Our CO 2 -derived carbon demonstrates remarkable specific capacity, superior rate capability, and stable cycling performance as a SIB anode. This innovative strategy harnesses waste CO 2 toward advancing SIB energy technology.

CO2-derived carbon↗
DOE OSTI2024

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes PE for high-temperature processing. After removal of the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using an Fe-based catalytic process. The PE-derived graphite anode in a lithium-ion coin cell showed a specific capacity of 345 mAh/g at 0.05C with an initial Coulombic efficiency of 87% and reversible capacity retention of ~100% at different current rates. It also showed a specific capacity of up to 313 mAh/g at 0.5 discharge/charge cycles per hour (0.5C) and Coulombic efficiency of 99.9% after 250 cycles, indicating excellent electrochemical performance as an anode material for lithium-ion batteries. This method illustrates that there are opportunities for upcycling large quantities of PE waste to produce graphite powders suitable for use in LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material

Cation-disordered rock-salt (DRX) materials receive intensive attention as a new class of cathode candidates for high-capacity lithium-ion batteries (LIBs). Unlike traditional layered cathode materials, DRX materials have a three-dimensional (3D) percolation network for Li + transportation. The disordered structure poses a grand challenge to a thorough understanding of the percolation network due to its multiscale complexity. In this work, we introduce the large supercell modeling for DRX material Li 1.16 Ti 0.37 Ni 0.37 Nb 0.10 O 2 (LTNNO) via the reverse Monte Carlo (RMC) method combined with neutron total scattering. Here, through a quantitative statistical analysis of the material’s local atomic environment, we experimentally verified the existence of short-range ordering (SRO) and uncovered an element-dependent behavior of transition metal (TM) site distortion. A displacement from the original octahedral site for Ti 4+ cations is pervasive throughout the DRX lattice. Density functional theory (DFT) calculations revealed that site distortions quantified by the centroid offsets could alter the migration barrier for Li + diffusion through the tetrahedral channels, which can expand the previously proposed theoretical percolating network of Li. The estimated accessible Li content is highly consistent with the observed charging capacity. The newly developed characterization method here uncovers the expandable nature of the Li percolation network in DRX materials, which may provide valuable guidelines for the design of superior DRX materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Uranium Single Particle Analysis for Simultaneous Fluorine and Uranium Isotopic Determinations via Laser-Induced Breakdown Spectroscopy/Laser Ablation–Multicollector–Inductively Coupled Plasma–Mass Spectrometry

Uranyl fluoride (UO 2 F 2 ) particles (<20 μm) were subjected to first-of-its-kind analysis via simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation multi-collector inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS). Briefly, a nanosecond pulsed high-energy laser was focused onto the sample (particle) surface. In a single laser pulse, the UO 2 F 2 particle was excited/ionized within the microplasma volume, and the emission of light was collected via fiber optics such that emission spectroscopy could be employed for the detection of uranium (U) and fluorine (F). The ablated particle was simultaneously transported into the MC–ICP–MS for high precision isotopic (i.e., 234 U, 235 U, and 238 U) analysis. This method, LIBS/LA–MC–ICP–MS was optimized and employed to rapidly measure 80+ UO 2 F 2 particles, which were subjected to different calcination processes, which results in varying degrees of F loss from the individual particles. In measuring the particles, the average F/U ratios for the populations treated at 100 and 500 °C were 2.78 ± 1.28 and 1.01 ± 0.50, respectively, confirming loss of F through the calcination process. The average 235 U/ 238 U on the particle populations for the 100 and 500 °C were 0.007262 (22) and 0.007231 (23), which was determined to be <0.2% from the expected value. The 234 U/ 238 U ratios on the same particles were 0.000053 (11) and 0.000050 (10) for the 100 and 500 °C, respectively, <10% from the expected value. Notably, each population was analyzed in under 5 min, demonstrating the truly rapid analysis technique presented here in this paper.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

Traditional Li-ion intercalation chemistry into graphite anode exclusively utilizes the co-intercalation-free or co-intercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfied cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in-situ synthesis of t-THF-GICs in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GICs and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional co-intercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10,000 cycles. Full cells coupled with layered cathode, display remarkable cycling stability upon a 15-min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach to achieving fast-charging and low-temperature batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Synergistic Anion and Solvent-Derived Interphases Enable Lithium-Ion Batteries under Extreme Conditions

Lithium-ion batteries (LIBs) face increasingly stringent demands as their application expands into new areas, including extreme temperatures and fast charging. To meet these demands, the electrolyte should enable fast lithium-ion transport and form stable interphases on electrodes simultaneously. In practice, however, improving one aspect often compromises another. For instance, the trend toward electrolytes forming anion-derived interphases typically reduces transport efficiency due to weak-solvating solvents. Here, we propose that instead of relying on anions to form the interphase, leveraging both solvents and anions to form interphases can potentially lead to a balancing point between robust interphase formation and effective ion transport. Guided by this design principle, 2,2-difluoroethyl ethyl carbonate (DFDEC) was identified as the promising solvent. With the new electrolyte using DFDEC as the major solvent and lithium bis(fluorosulfonyl) imide (LiFSI) as the salt, graphite||LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cells are capable of fast charging and demonstrate long-term cycling stability with a cutoff voltage of 4.5 V. Notably, the battery shows a capacity retention of 84.3% after 500 cycles with an average Coulombic efficiency (CE) as high as 99.93%. This new electrolyte also enables stable battery cycling across a wide temperature range (-20 to 60 °C), with excellent capacity retention.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2025

Porous and Amorphous Mn x Mo 3 S 13 Chalcogel Electrode for High-Capacity Conversion-Based Lithium-Ion Batteries

While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, in this study, we present a porous, amorphous, sulfide-based Mn x Mo 3 S 13 chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn x Mo 3 S 13 (x = 0.25) chalcogel exhibits a local structure that resembles the Mo 3 S 13 cluster with Mn 2+ distributed across the Mo 3 S 13 matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn 2+ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo 3 S 13 chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn 0.25 Mo 3 S 13 half-cell delivers 897 mAh g –1 capacity during the first discharge and retains 571 mAh g –1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo 3 S 13 cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn 0.25 Mo 3 S 13 structure and the strong affinity of Lewis-acidic Mn 2+ for polysulfide anions generated during the charge–discharge process of the Li/Mn 0.25 Mo 3 S 13 cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes

High nickel content in LiNi x Co y Mn z O 2 (NCM, x ≥ 0.8, x + y + z = 1) layered cathode material allows high specific energy density in lithium-ion batteries (LIBs). However, Ni-rich NCM cathodes suffer from performance degradation, mechanical and structural instability upon prolonged cell cycling. Although the use of single-crystal Ni-rich NCM can mitigate these drawbacks, the ion-diffusion in large single-crystal particles hamper its rate capability. Herein, we report a strategy to construct an in situ Li 1.4 Y 0.4 Ti 1.6 (PO 4 ) 3 (LYTP) ion/electron conductive network which interconnects single-crystal LiNi 0.88 Co 0.09 Mn 0.03 O 2 (SC-NCM88) particles. The LYTP network facilitates the lithium-ion transport between SC-NCM88 particles, mitigates mechanical instability and prevents detrimental crystalline phase transformation. When used in combination with a Li metal anode, the LYTP-containing SC-NCM88-based cathode enables a coin cell capacity of 130 mAh g -1 after 500 cycles at 5 C rate in the 2.75-4.4 V range at 25 °C. Tests in Li-ion pouch cell configuration (i.e., graphite used as negative electrode active material) demonstrate capacity retention of 85% after 1000 cycles at 0.5 C in the 2.75-4.4 V range at 25 °C for the LYTP-containing SC-NCM88-based positive electrode.

25 ENERGY STORAGE↗
DOE OSTI2026

Unconventional polaronic ground state in superconducting LiTi 2 O 4

Geometrically frustrated lattices can display a range of correlated phenomena, ranging from spin frustration and charge order to dispersionless flat bands due to quantum interference. One particularly compelling family of such materials is the half-valence spinel LiB 2 O 4 materials. On the B-site frustrated pyrochlore sublattice, the interplay of correlated metallic behavior and charge frustration leads to a superconducting state in LiTi 2 O 4 and heavy fermion behavior in LiV 2 O 4 . To date, however, LiTi 2 O 4 has primarily been understood as a conventional BCS superconductor despite a lattice structure that could host more exotic ground states. Here, we present a multimodal investigation of LiTi 2 O 4 , combining ARPES, RIXS, proximate magnetic probes, and ab-initio many-body theoretical calculations. Our data reveals a novel mobile polaronic ground state with spectroscopic signatures that underlie co-dominant electron-phonon coupling and electron-electron correlations also found in the lightly doped cuprates. The cooperation between the two interaction scales distinguishes LiTi 2 O 4 from other superconducting titanates, suggesting an unconventional origin to superconductivity in LiTi 2 O 4 . Our work deepens our understanding of the rare interplay of electron-electron correlations and electron-phonon coupling in unconventional superconducting systems. In particular, our work identifies the geometrically frustrated, mixed-valence spinel family as an under-explored platform for discovering unconventional, correlated ground states.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Electron leakage through heterogeneous LiF on lithium–metal battery anodes

The solid–electrolyte interphase (SEI) that forms on lithium ion battery (LIB) anodes prevents degradation-causing transfer of electrons to the electrolyte. Grain boundaries (GBs) between different SEI components, like LiF, have been suggested to accelerate Li+ transport. However, using the non-equilibrium Green's function technique with density functional theory (NEGF-DFT), we find that GBs enhance electron tunneling in thin LiF films by 1–2 orders of magnitude, depending on the bias. Extrapolating to thicker films using the Wentzel–Kramers–Brillouin (WKB) method emphasizes that safer batteries require passivation of GBs in the SEI.

25 ENERGY STORAGE↗
DOE OSTI2020

Impact of surface coating on electrochemical and thermal behaviors of a Li-rich Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 cathode

Lithium-rich layered oxide materials are considered as potential cathode materials for future high-performance lithium-ion batteries (LIBs) owing to their high operating voltage and relatively high specific capacity. However, perceptible issues such as poor rate performance, poor capacity retention, and voltage degradation during cycling need to be improved before the successful commercialization of the material. In this report, zirconia coated Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 2 = 1.0, 1.5 and 2.0 wt%) materials are synthesized using a sol–gel assisted ball milling approach. A comparison of structural, morphological and electrochemical properties is examined to elucidate the promising role of ZrO 2 coating on the performance of the NMC cathode. A uniform and homogeneous ZrO 2 coating is observed on the surface of NMC particles as evident by TEM elemental mapping images. The ZrO 2 coated NMCs exhibit significantly improved electrochemical performance at a higher C-rate as compared to pristine material. 1.5% ZrO 2 coated NMC demonstrates better cycling stability (95% capacity retention) than pristine NMC (77% capacity retention) after 50 cycles. All ZrO 2 coated NMC materials demonstrated improved thermal stability compared to pristine material. The difference in onset temperature of 2 wt% ZrO 2 coated and pristine NMC is 20 °C. The improved electrochemical performance of ZrO 2 coated NMC can be attributed to the stabilization of its surface structure due to the presence of ZrO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗