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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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DOE OSTI2023

Trimer Quinoxalines as Organic Cathode Materials for Lithium-Ion Batteries

Due to synthetic ease, high redox potentials, low solubility in polar electrolytes, and good electric conductivity of their semiconducting crystals, discotic quinoxaline trimers (3Q) have been considered as possible candidates for 4 V organic cathodes in lithium-ion batteries. To assess their feasibility as such materials, several 3Q derivatives have been synthesized and tested in half-cells. In voltage limited cycling tests at 1.2–3.9 V vs Li/Li + , the specific discharge capacities of 40–180 mAh g -1 were obtained at a rate of 1 C, and multiple lithiation of 3Q and its derivatives was observed during discharge. However, the obtained discharge capacity was only a fraction of the theoretical capacity expected for reversible six-electron reduction; there was also rapid capacity fade. Our spectroscopic studies indicate the reversible three-electron lithiation at 2 V vs Li/Li + , but suggest instability of more highly discharged states. Finally, our conclusion is that while the 3Q derivatives combine several traits that are desirable in an organic cathode material (including negligible solubility, capacity for multiple charging, and near-100% coulombic efficiency), these materials are still impractical to use.

25 ENERGY STORAGE↗
DOE OSTI2023

Experimental Aging and Lifetime Prediction in Grid Applications for Large-Format Commercial Li-Ion Batteries

Due to the growth of electric vehicle and stationary energy storage markets, the production and use of lithium-ion batteries has grown exponentially in recent years. For many of these applications, large-format lithium-ion batteries are being utilized, as large cells have less inactive material relative to their energy capacity and require fewer electrical connections to assemble into packs. And especially for stationary energy storage systems, where energy delivered is the only revenue source, the economics of these battery systems is highly dependent on cell lifetime. However, testing of large-format lithium-ion batteries is time consuming and requires high current channels and large testing chambers, making information on the performance of commercial, large-format lithium-ion batteries hard to come by. Here, accelerated aging test data from four commercial large-format lithium-ion batteries is reported. These batteries span both NMC-Gr and LFP-Gr cell chemistries, pouch and prismatic formats, and a range of cell designs with varying power capabilities. Accelerated aging test results are analyzed to examine both cell performance, in terms of efficiency and thermal response under load, as well as cell lifetime. Cell thermal response is characterized by measuring temperature during cycle aging, which is used to calculated a normalized thermal resistance value that may help estimate both cell cooling needs or to help extrapolate aging test results to different thermal environments. Cell lifetime is evaluated qualitatively, considering simply the average calendar and cycle life across a range of conditions, as well as quantitatively, using statistical modeling and machine-learning methods to identify predictive aging models from the accelerated aging data. These predictive aging models are then used to investigate cell sensitivities to stressors, such as cycling temperature, voltage window, and C-rate, as well as to predict cell lifetime in various stationary storage applications. Results from this work show that cell lifetime and sensitivity to aging conditions varies substantially across commercial cells, necessitating testing for specific cell formats to make quantitative lifetime predictions. That being said, all commercial cells tested here are predicted to reach at least 10-year lifetimes for stationary storage applications. Based on the aging test results and modeling, some cells are expected to be relatively insensitive to temperature and use-case, making them suited for simple use cases with little or no thermal management and simple controls, while the lifetime of other cells could be extended to 20+ years if operated with thermal management and degradation-aware controls.

battery↗
DOE OSTI2026

Origin of Electrochemical Activation Leading to Enhanced Cycling Stability of Li‐ and Mn‐Rich Cathodes

Electrochemical activation is a critical step for optimal functioning of Li- and Mn-rich (LMR) cathodes, yet the underlying mechanism for such activation remains elusive. Here, by using scanning/transmission electron microscopy (S/TEM) combined with the associated energy-dispersive x-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS), we decipher the origin of the activation enhanced electrochemical properties. We reveal that activation induces the formation of a spinel-like phase within the C2/m domains of the LMR cathode, where the transition-metal ions partially occupy both the tetrahedral (8a) and octahedral (16c) sites of the $Fd\bar{3}m$ spinel lattice, distinguishing the spinel-like phase from the conventional high-voltage spinel. Systematic varying the cycling voltage reveals a critical activation voltage above which this spinel-like phase forms, while lower voltages preserve the layered bulk structure. As the spinel-like phase is a stable structure for electrochemical cycling, the present findings provide direct mechanistic insight into the voltage-dependent activation process and explain how the C2/m to spinel-like transformation upon activation contributes to the electrochemical performance of LMR cathodes, providing guidance for the rational design of Li-rich cathodes with enhanced cycling durability.

Li-rich and Mn-rich cathode↗
DOE OSTI2024

Mechanisms of Hysteresis and Reversibility across the Voltage-Driven Perovskite–Brownmillerite Transformation in Electrolyte-Gated Ultrathin La 0.5 Sr 0.5 CoO 3−δ

Perovskite cobaltites have emerged as archetypes for electrochemical control of materials properties in electrolyte-gate devices. Voltage-driven redox cycling can be performed between fully oxygenated perovskite and oxygen-vacancy-ordered brownmillerite phases, enabling exceptional modulation of the crystal structure, electronic transport, thermal transport, magnetism, and optical properties. The vast majority of studies, however, have focused heavily on the perovskite and brownmillerite end points. In contrast, here we focus on hysteresis and reversibility across the entire perovskite ↔ brownmillerite topotactic transformation, combining gate-voltage hysteresis loops, minor hysteresis loops, quantitative operando synchrotron X-ray diffraction, and temperature-dependent (magneto)transport, on ion-gel-gated ultrathin (10-unit-cell) epitaxial La 0.5 Sr 0.5 CoO 3-δ films. Further, gate-voltage hysteresis loops combined with operando diffraction reveal a wealth of new mechanistic findings, including asymmetric redox kinetics due to differing oxygen diffusivities in the two phases, nonmonotonic transformation rates due to the first-order nature of the transformation, and limits on reversibility due to first-cycle structural degradation. Minor loops additionally enable the first rational design of an optimal gate-voltage cycle. Combining this knowledge, we demonstrate state-of-the-art nonvolatile cycling of electronic and magnetic properties, encompassing >10 5 transport ON/OFF ratios at room temperature, and reversible metal-insulator-metal and ferromagnet-nonferromagnet-ferromagnet cycling, all at 10-unit-cell thickness with high room-temperature stability. This paves the way for future work to establish the ultimate cycling frequency and endurance of such devices.

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

Synthesis, structural and electrochemical properties of V4O9 cathode for lithium batteries

Single-phase three-dimensional vanadium oxide (V 4 O 9 ) was synthesized by reduction of V 2 O 5 using a gas stream of ammonia/argon (NH 3 /Ar). The as-synthesized oxide, prepared by this simple gas reduction method was subsequently electrochemically transformed into a disordered rock salt type-“Li3.7V4O9” phase while cycling over the voltage window 3.5 to 1.8 V versus Li. The Li-deficient phase delivers an initial reversible capacity of ∼260 mAhg −1 at an average voltage of 2.5 V vs. Li + /Li 0 . Further cycling to 50 cycles yields a steady 225 mAhg −1 . Ex situ X-ray diffraction studies confirmed that (de) intercalation phenomena follows a solid-solution electrochemical reaction mechanism. As demonstrated, the reversibility and capacity utilization of this V 4 O 9 is found to be superior to battery grade, micron-sized V 2 O 5 cathodes in lithium cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Enabling Stable Cycling of 4.2 V High-Voltage All-Solid-State Batteries with PEO-Based Solid Electrolyte

Poly(ethylene oxide) (PEO)-based solid electrolytes are expected to be exploited in solid-state batteries with high safety. Its narrow electrochemical window, however, limits the potential for high voltage and high energy density applications. In this paper, the electrochemical oxidation behavior of PEO and the failure mechanisms of LiCoO 2 -PEO solid-state batteries are studied. It is found that although for pure PEO it starts to oxidize at a voltage of above 3.9 V versus Li/Li + , the decomposition products have appropriate Li + conductivity that unexpectedly form a relatively stable cathode electrolyte interphase (CEI) layer at the PEO and electrode interface. The performance degradation of the LiCoO 2 -PEO battery originates from the strong oxidizing ability of LiCoO 2 after delithiation at high voltages, which accelerates the decomposition of PEO and drives the self-oxygen-release of LiCoO 2 , leading to the unceasing growth of CEI and the destruction of the LiCoO 2 surface. When LiCoO 2 is well coated or a stable cathode LiMn 0.7 Fe 0.3 PO 4 is used, a substantially improved electrochemical performance can be achieved, with 88.6% capacity retention after 50 cycles for Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 coated LiCoO 2 and 90.3% capacity retention after 100 cycles for LiMn 0.7 Fe 0.3 PO 4 . The results suggest that, when paired with stable cathodes, the PEO-based solid polymer electrolytes could be compatible with high voltage operation.

25 ENERGY STORAGE↗
DOE OSTI2023

Li–Mn–O Li-rich cation disordered rock-salt cathode materials do not undergo reversible oxygen redox during cycling

An in-depth study of “Li 4 Mn 2 O 5 ”, a nanocomposite of Li 2 O and Li 4-x Mn 2 O 5 with a disordered rock salt structure (LMO), was conducted to determine the origins of the observed anomalously high charge and discharge capacity in lithium cells, which can exceed 350 mA h g -1 . Using soft and hard X-ray absorption spectroscopy (XAS), mapping of resonant inelastic X-ray scattering (mRIXS), and X-ray Raman spectroscopy (XRS), it was determined that electrochemical decomposition of Li 2 O upon charge and reduction of Mn to below 3+ during discharge is responsible for the capacities that are observed, with no evidence of contributions from reversible oxygen redox. Here, the over-reduction is exacerbated when charging limits of 4.5–4.8 V are used due to side reactions between electrolytic solution and the highly oxidized active material. These side reactions result in dissolution of Mn at room temperature and release of oxygen and other gases during initial cycles, which, in turn, cause rapid capacity fading. This is accompanied by evolution of the voltage profile upon cycling towards one that resembles that of manganese oxide spinels. The cycling behavior can be improved somewhat by reducing the upper voltage limit, although this results in a diminishment of the discharge capacities below 200 mA h g -1 . By adding various amounts of spinel LiMn 2 O 4 during synthesis, it was possible to produce LMOs with rock salt structures having significantly improved cycling behavior but still having capacities in excess of 250 mA h g -1 . An optimized modified material also exhibits better rate capability and much less gas evolution during initial cycles than the unmodified LMO. Interestingly, as-made modified materials generally exhibited lower than expected average Mn oxidation states attributable to oxygen loss during the synthesis process, as well as higher capacities than expected based on their manganese contents. The oxygen loss during processing may reduce the activity of the remaining oxygen and account for the lower reactivity of the spinel-modified material.

25 ENERGY STORAGE↗
DOE OSTI2020

Multi-scale stabilization of high-voltage LiCoO 2 enabled by nanoscale solid electrolyte coating

LiCoO 2 (LCO) possess a high theoretical specific capacity of 274 mAh g -1 , and currently LCO charged to 4.48 V with a capacity of ~190–195 mAh g -1 is penetrating the commercial markets. Scalable strategies to further enhance the performance of LCO are highly attractive. Here, we develop a scalable ball-milling and sintering method to tackle this long-standing challenge by modifying LCO surface with only 1.5–3.5% ceramic solid electrolyte nanoparticles, specifically Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) as an example. Consequently, the atomic-to-meso multiscale structural stabilities have been significantly improved, even with a high cut-off voltage of 4.5 V vs. Li/Li + , leading to excellent electrochemical stabilities. The nano-LAGP modified Li|LCO cell exhibits high discharge capacity of 196 mAh g -1 at 0.1 C, capacity retention of 88% over 400 cycles, and remarkably enhanced rate capability (163 mAh g -1 at 6 C). These results show significant improvement compared to the Li|LCO cells. The as-prepared graphite|LAGP-LCO full cells also show steady cycling with 80.4% capacity retention after 200 cycles with a voltage cut-off of 4.45 V. This work provides a simple and scalable approach to achieve stable cycling of LCO at high voltage with high energy density.

25 ENERGY STORAGE↗
DOE OSTI2021

High-voltage insulator having multiple materials

High-voltage insulators are disclosed that are capable of handling diverse requirements, such as providing high standoff voltages, high temperature cycling, and the ability to withstand flexural stress. One high-voltage insulator includes a first piece formed from a first material, a second piece formed from a second material, and an interface section where the first piece contacts with and forms a seal with the second piece. The interface includes a first groove located that accommodates a first gasket, sets of matching threads on the first and second pieces. The interface section further accommodates a second gasket. In this multi-piece high-voltage insulator, the first material can have a first set of flexural, heat resistance, and electrical standoff characteristics suitable for a first environment, and the second material can have a second set of flexural, heat resistance and electrical standoff characteristics suitable for a second environment.

Podpaly, Yuri Anatoly↗
DOE OSTI2023

High-voltage insulators having multiple materials

High-voltage insulators are disclosed that are capable of handling diverse requirements, such as providing high standoff voltages, high temperature cycling, and the ability to withstand flexural stress. One high-voltage insulator includes a first piece formed from a first material, a second piece formed from a second material, and an interface section where the first piece contacts with and forms a seal with the second piece. The interface includes a first groove located that accommodates a first gasket, sets of matching threads on the first and second pieces. The interface section further accommodates a second gasket. In this multi-piece high-voltage insulator, the first material can have a first set of flexural, heat resistance, and electrical standoff characteristics suitable for a first environment, and the second material can have a second set of flexural, heat resistance and electrical standoff characteristics suitable for a second environment.

Podpaly, Yuri Anatoly↗
DOE OSTI2021

Unveiling decaying mechanism through quantitative structure-activity relationship in electrolytes for lithium-ion batteries

Understanding the decaying mechanism in lithium-ion batteries (LIBs) is critical to establishing a stable electrolyte system. Despite the advent of various novel electrolyte solvents designated for high-voltage LIBs, their working principles are not fully understood. Currently, oxidative decomposition of electrolytes is believed to be the major cause of capacity fade, and tremendous effort has been devoted to discovering a new electrolyte with enhanced anodic stability. However, the oxidative decomposition process cannot solely explain the rapid decay of some electrolyte systems with intrinsic high anodic stability when used with a high-nickel layered oxide cathode such as LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622). In this report, a study of the quantitative structure-activity relationship was conducted to deepen the mechanistic understanding of the decay in high-voltage LIBs. Here, the results obtained from the newly introduced molecular pair analysis and linear free-energy relationship (LFER) studies were highly consistent with the solvation-involved decaying mechanism in a high-nickel layered oxide cathode cycling at high voltage (> 4.5 V vs. Li/Li + ). There was no evidence correlating the solvation ability of electrolyte solvents with the decay of a high-nickel layered oxide cathode cycling at a relatively low voltage (< 4.3 V vs. Li/Li + ), nor with the high-voltage spinel cathode LiNi 0.5 Mn 1.5 O 4 (LNMO). Undoubtedly, the unveiled mechanistic insight provides a critical guideline for the development of an appropriate electrolyte system targeting different high-voltage cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Manganese-rich high entropy oxides for lithium-ion batteries:materials design approaches to address voltage fade

Lithium- and manganese-rich oxides are of interest as lithium-ion battery cathode materials as Mn is earth abundant, low cost, and can deliver high capacity. Herein, a high entropy strategy was used to prepare Mn rich high entropy oxide (HEO) materials by including four additional metals (Ni, Co, Fe and Al) in the compositions using a mild co-precipitation method. Two HEOs (Li x Ni 0.1 Mn 0.6 Co 0.1 Al 0.1 Fe 0.1 O y , where x = 1.5 for HEO-L and x = 0.5 for HEO-H) with layered and spinel-layered hybrid structures were investigated where the morphology, elemental composition, structure, atomic level phase distribution, and electrochemistry were determined. The HEO-L samples involve a Li 2 TMO 3 layered structure with ~39% stacking faults. HEO-H is a hybrid structure comprised of 80 wt% spinel and 20 wt% LiMO 2 layered structure. The high entropy manganese-rich HEO-L showed higher capacity and 93% retention of the average voltage after 100 cycles while HEO-H showed higher capacity retention and near 100% average voltage retention. Finally, operando X-ray absorption spectroscopy revealed that the Ni, Co, and Mn are redox active in both materials while the Fe center remains at the Fe 3+ oxidation state throughout cycling, where the changes in the oxidation states for both materials during discharge were consistent with the delivered electrochemical capacity rationalizing the observed electrochemistry.

25 ENERGY STORAGE↗
DOE OSTI2024

Halting Oxygen Evolution to Achieve Long Cycle Life in Sodium Layered Cathodes

Oxygen redox chemistries at high voltage have materialized as a revolutionary paradigm for cathodes with high-energy density; however, they are plagued by the challenges of labile oxygen loss and rapid degradations upon cycling, even after concerted endeavors from the research community. Here we propose a multi-concentration stratagem propelled by entropy reinforcement to enhance the electronic structure disorder (ESD) at high desodiation states for impeding undesired oxygen mobility and ensuring controlled oxygen activity, elucidated by density functional theory calculations. The increased disorder strengthens the reversible electrochemistry of lattice oxygen redox, leading to effectively suppressed P−O structural evolution and highly stable localized TMO 6 octahedral environments, as demonstrated by soft/hard X-ray absorption spectroscopy. Furthermore, through a comparative analysis of sodium-layered cathodes with different configuration entropy, we reveal that a high-entropy state induced by cationic disordering has the capacity to perturb cationic redox boundaries, significantly restraining the formation of detrimental O′3 phases. As a consequence, the high-voltage cycling stability has been greatly upgraded, up to 4.4 V versus Na + /Na, with an impressive 90.1 % capacity retention at 1 C over 100 cycles and 76.1 % capacity retention at 2 C over 300 cycles. In conclusion, the resilient oxygen redox, enabled through the control of ESD, broadens the horizons for entropy engineering and lays the foundation for advancements in high-energy, long-cycling, and safe batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Perspective—Potential Benefit of Li-Rich Cathode Materials: Reduction of Co and Ni Content Rather than Achievement of Ultra-High Capacities

In the conventional cycling protocol for lithium and manganese rich NMC layered oxides (LMRNMC), the upper cutoff voltage V cut is extended to ~ 4.8, to achieve capacities of similar to 250 mAh g -1 . With this mode of operation, structural rearrangements result in voltage fade upon cycling. Herein, a strategy is proposed to avoid these structural rearrangements based on (a) restricting V cut to values < ~ 4.6 to shut down the bulk instabilities, and (b) application of a (preferably) semi-coherent coating that protects the surface oxygen. The potential benefit of this strategy would be to minimize Co and Ni content, compared to Ni-rich NMC.

25 ENERGY STORAGE↗
DOE OSTI2022

Initiating a Roadmap for Solar Fuels R&D: Imagining Beyond Thermochemical Cycles

Sandia National Laboratories in collaboration with the National Renewable Energy Laboratory outline a framework for developing a solar fuels roadmap based on novel concepts for hybridizing gas-splitting thermochemical cycle s with high-temperature electro chemical steps. We call this concept SoHyTEC, a Solar Hybrid Thermochemical-Electrochemical Cycle. The strategy focuses on transforming purely thermochemical cycles that split water (H 2 O) and carbon dioxide (CO 2 ) to produce hydrogen (H 2 ) and carbon monoxide (CO) , respectively, the fundamental chemical building blocks for diverse fuels and chemicals , by substituting thermochemical reactions with high-temperature electrochemical steps. By invoking high-temperature electrochemistry, the energy required to complete the gas-splitting cycle is divided into a thermal component (process temperature) and an electrical component (applied voltage). These components, sourced from solar energy, are independently variable knobs to maximize overall process efficiency. Furthermore, a small applied voltage can reduce cycle process temperature by hundreds of degrees , opening the door to cost-effective solar concentrators and practical receiver/reactor de signs. Using the SoHyTEC concept as a backdrop, we outline a framework that advocates developing methods for automating information gathering, critically evaluating thermochemical cycles for adapting into SoHyTEC, establishing requirements based on thermodynamic analysis, and developing a model-based approach to benchmarking a SoHyTEC system against a baseline concentrating solar thermal integrated electrolysis plant. We feel these framework elements are a necessary precursor to creating a robust and adaptive technology development roadmap for producing solar fuels using SoHyTEC. In one example, we introduce high-temperature electrochemistry as a method to manipulate a fully stoichiometric two-step metal oxide cycle that circumvents costly separation processes and ultra-high cycle temperatures. We also identify and group water-splitting chemistries that are conceptually amenable to hybridization.

14 SOLAR ENERGY↗
DOE OSTI2022

Constructing O2/O3 homogeneous hybrid stabilizes Li-rich layered cathodes

With the advantages of high energy density and low manufacture cost, lithium-rich layered oxides (LLOs), typically with a layered O3-type structure, are regarded as promising cathodes for lithium-ion batteries (LIBs), but their broad usages are hindered by severe voltage decay over cycling. Although recent progress in O2-type LLOs has aroused interest for their less voltage decay, the critical barrier of unsatisfactory capacity retention has not been overcome yet. In this work, to tackle these handicaps, we design a new type of LLO (O2/O3-type LLO) with a homogeneous hybrid structure, where the O2 and O3 lattice stacking sequences are arranged alternatively. Benefitting from this novel O2/O3 hybrid structure, the designed material shows greatly improved voltage and capacity stability than that of pure O2- and O3-type LLOs. Revealed by in-situ synchrotron X-ray diffraction and operando differential electrochemical mass spectra, the O2/O3-hybrid LLO cathode shows a more reversible structural evolution, smaller volume change and suppressed oxygen loss during the electrochemical processes. Our approach has initiated a new way to reduce the capacity and voltage decay of LLOs, which endows great promise to the development of high-energy-density LIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

The Impact of Different Substituents in Fluorinated Cyclic Carbonates in the Performance of High Voltage Lithium-Ion Battery Electrolyte

Ethylene carbonate (EC) has been used as the Solid-Electrolyte Interphase (SEI) former in the conventional electrolyte for decades. However, its low anodic stability leads to severe capacity decay during cycling under high voltage operation. Therefore, finding a viable electrolyte with high anodic stability and the ability to form robust SEI for high voltage lithium-ion batteries is of primary importance. In this study, a series of electrolytes containing various fluorinated cyclic carbonates as the SEI former have been designed, synthesized and evaluated. Linear sweep voltammetry study suggested that fluorinated cyclic carbonates generally possess higher anodic stability than EC. Based on the cycling performance of LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC532)/ graphite full cells, the electrolyte with DFEC/FEMC (1.0 M LiPF 6 ) inhibited the oxidation side reaction on the cathode and forms a vigorous SEI on the anode. The high voltage NMC532/Graphite cell utilizing the novel electrolyte exhibits excellent cycling durability under both room and elevated temperature. The superior performance of the DFEC based electrolyte was further unveiled by SEM, EDAX and XRD. Both the anode and cathode of the full cell employing DFEC based electrolyte retained their intrinsic structures after cycling while the electrodes cycled in conventional electrolyte showed severe degradation.

25 ENERGY STORAGE↗