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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Identifying the Critical Role of Li Substitution in P2-Na x [Li y Ni z Mn 1-y-z ]O 2 (0 < x, y, z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries

Li-substituted layered P2–Na 0.80 [Li 0.12 Ni 0.22 Mn 0.66 ]O 2 is investigated as an advanced cathode material for Na-ion batteries. Both neutron diffraction and nuclear magnetic resonance (NMR) spectroscopy are used to elucidate the local structure, and they reveal that most of the Li ions are located in transition metal (TM) sites, preferably surrounded by Mn ions. To characterize structural changes occurring upon electrochemical cycling, in situ synchrotron X-ray diffraction is conducted. It is clearly demonstrated that no significant phase transformation is observed up to 4.4 V charge for this material, unlike Li-free P2-type Na cathodes. The presence of monovalent Li ions in the TM layers allows more Na ions to reside in the prismatic sites, stabilizing the overall charge balance of the compound. Consequently, more Na ions remain in the compound upon charge, the P2 structure is retained in the high voltage region, and the phase transformation is delayed. Ex situ NMR is conducted on samples at different states of charge/discharge to track Li-ion site occupation changes. Surprisingly, Li is found to be mobile, some Li ions migrate from the TM layer to the Na layer at high voltage, and yet this process is highly reversible. Novel design principles for Na cathode materials are proposed on the basis of an atomistic level understanding of the underlying electrochemical processes. These principles enable us to devise an optimized, high capacity, and structurally stable compound as a potential cathode material for high-energy Na-ion batteries.

Xu, Jing↗
DOE OSTI2014

Insight into the Atomic Structure of High-Voltage Spinel LiNi 0.5 Mn 1.5 O 4 Cathode Material in the First Cycle

Application of high-voltage spinel LiNi 0.5 Mn 1.5 O 4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi 0.5 Mn 1.5 O 4 cathode material. Although it is well-known that the structure of LiNi 0.5 Mn 1.5 O 4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood. Here, we report detailed investigations of local atomic-level and average structure of LiNi 0.5 Mn 1.5 O 4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi 0.5 Mn 1.5 O 4 //Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi 0.5 Mn 1.5 O 4 particles show migration of TM ions into tetrahedral Li sites to form a Mn 3 O 4 -like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely related to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi 0.5 Mn 1.5 O 4 cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi 0.5 Mn 1.5 O 4 structure to obtain better electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2018

Evaluation of Cation Migration in Lanthanum Strontium Cobalt Ferrite Solid Oxide Fuel Cell Cathodes via In-Operando X-ray Diffraction

Anode-supported SOFC button cells with LSCF-6428 cathodes were operated at various temperatures under constant current conditions for hundreds of hours in dry or humid (~3% water) cathode air while continuously collecting 1 hour XRD scans throughout the test duration. Additionally, one cell in dry air was held at OCV, and 12% CO2 was added to the humid air for another cell. Long cumulative XRD count times allowed minor phases in concentrations of less than 0.1 wt% to be identified. In humid air, cell performance increased during the first couple of hundred hours. XRD measured a gradual shift of Fe-rich Fe,Co spinel peaks to lower angles while post-mortem SEM discovered nano-nodules on the LSCF surfaces. When 12% CO2 was added to humid air, performance degradation was observed after the initial conditioning response, unlike in tests without CO2, which were stable after conditioning. XRD also measured a shift in the peaks of the major LSCF phase in the test with CO2 indicative of some degree of gradual decomposition. Cells tested at constant current in dry air exhibited fast initial degradation that decelerated over time, while the cell held at OCV maintained a stable voltage. XRD of the cathodes held at OCV at 750 °C and operated at constant current at 700 °C in dry air measured a slower shift of the Fe-rich spinel peaks to lower angles than was seen in tests in humid air, along with a shift in the peaks of a Co-rich Fe,Co spinel to higher angles. Post-mortem SEM of cells exposed to dry air discovered smaller nano-nodules on the LSCF surfaces than had been present in cells tested in humid air. Cells tested at constant current in dry air at 750 °C and 800 °C did not exhibit any gradual changes in the XRD patterns nor were nano-nodules discovered.

Hardy, John S.↗
DOE OSTI2021

Computational and experimental search for potential polyanionic K-ion cathode materials

Discovering high-energy cathode materials is critical to construct K-ion batteries for practical applications. Owing to the great success of layered oxides in Li- and Na-ion systems, K layered cathodes have also been investigated in recent years. However, the much larger size of K + compared to Li or Na introduces strong K + –K + interaction within the layer, which results in a sloped voltage profile thereby limiting the specific capacity and operating voltage. In contrast, polyanionic materials with a three-dimensional K + arrangement can effectively mitigate K + –K + interaction. In this work, ten K polyanionic compounds with theoretical capacity >100 mA h g –1 are screened from the Inorganic Crystal Structure Database as potential cathode materials for K-ion batteries. Among the ten proposed compounds, K 2 MnP 2 O 7 , K 2 Mn 2 P 2 O 7 F 2 , K 2 Fe 2 P 2 O 7 F 2 , and K 6 V 2 (PO 4 ) 4 with average voltage <4.5 V are synthesized and evaluated electrochemically. While the re-insertion of K into these compounds is not fully reversible, it may be related to the very high migration barrier that we compute for K ions. In addition, we show the successful synthesis of a series of K 3 V 3–x Cr x (PO 4 ) 4 (x = 0, 1, 2, 3) compounds. Among these, K 3 V 2 Cr(PO 4 ) 4 exhibits the largest reversible capacity, as revealed by the in situ investigation. Lastly, we find that the redox couples in many of these compounds sit at remarkably high potential, even higher than in equivalent Li compounds, which brings both opportunities and challenges in the future research of K polyanion cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Recent Progress in Cathode Materials for Sodium-Metal Halide Batteries

Transitioning from fossil-fuels to renewable energy sources is a critical goal of greenhouse gas re-duction and climate control. Major improvements have made wind and solar power increasingly cost-competitive with fossil fuels. However, the inherent intermittency of renewable power sources such motivates pairing these resources with energy storage. Electrochemical energy storage in batteries is widely used in many fields and increasingly for grid-level storage, but current battery technologies still fall short of performance, safety, and cost. This review focuses on sodium metal halide (Na-MH) batteries, such as well-known Na-NiCl2 batteries, as a promising solution to safe and economical grid-level energy storage. Important features of conventional Na-MH batteries are discussed, and recent literature on the development of intermediate temperature, low-cost cathodes for Na-MH batteries is highlighted. By employing lower cost metal halides (e.g. FeCl2, ZnCl2, and CuCl2, etc.) in the cathode and operating at lower temperatures (e.g. 190 °C vs. 280 °C), new Na-MH batteries have the potential to offer comparable performance at much lower overall costs, providing an exciting alternative technology to enable widespread adoption of renewables plus storage for the grid.

Zhan, Xiaowen↗
NASA NTRS2018

Hollow Cathode Thermal Modelling and Self-Consistent Plasma Solution: Work Function Evaluation for a LaB6 Cathode.

Self-heating hollow cathodes are central components in modern electric thrusters. The plasma discharge inside these devices heats the internal components, thus maintaining the temperatures required for electron emission. Precise knowledge of the physical phenomena governing hollow cathode operation is key to predict their lifetime, specifically, their thermionic emission characteristics. A simulation platform has been built to couple plasma and thermal models of the self-heating hollow cathode to produce a self-consistent solution. A self-consistent solution has been found for a LaB6 hollow cathode operating at 25A and 13 sccm where the work function is assumed to be spatially uniform along the emitter with a value which is allowed to vary as the coupled model iterates to a self-consistent solution. The emitter temperature from the converged solution does not agree with experimental temperature measurements, however. The results of a sensitivity analysis suggest that none of the tolerances in the measurement are responsible for the discrepancy. We hypothesize that either the work function needs to be a function of position along the emitting surfaces or the heat fluxes have been overestimated in the plasma solver.

Meiron, Daniel I.↗
DOE OSTI2018

Hybrid Lithium-Sulfur Batteries with an Advanced Gel Cathode and Stabilized Lithium-Metal Anode

The insulating nature of sulfur, polysulfide shuttle effect, and lithium metal deterioration cause a decrease in practical energy density and fast capacity fade in lithium-sulfur batteries. Here, we present an integrated strategy for the development of hybrid Li-S batteries based on a gel sulfur cathode, a solid electrolyte, and a protective anolyte composed of highly-concentrated salt electrolyte containing mixed additives. The dense solid electrolyte completely blocks polysulfide diffusion, and also makes it possible to investigate the cathode and anode independently. This gel cathode effectively traps the polysulfide active material while maintaining a low electrolyte to sulfur ratio (E/S) of 5.2 mL/g. The anolyte effectively protects the Li metal and suppresses the consumption of liquid electrolyte, enabling stable long-term cycling for over 700 hours in Li symmetric cells. This advanced design can simultaneously suppress the polysulfide shuttle, protect Li metal, and reduce the liquid electrolyte usage. The assembled hybrid batteries exhibit remarkably stable cycling performance over 300 cycles with high capacity. Finally, surface-sensitive techniques were carried out to directly visualize and to probe the interphase formed on the surface of the LAGP pellet, which may help stabilize the solid-liquid interface.

25 ENERGY STORAGE↗
DOE OSTI2026

Understanding Discharge‐Driven Growth of Cathode Impedance in Ni‐Rich NMC Cathodes

Degradation of LiNi x Mn y Co 1-x-y O 2 (NMC)-based lithium-ion batteries depends strongly on cut-off voltage ranges. In addition to the high upper cut-off voltage, a high depth of discharge (i.e., lower cut-off voltage) significantly worsens cathode impedance growth and capacity fade during long-term cycling. However, there is currently no consensus on the mechanism behind the negative role of a deep discharge. Here, this phenomenon was investigated in graphite||NMC cells with single-crystal cathodes (LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC622) or LiNi 0.76 Co 0.14 Mn 0.10 O 2 (NMC76)) using targeted aging protocols (constant high-voltage holds vs. charge–discharge cycling), while monitoring transition-metal (TM) dissolution, cathode-electrolyte interface (CEI) impedance, and NMC surface composition. We demonstrate a correlation between discharge-driven CEI impedance growth and increased TM dissolution. Furthermore, this degradation pathway is more pronounced in lower-Ni NMC622 than in higher-Ni (NMC76) under comparable delithiation states at charge, with both compositions undergoing the H2→H3 phase transition. X-ray photoelectron spectroscopy (XPS) reveals NMC composition-dependent evolution of surface lattice oxygen and restructured surface layer composition between charged and discharged states. These findings add mechanistic depth to the role of discharge as an active driver of interfacial degradation and provide new insights into its composition dependence.

25 ENERGY STORAGE↗
DOE OSTI2022

Decomposition of PVDF to delaminate cathode materials from end-of-life lithium-ion battery cathodes

The growing demand of electric vehicles and rapid consumption of rechargeable lithium-ion batteries (LIBs) require recycling of spent cathode active materials (CAMs) to reduce hazardous wastes and supply raw materials to LIB production. To separate CAMs from the cathode, direct calcination of polyvinylidene fluoride (PVDF) binder is widely applied, which leads to high energy consumption and release of toxic hydrogen fluoride. It is desirable to have an environmentally friendly and effective alternative to traditional direct calcination. In this study, five lithium salts, LiOAc (lithium acetate), LiNO 3 , LiCl, Li 2 CO 3 , and Li 2 SO 4 , were deployed and compared for their performance in recycling CAMs. A peel-off efficiency of up to 98.5% was achieved at a LiOAc to LiNO 3 molar ratio of 3:2, salt to cathode mass ratio of 10:1, and temperature of 300 °C at a holding time of 30 min. This system avoids corrosive chemicals and minimizes particle agglomeration of recycled products. Compared with sodium salt systems (NaOAc-NaNO 3 ) or direct calcination, the LiOAc-LiNO 3 system prevented high reaction temperature or further lithium loss and minimized crystal structure and morphological changes. In conclusion, a decomposition mechanism of PVDF through adsorption of HF and fluorine substitution was proposed.

25 ENERGY STORAGE↗
DOE OSTI2016

Structural integrity--Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. Here, our study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2 Ru 0.5 Mn 0.5 O 3 cathode particles at the meso to nano scale. We performed combined X-ray spectroscopy, diffraction and microscopy experiments to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scale morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. It also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.

25 ENERGY STORAGE↗
DOE OSTI2020

Unravelling high-temperature stability of lithium-ion battery with lithium-rich oxide cathode in localized high-concentration electrolyte

Lithium (Li)-rich manganese (Mn)-rich oxide (LMR) cathode materials, despite of the high specific capacity up to 250 mAh g-1 suffer from instability of cathode/electrolyte interfacial layer at high working voltages, causing continuous voltage decay and capacity fading, especially at elevated temperatures. In various battery systems, localized high-concentration electrolytes (LHCEs) have been widely reported as a promising candidate to form effective electrode/electrolyte interphases. Here, an optimized LHCE is studied in graphite (Gr)-based full cells being cycled at 25, 45 and 60 °C with the reference of a conventional LiPF6-based electrolyte. It is revealed that the LHCE can effectively suppress continuous electrolyte decompositions and mitigate the dissolution of Mn ions due to the formation of more protective electrode/electrolyte interphases on both anode and cathode, which, in turn, lead to significantly improved cycling stability and enhanced rate capability under the selected temperatures. The mechanistic understanding on the failure of the conventional LiPF6-containing electrolyte and the function of the LHCE in Gr||LMR cells under high temperatures provides valuable perspectives of electrolyte development for practical application of LMR cathodes in high energy density batteries over a wide temperature range.

Localized high-concentration electrolyte, Lithium-↗
DOE OSTI2020

Complementary Effects of Mg and Cu Incorporation in Stabilizing the Cobalt-Free LiNiO 2 Cathode for Lithium-Ion Batteries

Since the discovery of LiNiO 2 several decades ago, a new era of electric vehicles demanding high-energy-density lithium-ion batteries (LIBs) has recently rebooted the interest in this cathode material to eliminate the dependence on expensive and scarcely available cobalt. However, LiNiO 2 has been plagued by cycle instability, thermal instability, and air instability. We present here an exploration of the mutual interaction of magnesium and copper in stabilizing the cobalt-free LiNiO 2 cathode. Although Mg doping is beneficial for the robustness of the bulk structure of LiNiO 2 , surface characterization results of Mg-doped LiNiO 2 implies the need for further surface protection. To that end, we have incorporated Cu in addition to Mg in that Cu stabilizes the surface of Mg-doped LiNiO 2 by forming a protective stable surface layer without harming the bulk. Notable variations of the surface residual lithium composition (Li Li 2 CO 3 /Li LiOH ) along with the incorporation of stabilizers are also discussed. The harmony between Mg and Cu with as little as 0.5 atom % Mg and 0.3 atom % Cu significantly enhances the specific energy and cycle life of LiNiO 2 . Furthermore, this study demonstrates how the co-incorporation of optimal dopants can help stabilize both the bulk and surface and provides new insights toward developing cobalt-free layered oxide cathodes for high-energy-density LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Insights into the Chemistry of the Cathodic Electrolyte Interphase for PTFE-Based Dry-Processed Cathodes

Dry processing is a promising method for high-performance and low-cost lithium-ion battery manufacturing which uses polytetrafluoroethylene (PTFE) as a binder. However, the electrochemical stability of the PTFE binder in the cathodes and the generated chemistry of the cathode electrolyte interphase (CEI) layers are rarely reported. In this work, the CEI properties and PTFE electrochemical stability are studied via cycling the high-loading dry-processed electrodes in electrolytes with LiPF 6 or LiClO 4 salt. Using LiClO 4 salt can eliminate other possible F sources, allowing the decomposition of PTFE to be studied. The detection of LiF in cells with the LiClO 4 salt confirms that PTFE undergoes side reaction(s) in the cathodes. When compared with LiClO 4 , the CEI layer is much thicker when LiPF 6 is used as the electrolyte salt. These results provide insights into the CEI layer and may potentially enlighten the development of binders and electrolytes for the high efficiency and long durability of DP-based LIBs.

25 ENERGY STORAGE↗