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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Stable Cycling with Intimate Contacts Enabled by Crystallinity–Controlled PTFE–Based Solvent–Free Cathodes in All–Solid–State Batteries

All-solid-state batteries (ASSBs) employing Li-metal anodes and inorganic solid electrolytes are attracting great attention due to high safety and energy density for next-generation energy storage devices. However, the volume change of cathode active materials can cause contact loss, resulting in charge carrier isolation, heterogeneous current distribution, and poor electrochemical properties in ASSBs. Here, a simple, yet effective, solvent-free electrode engineering approach with polytetrafluoroethylene (PTFE) as a binder for ASSBs is reported, enabling intimate contact and stable interfaces with the cathode. It is substantiated that the crystallinity of PTFE can be controlled depending on the heat history, and highly crystalline PTFE displays robust mechanical properties. High-nickel LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode prepared with crystalline PTFE show improved cycle and rate performances in ASSBs. In addition, it is revealed that the intimate contact between cathode particles with a stable cathode electrolyte layer is maintained during cycling by postmortem studies. Furthermore, this simple engineering method can be applied to prepare cathodes with a variety of active materials and solid electrolytes in ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2015

Performances of YBaCo 1.4 Cu 0.6 O 5+δ –Ce 0.8 Sm 0.2 O 1.9 composite cathodes for intermediate-temperature solid oxide fuel cells

In this paper, the electrochemical properties of YBaCo 1.4 Cu 0.6 O 5+δ –xCe 0.8 Sm 0.2 O 1.9 (YBCC–xSDC, x=20, 30, 40, 50 wt%) have been investigated for the potential application in intermediate-temperature solid oxide fuel cells (IT-SOFCs). No chemical reactions between YBCC cathode and SDC electrolyte, and YBCC and La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM) occur. The thermal expansion coefficient (TEC) of YBCC cathode decreases with SDC addition. The TEC of YBCC–30SDC cathode is 13.60×10 –6 K -1 from 30 to 850 °C in air and it exhibits the best electrochemical performance among the YBCC–xSDC cathodes. The polarization resistance (R p ) of YBCC–30SDC is 0.027 Ω cm 2 at 850 °C, 0.044 Ω cm 2 at 800 °C and 0.075 Ω cm 2 at 750 °C. The maximum power density value of electrolyte-based cell with YBCC–30SDC cathode is 662, 483 and 319 mW cm -2 at 850, 800 and 750 °C, respectively. Finally, preliminary results indicate that YBCC–30SDC is especially promising as a cathode for IT-SOFCs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Decoupling mass transport and electron transfer by a double-cathode structure of a Li-O 2 battery with high cyclic stability

Aprotic lithium-oxygen (Li-O 2 ) batteries have attracted extensive attention due to their ultrahigh theoretical energy density. However, slow and undesired electron transfer during cathodic reactions causes low cyclic stability in these batteries. Here, in this paper, we demonstrate that O 2 mass transport and electron transfer for cathodic reactions in Li-O 2 batteries could be decoupled by a double-cathode structure that efficiently enables stable electron transfer between the cathode and Li 2 O 2 /O 2 . This resolves various side reactions and slow Li 2 O 2 reaction kinetics issues in conventional Li-O 2 batteries, leading to stable operation of the cell for nearly 2 months at a capacity of 0.2 and 5 mAh cm -2 , with more than 4- and 10-fold increases in cycle life when compared with single-cathode batteries. These remarkable improvements in the cyclic stability of Li-O 2 batteries with double cathodes provide an interesting concept for improving the operational stability of other metal-rechargeable batteries with conversion-type chemistry.

25 ENERGY STORAGE↗
DOE OSTI2024

Assessing cathode–electrolyte interphases in batteries

The cathode-electrolyte interphase plays a pivotal role in determining the usable capacity and cycling stability of electrochemical cells, yet it is overshadowed by its counterpart, the solid-electrolyte interphase. This is primarily due to the prevalence of side reactions, particularly at low potentials on the negative electrode, especially in state-of-the-art Li-ion batteries where the charge cutoff voltage is limited. However, as the quest for high-energy battery technologies intensifies, there is a pressing need to advance the study of cathode-electrolyte interphase properties. Here, we present a comprehensive approach to analyse the cathode-electrolyte interphase in battery systems. We underscore the importance of employing model cathode materials and coin cell protocols to establish baseline performance. Additionally, we delve into the factors behind the inconsistent and occasionally controversial findings related to the cathode-electrolyte interphase. In conclusion, we also address the challenges and opportunities in characterizing and simulating the cathode-electrolyte interphase, offering potential solutions to enhance its relevance to real-world applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Coupling Anionic Oxygen Redox with Selenium for Stable High‐Voltage Sodium Layered Oxide Cathodes

Utilizing anion redox reaction is crucial for developing the next generation of high-energy density, low-cost sodium-ion batteries. However, the irreversible oxygen redox reaction in Na-ion layered cathodes, which leads to voltage fading and reduced overall lifespan, has hindered their practical application. In this study, selenium is incorporated as a synergistic redox active center of oxygen to improve the stability of Na-ion cathodes. The redesigned cathode maintains stable voltage by demonstrating reversible oxygen redox while significantly suppressing the redox activity of manganese. The anionic redox contribution capacity of the selenium-doped Na 0.6 Li 0.2 Mn 0.8 O 2 cathode remains as high as 84% after 50 cycles, while the pristine Na 0.6 Li 0.2 Mn 0.8 O 2 cathode experiences a reduction to 39% of its initial capacity. The X-ray photoelectron spectroscopy data and computational analysis further revealed that selenium doping participates in redox as Se +4/5 which stabilizes the charged state and increases the energy step for O─O dimerization, thus improving the stability and lifespan of Na 0.6 Li 0.2 Mn 0.8 O 2 cathodes. In conclusion, the findings highlight the potential of redox coupling design to address the issue of voltage fade caused by irreversible anionic redox.

25 ENERGY STORAGE↗
DOE OSTI2024

Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni‐Rich Sodium Cathodes

Abstract Protonation of oxide cathodes triggers surface transition metal dissolution and accelerates the performance degradation of Li‐ion batteries. While strategies are developed to improve cathode material surface stability, little is known about the effects of protonation on bulk phase transitions in these cathode materials or their sodium‐ion battery counterparts. Here, using NaNiO 2 in electrolytes with different proton‐generating levels as model systems, a holistic picture of the effect of incorporated protons is presented. Protonation of lattice oxygens stimulate transition metal migration to the alkaline layer and accelerates layered‐rock‐salt phase transition, which leads to bulk structure disintegration and anisotropic surface reconstruction layers formation. A cathode that undergoes severe protonation reactions attains a porous architecture corresponding to its multifold performance fade. This work reveals that interactions between electrolyte and cathode that result in protonation can dominate the structural reversibility/stability of bulk cathodes, and the insight sheds light for the development of future batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Formation and Detriments of Residual Alkaline Compounds on High-Nickel Layered Oxide Cathodes

High-nickel layered oxides LiNi x M 1-x O 2 (x ≥ 0.9) have emerged as promising cathode materials for automotive batteries due to their high energy density and lower cost. However, the formation and accumulation of surface alkaline compounds during storage hinder their mass production and commercialization. Here, in this study, a validated chemical method is employed to deconvolute and quantify the evolution of each residual lithium compound in four representative cathodes during ambient-air storage, viz., LiNiO 2 (LNO), LiNi 0.95 Co 0.05 O 2 (NC), LiNi 0.95 Mn 0.05 O 2 (NM), and LiNi 0.95 Al 0.05 O 2 (NA). Furthermore, the activation energy of the reaction between water and the cathode is determined by measuring the leached LiOH concentration at various temperatures. While residual lithium and time-of-flight secondary-ion mass spectrometry measurements collectively reveal that the air stability overall follows the trend of NM > NA ≈ NC > LNO, the aged NM exhibits the highest charge-transfer resistance and the worst electrochemical performance among the cathodes. In situ, X-ray diffraction and scanning transmission electron microscopy unveil that the aged NM is plagued by a large area of resistive spinel-like M 3–x Li x O 4 phases, leading to aggravated particle reaction heterogeneity. Finally, a one-step recalcination method is demonstrated effective in fully restoring the degraded cathodes. This work provides insights into overcoming air sensitivity issues of high-Ni cathodes.

(S)TEM↗
DOE OSTI2017

Exploring Lithium Deficiency in Layered Oxide Cathode for Li-Ion Battery

Abstract or short description: The ever-growing demand for high capacity cathode materials is on the rise since the futuristic applications are knocking on the door. Conventional approach to developing such cathode relies on the lithium-excess materials to operate the cathode at high voltage and extract more lithium-ion. Yet, they fail to satiate the needs because of their unresolved issues upon cycling such as, for lithium manganese-rich layered oxides – their voltage fading, and for as nickel-based layered oxides – the structural transition. Here, in contrast, lithium-deficient ratio is demonstrated as a new approach to attain high capacity at high voltage for layered oxide cathodes. Rapid and cost effective lithiation of a porous hydroxide precursor with lithium deficient ratio acted as a driving force to partially convert the layered material to spinel phase yielding in a multiphase structure (MPS) cathode material. Upon cycling, MPS revealed structural stability at high voltage and high temperature and resulted in fast lithium-ion diffusion by providing a distinctive SEI chemistry – MPS displayed minimum lithium loss in SEI and formed a thinner SEI. MPS thus offer high energy and high power applications and provides a new perspective compared to the conventional layered cathode materials denying the focus for lithium excess material.

25 ENERGY STORAGE↗
DOE OSTI2022

Anomalous Redox Features Induced by Strong Covalency in Layered NaTi 1-y V y S 2 Cathodes for Na-Ion Batteries

The rising demand for energy density of cathodes means the need to raise the voltage or capacity of cathodes. Transition metal (TM) doping has been employed to enhance the electrochemical properties in multiple aspects. The redox voltage of doped cathodes usually falls in between the voltage of undoped layered cathodes. However, in this study, we found anomalous redox features in NaTi 1-y V y S 2 . The first discharge platform potential (2.4 V) is significantly higher than that of undoped NaTiS 2 and NaVS 2 (both around 2.2 V), and the energy density is raised by 15%. We speculate that the anomalous voltage is mainly attributed to the strong hybridization in the Ti-V-S system. Ti 3+ and V 3+ undergo charge transfer and form a more stable Ti (t 2g 0 e g 0 ) and V (t 2g 3 e g 0 ) electronic configuration. Our results indicate that higher voltage of cathode materials could be achieved by strong TM-ligand covalency, and this conclusion provides possible opportunities to explore high voltage materials for future layered cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Unveiling the High-valence Oxygen Degradation Across the Delithiated Cathode Surface

Charge compensation on anionic redox reaction (ARR) has been promising to realize extra capacity beyond transition metal redox in battery cathodes. The practical development of ARR capacity has been hindered by high-valence oxygen instability, particularly at cathode surfaces. However, the direct probe of surface oxygen behavior has been challenging. Here, the electronic states of surface oxygen are investigated by combining mapping of resonant Auger electronic spectroscopy (mRAS) and ambient pressure X-ray photoelectron spectroscopy (APXPS) on a model LiCoO 2 cathode. The mRAS verified that no high-valence oxygen can sustain at cathode surfaces, while APXPS proves that cathode electrolyte interphase (CEI) layer evolves and oxidizes upon oxygen gas contact. In conclusion, this work provides valuable insights into the high-valence oxygen degradation mode across the interface. Oxygen stabilization from surface architecture is proven a prerequisite to the practical development of ARR active cathodes.

25 ENERGY STORAGE↗
DOE OSTI2025

Anionic‐Based Layered Oxide Cathodes with High Electrochemical Performance through Dual‐Site Substitutions for Sodium‐Ion Batteries

Mn-rich layered oxide cathodes with anionic redox promise high energy density for sodium-ion batteries (SIBs) due to ultra-high capacity derived from both Mn and O redox couples. Nevertheless, instability of the reactions that lead to poor electrochemical stability hinders the cathodes from practical applications. Here, the Al and Zn dual-site substitution strategy is proposed to enhance electrochemical performance. Here, the designed cathode, Na 0.73 Zn 0.03 Li 0.25 Mn 0.76 Al 0.01 O 2 (AlZn), delivers a high discharge capacity of 242 mAh g −1 with an impressive rate capability (162 mAh g −1 at 1000 mA g −1 ) and excellent capacity retention (89.69% over 150 cycles). In addition, full-cell SIB based on AlZn coupled with hard carbon exhibits a high energy density of 317 Wh kg −1 (based on both cathode and anode mass) and a reasonable capacity retention of 80.8% after 250 cycles. Revealed by advanced investigations, the synergy of robust Al–O in TM layers and O–Zn–O pillars in Na layers helps alleviate severe inactive spinel/rock-salt phase transformation and intragranular cracks in the AlZn cathode. This consequently leads to greatly enhanced electrochemical performance over the pristine cathode. This work provides insight into improving electrochemical properties of anionic-redox-based layered oxides by Al/Zn co-substitutions toward high-energy SIBs.

25 ENERGY STORAGE↗
DOE OSTI2018

Angular Distributions of Plasma Flows in a Vacuum Arc with Boride Cathodes

Results of investigation of the angular distribution and mass-to-charge fractions of the ion flow generated in a pulsed vacuum arc with lanthanum hexaboride and boron carbide cathodes are presented. It is shown that the discharge with such cathodes provides efficient generation of the plasma with a high fraction of boron ions with charge states from 1+ to 3+ whose total fraction is determined by the fraction of the boron atoms in the cathode material. The angular distributions of ions in the plasma flow depend on the relationship between the masses of components of cathode materials: in the case of lanthanum hexaboride cathode, the distribution of boron ions is wider than that of lanthanum ions, and in the case of boron carbide cathode, the boron and carbon ion distributions are practically identical.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

LiCoO 2 -Based Fiber Cathodes for Electrospun Full Cell Li-ion Batteries

Here, particle/polymer electrospinning was used to prepare fiber mat cathodes containing LiCoO 2 nanoparticles, carbon powder, and poly(vinylidene fluoride) for Li-ion batteries. The fibers had a high LiCoO 2 particle content (70 wt%) which allowed for a high gravimetric capacity of 90 mAh g -1 (corresponding to 128 mAh g$-1\atop{LiCoO2}$) at 0.1C (1C = 274 mAh g$-1\atop{LiCoO2}$). Cathode performance was stable in a half cell with 78% capacity retention over 200 cycles at 0.5C. Unlike previous work on electrospun LiCoO 2 nanofibers prepared using sol-gel chemistry and high temperature processing, the particle/polymer fiber mat cathodes reported here were made thick with a high fiber volume fraction for high areal and volumetric capacities at fast charge/discharge rates (e.g., 0.81 mAh cm -2 and 62 mAh cm -3 at 2C) which were much greater than that of a slurry cast cathode of the same composition (0.004 mAh cm -2 and 0.30 mAh cm -3 at 2C). Full cells containing a LiCoO 2 /C/PVDF fiber mat cathode and C/PVDF fiber mat anode were also prepared and characterized. These electrospun batteries exhibited a high energy density of 144 Wh kg -1 at 0.1C and an areal capacity of 1.03 mAh cm -2 at 1C. The excellent performance of the electrospun particle/polymer cathodes and anodes is attributed to electrolyte penetration throughout the 3D fiber electrode mats, a large electrode/electrolyte interfacial area, and short Li + transport pathways between the electrolyte and active material nanoparticles in the radial fiber direction.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Unraveling the nature of sulfide ions in hydrometallurgical recycling of NCM622 cathode material

The use of lithium-ion batteries (LIBs) has increased dramatically since its initial inception in the late 20th century. Such a surge in the LIB market and industry has resulted in a huge demand for mineral resources. Besides, the large scale of production will lead to massive amounts of waste batteries in the end. As such, recycling is seen as an end-of-pipe process to resolve sustainability and environmental concerns. The hydrometallurgical recycling is considered to be the most prominent method to recover cathode materials from spent LIBs owing to its high leaching efficiency and low energy costs. A series of procedures including pretreatment of the spent LIBs, acid leaching of the black mass, chemical co-precipitation of the hydroxide precursor, and sintering of the cathode active material need to be operated precisely. In this aspect, the impurities introduced during the process could pose a serious threat to the reaction stability as well as recycling consistency. Here, the impact of sulfide ions on recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode material with the method of hydrometallurgy is first investigated in detail. This study shows that hydrometallurgical process is not obviously influenced by sulfide impurity. No signs of secondary phase or impurity inclusion are spotted in synthesized cathodes. Under 5 at % sulfide concentration conditions, the obtained NCM622 cathode exhibits a capacity of 159.4 mAh/g after 100 cycles at 1/3C, which is at the same level as virgin benchmark. The difference in rate performance between cathodes with and without additional sulfide is less than 2 % or even smaller. In short, the results indicate a neutral status of sulfide ions in hydrometallurgical recycling.

25 ENERGY STORAGE↗
DOE OSTI2022

Hydrothermal synthesis of Co-free NMA cathodes for high performance Li-ion batteries

Scalable and sustainable production of high voltage cathodes is required to meet the increasing demands for Li-ion batteries. Additionally, the anticipated scarcity of critical materials like cobalt necessitates demonstration of Co-free alternatives that can match the performance metrics of conventional cathodes. Herein, a hydrothermal synthesis route for production of a new class of high-capacity, cobalt-free cathode material, LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA9055) for next-generation Li-ion batteries is reported. In this work, the synthesized cathode material shows high crystallinity and purity with monodispersed spherical morphology. Extensive electrochemical, structural, and post-mortem characterization of this novel NMA material is carried out. NMA-Li half cells show an initial discharge capacity of 200 mAh/g with a 96% capacity retention over 100 cycles when cycled between 3.0 and 4.4 V. On the other hand, NMA full cells with Li 4 Ti 5 O 12 (LTO) electrodes as the anode, show an initial discharge capacity of 186 mAh/g with 81% capacity retention over 200 cycles. Post-mortem structural and morphological characterization show that the NMA morphology and crystal structure do not degrade significantly over 200 charge/discharge cycles. This new class of cobalt free cathode material containing nickel, manganese and aluminum synthesized by an ammonia-free synthesis route is expected to provide a facile solution towards sustainable cathode production.

25 ENERGY STORAGE↗
DOE OSTI2014

Chemical compatibility study of melilite-type gallate solid electrolyte with different cathode materials

Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25} has been extensively investigated by X-ray powder diffraction in a wide temperature range (up to 1573 K). Perovskite-type La{sub 0.8}Sr{sub 0.2}MnO{sub 3−d} and La{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−d} and K{sub 2}NiF{sub 4}-type La{sub 2}NiO{sub 4+d} were selected as cathode materials. The results of this study allow identifying the most suitable electrode material to be used in combination with the melilite-type gallate electrolyte and set the basis for future work on this novel system. - Graphical abstract: Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25} has been extensively investigated by means of X-ray powder diffraction. - Highlights: • Chemical compatibility between melilite-type gallate and cathodes for SOFCs up to 1573 K. • No reactivity observed between La{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}. • Reactivity observed between La{sub 0.80}Sr{sub 0.20}MnO{sub 3−d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}. • Significant reactivity observed between La{sub 2}NiO{sub 4+d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

LiMn{sub 2}O{sub 4} nanorod arrays: A potential three-dimensional cathode for lithium-ion microbatteries

Highlights: • Self-supported LiMn{sub 2}O{sub 4} nanorod arrays are prepared on the Pt substrates. • LiMn{sub 2}O{sub 4} nanorod array cathode exhibits a large areal capacity of 0.25 mAh cm{sup −2}. • LiMn{sub 2}O{sub 4} nanorod array cathode exhibits good cycle performance and rate capability. • LiMn{sub 2}O{sub 4} nanorod arrays are potential cathodes for 3D microbatteries. - Abstract: Although three-dimensional (3D) microbatteries represent great advantage compared to their two-dimensional counterparts, the fabrication of 3D cathode is still a challenge, which holds back the further development of 3D microbatteries. In this work, we present a novel approach for fabrication of LiMn{sub 2}O{sub 4} nanorod arrays as 3D cathode for microbatteries. α-MnO{sub 2} nanotube arrays are firstly grown on the Pt substrate as the template, and LiMn{sub 2}O{sub 4} nanorod arrays are then prepared by lithiation of α-MnO{sub 2} nanotube arrays in molten salt followed by 800 °C annealing in air. In the half cell test, the 3D LiMn{sub 2}O{sub 4} nanorod arrays exhibit both high gravimetric capacity (∼130 mAh g{sup −1}) and areal capacity (∼0.25 mAh cm{sup −2}), while maintaining good cycling stability and rate capability. The facile synthesis and superior electrochemical performance of the three-dimensional LiMn{sub 2}O{sub 4} cathode make it promising for application in microbatteries.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Embedding sulfur into N-doped carbon nanospheres as enhanced cathode for high-performance lithium-sulfur batteries

Graphical abstract: S has been successfully embedded into N-doped carbon nanospheres as enhanced cathode exhibiting good performance with high specific capacity and cycling stability. - Highlights: • Construct N-doped carbon nanospheres (N-CNSs) are host for sulfur. • N-CNSs/S cathode show high capacity and good cycles. • N doping is favorable for fast ion/electron transfer. - Abstract: Lithium-sulfur (Li-S) batteries are considered as one of the most efficient power candidates owing to high energy density about 7–10 times larger than the commercial cathode materials. However, its practical application is impeded by severe “shuttle effect” and low cycle stability. As a consequence, in this work, we report N-doped carbon nanospheres (N-CNSs) composited with S as cathode for Li-S batteries. The stacked carbon nanosphere structure can not only improve the conductivity of cathode, but also work as barriers to retard diffusion of intermediate polysulfide. Owing to the unique structure, the N-CNSs/S cathode exhibits superior electrochemical performances with high specific capacity (1228 mAh g{sup −1} at 0.1 C), and excellent rate capability as well as good cyclic life. Our smart designed strategy may promote the development of high performance Li-S batteries.

36 MATERIALS SCIENCE↗