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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Low-cost iron trichloride cathode for all-solid-state lithium-ion batteries

The dominant chemistries of lithium-ion batteries on the market today still rely on flammable organic liquid electrolytes and cathodes containing scarce metals, such as cobalt or nickel, raising safety, cost and environmental concerns. Here we show a FeCl 3 cathode that costs as little as 1% of the cost of a LiCoO 2 cathode or 2% of a LiFePO 4 cathode. Once coupled with a solid halide electrolyte and a lithium-indium (Li–In) alloy anode, it enables all-solid-state lithium-ion batteries without any liquid components. Notably, FeCl 3 exhibits two flat voltage plateaux between 3.5 and 3.8 V versus Li + /Li, and the solid cell retains 83% of its initial capacity after 1,000 cycles with an average Coulombic efficiency of 99.95%. Combined neutron diffraction and X-ray absorption spectroscopy characterizations reveal a Li-ion (de)intercalation mechanism together with a Fe 2+ /Fe 3+ redox process. Further, our work provides a promising avenue for developing sustainable battery technologies with a favourable balance of performance, cost and safety.

25 ENERGY STORAGE↗
DOE OSTI2013

Hybrid Li-air battery cathodes with sparse carbon nanotube arrays directly grown on carbon fiber papers

Sparsely populated, vertically aligned nitrogen doped carbon nanotube arrays (CNTAs) with dislocated-graphene stacking were grown directly on carbon fiber papers and investigated as hierarchical air cathodes in hybrid Li-air batteries with aqueous catholytes. The CNTAs were made with electrodeposited Ni nanocatalysts, followed by plasma-enhanced chemical vapor deposition. The thus obtained CNTAs can reach a population number density as low as similar to 10(7) per cm(2) on the carbon fibers, achieving an extremely high porosity of over 99% for the active layer in the cathode. The sparse CNTAs not only provide effective pathways for the reacting species, but also show a significantly high catalytic activity, which is found to be comparable to that of a supported Pt electrocatalyst. The high activity of the CNTAs is attributed to the rich graphene edges exposed on the CNT surface and nitrogen doping. Hybrid Li-air batteries with such cathodes have shown a consistent discharging capacity of 710 mA h g(-1) and a specific energy of 2057 W h kg(-1) at 0.5 mA cm(-2). Stable charge-discharge cycling at 0.5 mA cm(-2) showed an average potential difference of 1.35 V, indicative of a relatively small overpotential and high round trip efficiency (71%). Furthermore, the hybrid Li-air battery based on the hierarchical cathode can reach a power density as high as 10.4 mW cm(-2).

Li, YF↗
DOE OSTI2016

Exceptional energy and new insight with a sodium–selenium battery based on a carbon nanosheet cathode and a pseudographite anode

We created a unique sodium ion battery (NIB, SIB) cathode based on selenium in cellulose-derived carbon nanosheets (CCNs), termed Se-CCN. The elastically compliant two-dimensional CCN host incorporates a high mass loading of amorphous Se (53 wt%), which is primarily impregnated into 1 cm 3 g -1 nanopores. The results in facile sodiation kinetics due to short solid-state diffusion distances and a large charge transfer area of the nanosheets were established. The architecture also leads to an intrinsic resistance to polyselenide shuttle and to disintegration/coarsening. As a Na half-cell, the Se-CCN cathode delivers a reversible capacity of 613 mA h g -1 with 88% retention over 500 cycles. The exceptional stability is achieved by using a standard electrolyte (1 M NaClO4 EC-DMC) without secondary additives or high salt concentrations. The rate capability is also superb, achieving 300 mA h g -1 at 10C. Compared to recent state-of-the-art literature, the Se-CCN is the most cyclically stable and offers the highest rate performance. As a Se–Na battery, the system achieves 992 W h kg -1 at 68 W kg -1 and 384 W h kg -1 at 10144 W kg -1 (by active mass in a cathode). We are the first to fabricate and test a Se-based full NIB, which is based on Se-CCN coupled to a Na intercalating pseudographitic carbon (PGC) anode. It is demonstrated that the PGC anode increases its structural order in addition to dilating as a result of Na intercalation at voltages below 0.2 V vs. Na/Na+. The {110} Na reflections are distinctly absent from the XRD patterns of PGC sodiated down to 0.001 V, indicating that the Na metal pore filling is not significant for pseudographitic carbons. Lastly, the battery delivers highly promising Ragone chart characteristics, for example yielding 203 and 50 W h kg -1 at 70 and 14 000 W kg -1 (via total material mass in the anode and cathode).

25 ENERGY STORAGE↗
DOE OSTI2016

Effective recycling of manganese oxide cathodes for lithium based batteries

Rechargeable lithium ion batteries (LIBs) occupy a prominent consumer presence due to their high cell potential and gravimetric energy density, there are also limited opportunities for electrode recycling. Currently used or proposed cathode recycling processes are multistep procedures which involve sequences of mechanical, thermal, and chemical leaching, where only the base material is recovered and significant processing is required to generate a recycled electrode structure. Another significant issue facing lithium based batteries is capacity fade due to structural degradation of the electroactive material upon extending cycling. Herein, inspired by heterogeneous catalyst thermal regeneration strategies, we present a new facile cathode recycling process, where previously used cathodes are removed from a cell, heat treated, and then inserted into a new cell restoring the delivered capacity and cycle life. An environmentally sustainable manganese based material is employed, where binder-free self-supporting (BFSS) electrodes are prepared using a fibrous, high aspect ratio manganese oxide active material. After 200 discharge–charge cycles, the recycled BFSS electrodes display restored crystallinity and oxidation state of the manganese centers with the resulting electrochemistry (capacity and coulombic efficiency) reminiscent of freshly prepared BFSS cathodes. Of note, the BFSS electrode structure is robust with no degradation during the cell disassembly, electrode recovery, washing, and heat treatment steps; thus no post-processing is required for the recycled electrode. Furthermore, this work shows for the first time that a thermal regeneration method previously employed in catalyst systems can fully restore battery electrochemical performance, demonstrating a novel electrode recycling process which could open up new possibilities for energy storage devices with extended electrode lifecycles.

25 ENERGY STORAGE↗
DOE OSTI2017

Highly flexible, freestanding tandem sulfur cathodes for foldable Li–S batteries with a high areal capacity

Li–S batteries with a high theoretical capacity are considered as the most promising candidate to satisfy the increasing demand for batteries with a high areal capacity. However, the low sulfur loading (<2 mg cm -2 ) and poor flexibility of current Li–S batteries limit their application in establishing foldable Li–S batteries with a high areal capacity. Here, to solve this problem, we employ here a free-standing flexible tandem sulfur cathode with a remarkably high sulfur loading to demonstrate foldable, high-areal-capacity Li–S batteries. The design of the tandem cathode readily increases the sulfur loading and effectively retards the migration of polysulfides. Therefore, the Li–S cell employing the tandem cathode exhibits a high initial areal capacity of 12.3 mA h cm -2 with stable cycling stability even with a high sulfur loading of up to 16 mg cm -2 . These tandem cathodes are promising for foldable Li–S cells with a high areal capacity and energy density.

25 ENERGY STORAGE↗
DOE OSTI2019

Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles

The structural integrity of layered Ni-rich oxide cathode materials is one of the most significant factors that critically affect the performance and reliability of lithium-ion batteries. Prolonged battery operation many times involves repeated phase transitions, buildup of mechanical stresses, and could provoke thermal spikes. Such sophisticated chemo-thermo-mechanical interplay can cause performance degradation through structural disintegration of the cathode active materials (CAMs). In this work, we systematically investigate the thermal decomposition, fracture, and oxygen evolution of chemically delithiated Li 0.3 Ni 0.8 Co 0.15 Al 0.05 O 2 (NCA) particles upon heating from 25 °C to 450 °C using a number of advanced X-ray and electron probes. We observed a continuous reduction of the Ni oxidation state upon heating, as well as the release of oxygen from the NCA lattice that undergoes the thermally induced phase transformations. The release of oxygen also created numerous mesopores throughout the analyzed particles, which could significantly affect the chemical and mechanical properties of the electrode. In addition, intergranular and intragranular fracturing at elevated temperatures also contribute to the degradation of the NCA cathode under these conditions. Our investigation of the mechanical integrity at elevated temperatures provides a fundamental understanding of the thermally driven chemomechanical breakdown of the NCA cathode active materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Strain-driven surface reconstruction and cation segregation in layered Li(Ni 1– x – y Mn x Co y )O 2 (NMC) cathode materials

The composition, structure and phase transformations occurring on cathode surfaces greatly affect the performance of Li-ion batteries. Li-Ion diffusion and surface–electrolyte interaction are two major phenomena that impact the capacity and cell impedance. The effects of surface reconstruction (SR) of cathode materials on the performance of Li-ion batteries are of current interest. However, the origin and evolution of the SR are still not well understood. In this work, density functional theory (DFT) calculations are used to investigate the processes taking place during surface segregation and reconstruction. Facet dependent segregation was found in Li(Ni 1– x – y Mn x Co y )O 2 (NMC) cathodes. Specifically, Co tends to segregate to the (104) surface of the primary particles within the transition metal layer, while Ni ions tend to segregate to the (012) surface in the Li layer, forming a SR. Experimental evidence shows the SR to be epitaxial with the bulk of the as-synthesized material, and the new SR phase is pinned to the NMC unit cell leading to a strained SR. Here, we demonstrate that strain can stabilize a spinel structure of the SR layers. Understanding the effects of surface strain opens a new avenue for the design of cathode materials with enhanced surface properties.

25 ENERGY STORAGE↗
DOE OSTI2021

Revisiting the role of Zr doping in Ni-rich layered cathodes for lithium-ion batteries

We report the realization of high performance Ni-rich layered cathodes remains a challenge because of the multiple degradation factors that concurrently operate during battery cycling. In particular, depletion of oxygen charge and consequent lattice oxygen instability at deep charge state accelerate the subsequent chemomechanical degradation mechanisms. Among the proposed methodologies, doping has proven to be effective in enhancing the cathode cycle life by stabilizing the layered structure. Herein, we achieved the electrochemically stabilized Ni-rich LiNi 0.92 Co 0.04 Mn 0.04 O 2 through Zr doping, resulting in a 15% increase of the capacity retention after 100 cycles. In-depth investigations are conducted to unveil the effects of Zr doping on the layered cathode, and in particular, the critical role of Zr doping on the lattice oxygen stability is systematically studied. By combining state-of-the-art magnetometer characterization, X-ray analysis, and first-principles calculation, we reveal that Zr doping positively contributes the to lattice oxygen stability by alleviating the oxygen charge loss at deep charge, thereby improving the cathode electrochemical reversibility. Our findings provide an insight into the Zr doping mechanism and help to design the Ni-rich layered oxides for future applications.

25 ENERGY STORAGE↗
DOE OSTI2021

Effect of cathode on crosstalk in Si-based lithium-ion cells

Crosstalk between the cathode and the anode in Li-ion batteries has a great impact on performance, safety and cycle lifetime. However, a systematic investigation of crosstalk behavior in silicon (Si)-based cells with various cathode materials has not been reported. We investigated the crosstalk behavior of a Si anode coupled with one of the following cathodes—LiCoO 2 (LCO), LiNi 0.5 Mn 0.3 Co 0.2 (NMC532), and LiFePO 4 (LFP)—in a full cell. For each electrochemical couple, we compared electrolyte decomposition products, solid electrolyte interphase (SEI) chemistry, and degradation mechanisms during cycling. From a very early stage of cycling, each couple showed different crosstalk behavior; different electrolyte decomposition products and SEI chemistry on the Si anodes were seen. Specifically, the formation and growth mechanism of Si SEI differ depending on cathode materials. For the LFP system, the Si SEI rich in LiF and inorganic species, which is stable and robust. It forms at an early stage of cycle. As a result, the SEI of Si from the LFP system well tolerates SEI breakage due to mechanical changes of Si and suppresses Li loss, resulting in stable cycle life.

25 ENERGY STORAGE↗
DOE OSTI2022

Highly reversible Li 2 RuO 3 cathodes in sulfide-based all solid-state lithium batteries

The practical application of high-capacity lithium-rich cathode materials in lithium-ion batteries has been largely restricted by severe side reactions with electrolytes. Herein, we report a highly stable lithium-rich Li 2 RuO 3 cathode by forming a passivating solid electrolyte interphase at the interface with a sulfide solid electrolyte such as Li 6 PS 5 Cl in all-solid-state lithium batteries (ASSLBs), which efficiently suppresses serious parasitic interfacial reactions and fast-increasing interfacial impedance normally observed in liquid electrolytes. The exceptionally high interfacial stability of the Li 2 RuO 3 /sulfide electrolyte interface contributes to a high reversible capacity of 257 mA h g –1 of Li 2 RuO 3 at 0.05C rate, and unprecedented cycling stability with 90% capacity retention after 1000 cycles at 1C rate. Iin this work, comprehensive experimental characterizations and first-principles calculations disclose that electronically insulating interfacial reaction products forming at the interface between the Li 2 RuO 3 cathode and Li 6 PS 5 Cl facilitate the formation of a stable and passivating interphase and block the continuous side reactions. Importantly, reversible oxygen redox activity of Li 2 RuO 3 is well-maintained in this configuration of ASSLBs even after 600 cycles, thus the common voltage decay of the Li-rich material is also significantly reduced. These new discoveries demonstrate the critical role of interface design for achieving prolonged cycling stability of lithium-rich cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Cathode regeneration and upcycling of spent LIBs: toward sustainability

‘Green ambition towards sustainability’ is one of the hot research topics of the 21st century. With the sharp steering of the energy infrastructure toward fulfilling this radical expectation, the last decade has seen a global trend toward diversified sustainable renewable energy sources (such as solar, wind, and hydroelectric power) and electrification. Lithium-ion batteries (LIBs) are playing a significant role in this energy revolution. However, with the massive scale of the production of LIBs and their eventual retirement, attention has been turned to the erratic supply of raw materials used to manufacture these batteries and their disposal. Cathode regeneration technology is likely to be an optimal solution for the disposal of waste cathodes, aimed at non-destructively repairing and straightforwardly reusing degraded cathode materials for re-manufacturing LIBs with a shortened circular process, reasonable profits, and excellent efficiency. Additionally, cathode upcycling technology, aimed at upgrading the electrochemical performance of degraded materials, can be well adapted to the upgrading of battery chemistry and show excellent flexibility and potential for transforming the LIB industry from a resource-based to a circular economy. Thus, a holistic perspective based on the complete life cycle of LIBs is encouraged, and sustainability must be at the forefront regarding battery and pack design, raw material acquisition, materials synthesis, manufacturing, operating, retiring, and recycling processes of LIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Deciphering the morphology of transition metal carbonate cathode precursors

The performance and life of Li-ion battery cathode materials are determined by both the composition (crystal structure and transition metal ratio) and the morphology (particle size, size distribution, and surface area). Careful control of these two aspects is the key to long lasting, high-energy batteries that can undergo fast charge. Developing such cathodes requires manipulation of the synthesis conditions, namely the coprecipitation process to develop the precursor and a calcination step to lithiate and convert it to a transition metal oxide. In this paper, we utilize a combination of controlled synthesis, microscopic and spectroscopic characterization, and multi-scale mathematical modeling to shed light on the synthesis of cathode precursors. The complex interplay between the various chemical reactions in the co-precipitation process is studied to provide experimentalists with guidance on achieving composition control during synthesis. Further, the formation of a variety of morphologies of the primary particles and the driving force for agglomeration is mathematically described, for the first time, based on an energy minimization approach. Results suggest that the presence of Ni and/or Co significantly lowers the reaction rate constant compared to Mn, resulting in agglomerated growth in the former and single crystal growth in the latter. Modeling studies are used to provide a phase map describing the synthesis conditions needed to control the secondary particle size and corresponding size distribution. Finally, this paper represents an important step in developing a computationally guided approach to the synthesis of battery cathode materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Effects of catholyte aging on high-nickel NMC cathodes in sulfide all-solid-state batteries

Sulfide solid-state electrolytes (SSEs) in all-solid-state batteries (SSBs) are recognized for their high ionic conductivity and inherent safety. The LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode offers a high thermodynamic potential of approximately 3.8 V vs. Li/Li + and a theoretical specific capacity of 200 mA h g −1 . However, the practical utilization of NMC811 in sulfide SSBs faces significant interfacial challenges. The oxidation instability of sulfide solid electrolytes against NMC811 and the formation of the cathode electrolyte interphase (CEI) during cycling lead to degradation and reduced cell performance. Volumetric changes in NMC during lithiation and de-lithiation can also cause detachment from sulfide electrolytes or internal particle cracking. Despite extensive galvanostatic cycling studies to address the issues, the calendar life of sulfide SSBs remains poorly understood. Here, we systematically studied the effects of four different catholytes on the calendar aging of LiNbO 3 (LNO)-coated NMC811, including Li 6 PS 5 Cl (LPSCl), Li 3 InCl 6 –Li 6 PS 5 Cl (LIC–LPSCl), Li 3 YCl 6 –Li 6 PS 5 Cl (LYC–LPSCl), and Li 10 GeP 2 S 12 (LGPS). Our results indicate that LPSCl provides optimal capacity retention when stored at high state-of-charge (SOC) at room temperature, but the LIC–LPSCl cathode shows significant capacity degradation and chemical incompatibility. We also established an effective electrochemical calendar aging testing protocol to simulate daily usage, enabling quick inference of the calendar life of SSBs. In conclusion, this new testing approach accelerates materials selection strategies for high-nickel NMC composite cathodes in sulfide SSBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Structural origin of disorder-induced ion conduction in NaFePO 4 cathode materials

Diffusion in NaFePO 4 can be enhanced through amorphization. Based on computations using DFT and machine learning potentials, we ascribe this phenomenon to the formation of less constrained Na-ion environments upon disordering. Most modern battery technologies depend on solid-state crystalline cathode materials. However, some of these materials are constrained by the low ionic conductivity of their most stable phases. An example of this is maricite (NaFePO 4 ). Interestingly, experiments have shown that maricite can improve its rate capability through disordering (amorphization). However, experimental characterization of amorphous cathode materials remains a major challenge, hindering a clear understanding of the structural origin of the disorder-induced improvement in sodium-ion mobility. To address this, we here employ molecular dynamics simulations by first training a machine learning potential for NaFePO 4 based on the atomic cluster expansion approach and a batch active learning potential parameterization scheme. This potential is then applied to explore the structural and dynamical properties of NaFePO 4 glasses as cathode materials. Specifically, we investigate the effect of glass structure on sodium-ion diffusion, revealing the relative influences of short-range and medium-range order features. We find significant heterogeneity in sodium-ion diffusivity in the glass, with fast-conducting ions residing in less constrained atomic environments with fewer P and Fe neighbors. These more mobile ions are also surrounded by larger ring-type structures. Overall, the results and developed approach present promising avenues for developing high-performance glassy cathodes for next-generation batteries.

Christensen, Rasmus↗
DOE OSTI2017

Transition characteristics of low-pressure discharges in a hollow cathode

Based on a two-dimensional (2-D) fluid model, the transition processes of discharges in a hollow cathode at low pressure are observed by changing three parameters, i.e., applied voltage U 0 , gas pressure p, and external circuit ballast resistance R b . The voltage-current characteristic curves, electron density distributions, and electric potential distributions of different discharge operating points in a hollow cathode are obtained. The transition processes are characterized by the voltage-current characteristic curves, the electron density distributions, and the electrical potential distributions. The transition modes observed from the voltage-current characteristics include the low-current abnormal mode, normal mode, and high-current abnormal mode. Increasing the applied voltage U0 can have a similar effect on the discharge transition processes to decreasing the ballast resistance. By increasing U0 from 200V to 500V and decreasing Rb from 5000 kX to 100 kX independently, it is observed that the discharge transfers from the outside to the inside of the hollow cavity, thus forming the virtual anode potential. By increasing the gas pressure p from 50 Pa to 5 kPa, the discharge also moves into the hollow cavity from the outside; however, a further increase in the gas pressure leads to the discharge escaping from the hollow cavity. Simulation results and characterizations for different parameters are presented for the transition properties of low-pressure discharges in a hollow cathode. It is verified that the hollow cathode discharge only exists under certain ranges of the above parameters.

42 ENGINEERING↗
DOE OSTI2017

Amorphous MoS 3 as the sulfur-equivalent cathode material for room-temperature Li–S and Na–S batteries

Significance We propose a concept of “sulfur-equivalent cathode materials,” and reason that instead of using problematic elemental sulfur, one can use sulfur-containing compounds as the alternatives with a comparable electrochemical property but free of any polysulfide generation. We demonstrate here the great potential of amorphous MoS 3 as such a sulfur-equivalent cathode material for room-temperature Li–S and Na–S batteries. More remarkably, we find that MoS 3 is fully cyclable in the carbonate electrolyte (which is known to kill conventional sulfur cathodes) under a relatively high temperature of 55 °C. MoS 3 can also be used as the cathode material of even more challenging Na–S batteries to enable an impressive performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Impact of fabrication methods on binder distribution and charge transport in composite cathodes of all-solid-state batteries

Abstract The manufacturing process of all-solid-state batteries necessitates the use of polymer binders. However, these binders, being ionic insulators by nature, can adversely affect charge transport within composite cathodes, thereby impacting the rate performance of the batteries. In this work, we aim to investigate the impact of fabrication methods, specifically the solvent-free dry process versus the slurry-cast wet process, on binder distribution and charge transport in composite cathodes of solid-state batteries. In the dry process, the binder forms a fibrous network, while the wet process results in binder coverage on the surface of cathode active materials. The difference in microstructure leads to a notable 20-fold increase in ionic conductivity in the dry-processed cathode. Consequently, the cells processed via the dry method exhibit higher capacity retention of 89% and 83% at C/3 and C/2 rates, respectively, in comparison to 68% and 58% for the wet-processed cells at the same rate. These findings provide valuable insights into the influence of fabrication methods on binder distribution and charge transport, contributing to a better understanding of the binder’s role in manufacturing of all-solid-state batteries.

Emley, Benjamin↗
DOE OSTI2025

Two Mechanisms Limiting the Emitted Electron Current from a Cathode to an Anode

It is known that the current of emitted electrons flowing through a plasma can saturate upon formation of a potential well adjacent to the cathode (the “space charge effect”). Here, we demonstrate another saturation mechanism that will often set a more restrictive limit on the global current. When “backflow saturation” occurs, the cathode sheath weakens to allow emitted electrons that already entered the plasma to backflow to the cathode. This effect could not be captured by studies modelling the cathode sheath by itself because its origin is coupled to processes in the interior plasma and anode sheath. By modeling a full plasma diode, we show that depending on conditions the global current can be limited in four ways; by backflow alone, by space charge alone, by both mechanisms in a stable cooperative form, or by both in a competing oscillatory form. Published by the American Physical Society 2025

Laboratory plasma↗