Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “lithium ion cathode”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Decoding Li + /Na + Exchange Route Toward High-Performance Mn-Based Layered Cathodes for Li-Ion Batteries

Li + /Na + exchange has been extensively explored as an effective method to prepare high-performance Mn-based layered cathodes for Li-ion batteries, since the first report in 1996 by P. G. Bruce (Nature, 1996. 381, 499–500). Understanding the detailed structural changes during the ion-exchange process is crucial to implement the synthetic control of high-performance layered Mn-based cathodes, but less studied. Herein, in situ synchrotron X-ray diffraction, density functional theory calculations, and electrochemical tests are combined to conduct the systemic studies into the structural changes during the ion-exchange process of an Mn-only layered cathode O3-type Li 0.67 [Li 0.22 Mn 0.78 ]O 2 (LLMO) from the corresponding counterpart P3-type Na 0.67 [Li 0.22 Mn 0.78 ]O 2 (NLMO). The temperature-resolved observations combined with theoretical calculations reveal that the Li + /Na + exchange is favorable thermodynamically and composited with two tandem topotactic phase transitions: 1) from NLMO to a layered intermediate through ≈60% of Li + /Na + exchange. 2) then to the final layered product LLMO through further Li insertion. Moreover, the intermediate-dominate composite is obtained by slowing down the exchange kinetics below room temperature, showing better electrochemical performance than LLMO obtained by the traditional molten-salt method. Finally, the findings provide guides for the synthetic control of high-performance Mn-based cathodes under mild conditions.

25 ENERGY STORAGE↗
DOE OSTI2021

Fast-Charging Aging Considerations: Incorporation and Alignment of Cell Design and Material Degradation Pathways

Fast charging of batteries for electric vehicles is seen as one of the most direct ways to enhance adoption. Currently, fast charging is limited by increased cell aging, which is primarily driven by Li plating and degradation of cathode materials. Here, using combined sets of experimental and computational analysis and a suite of different charge protocols, we begin to examine the interplay between failure mode, cell designs, and ultimately aging mechanisms. Slight variation in cell design and the subsequent impacts that charge protocols have on aging can create distinct cell-to-cell variation. As little as 2% difference in porosity change at the cell negative electrode during cycling due to early Li metal plating has been found to alter the aging pathway and either accelerate or inhibit the loss due to Li plating.

25 ENERGY STORAGE↗
DOE OSTI2022

Enabling Extreme Fast-Charging: Challenges at the Cathode and Mitigation Strategies

We report charging lithium-ion batteries (LiBs) in 10 to 15 min via extreme fast-charging (XFC) is important for the widespread adoption of electric vehicles (EVs). Lately, the battery research community has focused on identifying XFC bottlenecks and determining novel design solutions. Like other LiB components, cathodes can present XFC bottlenecks, especially when considering long-term battery life. Therefore, it is necessary to develop a comprehensive understanding of how XFC conditions degrade LiB cathodes. The present article reviews relevant cathode-focused studies and summarizes the current understanding regarding cathode performance and aging issues under XFC conditions. Dominant aging modes and mechanisms are identified at different length-scales with electrochemical correlations for LiNi x Mn y Co z O 2 (NMC)-based cathodes. A range of electrochemical techniques and models provide key insights into cathode performance and life issues. A suite of multimodal and multiscale microscopy and X-ray techniques is surveyed to quantify chemical, structural, and crystallographic NMC-cathode degradation. Cathode cycle-life is scaled to equivalent EV miles to illustrate how cathode degradation translates to real-world scenarios and quantifies cathode-related bottlenecks that hinder XFC adoption. Finally, the article discusses several cathode cycle-life aging mitigation strategies with example case studies and identifies remaining challenges.

25 ENERGY STORAGE↗
DOE OSTI2023

Constructing uniform oxygen defect engineering on primary particle level for high-stability lithium-rich cathode materials

Lithium-rich layered cathode materials are considered to be research focus of cathode candidates for next generation lithium-ion batteries due to their high specific capacity and low cost. However, lattice deoxidation associated with elemental migration and internal local shrinkage usually results in deteriorated cyclic performance and notorious voltage attenuation, severely limiting its application. In this paper, we have successfully injected uniform oxygen defects into surface region of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 primary particles under the high-pressure and weak carbonate environment. Various experimental investigations indicate that the injected robust oxygen defects can not only mitigate detrimental interfacial reactions but also suppress unfavorable lattice variation and particle breakage. More importantly, theoretical calculations unravel the critical roles of oxygen defects in regulating energy band structure for strengthened anionic reversibility. Owing to stabilization effects of unique oxygen defect engineering, the modified Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 cathode has harvested dramatically enhanced electrochemical performance including a high initial coulombic efficiency of 96.6%, an outstanding capacity retention of 91.96% (1C, 200 cycles) and suppressed voltage decay of only 1.62 mV per cycle. Therefore, this facile and effective defect engineering strategy could establish new guidance for promoting practical application of Li-rich Mn-based cathode material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Modeling Chemo-Mechanics with Electrolyte Infiltration to Quantify Degradation of Cathode Particles

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. To that end, this talk investigates the formation of stress-induced fracture within polycrystalline cathode particles and the impact on capacity loss. Physically based cathode aging dynamics is simulated in a 3D, continuum-level chemo-mechanical model. The model captures anisotropic Li diffusion within a single polycrystalline particle comprised of hundreds to thousands of randomly oriented grains. A recent addition to this model includes electrolyte infiltration, which occurs when the electrolyte seeps into surface cracks within the particle. The model predicts that particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains are misaligned, they expand a different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. The model predicts that small particles with large grains develop significantly less damage than larger particles with small grains. Finally, the model predicts most of the chemo-mechanical damage accumulates in the first charge after formation. This chemo-mechanical "damage saturation" effect indicates that initial particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced. The principle contribution of this research is the use of an anisotropic chemo-mechanical model to test how particle geometry affect capacity fade, which predicts that particle size has a stronger effect on capacity fade than grain size and ultimately that small particles with large grains have the least capacity fade.

cathode↗
DOE OSTI2022

Reviving the rock-salt phases in Ni-rich layered cathodes by mechano-electrochemistry in all-solid-state batteries

The rock-salt phase (RSP) formed on the surface of Ni-rich layered cathodes in liquid-electrolyte lithium-ion batteries is conceived to be electrochemically "dead". Here we show massive RSP forms in the interior of LiNi x Mn y Co (1–x-y) O 2 (NMC) crystals in sulfide based all solid state batteries (ASSBs), but the RSP remains electrochemically active even after long cycles. The RSP and the layered structure constitute a two-phase mixture, a material architecture that is distinctly different from the RSP in liquid electrolytes. The tensioned layered phase affords an effective percolation channel into which lithium is squeezed out of the RSPs by compressive stress, rendering the RSPs electrochemically active. Consequently, the ASSBs with predominant RSP in the NMC cathode deliver remarkable long cycle life of 4000 cycles at high areal capacity of 4.3 mAh/cm 2 . Our study unveils distinct mechano-electrochemistry of RSPs in ASSBs that can be harnessed to enable high energy density and durable ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Selectively extracting lithium from single and mixed cathode materials

With the burgeoning reliance on lithium-ion batteries for sustainable energy solutions and electric transportation, the environmental and resource management associated with battery disposal are increasingly critical. Addressing these challenges necessitates innovative recycling techniques that recover valuable battery components, particularly lithium. This research introduces a universal, eco-friendly approach tailored for the efficient selective extraction of lithium from both single and mixed cathode materials, achieving impressive selective leaching efficiencies of lithium (99.51 % for LFP, 90 % for NMC, and 97.24 % for mixed cathode). Surprisingly, leaching efficiency of lithium from NMC can be significantly improved by introducing LFP since LFP can remove the dense transition-metal salts on the surface of NMC. The extracted lithium is recovered as lithium carbonate with battery-grade purity. This study also highlights the reuse of formic acid and the adoption of oxygen as an oxidizing agent to prevent wastewater production. Therefore, this method provides a robust foundation for sustainable lithium battery recycling.

economically and environmentally feasible↗
DOE OSTI2021

Degradation Diagnostics from the Subsurface of Lithium-Ion Battery Electrodes

Despite the long-established rocking-chair theory of lithium-ion batteries (LIBs), developing novel characterization methodology with higher spatiotemporal resolution facilitates a better understanding of the solid electrolyte interphase studies to shape the reaction mechanisms. In this work, we develop a Xenon ion plasma focused ion beam (Xe + PFIB)-based characterization technique to probe the cross-sectional interface of both ternary cathode and graphite anode electrodes, with the focus on revealing the chemical composition and distribution underneath the electrode surface by in-depth analysis of secondary ions. Particularly, the lithium fluoride is detected in the pristine cathode prior to contact with the electrolyte, reflecting that the electrode degradation is in the form of the loss of lithium inventory during electrode preparation. This degradation is related to the hydrolysis of the cathode material and the decomposition of the PVDF binder. Here, through the quantitative analysis of the transition-metal degradation products, manganese is found to be the dominant element in the newly formed inactive fluoride deposition on the cathode, while no transition metal signal can be found inside the anode electrode. These insights at high resolution implemented via a PFIB-based characterization technique not only enrich the understanding of the degradation mechanism in the LIBs but also identify and enable a high-sensitivity methodology to obtain the chemical survey at the subsurface, which will help remove the capacity-fade observed in most LIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗
DOE OSTI2024

Stabilizing high-Ni cathodes with gradient surface Ti-enrichment

High-Ni cathodes are being intensely pursued worldwide for electric vehicles and other energy-dense applications due to their high capacity and low cost. However, structural instabilities during electrochemical cycling and when subjected to thermal treatment have been the major issues hindering their practical deployment. We here report a rational design of coating-integrated-into-synthesis protocol for fabricating surface Ti-enriched LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811#Ti) material. The coating to intermediates is crucial to obtain high structural ordering, both in the bulk and surface of high-Ni cathodes, and the Ti substitute has a unique tri-valence (Ti 3+ ) in a gradient surface distribution. Further, the simulations of projected density of states in the atomistic understanding further certify significantly enhanced stability of lattice oxygen for the NMC811 through such a Ti 3+ -based structure reinforcement. Consequently, the NMC811#Ti cathode delivers a high capacity up to 200mAhg -1 at 0.1 C, along with superior stabilities during air-storage and thermal treatment (up to 297°C at the fully charged state under differential scanning calorimetric measurements). The corresponding NMC811#Ti||graphite full cell exhibits a desired 83.6% capacity retention after 1000 cycles at 0.5 C in a voltage range of 2.8–4.3V. This work demonstrates a delicate surface reinforcement to stabilize high-Ni cathodes for long-life and safe lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Dry-pressed lithium nickel cobalt manganese oxide (NCM) cathodes enabled by holey graphene host

There is an increasing demand for electric vehicle batteries with higher energy densities that can be manufactured with low cost utilizing environmentally friendly processes. Lithium nickel cobalt manganese oxides (NCM), such as LiNi(0.5)Co(0.2)Mr(0.3)O(2) (NCM523), are commonly used in commercial lithium ion batteries for electric vehicle applications. These cathodes are typically fabricated using environmentally hazardous, energy intensive, and time-consuming solvent-based slurry casting processes. Polymeric binders, also required for cathode preparation, add weight and can undergo parasitic reactions during battery cycling. Here we report a facile, solvent-free, binder-free, and rapid cold-press electrode fabrication process to prepare high mass loading NCM cathodes within minutes. This process is enabled by the use of holey graphene, a unique lightweight, compressible carbon nanomaterial that serves as both a binder and an electrically conductive matrix. NCM cathodes fabricated by this method are stable and exhibit good active material utilization. A significant advantage for the dry-press process is that the electrode mass loadings can be readily increased simply by adding more composite powder to the compression molding die, resulting in improved areal capacities that are attractive for applications requiring high energy per unit footprint. (C) 2020 Elsevier Ltd. All rights reserved.

25 ENERGY STORAGE↗
DOE OSTI2021

Simultaneously Blocking Chemical Crosstalk and Internal Short Circuit via Gel-Stretching Derived Nanoporous Non-Shrinkage Separator for Safe Lithium-Ion Batteries

The separator, an ionic permeable and electronic insulating membrane between cathode and anode, plays a crucial role in the electrochemical and safety performance of batteries. However, the commercial polyolefin separators not only suffer from inevitable thermal shrinkage at elevated temperature, but also fail to inhibit the hidden chemical crosstalk of reactive gases such as O 2 , leading to often reported thermal runaway (TR) and hence preventing large-scale implementation of high-energy-density lithium-ion batteries. Herein, a nanoporous non-shrinkage separator (GS-PI) was fabricated via a novel gel-stretching orientation approach to eliminate TR. In situ synchrotron small angle X-ray scattering during heating clearly showed that the as-prepared thin GS-PI separator exhibits superior mechanical tolerance at high temperature, thus effectively preventing internal short circuit. Meanwhile, the unique nanoporous structure design further blocks chemical crosstalk and the associated exothermic reactions. Accelerating Rate Calorimetry test revealed that the practical 1 Ah LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)/graphite pouch cell using GS-PI nanoporous separator show a maximum temperature rise (dT/dt max ) of only 3.7 °C s -1 compared to 131.6 °C s -1 in the case of Al 2 O 3 @PE macroporous separator. Furthermore, despite the reduced pore size, the GS-PI separator demonstrates better cycling stability than conventional Al 2 O 3 @PE separator at high temperature without sacrificing specific capacity and rate capability.

25 ENERGY STORAGE↗
NASA NTRS2007

NASA Tech Briefs, April 2007

Topics include: Wearable Environmental and Physiological Sensing Unit; Broadband Phase Retrieval for Image-Based Wavefront Sensing; Filter Function for Wavefront Sensing Over a Field of View; Iterative-Transform Phase Retrieval Using Adaptive Diversity; Wavefront Sensing With Switched Lenses for Defocus Diversity; Smooth Phase Interpolated Keying; Maintaining Stability During a Conducted-Ripple EMC Test; Photodiode Preamplifier for Laser Ranging With Weak Signals; Advanced High-Definition Video Cameras; Circuit for Full Charging of Series Lithium-Ion Cells; Analog Nonvolatile Computer Memory Circuits; JavaGenes Molecular Evolution; World Wind 3D Earth Viewing; Lithium Dinitramide as an Additive in Lithium Power Cells; Accounting for Uncertainties in Strengths of SiC MEMS Parts; Ion-Conducting Organic/Inorganic Polymers; MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells; Counterrotating-Shoulder Mechanism for Friction Stir Welding; Strain Gauges Indicate Differential-CTE-Induced Failures; Antibodies Against Three Forms of Urokinase; Understanding and Counteracting Fatigue in Flight Crews; Active Correction of Aberrations of Low-Quality Telescope Optics; Dual-Beam Atom Laser Driven by Spinor Dynamics; Rugged, Tunable Extended-Cavity Diode Laser; Balloon for Long-Duration, High-Altitude Flight at Venus; and Wide-Temperature-Range Integrated Operational Amplifier.

Source record↗
DOE OSTI2020

(Invited) All-Solid-State Batteries Using Li 7 La 3 Zr 2 O 12 Garnet Electrolyte Framework

All-solid-state batteries (ASSB) using LLZO (variants of Li 7 La 3 Zr 2 O 12 ) garnet solid electrolyte with lithium metal anode potentially offer higher energy density and improved safety. Rational design of cell architecture as well as manufacturing scalability are key aspects to consider as the technology readiness level advances. A thick composite cathode layer attached to a thin solid electrolyte layer is desirable to obtain superior energy densities. Furthermore, the architecture within the composite cathode may be engineered to contain directional conduction paths of lithium ions or electrons for enhanced rate capabilities. Here, we demonstrate a functioning bulk-type LLZO based all-solid-state battery with a practical form factor incorporating the above described design concepts. Freeze-tape-casting (FTC), a scalable and environmentally friendly ceramic processing method, is used to construct 3D porous LLZO scaffolds composed of vertical arrays of LLZO walls. The thin solid-electrolyte layer is fabricated by tape-casting (TC). By sintering the stacks of FTC and TC green tapes, porous/dense bilayers and porous/dense/porous trilayers of LLZO frameworks are obtained. An ASSB was constructed using a porous/dense bilayer by infiltrating LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode powder and carbon black into the porous layer and adhering lithium metal foil to the dense side. We find it crucial to introduce a plastic crystal based soft solid electrolyte to the porous layer to electrochemically connect all cathode components, obviating the need for co-sintering to establish contact. The soft nature of the plastic crystal based solid-electrolyte may be able to accommodate the volume change of the cathode material as it cycles. In this device, which contained no liquid component, the initial discharge capacities were similar to those observed in a lithium ion battery configuration using the same cathode powder at C/10 rates.

25 ENERGY STORAGE↗
DOE OSTI2024

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗
DOE OSTI2020

Predicting Morphological Evolution during Coprecipitation of MnCO 3 Battery Cathode Precursors Using Multiscale Simulations Aided by Targeted Synthesis

The performance of lithium-ion batteries is intimately linked to both the structure and the morphology of the cathode material, which in turn is critically linked to the synthesis conditions. However, few studies focus on understanding synthesis, especially during the coprecipitation of metal oxide precursors, a process that largely determines the final morphology of the material. In this paper, we go beyond the typical equilibrium particle shape analysis conducted in the literature and incorporate kinetic aspects of morphology evolution. We perform these studies using controlled synthesis on a well-defined metal salt system (MnCO 3 ) combined with multiscale simulations and high-resolution microscopy. Results show that with increasing metal concentration, the particles transition from rhombohedral to cubic to spherical shapes. Computational analysis using density functional theory (DFT) reveals that rhombohedral shaped particles evolve under equilibrium conditions. Phase field techniques indicate that at higher metal concentrations, fast growth kinetics of the precipitates result in the transition to cubic and, subsequently, spherical shapes, accompanied by a decrease in particle size. This study, while limited to the one metal salt system, provides an approach to shed light on the synthesis process of mixed transition metal salts, gradient materials, and other cathode materials of interest to the battery community.

25 ENERGY STORAGE↗
DOE OSTI2020

Molten Lithium-Brass/Zinc Chloride System as High-Performance and Low-Cost Battery

Batteries with high safety, low cost, and reasonable energy density are essential for grid-scale energy storage and still remain elusive. In this paper, we report a solid electrolyte-based liquid lithium-brass/zinc chloride (SELL-brass/ZnCl 2 ) battery using garnet-type lithium-ion solid electrolyte, lithium anode, and brass/ZnCl 2 cathode. The chemistry of the cell reaction and the ability of being assembled in discharged state ensures a high safety. The use of low-cost ZnCl 2 cathode can realize a low cell material cost of $16 kWh –1 . The adoption of lithium anode guarantees a high theoretical energy density of 750 Wh kg –1 and 2,250 Wh L –1 . Moreover, by using brass powder as a Zn source in the cathode, the Zn particle growth issue is successfully solved, and a good cycling stability of the battery can be obtained. As full cell performance and scalability are also verified, our SELL-brass/ZnCl 2 battery shows a high potential for practical use in grid energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

Investigation and Suppression of Oxygen Release by LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cathode under Overcharge Conditions

The safety issue of lithium-ion batteries is a crucial factor limiting their large-scale application. Therefore, it is of practical significance to evaluate the impact of their overcharge behavior because of the severe levels of oxygen release of cathode materials during this process. Here, by combining a variety of in situ techniques of spectroscopy and electron microscopy, this work studies the structural degradation of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) accompanying the oxygen release in the overcharge process. It is observed that a small amount of O 2 evolves from the initial surface at ≈4.7V. When charging to a higher voltage (≈5.5V), a large amount of O 2 evolves on the newly formed surface due to the occurrence of microcracks. Based on experimental results and theoretical calculations, it is determined that the oxygen release mainly occurs in the near-surface regions, where the remaining oxygen vacancies accumulate to create voids. To suppress the oxygen release, single-crystalline NCM811 with integrated structure is introduced and serves as a cathode, which can effectively inhibit morphology destruction and reduce the activation of lattice oxygen in the surface region. These findings provide a theoretical basis and effective strategy for improving the safety performance of Ni-rich cathode materials in practical applications.

25 ENERGY STORAGE↗