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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 OSTI2020

A Quantitative Failure Analysis on Capacity Fade in Rechargeable Lithium Metal Cells

Rechargeable lithium battery (RLB) technology is transforming portable devices, vehicle electrification, and grid modernization. To make RLB durable, reliable and safe, conducting failure mode and effect analysis (FMEA) to identify failure mechanism under the operating conditions is very desirable. However, this ability is often overlooked or even lacking. The failure analysis (FA) is often conducted by laboratory testing and postmortem analysis, and the knowledge typically empirical. Here we present a quantitative approach for FMEA that can reveal how failure modes and effects reduce the capacity of a RLB. This approach is based on the state of the battery for FMEA, contrary to the conventional approach based on operating or testing conditions. The key aspect of this FMEA method is to convert the experimental results to a state-of-charge (SOC)-based analytic methodology. Such a conversion can separate the thermodynamic and kinetic attributes of capacity fade based on compositional correspondence in the electrode, so the loss and the decreased utilization of the active materials can be determined respectively.

25 ENERGY STORAGE↗
DOE OSTI2020

In Operando XANES Imaging of High Capacity Intermetallic Anodes for Lithium Ion Batteries

In operando 2D X-ray absorption near edge structure (XANES) imaging was performed near the Cu K-edge during cycling of Cu 6 Sn 5 composite anodes for lithium ion batteries. Galvanostatic lithiation and delithiation with intermittent constant voltage holds near reaction plateaus show evolution of absorption spectra for active material particles. XANES spectra obtained from images taken during cycling were compared to standard spectra for Cu, Cu 6 Sn 5 , and Li 2 CuSn. Chemical composition was assessed for Cu-containing phases. Distinct Cu, Cu 6 Sn 5 , and Li 2 CuSn regions were identified for each voltage plateau. Mechanical degradation, electrode particle fracture and expansion were observed during delithiation. Furthermore, movement of particles during cycling suggests that expansion also impacts the supporting secondary phases and the transport networks therein. These results demonstrate that spectroscopic X-ray imaging methods can clearly distinguish chemically distinct phases in alloy electrodes and have the versatility to observe the evolution of these phases during lithiation and delithiation.

25 ENERGY STORAGE↗
DOE OSTI2020

Lithium-Sulfur Batteries with a Block Copolymer Electrolyte Analyzed by X-ray Microtomography

Most of the work on Lithium-sulfur (LiS) batteries use liquid electrolytes that have limited stability when coupled with Li metal anodes. We have studied LiS batteries with a solid block copolymer electrolyte which exhibits improved stability against Li anodes. Additionally, the electrolyte comprises a polystyrene-b-poly(ethylene oxide) (SEO) copolymer doped with a Li salt. Hollow carbon nanospheres impregnated with sulfur were used to build a composite cathode. Two types of sulfur-impregnated functionalized carbon nanospheres were used: One with carboxylic acid groups and the other with short lithium poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (PSTFSI-Li) chains. Cells with Li S dissolved in the SEO based electrolyte served as the baseline. After cycling, the reason for capacity fade was determined by imaging the batteries using synchrotron hard X-ray microtomography. It is generally assumed that LiS cells fail due to dissolution of polysulfide into the liquid electrolyte, i.e., the main problems related to the cathode. In our all-solid cells, failure was primarily due to delamination of the Li foil from the polymer electrolyte layer. Delamination is also observed at the sulfur cathode. It is likely that the large changes in volume of the active materials during cycling induce delamination in all-solid LiS cells. 2 8

25 ENERGY STORAGE↗
DOE OSTI2020

A Durable, Inexpensive and Scalable Redox Flow Battery Based on Iron Sulfate and Anthraquinone Disulfonic Acid

A new redox flow battery system based on iron sulfate and anthraquinone disulfonic acid (AQDS) is shown here to have excellent electrical performance, capacity retention, and chemical durability. While these redox couples, iron(II)/iron(III) and AQDS are well known individually, their combination in a redox flow battery is shown here for the first time to provide unique benefits for large-scale energy storage. Based on iron sulfate, a waste product of the steel industry, the active materials cost for this battery is anticipated to be $66/kWh. Cycling studies of over 500 cycles in the symmetric cell configuration show a negligibly low capacity fade rate of 7.6 × 10 −5 % per cycle. This symmetric cell also shows a notably high average coulombic efficiency of 99.63%. Using a graphite felt electrode modified with multi-walled carbon nanotubes (MWCNTs), we could achieve a peak power density of 194 mW cm −2 . The major voltage losses are ascribed to the ohmic resistance of the electrode and electrolyte. Despite the lower cell voltage of the system relative to the vanadium flow battery, the iron–AQDS flow battery system presents a good prospect for simultaneously meeting the demanding requirements of cost, durability and scalability for large-scale sustainable energy storage.

Yang, Bo↗
DOE OSTI2020

Model-Instructed Design of Novel Charging Protocols for the Extreme Fast Charging of Lithium-Ion Batteries Without Lithium Plating

Relatively long recharge time of high-energy density lithium-ion batteries (LIBs) is one of the major obstacles to the widespread deployment of electric vehicles (EVs). Excessive fast charge of LIBs can cause severe safety issues, the most significant of which is lithium plating. In addition to the consumption of cyclable lithium, dendrite-like lithium plating can cause short-circuiting within the cell, which could lead to catastrophic failure. In addition to the developments of advanced electrolytes, active materials and electrodes, the fast charging capability of LIBs can be improved by using optimized charging protocol. In this paper, the Pseudo2D battery model is first used to screen some conventional charging protocols proposed for fast charging, including the constant-current constant-voltage charging (CCCV), constant-power constant-voltage charging (CPCV), multi-stage constant-current charging, and pulse current charging. A semi-optimal charging protocol is then developed by automatically modifying the charge current such that the cell is charged at close-to-maximum current without lithium plating. Based on the features of the semi-optimal protocol, two practical novel fast charging protocols are proposed which allow charging the cell at a higher rate without lithium plating. Through simulation, we show that the no-plating capacity after 10 min charge can be improved by up to ~10.7% compared to CCCV charging for a 2.5 mAh cm -2 cell and ~18.8% for a 4 mAh cm -2 cell, when the proposed charging protocols are used.

25 ENERGY STORAGE↗
DOE OSTI2020

Rate-Dependent Aging Resulting from Fast Charging of Li-Ion Cells

The mass electrification of personal and service vehicles is reliant on the ability of battery packs to undergo extreme fast recharging. A central challenge is that the repeated exposure to high currents can trigger and/or accelerate mechanisms of performance degradation, such as lithium deposition, mechanical damage of active material particles, and impedance rise. Here, we investigate whether constraining high-rate charging to limited state-of-charge (SOC) ranges can mitigate these aging processes. Our experiments map the boundaries of lithium plating conditions, and also indicate that permanent losses of electrode capacity appear to be a function of cycle number, but not charging rate. Interestingly, we show that impedance rise appears to depend on charging rate alone, and not on the amount of charge passed at each cycle. This observation suggests that limiting fast charging to a narrow SOC range would only delay cell aging, but not fully prevent it from happening. We identify oxide-particle cracking as the likely mechanism for this impedance rise, suggesting that particle and electrode design are essential to enable fast charging. The findings of this work can inform the development of fast-charging protocols that are less damaging to cell health.

25 ENERGY STORAGE↗
DOE OSTI2020

Beneficial Effect of Li 5 FeO 4 Lithium Source for Li-Ion Batteries with a Layered NMC Cathode and Si Anode

The energy density of lithium-ion batteries can be increased by replacing the traditional graphite anode with a high capacity silicon anode. However, volume changes and interfacial instabilities cause a large irreversible capacity and a continual loss of lithium during cycling, which lead to rapid capacity loss. In this work, we add Li 5 FeO 4 (LFO) to a LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC) cathode as a pre-lithiation additive, which increases the lithium inventory and extends the cycle life of Si-graphite/NMC full cells, and decreases the NMC particle degradation. LFO delivers a large 764 mAh g –1 LFO capacity below 4.7 V vs Li/Li + . By tuning the LFO content in Si-graphite/LFO-NMC full cells, we show higher capacity, improved retention, lower impedance, and superior rate performance compared to full cells without LFO. Post-test characterizations demonstrate that LFO inclusion in the cathode matrix leads to less NMC secondary particle segregation/cracking and a thinner surface reduced layer on the NMC particles. The beneficial effects of LFO endure after the lithium reserve has been exhausted, highlighting a lasting synergy between the lithium source and electrode active materials. This study introduces a new approach to simultaneously increase lithium inventory and reduce cathode degradation, and makes critical advances toward enabling Si anodes for lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Reducing Zinc Redistribution and Extending Cycle Life Via Electrochemical Synthesis of Zinc/Zinc Oxide Anodes in Rechargeable Alkaline Batteries

Redistribution of zinc over the electrode surface, also known as shape change, is a major problem and a cause of failure in alkaline zinc anode batteries. To mitigate this phenomenon, we propose a scalable approach based on an in situ formed, highly porous electrochemically synthesized ZnO matrix with uniformly electrodeposited zinc particles. This results in ∼70% improvement in cycle life performance at a rate of 10 mA cm −2 compared to control Zn anodes, which have not gone through the formation process. A quantitative electrolyte analysis revealed under-saturated zincate ion concentration in the electrochemically synthesized ZnO/Zn cells indicating reduced zincate movement. Post mortem analysis of the anodes indicated higher retention of both Zn and ZnO on the electrochemically synthesized ZnO anodes signifying reduced redistribution of active material. Image analysis of the cycled anodes revealed a narrower Zn particle size distribution (62−79 μ m) in contrast to a wider particle size distribution of 51–96 μ m observed in the control anodes. The formation approach results in electrochemically synthesized ZnO/Zn anodes providing a stable ZnO matrix in which Zn particles retain their localized distribution on cycling better than control electrodes conventionally made by pasting zinc particles together with a binder.

Kolhekar, Snehal (ORCID:0000000210321153)↗
DOE OSTI2021

Critical Barriers to Successful Implementation of Earth-Abundant, Mn-Rich Cathodes for Vehicle Applications and Beyond: A Detailed Study of Low SOC Impedance

We report that earth-abundant, sustainable cathode chemistries based on Mn are increasingly attractive for enabling a broader portfolio of cathode oxides. The well-known class of lithium- and manganese-rich cathodes still represents very viable options. However, despite the important work on understanding the mechanisms of voltage fade, hysteresis, and oxygen activity, relatively little attention has been given to understanding the impedance characteristics of these electrodes. In particular, an anomalous rise in area specific impedance at lower states of charge, as well as overall impedance rise and surface damage due to electrolyte interactions, represent critical barriers to implementation. This work presents a comprehensive study of impedance behavior in cobalt-free, lithium- and manganese-rich electrodes. The use of a robust surface treatment allows for long-term behavior to be probed in the absence of surface damage, capacity loss, and impedance rise due to electrolyte interactions. The anomalous rise in impedance could not be correlated to surface changes, or surface phase formation, but could be directly correlated with the bulk processes of voltage fade and voltage hysteresis. The activated material can be explained as a percolating network of higher-voltage, layered-type sites having facile Li diffusion. Interspersed throughout this network are lower-voltage, disordered sites that represent a significant barrier.

25 ENERGY STORAGE↗
DOE OSTI2021

Ambient Temperature Sodium Polysulfide Catholyte for Nonaqueous Redox Flow Batteries

This study reports a sodium polysulfide catholyte for nonaqueous redox flow batteries (RFBs). We demonstrate reversible capacities up to 200 mAh/gS with negligible fade over 250 cycles at room temperature for sodium polysulfide|biphenyl full cells containing Na + ß '' -Al 2 O 3 solid electrolyte (BASE) membranes. Interestingly, formation of insoluble S and Na 2 S 4 phases did not inhibit the catholyte's cycle life which is likely due to the low concentrations used in the lab-scale prototypes. 3-electrode galvanostatic AC impedance measurements demonstrate that voltage losses were dominated by charge transfer at the cathode, and relevant kinetic parameters (i.e., transfer coefficients and exchange current density) were calculated through a Tafel analysis. To the best of our knowledge, this is the first report applying such an impedance approach to nonaqueous RFBs. Overall, the use of low-cost active materials makes sodium polysulfide|biphenyl RFBs promising for long duration energy storage applications. Furthermore, if strategies are developed to increase the solubility of S and/or low order polysulfides (Na 2 S x , x ≤ 4), specific energies up to 100 Wh kg -1 (including combined mass of the anolyte and catholyte) can be achieved.

25 ENERGY STORAGE↗
DOE OSTI2021

Time-Resolved X-ray Operando Observations of Lithiation Gradients across the Cathode Matrix and Individual Oxide Particles during Fast Cycling of a Li-Ion Cell

Lithiated transition metal oxides serve as active materials in the positive electrode (cathode) of lithium-ion cells. During electrochemical cycling, lithium ions intercalate and deintercalate into these oxide particles. This behavior causes two types of lithiation gradients to emerge: (i) a bulk gradient across the depth of the cathode matrix (averaged over individual oxide particles) and (ii) a microscopic gradient across the particles themselves, which also depends on their location in the electrode. Here we show how both gradients can be studied using operando X-ray diffraction during 4C charge and 4C discharge. The oxide (de)lithiation is estimated from the unit cell parameters by indexing the X-ray diffraction spectra. By fitting the lithiation profiles with orthogonal polynomials, the bulk gradients across the electrode thickness are quantified. These gradients develop as the current flows through the cell and dissipate during open-circuit and potentiostatic-hold periods. Further details of lithiation dynamics can be obtained through shape analysis of the Bragg peaks. In particular, from electrochemical model simulations, we show that the width and skewness of the (003) peak track (de)lithiation fronts moving across the individual oxide particles.

(003) peak↗
DOE OSTI2021

An In-Depth Analysis of the Transformation of Tin Foil Anodes during Electrochemical Cycling in Lithium-Ion Batteries

Tin foils have an impressive lithium-storage capacity more than triple that of graphite anodes, and their adoption could facilitate a drastic improvement in battery energy density. However, implementation of a dense foil electrode architecture represents a significant departure from the standard blade-cast geometry with a distinct electrochemical environment, and this has led to confusion with regards to the first cycle efficiency of the system. In this work, we investigate the unique behavior of a tin active material in a foil architecture to understand its performance as an anode. We find shallow cycling of the foil results in an irreversible formation (< 40%) due to diffusional trapping, but intermediate and complete utilization allows for a remarkably reversible formation reaction (> 90%). This striking nonlinearity stems from an in situ transformation from bulk metal to porous electrode that occurs during formation cycles and defines electrode-level lithium-transport on subsequent cycles. As a result, an alternative cycling procedure for assessing the stability of foils is proposed to account for this chemomechanical effect.

25 ENERGY STORAGE↗
DOE OSTI2022

Critical Evaluation of Potentiostatic Holds as Accelerated Predictors of Capacity Fade during Calendar Aging

Li-ion batteries will lose both capacity and power over time due to calendar aging caused by slow parasitic processes that consume Li + ions. Studying and mitigating these processes is traditionally an equally slow venture, which is especially taxing for the validation of new active materials and electrolyte additives. Here, we evaluate whether potentiostatic holds can be used to accelerate the diagnosis of Li + loss during calendar aging. The technique is based on the idea that, under the right conditions, the current measured as the cell voltage is held constant can be correlated with the instantaneous rate of side reactions. Thus, in principle, these measurements could capture the rate of capacity fade in real time . In practice, we show that this method is incapable of quantitatively forecasting calendar aging trends. Instead, our study demonstrates that potentiostatic holds can be applied for initial qualitative screening of systems that exhibit promising long-term stability, which can be useful to shrink the parameter space for calendar aging studies. By facilitating the identification of improved formulations, this approach can help accelerate innovation in the battery industry.

25 ENERGY STORAGE↗
DOE OSTI2023

Review—Earth-Abundant, Mn-Rich Cathodes for Vehicle Applications and Beyond: Overview of Critical Barriers

Broadening the portfolio of cathode active materials for Li-ion battery applications is now more important than ever. Recent focus on enabling diversity and security in supply chains, as well as concerns over sustainability of a massively growing energy storage market, have put emphasis on enabling more Earth-abundant cathode materials as an attractive strategy. With respect to relatively near-term options, manganese-based cathodes are particularly interesting. In this work, we discuss some of the challenges associated with advancing the development of manganese-based oxides and, in particular, those that take advantage of complex local structures and/or over-lithiated compositions. Discussion centers on the representative, lithium- and manganese-rich class of cathodes and considerations to future development are given that range from the atomic-scale to the electrode level.

25 ENERGY STORAGE↗
DOE OSTI2023

The Effects of Lithium Ions and pH on the Function of Polyacrylic Acid Binder for Silicon Anodes

Binder plays a critical role in the performance of silicon anodes for lithium-ion batteries, specifically by connecting particles of active material and promoting adhesion to the current collector. Recent studies have differed on the relative cycle life of silicon anodes made from water-based polyacrylic acid (PAA) vs LiOH-PAA binders. Differences between the two may be due to the pH value or the extra Li + in the binder, both of which change when LiOH is added to PAA. Here we investigate the impact of these two variables on the performance of silicon anodes. Regarding the effect of Li + , cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results confirm our hypothesis that the extra Li + facilitates ion transport. Regarding pH, we find that high pH in binders is detrimental to the electrode mechanical integrity, as observed in peeling tests and cross-sectional imaging. However, viscosity tests reveal that increased pH benefits the coating and mixing process. Further, our cycling results show that LiOH-PAA binder maintains greater cell capacity than does PAA, and further that LiOH-PAA at pH 4.5 leads to a cell with the highest capacity. Therefore, an intermediate pH is an optimal compromise between benefits observed for the low and high pH experiments.

25 ENERGY STORAGE↗
DOE OSTI2023

Improving the Long-term Cycle Performance of xLi 2 MnO 3 ·(1-x)LiMeO 2 /Li 4 Ti 5 O 12 Cells via Prelithiation and Electrolyte Engineering

Toward the development of high energy density and long lifetime batteries for behind-the-meter storage (BTMS) applications, Li- and Mn-rich layered oxide cathode (xLi 2 MnO 3 ·(1-x)LiMeO 2 , Me = Ni, Mn, and etc., LMR-NM) and Li 4 Ti 5 O 12 (LTO) anode system was examined. To mitigate the major degradation mechanisms at each electrode (i.e., loss of Li inventory (LLI) at the anode and transition metal dissolution and oxygen release at the cathode), two approaches were taken—prelithiating the LTO electrode and varying the electrolyte solvent compositions. The effect of prelithiation and electrolyte engineering on the long-term cycle performance of LMR-NM/LTO cells were systematically evaluated via electrochemical analyses and post-mortem characterizations. By using a prelithiated LTO anode and supplying additional Li to the system, the capacity retention of LMR-NM/LTO system was improved. The degree of enhancement was dependent on the types of electrolytes used, as their decomposition products determined the level of LLI. With increased capacity retention, however, the cathode was utilized to a greater extent, resulting in more severe loss of the cathode active material. Thus, all degradation mechanisms should be considered comprehensively when designing high performance LMR-NM/LTO cells to account for their complex interplay.

25 ENERGY STORAGE↗
DOE OSTI2024

Improved Stability of Oxysulfide Solid-State Electrolytes in Li(G3)TFSI Solvate Ionic Liquid Electrolyte

The performance of all solid-state batteries is limited by poor interfacial contact between active material and solid-state electrolyte (SSE) particles. Semi-solid batteries utilize a secondary electrolyte phase to wet the SSE/AM interface to improve cell performance. Solvate ionic liquids (SILs) are one class of liquid electrolytes under consideration for use in semi-solid batteries. This paper focuses on the Li(G3)TFSI SIL consisting of the bis(trifluoromethanesulfonyl)imide (TFSI − ) anion coupled to a [Li(G3)] + solvate cation. Sulfide SSEs are normally subject to nucleophilic attack by trigylme (G3), however, strong coordination of Li + to G3 in the [Li(G3)] + solvate cation prevents this reaction from taking place. Consequently, the stability of sulfide SSE depends on the ideal 1:1 molar ratio of G3 to TFSI, which may be difficult to maintain. We studied the chemical stability of 70Li 2 S·(30-x)P 2 S 5 ·xP 2 O 5 (x = 0, 2, 5, 10) (oxy)sulfide solid-state electrolyte in Li(G3)TFSI SIL. By physical measurement, UV–vis spectroscopy, electrochemical evaluation, X-ray photoelectron spectroscopy, and first principles calculation it is shown that increased oxygen content improves the stability of SSE in various Li(G3) x TFSI (x = 1, 2, 3, 4) liquid electrolytes. The results suggest that an oxysulfide SSE + SIL semi-solid electrolyte is a good choice for future semi-solid battery designs.

Electrochemistry↗
DOE OSTI2024

Shape Matters: Understanding the Effect of Electrode Geometry on Cell Resistance and Chemo-Mechanical Stress

Rechargeable batteries that incorporate shaped three-dimensional electrodes have been shown to have increased power and energy densities when compared to a conventional geometry, i.e. a planar cathode and anode that sandwich an electrolyte. Electrodes can be shaped to enable a higher active material loading, while keeping ion transport distances small. However, the relationship between electrical and mechanical performance of shaped electrodes remains poorly understood. Many electrode designs have been explored, where the electrodes are individually shaped or intertwined, and advances in manufacturing and shape/topology optimization have made such designs a reality. Here, we explore sinusoidal half cells and interdigitated full cells. First, we use a simple electrostatics model to understand the cell resistance as a function of shape. Here we focus on low-temperature conditions, where the electrolyte conductivity decreases relative to that of the electrode; here, LiPF 6 EC:DMC electrolyte and MnO 2 electrode are considered. Next, we use a chemo-mechanics model to examine the stress that arises due to intercalation-driven volume expansion. We show that shaped electrodes provide a significant reduction in resistance in low-temperature conditions, however, they exhibit unfavorable stress concentrations. Overall, we find that the fully interdigitated electrodes may provide the best balance with respect to this resistance-stress trade-off.

25 ENERGY STORAGE↗