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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Tackling issues of lithium metal anodes with a novel polymeric lithicone coating

Lithium metal (Li) has been hindered from as anodes in commercial batteries for over 50 years, due to two main issues: continuous formation of solid electrolyte interphase (SEI) and lithium dendritic growth. In this work, we report a new strategy to tackle these issues, i.e., using molecular layer deposition (MLD) to grow an ionically conducting but electrically insulating polymeric lithicone coating, an Li-containing triethanolamine (LiTEA). Our electrochemical tests revealed that this LiTEA coating could serve as an exceptional protection layer over Li anodes. Consequently, the LiTEA-coated Li electrodes could achieve a superior cyclability of > 10000 Li stripping/plating cycles at a current density of 5 mA cm -2 and a long cyclability of > 5500 cycles at 2 mA cm -2 in Li||Li symmetric cells without failures, under a fixed areal capacity of 1 mAh cm -2 . Characterizations using scanning electron microscopy and X-ray photoelectron microscopy verified that Li + ions could be easily extracted through and deposited under the LiTEA coating during the stripping/plating processes. Consequently, this LiTEA coating significantly inhibited the formation of SEI and Li dendrites. This underlies the long cycling lifetime of the LiTEA-coated Li||Li cells. Coupling with the nickel-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes, more encouragingly, the LiTEA-coated Li anodes could remarkably extend the cyclability and sustainable capacity of the resultant Li||NMC full cells. Finally, we also demonstrated that the performance of Li||NMC cells could be further improved through combining an LiTEA-coated Li anode with an Li 2 S-modified NMC811 via atomic layer deposition (ALD). Thus, this study is inspiring for developing high-energy Li||NMC lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Failure analysis of solid oxide fuel cells nickel-yttria stabilized zirconia anode under siloxane contamination

In this study, the failure process of the solid oxide fuel cell (SOFC) Ni-yttria-stabilized zirconia (YSZ) anode is investigated with D4 siloxane (octamethylcyclotetrasiloxane) contamination. In order to evaluate the influence of the electrochemical reaction on the siloxane deposition process, the SOFC experiments were operated at open circuit voltage (OCV) and 50 mA cm -2 conditions at 800°C. During the failure process, electrochemical, morphology and exhaust gas component analysis testing are conducted at the critical points. An equivalent circuit model and corresponding microstructure parameter calculations for separated physicochemical processes were utilized for the quantitative analysis of the failure process. Further, the results confirm the siloxane chemical adsorption deposition mechanism proposed in previous work. As a result, the failure of the anode was attributed to the gas diffusion blockage by dense silicon dioxide layer formation. The anode failure process with siloxane contamination is faster when the anode is operated under polarization.

25 ENERGY STORAGE↗
DOE OSTI2022

Coal-derived graphene foam and micron-sized silicon composite anodes for lithium-ion batteries

Silicon-based materials demonstrate significant potential as lithium-ion batteries (LIBs) anode, but their expansion and degradation present engineering design challenges for commercial application. In this study, a porous three-dimensional (3D) graphene and micron-sized silicon composite anode (Si@G foam) was synthesized using humic acid (HA) derived from coal as a graphene precursor. In-situ formation of graphene structure through reducing HA was confirmed by Raman spectra. The reduced HA (rHA) shows similar electrical conductivity compared to the commercial conductive carbon. SEM images depict a 3D skeleton of coal-derived graphene, with silicon particles distributed on the 3D graphene foam's internal surface. The Si@G composite-anode displays a good reversible capacity of ~656 mAh/g at a current density of 50 mA/g, as well as a high-rate capability of ~433 mAh/g at a current density of 800 mA/g, and outstanding cycling stability –89.8% capacity retention after 300 cycles, which is significantly higher than that of other foam structures. During lithiation and de-lithiation, the graphene foam serves as a matrix of electrical conductors and a volume expansion support for silicon. This 3D graphene network will be beneficial for developing advanced silicon-based anodes for high-performance LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Multi-layer anodes for high-current applications

In this work, we present a combination of experiments and modeling of a two-layer anode structure designed by EnPower Inc. for high-energy and fast-charge capabilities. The anode consists of lower porosity near the current collector and higher porosity near the separator with comparable active materials in both regions. A pseudo-two-dimensional electrochemical–thermal model was designed to represent the performance of this electrode. Simulations, consistent with experiments, show superior ion transport and lithiation in the multi-layer anode (MLA) compared to a conventional single-layer anode (SLA). Surprisingly, this improved transport in MLA manifests as enhanced cathode performance during high-rate discharge and this, in turn, provides higher energy density for MLA. Similarly, during fast charge, less irreversible lithium is deposited due to this improved transport in MLA, and hence MLA exhibits less capacity fade compared to SLA. Polarization analysis demonstrates marginally lower cumulative overpotential for MLA in different case studies; however, MLA cells maintain a significantly higher capacity in the same conditions and have more than double the cycle life. Further, this means despite the apparently limited polarization benefit provided by MLA; the MLA structure can more reliably be employed in cell designs. Additional design changes are also analyzed by means of the model.

25 ENERGY STORAGE↗
DOE OSTI2023

Sustainable Li-ion anode material from Fe-catalyzed graphitization of paper waste

We report a novel method for the conversion of paper towel waste to biographite anode material is developed and optimized for use in Li-ion batteries. The surge in demand for Li-ion battery anode materials coupled with the unsustainable and inefficient methods of producing battery-grade graphite necessitate alternative carbon feedstocks and graphitization technologies. Paper waste (PW) is identified as a suitable carbon feedstock for iron-catalyzed graphitization due to its sustainability, low cost, low ash content, and ample supply for the intended end use. A Box Behnken experimental design for statistical optimization is pursued for untreated and pre-carbonized PW with factors of temperature (1100-1300 °C), hold time (1-5 h), and iron catalyst loading (0.5-1.5x fixed carbon content) with biographite crystal size as the primary response variable. Temperature and iron catalyst loading are found to be significant factors, whereas hold time is found to be insignificant. Reversible capacities of the biographite anodes are found to be 340-355 mAh g-1 with 99% capacity retention over 100 cycles, indicating good electrochemical performance relative to commercial graphite anodes. The initial Coulombic efficiency of untreated and pre-carbonized biographites, however, are 77% and 75%, respectively, suggesting parasitic reactions including electrolyte decomposition.

25 ENERGY STORAGE↗
DOE OSTI2021

Tracking the evolution of processes occurring in silicon anodes in lithium ion batteries by 3D visualization of relaxation times

An unconventional electroanalytical method has been used for tracking processes in silicon anodes in lithium ion batteries: a 3D visualization of relaxation times. Impedance data of the electrodes were collected at different potentials and different cycles during cyclic voltammetry, and were treated by means of the Distribution of Relaxation Times (DRT) method. A 3D visualization of the results allowed to identify the formation of a solid electrolyte interphase on the anode, composed of two layers with different relaxation times. Such findings are not possible by conventional analysis of impedance data by modeling with equivalent circuits, nor by simple DRT alone. Additionally, it was possible to observe that the characteristic relaxation time of the lithiation of the Si anode becomes smaller upon cycling, indicating that the material experiences structural transformations that allow it to lithiate faster. The result is relevant to motivate the use of micron-sized particles in the anode.

25 ENERGY STORAGE↗
DOE OSTI2023

Structural and electrochemical evolution of alloy interfacial layers in anode-free solid-state batteries

“Anode-free” solid-state batteries feature high energy density since there is no anode active material. Although the beneficial effects of interfacial layers at the anode-solid electrolyte interface have been demonstrated, the mechanisms through which they influence lithium plating/stripping are unclear. Here, in this study, we reveal the evolution of 100-nm silver and gold interfacial layers during lithium plating/stripping using electrochemical methods, electron microscopy, X-ray microcomputed tomography, and modeling. The alloy layers improve Coulombic efficiency and resistance to short circuiting, even though the alloys form solute regions or particulates that detach from the current collector during plating. In situ electrochemical impedance spectroscopy shows that the alloys return to the interface and mitigate contact loss at the end of stripping, avoiding a critical vulnerability of anode-free cells. Contact retention is driven by even Li thickness that promotes spatially uniform stripping, as well as local alloy delithiation in response to current concentrations that homogenizes current and diminishes voiding.

25 ENERGY STORAGE↗
DOE OSTI2024

A novel polymeric lithicone coating for superior lithium metal anodes

Lithium metal (Li) is commonly regarded as the “holy grail” of rechargeable batteries and can serve as anodes for constituting various high-energy lithium metal batteries (LMBs). However, it suffers from two notorious issues: (1) continuous formation of inhomogeneous solid electrolyte interphase and (2) Li dendritic growth. Here, in this study, we developed a novel polymeric lithicone via a new molecular layer deposition (MLD) process, using lithium tert-butoxide (LTB) and hydroquinone (HQ) as precursors. We revealed that such an MLD process enabled the resultant LiHQ to grow linearly in a highly controllable and cyclic mode at a growth rate of 4 Å cycle −1 . Furthermore, its low process deposition temperature of 150 °C made it possible to practice high-quality coatings over Li anodes directly. We demonstrated that, very compellingly, this LiHQ coating could protect Li anodes from corrosion and dendritic growth. As a consequence, this LiHQ coating has enabled Li||Li symmetric cells an extremely long cyclability up to 8000 Li-plating/stripping cycles without failure. More excitingly, we demonstrated that, coupled with LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes, the LiHQ-modified Li anodes could help the resultant Li||NMC811 realize a much better capacity retention and much longer cyclability. Thus, this study represents a strategic route for developing commercializeable LMBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Quantifying lithium loss in amorphous silicon thin-film anodes via titration-gas chromatography

Silicon with a high theoretical capacity (3,579 mAh/g) is a promising anode candidate for lithium-ion batteries. However, commercialization is still impeded by low Coulombic efficiency, caused by solid electrolyte interphase (SEI) formation and trapped lithium (Li)-silicon (Si) alloy during repeated volume change. Quantifying capacity losses from each factor is crucial to formulate rational design strategies for further improvement. In this work, titration-gas chromatography and cryogenic transmission electron microscopy are applied to characterize the evolution of trapped Li-Si alloy and SEI growth in a silicon thin-film anode. It is found that continuous growth of the SEI is the dominant factor for lithium inventory loss during cycling, with only a marginal increase in trapped Li-Si alloy. This study offers a quantitative approach to differentiate Li in the SEI from trapped Li in Li-Si alloy through a silicon thin-film anode, providing unique insights into identifying critical bottlenecks for developing Si anodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Large Scale Synthesis of Manganese Oxide/Reduced Graphene Oxide Composites as Anode Materials for Long Cycle Lithium Ion Batteries

Manganese oxides have been frequently used as cathodes in primary batteries. Applications of manganese oxides in secondary batteries are limited by low electrical conductivity and rapid capacity fading because of electrode pulverization and aggregation. In this study, a solid-state synthetic strategy is presented that successfully combines nanosize (~ 50 nm) nickel doped α-MnO 2 with reduced graphene oxides as highly stable composite anodes in lithium ion batteries. The synthesis approach is easy to scale up and suitable for industrial applications. Here, the rationally designed Ni-α-MnO 2 /RGO was tested in galvanostatic half coin cells for Li + charge-discharge studies. The results show that this composite maintains a high capacity of 615 mAh g -1 even after 200 cycles at a high current rate of 1 C (830 mA g -1 ), and with a high Coulombic efficiency near 99%. The anodes exhibit excellent rate capability in a wide range of rate testing from 0.2 to 10 C, without showing capacity decay. This superior anode performance is ascribed to the reduced size of α-MnO 2 domains that are well dispersed in an RGO matrix, which affords good ionic/elec. cond., low charge transfer resistance and mitigates issues of vol. expansion of the anodic active materials. This study opens up an avenue for developing the manufacturing of high-performance electrodes for real applications, such as batteries in electrical vehicles.

25 ENERGY STORAGE↗
DOE OSTI2020

Nonpassivated Silicon Anode Surface

A stable solid electrolyte interphase (SEI) has been proven to be a key enabler to most advanced battery chemistries, where the reactivity between the electrolyte and the anode operating beyond the electrolyte stability limits must be kinetically suppressed by such SEIs. The graphite anode used in state-of-the-art Li-ion batteries presents the most representative SEI example. Because of similar operation potentials between graphite and silicon (Si), a similar passivation mechanism has been thought to apply on the Si anode when using the same carbonate-based electrolytes. Herein, we found that the chemical formation process of a proto-SEI on Si is closely entangled with incessant SEI decomposition, detachment, and reparation, which lead to continuous lithium consumption. Using a special galvanostatic protocol designed to observe the SEI formation prior to Si lithiation, we were able to deconvolute the electrochemical formation of such dynamic SEI from the morphology and mechanical complexities of Si and showed that a pristine Si anode could not be fully passivated in carbonate-based electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2021

Hydrophobic Molecule Monolayer Brush-Tethered Zinc Anodes for Aqueous Zinc Batteries

Aqueous zinc batteries are of great interest as a rechargeable energy storage system, particularly owing to the low cost and high safety of aqueous electrolytes, as well as the high capacity of zinc anodes. Unfortunately, the wide commercialization of aqueous zinc batteries is impeded by the irreversible water reduction and irregular zinc evolution issues on the anode side. Hereby, a hydrophobic and ultrathin polystyrene molecule brush layer is tethered onto the surface of zinc metal anodes to tackle the above limitations. Here, experimental investigations reveal that the waterproof artificial layer can sustain fast interfacial ionic transportation, minimize hydrogen evolution, and smoothen Zn deposition, thus conferring enhanced electrochemical performance to the as-protected Zn anode in both symmetric Zn//Zn cells and Zn//LiV 3 O 8 full cells.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI) 2 and Mg(TFSI) 2

Here, silicon is drawing attention as the upcoming anode material for the next generation of lithium-ion batteries due to its higher capacity compared to commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer is mitigated by utilizing the use of a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in-situ fashion and more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage than that of the baseline electrolyte due to reduced side reactions. Electron Microscopy, HRXRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface compared to Si electrodes with Gen2 + FEC and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing bulk and forming a more stable SEI.

25 ENERGY STORAGE↗
DOE OSTI2025

Comparative Study of Vinylene Carbonate and Lithium Difluoro(oxalate)borate Additives in a SiO x /Graphite Anode Lithium-Ion Battery in the Presence of Fluoroethylene Carbonate

The SiO x /graphite composite is recognized as a promising anode material for lithium-ion batteries (LIBs), owing to the high theoretical capacity of SiO x combined with the excellent stability of graphite. However, the inherent disadvantage of volume expansion in silicon-based anodes places significant challenges on the solid electrolyte interphase (SEI) and severely degrades the electrochemical performance. Rational formulation of electrolyte, including its additives, is crucial in accommodating and optimizing the composition of the SEI and enhancing the cell performance. In this work, we present a comparative study of vinylene carbonate (VC) and lithium difluoro(oxalate)borate (LiDFOB) additives combined with fluoroethylene carbonate (FEC) in the electrolyte for SiO x /graphite∥LiNi 1–x–y–z Co x Mn y Al z O 2 full cells. VC outperformed LiDFOB as an additive, delivering higher capacity cycling, higher Coulombic efficiency, and better cycle stability up to 400 cycles. XPS and impedance analyses reveal that LiDFOB contributed to SEI/CEI with both a lower proportion of LiF and a higher proportion of poly(VC), which tended to produce higher cell impedance. XRD and XANES further indicated that using the LiDFOB additive, the NCMA cycled to a shallower degree than that of the VC additive. Although the VC additive maintained a higher capacity up to 400 cycles, microstrain and SEM analyses show a higher strained NCMA along with clear evidence of cracking over the surface of the NCMA particle in VC-based electrolyte but not in LiDFOB. In conclusion, this suggests that the negative influence of LiDFOB at the anode (inferior SEI) supersedes the negative impact of both a cracked NCMA and a deeper cycled NCMA and SiO x -based anode.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Reactivity of Carbonate Solvent Electrolytes on Lithium Silicon Anodes

Silicon (Si) is promising for lithium-ion battery (LIB) anodes due to their high theoretical capacity and low electrochemical potential. However, significant challenges remain, including severe volumetric expansion during cycling and the electrochemical instability of electrolytes, which leads to the formation of a nonuniform solid electrolyte interphase (SEI). To investigate SEI formation mechanisms, computational molecular dynamics simulations offer valuable insights. In this work, we examine the trajectories and charge transfer behavior of lithium hexafluorophosphate (LiPF 6 ) salt with various solvent compositions using density functional theory (DFT) and ab initio molecular dynamics (AIMD). Among the tested electrolyte systems, LiPF 6 with vinylene carbonate (VC) added to ethyl methyl carbonate (EMC) exhibits the lowest reactivity with the Si anode. In contrast, the effects of fluoroethylene carbonate (FEC) and VC depend on whether the primary solvent is EMC alone or a mixture of ethylene carbonate (EC) and EMC. Moreover, we show that electrolyte reactivity varies with the degree of lithiation of the Si anode (LiSi vs Li 15 Si 4 ) and under different charge states. To decouple electrolyte reactivity from surface effects, we analyze the dissociation and formation energies of individual species from solvated configurations. Overall, these first-principles-based findings provide a strategic foundation for electrolyte design to improve cycling stability and extend calendar life in LIBs using Si anodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

On-Wafer Wide-Pore Anodic Aluminum Oxide

Anodized aluminum oxide (AAO) has been used as nanotemplates for nanomaterials and nanodevice fabrications. Microfabrication techniques are attracting attention for nanodevice synthesis. However, AAO requires a microfabrication-compatible substrate due to its brittleness. While there are studies that already show AAO on compatible substrates, the pore sizes may not be applicable for multicomponent nanodevices. In this study, wide pore AAOs with ohmic bottom contacts are fabricated on 76 mm Si wafers. Sputtering was used to deposit Al along with supporting layers to achieve this goal. A quiescent electropolishing technique was used to smooth the surface of Al. Standard photolithography was used to define the active area on the Al for anodization. Then 195 V two-step anodization was performed to fabricate wide pore AAOs with pore diameters ranging from 130 ± 32 nm to 400 ± 31 nm with interpore distance of 480 ± 47 nm. Furthermore, it also showed that the ordering of the pores depended on the current density over the more conventional anodization time.

25 ENERGY STORAGE↗
DOE OSTI2026

Time-Evolved Hetero-Alkali Interphases Enable Long-Life Sulfide-Based Anode-Free Solid-State Batteries

Sulfide-based anode-free solid-state batteries (AFSSBs) offer compelling advantages in terms of energy density and safety, yet their practical implementation is severely hindered by undesirable interfacial reactions between sulfide solid electrolytes (SEs) and freshly plated lithium (Li), as well as non-uniform Li plating/stripping behavior. Herein, an effective interfacial stabilization strategy by incorporating sodium bis(fluorosulfonyl)imide (NaFSI) additive into the Li5.4PS4.4Cl1.6 (LPSC) is investigated. Unlike conventional Li-based additives that form static passivation layers, NaFSI introduces a transient hetero-alkali chemistry that kinetically governs interphase evolution during fresh Li plating. NaFSI induces a timesequenced interphase evolution: an initial NaF/LiF-rich layer that suppresses early sulfide reduction, followed by a LiF/Li3N-rich layer that optimizes Li⁺ transport during repeated anode-free cycling. This evolved robust and fast ion conducting layer mitigates interfacial impedance growth, enhances Li + transport kinetics, and suppresses localized Li growth and filamentary shorting. As a result, the anode-free full cell with NaFSI modified LPSC as the interlayer exhibits an excellent cycling stability over 500 cycles at 0.2 C with a capacity retention of 77.6%, whereas the cell with bare LPSC suffers from rapid capacity decay after 100 cycles, retaining only 32.1% of its initial capacity. This work establishes dynamic heteroalkali additive chemistry as a general strategy to kinetically program solid-solid interphases, guiding the interface design in anode-free solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Li2O-Based Cathode Additives Enabling Prelithiation of Si Anodes

Low first-cycle Coulombic efficiency is especially poor for silicon (Si)-based anodes due to the high surface area of the Si-active material and extensive electrolyte decomposition during the initial cycles forming the solid electrolyte interphase (SEI). Therefore, developing successful prelithiation methods will greatly benefit the development of lithium-ion batteries (LiBs) utilizing Si anodes. In pursuit of this goal, in this study, lithium oxide (Li2O) was added to a LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode using a scalable ball-milling approach to compensate for the initial Li loss at the anode. Different milling conditions were tested to evaluate the impact of particle morphology on the additive performance. In addition, Co3O4, a well-known oxygen evolution reaction catalyst, was introduced to facilitate the activation of Li2O. The Li2O + Co3O4 additives successfully delivered an additional capacity of 1116 mAh/gLi2O when charged up to 4.3 V in half cells and 1035 mAh/gLi2O when charged up to 4.1 V in full cells using Si anodes.

25 ENERGY STORAGE↗