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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Stabilizing the Solid‐Electrolyte Interphase with Polyacrylamide for High‐Voltage Aqueous Lithium‐Ion Batteries

Abstract The introduction of “water‐in‐salt” electrolyte (WiSE) concept opens a new horizon to aqueous electrochemistry that is benefited from the formation of a solid‐electrolyte interphase (SEI). However, such SEI still faces multiple challenges, including dissolution, mechanical damaging, and incessant reforming, which result in poor cycling stability. Here, we report a polymeric additive, polyacrylamide (PAM) that effectively stabilizes the interphase in WiSE. With the addition of 5 molar % PAM to 21 mol kg −1 LiTFSI electrolyte, a LiMn 2 O 4 ∥L‐TiO 2 full cell exhibits enhanced cycling stability with 86 % capacity retention after 100 cycles at 1 C. The formation mechanism and evolution of PAM‐assisted SEI was investigated using operando small angle neutron scattering and density functional theory (DFT) calculations, which reveal that PAM minimizes the presence of free water molecules at the anode/electrolyte interface, accelerates the TFSI − anion decomposition, and densifies the SEI.

Hou, Xu↗
DOE OSTI2021

Stabilizing the Solid‐Electrolyte Interphase with Polyacrylamide for High‐Voltage Aqueous Lithium‐Ion Batteries

Abstract The introduction of “water‐in‐salt” electrolyte (WiSE) concept opens a new horizon to aqueous electrochemistry that is benefited from the formation of a solid‐electrolyte interphase (SEI). However, such SEI still faces multiple challenges, including dissolution, mechanical damaging, and incessant reforming, which result in poor cycling stability. Here, we report a polymeric additive, polyacrylamide (PAM) that effectively stabilizes the interphase in WiSE. With the addition of 5 molar % PAM to 21 mol kg −1 LiTFSI electrolyte, a LiMn 2 O 4 ∥L‐TiO 2 full cell exhibits enhanced cycling stability with 86 % capacity retention after 100 cycles at 1 C. The formation mechanism and evolution of PAM‐assisted SEI was investigated using operando small angle neutron scattering and density functional theory (DFT) calculations, which reveal that PAM minimizes the presence of free water molecules at the anode/electrolyte interface, accelerates the TFSI − anion decomposition, and densifies the SEI.

25 ENERGY STORAGE↗
DOE OSTI2025

Floatable Protective Layers: a Strategy to Minimize Solid Electrolyte Interphase Growth and Maximize the Lithium Utilization

Abstract Maximizing lithium (Li) utilization is crucial for enhancing the long‐term stability of Li‐based batteries. In anode‐free Li batteries (AFLBs), although the initial formation of solid electrolyte interphase (SEI) is beneficial on limiting further reaction between Li and electrolyte, large volume change of Li metal anode (LMA) during cycling often leads to continuous breakdown and re‐formation of SEI and formation of inactive Li, hindering its efficiency. In this study, a novel strategy is presented to protect Li metal by applying a floatable protection layer (FPL) on a copper substrate, enabling large Li particles to be primarily deposited below FPL, but SEI to be primarily formed above FPL. This approach effectively minimizes the direct contact between electrolyte and freshly deposited Li, therefore mitigating the continuous side reactions and early failure of AFLBs. As a result, Li consumption is minimized, and the overall stability of the battery is significantly enhanced. Further development of this approach can also be used to improve the performance of other Li‐based batteries for large‐scale applications.

Lim, Hyung‐Seok [Energy and Environment Directorat↗
DOE OSTI2024

Binary Cation Matrix Electrolyte and Its Effect on Solid Electrolyte Interphase Suppression and Evolution of Si Anode

An unstable solid electrolyte interphase (SEI) has been recognized as one of the biggest challenges to commercializing silicon (Si) anodes for high-energy-density batteries. This work thoroughly investigates a binary cation matrix of Mg 2+ +Li + electrolyte and its role in SEI development, suppression, and evolution of a Si anode. Findings demonstrate that introducing Mg ions dramatically reduces the SEI growth before lithiation occurs, primarily due to the suppression of solvent reduction, particularly ethylene carbonate (EC) reduction. The Mg 2+ alters the Li + cation solvation environment as EC preferably participates in the oxophyllic Mg 2+ solvation sheath, thereby altering the solvent reduction process, resulting in a distinct SEI formation mechanism. The initial SEI formation before lithiation is reduced by 70% in the electrolyte with the presence of Mg 2+ cations. While the SEI continues to develop in the postlithiation, the inclusion of Mg ions results in an approximately 80% reduction in the postlithiation SEI growth. Continuous electrochemical cycling reveals that Mg 2+ plays a crucial role in stabilizing the deep-lithiated Si phases, which effectively mitigates side reactions, resulting in controlled SEI growth and stable interphase while eliminating complex Li x Si y formation. Mg ions promote the development of a notably more rigid and homogeneous SEI, characterized by a reduced dissipation (ΔD) in the Mg 2+ +Li + ion matrix compared to the solely Li + system. In conclusion, this report reveals how the Mg 2+ +Li + ion matrix affects the SEI evolution, viscoelastic properties, and electrochemical behavior at the Si interface in real time, laying the groundwork for devising strategies to enhance the performance and longevity of Si-based next-generation battery systems.

25 ENERGY STORAGE↗
DOE OSTI2022

Delineating the Roles of Mn, Al, and Co by Comparing Three Layered Oxide Cathodes with the Same Nickel Content of 70% for Lithium-Ion Batteries

High-nickel layered oxides continue to prevail in the energy storage market as the frontmost cathode candidates for next-generation lithium-ion batteries. Demand and development of LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) cathodes are rampantly increasing, particularly for the electric vehicle (EV) industry. However, the continued presence of cobalt in NMC and NCA cathodes raises global concerns due to geopolitical and ethical issues attributed to Co sourcing. We herein introduce a novel cobalt-free, high-nickel cathode LiNi 0.7 Mn 0.25 Al 0.05 O 2 (NMA70) and benchmark it against Co-containing LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC70) as well as Co- and Al-free LiNi 0.7 Mn 0.3 O 2 (NM70) cathodes with equivalent 70% Ni contents that are all synthesized in-house. NMA70 displays a high initial C/10 capacity of 210 mA h g –1 , matching that of NMC70 in half cells with a cutoff voltage of 4.5 V. NMA70 also exhibits an impressive high-voltage full cell cycling performance with a cutoff voltage of 4.4 V with a nearly identical capacity retention of 83% compared to that of 82% for NMC70 after 300 cycles. Postmortem X-ray photoelectron spectroscopy (XPS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and electron energy loss spectroscopy (EELS) analyses indicate a thinner cathode–electrolyte interface (CEI) developed in NMA70 compared to that in NM70 and unveil a more robust solid-electrolyte interface (SEI) passivation on the graphite anode among all samples. The benefits of Al doping are additionally highlighted with enhanced high-voltage CEI and thermal stabilities in NMA70. Furthermore, this work assesses the roles of Mn, Al, and Co to demonstrate both the practicality and feasibility of synthesizing cobalt-free, high-nickel cathodes that are promising alternatives to current NMC- and NCA-based cathodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Insights into Chemical Prelithiation of SiO x /Graphite Composite Anodes through Scanning Electron Microscope Imaging

Initial Coulombic efficiency (ICE) is critical for determining the energy density of lithium-ion batteries (LIBs) used for practical applications; however, it is typically disregarded in anode research. We used SiO x and graphite composite anodes for commercial lithium-ion batteries in our preliminary research to achieve a balance between ICE, capacity, and cycling life. ICE reached 88%; however, it needs further improvement for commercial applications. Prelithiation is a process that involves the introduction of extra lithium ions into LIBs during their manufacturing to enhance the overall performance of the LIBs. We applied a chemical prelithiation method on our SiO x /graphite composite anodes, which comprised 95 wt % of the active material mass loading on the electrode. The ICE increased from 88% to 98% using an aryllithium reagent impregnation method within 2 min of prelithiation. The anode’s specific capacity density, rate, and cycle performance also significantly improved. Scanning electron microscopy (SEM) imaging enhanced by an osmium tetroxide staining method indicated that the P-anode contained a stable solid electrolyte interface (SEI) layer after the prelithiation process and cycling electrochemical test. The P-anode’s stable charge differential peak over 500 cycles also showcases a robust artificial SEI layer that was generated by the prelithiation procedure. Here, this prelithiation process has significant potential for adoption in the LIB industry’s current electrode manufacturing process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Evaluating the Effect of Electrolyte Additive Functionalities on NMC622/Si Cell Performance

Unstable electrode/electrolyte interface is the major cause of degradation for silicon (Si)-based anodes for lithium (Li)-ion batteries. Development of functional electrolyte additives can provide a viable path toward stabilizing the dynamic Si/electrolyte interface, which will benefit the development of high energy density Li-ion batteries. Here, we evaluate polymerizable electrolyte additives with varying functional groups (fluorocarbon, thiophosphate, and fluorophosphazene). The additives are examined using LiNi 0.6 Mn 0.2 Co 0.2 O 2 /Si full cells where the cycle performance and impedance are measured. Electrochemical tests show that the fluorine-containing additives provide better passivation at the Si electrode, leading to enhanced full cell performance. Here, among the three additives examined, best electrochemical performance is observed from the fluorocarbon-containing compound, followed by fluorophosphazene- and thiophosphate-containing compounds. Characterization of the solid electrolyte interphase (SEI) on cycled electrodes using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) reveal that higher concentration of fluorine and lithium oxide, and lower concentration of carbonate and organic species correlate with enhanced electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2021

On the crystallography and reversibility of lithium electrodeposits at ultrahigh capacity

Abstract Lithium metal is a promising anode for energy-dense batteries but is hindered by poor reversibility caused by continuous chemical and electrochemical degradation. Here we find that by increasing the Li plating capacity to high values ( e.g ., 10–50 mAh cm −2 ), Li deposits undergo a morphological transition to produce dense structures, composed of large grains with dominantly (110) Li crystallographic facets. The resultant Li metal electrodes manifest fast kinetics for lithium stripping/plating processes with higher exchange current density, but simultaneously exhibit elevated electrochemical stability towards the electrolyte. Detailed analysis of these findings reveal that parasitic electrochemical reactions are the major reason for poor Li reversibility, and that the degradation rate from parasitic electroreduction of electrolyte components is about an order of magnitude faster than from chemical reactions. The high-capacity Li electrodes provide a straightforward strategy for interrogating the solid electrolyte interphase (SEI) on Li —with unprecedented, high signal to noise. We find that an inorganic rich SEI is formed and is primarily concentrated around the edges of lithium particles. Our findings provide straightforward, but powerful approaches for enhancing the reversibility of Li and for fundamental studies of the interphases formed in liquid and solid-state electrolytes using readily accessible analytical tools.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Advanced Electrolyte Supporting 500 Wh/kg Li-C/NMC Batteries

Through this project, we developed three electrolytes (LiPF6-mix-THF, LiNO3 enhanced carbonate electrolytes, and ionic liquid) for Li/NMC, Li/SPAN, and Li/S cells. These electrolytes enable to form of LiF-rich SEI on Li and LiF-rich CEI on cathodes, which enable Li CE to reach >99.5%, and full cells to reach a long cycle life. The high CE for high capacity Li and high capacity cathode (NMC811 and SPAN) is attributed to the low binding between LiF SEI/CEI to the electrode with a large volume change, which LiF SEI/CEI will suffer less stress/strain during electrode volume changes.

25 ENERGY STORAGE↗
DOE OSTI2021

F and N Rich Solid Electrolyte for Stable All-Solid-State Battery

We report the instability of sulfide solid electrolytes to Li anode and high-voltage LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes limits the cyclic performance of all-solid-state lithium battery (ASSLB). Herein, the stability of Li 6 PS 5 Cl against Li anode is enhanced by mixing a small amount (0.32 wt%) of CuF 2 -LiNO 3 (CL) into Li 6 PS 5 Cl electrolyte layer to in-situ form a mixed-conductive-lithiophobic and self-healing LiF-Li 3 N-Cu solid electrolyte interphase (SEI) at Li 6 PS 5 Cl-CL/Li interface. The critical current density (CCD) of Li 6 PS 5 Cl-CuF 2 -LiNO 3 increases to 1.4 mA cm –2 /1.4 mAh cm –2 at room temperature, which is much higher than that of pristine Li 6 PS 5 Cl (0.4 mA cm –2 /0.4 mAh cm –2 ) even though mixing 0.32 wt% CL into Li 6 PS 5 Cl slightly reduces the ionic conductivity from 2.9 × 10 –3 to 1.5 × 10 –3 S cm –1 . The compatibility of Li 6 PS 5 Cl-CL electrolyte to single-crystalline NMC811 (S-NMC811) is further enhanced by adding a small amount (0.02 wt%) of AlF 3 into Li 6 PS 5 Cl-CL forming Li 6 PS 5 Cl-CuF 2- LiNO 3 -AlF 3 (Li 6 >PS 5 Cl-CLA) as a cathode electrolyte and by doing Cl – on S-NMC811 (Cl@S-NMC811) surface. The Cl@S-NMC811-Li 6 PS 5 Cl-CLA|Li 6 PS 5 Cl-CL|Li cells with areal capacity of 2.55 mAh cm -2 achieve a capacity retention of 69.4% after 100 cycles at 1C (1C = 200 mAh g -1 ). Adding a small amount of SEI and cathode/electrolyte interphase (CEI) former into the sulfide electrolytes with minimal reduction (48.3%) of ionic conductivity is an effective method to enhance the performance of ASSLB.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

25 ENERGY STORAGE↗
DOE OSTI2021

Advanced battery modeling for interfacial phenomena and optimal charging

Lithium ion batteries are one of the most promising energy storage systems for portable devices, transportation, and renewable grids. To meet the increasing requirements of these applications, higher energy density and areal capacity, long cycle life, fast charging rate and enhanced safety for lithium ion battery (LIBs) are urgently needed. To solve these challenges, the relevant physics at different length scale need to be understood. However, experimental study is time consuming and limited in small scale’s study. Modeling techniques provide us powerful tools to get a deep understanding of the relevant physics and find optimal solutions. This work focuses on studying the mechanism in advanced battery engineering techniques and developing a new charging algorithm by model-based optimization. The research topics are divided into six topics and each topic is reported as a form of journal publication. Paper Ⅰ provides a new aspect of how ALD coating improves the lithium ion diffusion at electrode particles. Paper Ⅱ explains the mechanisms by which 3D electrodes enhance battery performance and reveals guidelines for optimized 3D electrode designs by a 3D electrochemical-mechanical battery model. Paper Ⅲ investigates the electrolyte concentration impact on SEI layer growth and Li plating, especially under high charge rates. Paper Ⅳ proposes an optimized charging protocol for fast charging for reducing the charging time with minimal degradation. Paper Ⅴ reports a comprehensive degradation model for degradation estimation and life predication of energy storage system (ESS). Paper Ⅵ is a study of temperature-dependent state of charge (SOC) estimation for battery pack.

25 ENERGY STORAGE↗
DOE OSTI2023

Microstructure and defect engineering of graphite anodes by pulsed laser annealing for enhanced performance of lithium-ion batteries

We report nanosecond pulsed laser annealing significantly improves cyclability and current carrying capacity of lithium-ion batteries (LIBs). This improvement is achieved by engineering of microstructure and defect contents present in graphite in a controlled way by using pulsed laser annealing (PLA) to increase the number density of Li + ion trapping sites. The PLA treatment causes the following changes: (1) creates surface steps and grooves between the grains to improve Li + ion charging and intercalation rates; (2) removes inactive polyvinylidene difluoride (PVDF) binder from the top of graphite grains and between the grains which otherwise tends to block the Li + migration; and (3) produces carbon vacancies in (0001) planes which can provide Li + charging sites. From X-ray diffraction data, we find upshift in diffraction peak or reduction in planar spacing, from which vacancy concentration was estimated to be about 1.0%, which is higher than the thermodynamic equilibrium concentration of vacancies. The laser treatment creates single and multiple C vacancies which provide sites for Li + ions, and it also produces steps and grooves for Li + ions to enter the intercalating sites. It is envisaged that the formation of these sites enhances Li+ ion absorption during charge and discharge cycles. The current capacity increases from an average 360 mAh/g to 430 mAh/g, and C–V shows significant reduction in SEI layer formation after the laser treatment. If the vacancy concentration is too high and charge-discharge cycles are long, then trapping of electrons by Li + may occur, which can lead to Li 0 formation and Li plating causing reduction in current capacity.

25 ENERGY STORAGE↗
DOE OSTI2021

Engineering the Si Anode Interface via Particle Surface Modification: Embedded Organic Carbonates Lead to Enhanced Performance

Si nanoparticles (SiNPs) are recognized as a promising anode material for next-generation high-energy lithium-ion batteries. However, due to the more stringent requirements resulting from severe volume change, the solid-electrolyte interphase (SEI) on SiNPs plays a critical role in determining their cycling performance. Engineering the interface for higher stability has become an effective yet challenging approach to accommodate the deterioration of the silicon anode from the repeated lithiation/delithiation process. Herein, we report a novel approach of engineering a covalently bonded organic monolayer of ethylene carbonates onto the surface of the SiNPs that can help form a sturdy SEI. Finally, this molecule-level surface modification provides an effective approach to enable high-energy lithium-ion batteries with Si anodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Solid-state lithium metal batteries (SSLMBs) that utilize novel solid electrolytes (SEs) have garnered much attention because of their potential to yield safe and high-energy-density batteries. Sulfide-based argyrodite-class SEs are an attractive option because of their impressive ionic conductivity. Recent studies have shown that LiF at the interface between Li and SE enhances electrochemical stability. However, the synthesis of F-doped argyrodites has remained challenging because of the high temperatures used in the state-of-the-art solid-state synthesis methods. In this work, for the f irst time, we report F-doped Li 5+y PS 5 F y argyrodites with a tunable doping content and dual dopants (F-/Cl- and F-/Br-) that were synthesized through a solvent-based approach. Among all compositions, Li 6 PS 5 F 0.5 C l0.5 exhibits the highest Li-ion conductivity of 3.5 x 10 -4 S cm -1 at room temperature (RT). Furthermore, Li symmetric cells using Li 6 PS 5 F 0.5 Cl 0.5 show the best cycling performance among the tested cells. X-ray photoelectron spectroscopy and ab initio molecular dynamics simulations revealed that the enhanced interfacial stability of Li 6 PS 5 F 0.5 C l0.5 SE against Li metal can be attributed to the formation of a stable solid electrolyte interphase (SEI)-containing conductive species (Li 3 P), alongside LiCl and LiF. These findings open new opportunities to develop high-performance SSLMBs using a novel class of F-doped argyrodite electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2025

Two-Dimensional Siloxene Nanosheets: Understanding the Effect of Heat Treatment on the Surface Chemistry and Resulting Electrochemistry in Lithium-Based Batteries

Two-dimensional (2D) silicon materials are conceptually appealing as negative electrode materials in lithium-ion batteries due to their layered morphology, which can accommodate (de)lithiation-induced volume changes. Herein, heat treatment of 2D Siloxene materials was used to modify the surface functional groups to determine the impact on the electrochemical behavior. Spectroscopic characterization of the heat-treated nanosheets confirmed the loss of oxygenated and hydride surface functional groups with an increased annealing temperature. Formation and disproportionation of the amorphous suboxides with increasing heat treatment were affirmed with lab and synchrotron-based measurements. A reduced irreversible capacity was observed for Siloxene with a higher temperature heat treatment consistent with the formation of a more favorable surface electrolyte interphase (SEI). A Siloxene-400||NMC622 full cell (prepared with 400 °C-annealed Siloxene (Siloxene-400) and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)) showed significantly enhanced capacity and rate capability compared to a nano Si||NMC622 cell. Finally, these results illustrate the ability of thermal annealing to modify the surface functional groups of Siloxene and highlight the favorable impact of the appropriate surface functionality on the electrochemistry of Siloxene in lithium cells.

25 ENERGY STORAGE↗
DOE OSTI2026

Integrative Additive Design for Robust SEI Formation in NMC811||Silicon Batteries

Silicon (Si) is considered a promising replacement for graphite anodes in lithium-ion batteries (LIBs) due to its high abundance and exceptional specific capacity, but its widespread commercialization has been hindered by poor electrochemical performance. Among various strategies, the use of functional additives has emerged as one of the most effective and cost-efficient methods to enhance the electrochemical properties of LIBs. In this study, several additives—vinylene carbonate (VC), vinyl ethylene carbonate (VEC), lithium difluorophosphate (LiDFP), lithium difluoro(oxalato)borate (LiDFOB), lithium tetrafluorooxalatophosphate (LiTFOP), and lithium difluorobis(oxalato)phosphate (LiDFBOP)—were systematically investigated in LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811)||Si full cells. Notably, LiDFBOP, a lithium salt containing two oxalate groups, outperformed all other additives, delivering the best capacity retention after 300 cycles. Comprehensive characterizations, including FTIR, SEM, and XPS, revealed that LiDFBOP's superior performance stems from its ability to form a more stable solid electrolyte interphase (SEI) on the Si anode, owing to its favorable molecular structure that integrates the beneficial features of the other additives.

25 ENERGY STORAGE↗