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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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DOE OSTI2021

In Situ Formation of Polycyclic Aromatic Hydrocarbons as an Artificial Hybrid Layer for Lithium Metal Anodes

Nonuniform Li deposition causes dendrites and low Coulombic efficiency (CE), seriously hindering the practical applications of Li metal. Herein, we developed an artificial solid-state interphase (SEI) with planar polycyclic aromatic hydrocarbons (PAHs) on the surface of Li metal anodes by a facile in situ formation technology. The resultant dihydroxyviolanthron (DHV) layers serve as the protective layer to stabilize the SEI. In addition, the oxygen-containing functional groups in the soft and conformal SEI film can regulate the diffusion and transport of Li ions to homogenize the deposition of Li metal. The artificial SEI significantly improves the CEs and shows superior cyclability of over 1000 h at 4 mAh cm –2 . The LiFePO 4 /Li cell (2.8 mAh cm –2 ) enables a long cyclability for 300 cycles and high CEs of 99.8%. Furthermore, this work offers a new strategy to inhibit Li dendrite growth and enlightens the design on stable SEI for metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Intrinsic chemical reactivity of solid-electrolyte interphase components in silicon–lithium alloy anode batteries probed by FTIR spectroscopy

Herein we report the solid reaction products from the chemical reaction of aprotic battery electrolyte and three purported components of the Si-based anode SEI : SiO 2 nanoparticles (NPs), lithium silicate (Li x SiO y ) powders, and Si NPs. We use FTIR and classical molecular dynamics/density functional perturbation theory to assess the solid products remaining with these model materials after exposure to electrolyte. The absence of electrochemical bias provides a view of the chemical speciation resulting from early-stage chemical reactivity during battery assembly as well as under open circuit storage conditions. We believe these species represent the initial stages of SEI growth and predict they likely drive subsequent chemical and electrochemical reactions by controlling molecular interactons at the Si active material interface. We find that nominally equivalent materials react differently even before any electrochemistry is performed (e.g., acidic SiO 2 dissolves whereas alkaline SiO 2 is relatively robust), and derive new understanding of the chemical species that could and could not form stable SEI components in Si-based anodes. These results can be used to inform how to passivate Si anode surfaces and potentially generate an artificially engineered SEI that would be stable and enable next-generation battery anodes.

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

Role of Coatings as Artificial Solid Electrolyte Interphases on Lithium Metal Self-Discharge

Artificial solid electrolyte interphases have provided a path to improved cycle life for high energy density, next-generation anodes like lithium metal. Although long cycle life is necessary for widespread implementation, understanding and mitigating the effects of aging and self-discharge are also required. In this report we investigate several coating materials and their role in calendar life aging of lithium. We find that the oxide coatings are electronically passivating whereas the LiF coating slows charge transfer kinetics. Furthermore, the Coulombic loss during self-discharge measurements improves with the oxide layers and worsens with the LiF layer. It is found that none of the coatings create a continuous conformal, electronically passivating layer on top of the deposited lithium nor are they likely to distribute evenly through a porous deposit, suggesting that none of the materials are acting as an artificial solid electrolyte interphase. Instead, they likely alter performance through modulating lithium nucleation and growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Impact of Salt Chemistry and Interlayer Architecture on Solid Electrolyte Interphase Composition and Performance

Reversible lithium metal anodes require interphases that are chemically stable, mechanically robust, and compatible with scalable processing. Here, we use slot-die-coated, salt-rich PEO interlayers to design SEI nanolayers on Cu current collectors and isolate how salt anion chemistry controls interphase composition and lithium plating/stripping behavior in architectures relevant to Li plating and anode-free cells. Mesoscale modeling shows that dendrite initiation at SEI defects is governed by a tradeoff among interphase thickness, ionic conductivity, and stiffness through defect-driven current focusing, motivating controlled formation from thin precursor layers. Using UHV-transferred XPS and ToF-SIMS depth profiling after controlled Li deposition, we find that fluorinated sulfonylimide salts (LiTFSI, LiFSI) form mixed inorganic/organic interphases containing LiF and PEO-derived alkoxides, with LiFSI producing a more LiF-dominant Li-facing surface than LiTFSI under identical conditions. In contrast, LiNO 3 -containing interlayers yield a comparatively thick nitrate-derived interphase that reduces upon Li contact to an N-rich inorganic layer (Li–N/N 3− , LiN x O y ). In Cu| |Li cells, these designed interlayers reduce interfacial resistance and improve Coulombic efficiency (CE) and critical current density (CCD) relative to uncoated controls, with LiFSI- and LiNO 3 -based interlayers providing the highest CE/CCD. Overall, the results demonstrate a manufacturing-relevant approach to engineer SEI nanolayers by salt chemistry, providing pathways to improve reversible lithium metal anodes while reducing reliance on LiTFSI.

anion chemistry↗
DOE OSTI2024

Alumina – Stabilized SEI and CEI in Potassium Metal Batteries

Aluminum oxide (Al 2 O 3 ) nanopowder is spin-coated onto both sides of commercial polypropene separator to create artificial solid-electrolyte interphase (SEI) and artificial cathode electrolyte interface (CEI) in potassium metal batteries (KMBs). Here, this significantly enhances the stability, including of KMBs with Prussian Blue (PB) cathodes. For example, symmetric cells are stable after 1,000 cycles at 0.5 mA/cm 2 –0.5 mAh/cm 2 and 3.0 mA/cm 2 –0.5 mAh/cm 2 . Alumina modified separators promote electrolyte wetting and increase ionic conductivity (0.59 vs. 0.2 mS/cm) and transference number (0.81 vs. 0.23). Cryo-stage focused ion beam (cryo-FIB) analysis of cycled modified anode demonstrates dense and planar electrodeposits, versus unmodified baseline consisting of metal filaments (dendrites) interspersed with pores and SEI. Alumina-modified CEI also suppresses elemental Fe crossover and reduces cathode cracking. Mesoscale modeling of metal – SEI interactions captures crucial role of intrinsic heterogeneities, illustrating how artificial SEI affects reaction current distribution, conductivity and morphological stability.

25 ENERGY STORAGE↗
DOE OSTI2021

3D Artificial Solid-Electrolyte Interphase for Lithium Metal Anodes Enabled by Insulator–Metal–Insulator Layered Heterostructures

Despite considerable efforts to prevent lithium (Li) dendrite growth, stable cycling of Li metal anodes with various structures remains extremely difficult due to the direct contact of the liquid electrolyte with Li. Rational design of solid-electrolyte interphase (SEI) for 3D electrodes is a promising but still challenging strategy for preventing Li dendrite growth and avoiding lithium–electrolyte side reactions in Li-metal batteries. Here, a 3D architecture is constructed with g-C 3 N 4 /graphene/g-C 3 N 4 insulator–metal–insulator sandwiched nanosheets to guide uniform Li plating/stripping in the van der Waals gap between the graphene and the g-C 3 N 4 , and the function of which can be regarded as a 3D artificial SEI. Li deposition on the surface of g-C 3 N 4 is suppressed due to its insulating nature. However, its uniform lithiophilic sites and nanopore channels enable homogeneous lithium plating between the graphene and the g-C 3 N 4 , prohibiting the direct contact of the electrolyte with the Li metal. The use of the g-C 3 N 4 -layer-modified 3D anode enables long-term Li deposition with a high Coulombic efficiency and stable cycling of full cells under high cathode loading, limited Li excess, and lean electrolyte conditions. The concept of a 3D artificial SEI will shed light on developing safe and stable Li-metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2022

A Solution-Processable High-Modulus Crystalline Artificial Solid Electrolyte Interphase for Practical Lithium Metal Batteries

The solid electrolyte interphase (SEI) has been identified as a key challenge for Li metal anodes. The brittle and inhomogeneous native SEI generated by parasitic reactions between Li and liquid electrolytes can devastate battery performance; therefore, artificial SEIs (ASEIs) have been proposed as an effective strategy to replace native SEIs. Herein, as a collaboration between academia and industrial R&D teams, a multifunctional (crystalline, high modulus, and robust, Li + ion conductive, electrolyte-blocking, and solution processable) ASEI material, LiAl-FBD (where “FBD” refers to 2,2,3,3-tetra-fluoro-1,4-butanediol), for improving Li metal battery performance is designed and synthesized. The LiAl-FBD crystal structure consists of Al 3+ ions bridged by FBD 2– ligands to form anion clusters while Li + ions are loosely bound at the periphery, enabling an Li + ion conductivity of 9.4 × 10 –6 S cm –1 . Further, the fluorinated, short ligands endow LiAl-FBD with electrolyte phobicity and high modulus. The ASEI is found to prevent side reactions and extend the cycle life of Li metal electrodes. Specifically, pairing LiAl-FBD coated 50 μm thick Li with industrial 3.5 mAh cm –2 NMC811 cathode and 2.8 μL mAh –1 lean elec-trolyte, the Li metal full cells show superior cycle life compared to bare ones, achieving 250 cycles at 1 mA cm –2 .

25 ENERGY STORAGE↗
DOE OSTI2020

Pursuing graphite-based K-ion O 2 batteries: a lesson from Li-ion batteries

The replacement of lithium metal by lithium intercalated graphite was crucial for developing safe lithium-ion batteries. Superoxide-based potassium–oxygen batteries represent an exciting metal–oxygen battery with the highest energy efficiencies. However, using potassium metal is a more serious safety threat than lithium. Herein, we explore the possibility of graphite-intercalation anodes for potassium-ion oxygen batteries (PIOBs) with enhanced safety. This work demonstrates for the first time that establishing an artificial potassium salt-rich solid electrolyte interphase (SEI) enables a reversible graphite-intercalation anode (249.6 mA h g -1 after 600 cycles) in a potassium bis(trifluoromethanesulfonyl)imide (KTFSI)-based localized high-concentration electrolyte. Such an electrolyte is stable with the superoxide cathode. The PIOB delivers energy efficiencies above 90% at a depth of discharge (DOD) of 25% for 80 cycles. A three-electrode measurement shows that its overpotential mainly comes from the anode. The lifespan is limited to the gradual degradation of the artificial SEI caused by oxygen crossover. This work represents a step towards achieving holistic anode–electrolyte–cathode compatibility in a PIOB and its realistic evaluation under a controlled DOD.

25 ENERGY STORAGE↗
DOE OSTI2021

Enabling 4C Fast Charging of Lithium–Ion Batteries by Coating Graphite with a Solid–State Electrolyte

Enabling fast-charging (≥4C) of lithium-ion batteries is an important challenge to accelerate the adoption of electric vehicles. However, the desire to maximize energy density has driven the use of increasingly thick electrodes, which hinders rate capability. Herein, atomic layer deposition is used to coat a single-ion conducting solid electrolyte (Li 3 BO 3 -Li 2 CO 3 ) onto postcalendered graphite electrodes, forming an artificial solid-electrolyte interphase (SEI). When compared to uncoated control electrodes, the solid electrolyte coating: 1) eliminates natural SEI formation during preconditioning; 2) decreases interphase impedance by >75% compared to the natural SEI; and 3) extends cycle life under 4C charging conditions, enabling retention of 80% capacity after 500 cycles (compared to 12 cycles in the uncoated control) in pouch cells with >3 mAh cm –2 loading. Furthermore, this work demonstrates that 4C charging without Li plating can be achieved through purely interfacial modification without sacrificing energy density and sheds new light on the role of the SEI in Li plating and fast-charge performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Preventing Electrolyte Decomposition on a Ca Metal Electrode Interface Using an Artificial Solid‐Electrolyte Interphase

Abstract Calcium ion batteries are gaining attention as alternatives to lithium‐ion technology because they offer comparable properties at reduced cost and improved safety. However, progress has been limited because of the inability to efficiently and reversibly plate and strip Ca metal anodes in organic electrolytes. Moreover, the inorganic components of the solid‐electrolyte interphase (SEI) that form via decomposition of the electrolyte often do not allow for the diffusion of Ca ions. In this work, an approach combining density functional theory and ab initio molecular dynamics (AIMD) simulations is utilized to show that the use of a preformed artificial SEI layer of amorphous can potentially prevent electrolyte decomposition. First, Ca is shown to be able to intercalate into an amorphous layer (up to Ca 1.5 Al 2 O 3 ) and diffuse through on a reasonable time scale. Through calculation of the density of states, the system is found to remain insulating up to the equilibrium stoichiometry. Finally, AIMD simulations with a realistic organic electrolyte environment are used to show that this calcinated layer completely prevents the decomposition of solvent molecules. This approach can provide a route to efficient rechargeable Ca ion batteries, paving the way for cheap large‐scale energy storage.

Young, Joshua↗
DOE OSTI2022

Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal–Sulfur and Selenium Batteries

Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal–sulfur batteries remain challenged by several factors, including polysulfides’ (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li–S and the emerging Na–S and K–S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li–S are relatively mature, less progress has been made with Na–S and K–S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal–selenium and the metal–selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal–sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li–S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure–battery electrochemical performance interrelations. Finally, throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.

25 ENERGY STORAGE↗
DOE OSTI2021

Highly Ordered Hierarchical Anodes for Extreme Fast Charging Batteries (Final Report)

The goal of this project is to enable extreme fast charging (XFC) of Li-ion batteries, which was accomplished through a combination of 1) rational design and manufacturing of hierarchically structured anode architectures; 2) blending graphite/hard carbon into a bulk hybrid anode; 3) engineering artificial solid-electrolyte interphase (SEI) coatings with reduced interphase impedance; 4) computational modeling of coupled transport, kinetic, and electrochemical phenomena; and 5) improved fundamental understanding of lithium plating through operando analysis. This work integrated structural, compositional, and surface modification of graphite anodes, multi-physics modeling of ion transport, electrochemical activity, and heat transfer, advanced strategies to detect Li plating, and semi-automated roll-to-roll cell assembly. The unique facilities at the University of Michigan (UM) and Sandia National Laboratories (SNL) were leveraged to manufacture, prototype, and characterize commercially relevant >2Ah and >180 Wh/kg cells with a target of <20% capacity fade over 500 XFC cycles.

25 ENERGY STORAGE↗
DOE OSTI2021

Anatomy of Continuous Mars SEIS and Pressure Data from Unsupervised Learning

The seismic noise recorded by the Interior Exploration using Seismic Investigations, Geodesy, and Heat Transport (InSight) seismometer (Seismic Experiment for Interior Structure [SEIS]) has a strong daily quasi-periodicity and numerous transient microevents, associated mostly with an active Martian environment with wind bursts, pressure drops, in addition to thermally induced lander and instrument cracks. That noise is far from the Earth’s microseismic noise. Quantifying the importance of nonstochasticity and identifying these microevents is mandatory for improving continuous data quality and noise analysis techniques, including autocorrelation. Cataloging these events has so far been made with specific algorithms and operator’s visual inspection. We investigate here the continuous data with an unsupervised deep-learning approach built on a deep scattering network. This leads to the successful detection and clustering of these microevents as well as better determination of daily cycles associated with changes in the intensity and color of the background noise. We first provide a description of our approach, and then present the learned clusters followed by a study of their origin and associated physical phenomena. We show that the clustering is robust over several Martian days, showing distinct types of glitches that repeat at a rate of several tens per sol with stable time differences. We show that the clustering and detection efficiency for pressure drops and glitches is comparable to or better than manual or targeted detection techniques proposed to date, noticeably with an unsupervised approach. Finally, here we discuss the origin of other clusters found, especially glitch sequences with stable time offsets that might generate artifacts in autocorrelation analyses. We conclude with presenting the potential of unsupervised learning for long-term space mission operations, in particular, for geophysical and environmental observatories.

58 GEOSCIENCES↗
DOE OSTI2021

Balancing Interfacial Reactions to Achieve Long Cycle Life in High Energy Lithium Metal Batteries

Rechargeable lithium (Li) metal batteries have attracted wide attentions as the next generation energy storage technologies. However, simultaneously achieving high cell-level energy density and long cycle life in realistic batteries is still a great challenge. Here we investigate the cell degradation mechanisms of Li||LiNi0.6Mn0.2Co0.2O2 pouch cells using different, but representative cell configurations to understand the fundamental linkage among Li thickness, electrolyte depletion and the structure evolution of solid electrolyte interphase (SEI) layers. Different cell failure modes were discovered when tuning the anode to cathode capacity (N/P) ratio in compatible electrolyte. With a thick-Li anode (N/P ratio = 2.5), initial stable cycling is obtained because of the abundant Li supply from the anode together with an artificially inflated high Coulombic Efficiency, followed by a premature sudden cell death appears due to the enrichment of “ineffective SEI” which does not participate in the electrochemical reactions but keep increasing cell impedance. The anode-free cell (N/P 0:1) displays a steady capacity decay because cathode Li loss dominates from the beginning to the end of cell cycle life. An optimized thin-Li (N/P 1:1) well balances the Li consumption rate with the impedance buildup by minimizing the growth of ineffective SEI layer, thus decelerates cell polarization increasing and extends cycling. Contrary to conventional wisdoms, long cycle life is observed by using ultra thin-Li (20 µm) in balanced cells. A prototype 350 Wh kg-1 pouch cell (2.0 Ah) achieves over 600 long stable cycles with 76% capacity retention without sudden cell death.

Niu, Chaojiang↗