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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Tuning the Anode–Electrolyte Interface Chemistry for Garnet-Based Solid-State Li Metal Batteries

Lithium (Li) metal anode is a promising candidate for high energy density solid-state batteries. However, the interface issues, including large interfacial resistance and Li dendrite generation, have always frustrated the attempt to commercialize solid-state Li metal batteries (SSLBs). Here, we report that infusing the garnet-type solid electrolytes (GSEs) with air-stable electrolyte Li 3 PO 4 (LPO) dramatically reduces the interfacial resistance to ~1 Ω cm 2 and achieves a high critical current density of 2.2 mA cm -2 under ambient condition due to enhanced interfacial stability to Li metal anode. The coated and infused LPO electrolytes not only improve the mechanical strength and Li-ion conductivity of grain boundaries, but also form a stable Li-ion conductive but electron-insulating LPO-derived solid-electrolyte interphase between Li metal and GSEs, and consequently eliminates the Li dendrites growth and prevents the direct reduction of GSEs by Li metal over a long cycle life. This interface engineering approach together with grain-boundary modification on GSEs represents a promising strategy to revolutionize the anode-electrolyte interface chemistry for SSLBs and provides new design strategy for other-types of solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Atomic layer deposited aluminum nitride for interface protection of lithium germanium thiophosphate solid electrolytes

Lithium germanium thiophosphate (LGPS) is an attractive solid-state electrolyte material due to its exceptionally high ionic conductivity (~1.2 × 10 –2 S cm –1 ), comparable to many organic liquid electrolytes commonly used in batteries. Despite the high conductivity of LGPS, the susceptibility of LGPS to deleterious degradation reactions has impeded its commercial adoption into solid-state batteries. In particular, the poor voltage stability of LGPS with high-voltage cathode or lithium metal potentials often results in dramatically increasing cell impedance during galvanic cycling. Here, we use aluminum nitride (AlN) as a protection layer for Li metal anode, applied directly to the LGPS at 250 °C using plasma-enhanced atomic layer deposition, to enhance cell performance by preventing LGPS-Li metal reactions. We compare the surface chemistry and electrochemical cycling performance of atomic layer-deposited AlN grown using both plasma N 2 and NH 3 precursors. Galvanostatic cycling and electrochemical impedance spectroscopy show that AlN-coated LGPS cells perform better than bare LGPS cells in contact with Li metal anodes, with the AlN able to improve cycling longevity by over a factor of 3 in certain cases. Finally, we utilize x-ray photoelectron spectroscopy (XPS) line scans to highlight the slow room-temperature reactivity between AlN and evaporated lithium metal, and a computational model is built to aid further XPS analysis.

25 ENERGY STORAGE↗
DOE OSTI2018

Enhanced Interfacial Stability of Hybrid-Electrolyte Lithium-Sulfur Batteries with a Layer of Multifunctional Polymer with Intrinsic Nanoporosity

We report that the use of lithium-ion conductive solid electrolytes offers a promising approach to address the polysulfide-shuttle and the lithium-dendrite problems in lithium-sulfur (Li-S) batteries. One critical issue with the development of solid-electrolyte Li-S batteries is the electrode-electrolyte interfaces. We present herein a strategic approach by employing a thin layer of a polymer with intrinsic nanoporosity (PIN) on a Li + -ion conductive solid electrolyte, which significantly enhances the ionic interfaces between the electrodes and the solid electrolyte. Among the various types of Li + -ion solid electrolytes, NASICON-type Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) offers advantages in terms of Li + -ion conductivity, stability in ambient environment, and practical viability. However, LATP is susceptible to reaction with both the Li-metal anode and polysulfides in Li-S batteries due to the presence of easily reducible Ti 4+ ions in it. The coating with a thin layer of PIN presented in this study overcomes the above issues. At the negative-electrode side, the PIN layer prevents the direct contact of Li-metal with the LATP solid electrolyte, circumventing the reduction of LATP by Li metal. Lastly, at the positive electrode side, the PIN layer prevents the migration of polysulfides to the surface of LATP, preventing the reduction of LATP by polysulfides.

25 ENERGY STORAGE↗
DOE OSTI2025

Operando Infrared Nanospectroscopy of the Silicon/Electrolyte Interface during Initial Stages of Solid-Electrolyte-Interphase Layer Formation

The solid electrolyte interphase (SEI) is a critical component in Li-ion batteries; however, its nanoscale structure and composition and unstable nature make it difficult to characterize and ascertain primary functional mechanisms. We use operando nanoscale Fourier transform infrared spectroscopy (nano-FTIR) with a broadband synchrotron IR source to study the SEI formation on a thin-film Si electrode at nanometer-scale spatial resolution as a function of time and voltage. By probing the Si/carbonate electrolyte interface through a 25 nm-thick amorphous Si window/electrode, we detect molecular vibrational modes within a 10s of nanometers region adjacent to the Si surface and observe that PF6 – anions react to form LiF at 0.5 V. Spatially resolved nano-FTIR spectra showcase subtle nanoscale heterogeneities in the initial solid/liquid interface and the resulting deposited LiF. With its nanoscale resolution and high chemical specificity, operando nano-FTIR provides unique insights into the dynamics and heterogeneous formation of SEIs and opens opportunities for connecting nanoscale interfacial properties to bulk performance metrics.

Dopilka, Andrew↗
DOE OSTI2024

A Review on Solid State Batteries: Life Cycle Perspectives

This report briefly reviews the characteristics of solid-state batteries (SSBs) and the life-cycle analysis (LCA) studies that have been completed for SSBs. Compared with conventional lithium-ion batteries (LIBs), SSBs offer improved safety and potentially higher energy density — both enabled by replacing liquid electrolytes with solid electrolytes and using lithium metal anodes. Several challenges impede the commercialization of SSBs, primarily related to the stability of the interface between the solid electrolyte and the electrodes. Several options are under consideration for SSB electrolyte and cathode chemistries. As a result, the production processes for these components and the corresponding battery packs are still under development and can differ significantly from those used for conventional LIB pack production. A robust comparison of SSBs with LIBs through LCA is important to analyze the environmental benefits and challenges associated with this alternative battery system. While the literature provides only a few LCA studies focused on SSBs, with significant uncertainty in their life-cycle inventories (LCIs), those studies collectively suggest that solid electrolyte manufacturing is the major environmental hotspot, followed by cathode and anode production.

25 ENERGY STORAGE↗
DOE OSTI2025

Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte

Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.

Wang, Yixian [Materials Science and Engineering Pr↗
DOE OSTI2019

Incorporating Solvate and Solid Electrolytes for All‐Solid‐State Li 2 S Batteries with High Capacity and Long Cycle Life

Abstract The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN) 2 −LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li 2 S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g −1 at cycle 100 (330 mAh g −1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li 2 S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li 2 S loading, Li 2 S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.

Shin, Minjeong↗
DOE OSTI2024

Functionalization of Cathode–Electrolyte Interface with Ionic Liquids for High-Performance Quasi-Solid-State Lithium–Sulfur Batteries: A Low-Sulfur Loading Study

We introduce a quasi-solid-state electrolyte lithium-sulfur (Li–S) battery (QSSEB) based on a novel Li-argyrodite solid-state electrolyte (SSE), Super P–Sulfur cathode, and Li-anode. The cathode was prepared using a water-based carboxymethyl cellulose (CMC) solution and styrene butadiene rubber (SBR) as the binder while Li6PS5F0.5Cl0.5 SSE was synthesized using a solvent-based process, via the introduction of LiF into the argyrodite crystal structure, which enhances both the ionic conductivity and interface-stabilizing properties of the SSE. Ionic liquids (IL) were prepared using lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as the salt, with pre-mixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent, and they were used to wet the SSE–electrode interfaces. The effect of IL dilution, the co-solvent amount, the LiTFSI concentration, the C rate at which the batteries are tested and the effect of the introduction of SSE in the cathode, were systematically studied and optimized to develop a QSSEB with higher capacity retention and cyclability. Interfacial reactions occurring at the cathode–SSE interface during cycling were also investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy supported by ab initio molecular dynamics simulations. This work offers a new insight into the intimate interfacial contacts between the SSE and carbon–sulfur cathodes, which are critical for improving the electrochemical performance of quasi-solid-state lithium–sulfur batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Three-dimensional Zn-based alloys for dendrite-free aqueous Zn battery in dual-cation electrolytes

Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries and beyond.

25 ENERGY STORAGE↗
DOE OSTI2023

Na 3 Zr 2 Si 2 PO 12 Solid Electrolyte Membrane for High‐Performance Seawater Battery

Abstract Seawater batteries (SWBs) have gained tremendous interest in the electrochemical energy storage research field because of their low cost, natural abundance, and potential use for long‐duration energy storage. Advancing a SWB to demonstration projects is plagued by the poor electrochemical performance stemming from the poor interfaces of the solid electrolyte (SE), as well as the structural and chemical instabilities and sluggish ionic transport properties. In this study, the anode compartment of a surrogate SWB is constructed with a Na | SE | hard carbon configuration, and tailored dopants are introduced into the Nasicon‐type Na 3 Zr 2 Si 2 PO 12 (NZSP) SE membrane. After doping with TiO 2 , a much more densely packed pellet with uniformly distributed porous structure is obtained. Changes in surface chemistry and local structure in the bulk are observed, which are believed to contribute to the improved ionic conductivity and higher critical current density of the TiO 2 ‐doped NZSP. Stable cycling performance with reversible capacities based on different Na storage mechanisms are also demonstrated.

25 ENERGY STORAGE↗
DOE OSTI2025

Understanding LIB Battery Electrodes Through Classical Electrochemical Interface Theory

Classical models of the electrochemical interface can be applied to complex and dynamic electrodes to understand important mechanisms that are relevant to device-level phenomena like calendar aging or cycle life. Here, we show that negative alloy electrodes with wide electrochemical windows cannot be assumed to have static interfaces throughout all states of charge. Under high states of charge, the interface -including the solid electrolyte interphase - has characteristics that resemble a highly polarized electrode far from the point of zero charge. Under these conditions, the interface can be understood through the Helmholtz model. At lower states of charge, the interface capacitance decreases and the space charge layer length increases. This transformation resembles a metal electrode approaching the point of zero charge which is understood through the Gouy-Chapman-Stern-Grahame model of the electrochemical interface. This transformation happens at both silicon and carbon-coated silicon interfaces. From voltage-limited cycling experiments, in the limit of the diffuse double layer, the silicon electrode impedance rises significantly in the first few cycles. This rise is related to the continuous electrochemical reduction of electrolyte components from an interface that is not electronically screened from the electrolyte. In other words, an electrode interface for batteries should resemble a 'Helmholtz-like' structure.

anode↗
DOE OSTI2023

Degradation of Lithium Iron Phosphate Sulfide Solid-State Batteries by Conductive Interfaces

The superionic solid-state argyrodite electrolyte Li 6 PS 5 Br can improve lithium and lithium-ion batteries' safety and energy density. Despite many reports validating the conductivity of this electrolyte, it still suffers from passivating electrode degradation mechanisms. At first analysis, lithium iron phosphate (LFP) should be more thermodynamically stable in contact with sulfide electrolytes. However, without substantial improvements to interfacial engineering, we find that LFP is not inherently stable against Li 6 PS 5 Br. We hypothesize argyrodite oxidation favorably competes with LFPAs delithiation, insulating the electrolyte-electrode interface and causing large overpotential losses. We show that compared to LiNi x Mn y Co z O 2 , LFP has no actual electrochemical stability advantage despite operating at a lower voltage. We utilize tender energy XAS and XPS to show that chemical reactions occur between LFP and the Li 6 PS 5 Br solid electrolyte and these reactions are exacerbated by cycling. We also show that electrochemical degradation occurs at the interface between the solid electrolyte ion conductor and any electron conductor, namely the active material and carbon additives. We further demonstrate that LiNbO 3 cathode coatings on LFP can delay electrochemical degradation by electronically insulating the LFP-sulfide electrolyte interface but not prevent its occurrence at the carbon-electrolyte interface.

25 ENERGY STORAGE↗
DOE OSTI2023

The role of ionic liquids in resolving the interfacial chemistry for (quasi-) solid-state batteries

Interfacial issues impede the advancement of current solid state battery technology; thus, interface engineering approaches are necessary to enable solid-state configuration. The advantage of solid-state cells stems from their low flammability and high electrochemical stability. Ionic liquids are viscous and nonflammable compounds that possess the requisite physical properties while optimizing the interface between solid electrodes and solid electrolytes, accelerating interfacial ion transport and enabling the fabrication of engineered interphases via the supply of robust chemical building blocks. In conclusion, this review summarizes the roles of ionic liquids in solid-state batteries focusing on the interface, with insights into their functionality as well as highlighting their applicability in the next generation battery systems.

25 ENERGY STORAGE↗
DOE OSTI2019

Anisotropically Electrochemical-Mechanical Evolution in Solid-State Batteries and Interfacial Tailored Strategy

All-solid-state batteries have attracted attention owing to the potential high energy density and safety; however, little success has been made on practical applications of solid-state batteries, which is largely attributed to the solid–solid interface issues. A fundamental elucidation of electrode–electrolyte interface behaviors is of crucial significance but has proven difficult. The interfacial resistance and capacity fading issues in a solid-state battery were probed, revealing a heterogeneous phase transition evolution at solid–solid interfaces. The strain-induced interfacial change and the contact loss, as well as a dense metallic surface phase, deteriorate the electrochemical reaction in solid-state batteries. Furthermore, the in situ growth of electrolytes on secondary particles is proposed to fabricate robust solid–solid interface. Finally, our study enlightens new insights into the mechanism behind solid–solid interfacial reaction for optimizing advanced solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Method—Using Microelectrodes to Explore Solid Polymer Electrolytes

Solid polymer electrolytes are an emerging technology in electrochemistry driven by their use in energy applications such as fuel cells, electrolyzers, and solid-state batteries. Compared to traditional liquid electrolytes, solid polymer electrolytes provide safer, cheaper, and potentially improved device performance. However, there is a lack of standard experimental methods for studying solid electrolytes. Microelectrodes have inherent benefits capable of filling this experimental gap due primarily to their integration into model electrochemical cells with solid electrolytes that represent complex interfaces, enabling additional insight into reaction processes. In this tutorial review, we explore the use of microelectrodes to study solid polymer electrolytes, beginning with a brief history of the field including common experimental cell designs and their benefits and drawbacks. Methods of evaluating essential kinetic and mass-transport parameters are then examined. In addition, the key studies of the past 30 years utilizing microelectrode cells and solid polymer electrolytes are summarized, with important results highlighted and compared. Finally, future studies of solid polymer electrolytes with microelectrodes and potential new avenues of research are commented on.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A Diffuse-Interface Model for Predicting the Evolution of Metallic Negative Electrodes and Interfacial Voids in Solid-State Batteries with Homogeneous and Polycrystalline Solid Electrolyte Separators

Here, this paper presents a novel diffuse-interface electrochemical model that simultaneously simulates the evolution of the metallic negative electrode and interfacial voids during the stripping and plating processes in solid-state batteries. The utility and validity of this model are demonstrated for the first time on a cell with a sodium (Na) negative electrode and a Na-β″-alumina ceramic solid electrolyte (SE) separator. Three examples are simulated. First, stripping and plating with a perfect electrode/electrolyte interface; second, stripping and plating with a single interfacial void at the electrode/electrolyte interface; third, stripping with multiple interfacial voids. Both homogeneous and polycrystalline SEs with low and high-conductivity grain boundaries (GBs) are considered for all three examples. Heterogeneous GB conductivity marginally impacts the thickness of the Na electrode in cases with a perfect electrode/electrolyte interface. Moreover, it results in local changes to void growth due to the interactions between the void edge and the GBs. The void growth rate is a linear function of the flux of Na atoms at the void edge, which in turn depends on the applied current density. We also show that the void coalescence rate increases with applied current density and can be marginally influenced by GB conductivity.

batteries↗
DOE OSTI2023

Accelerated Short Circuiting in Anode-Free Solid-State Batteries Driven by Local Lithium Depletion

“Anode-free” solid-state batteries (SSBs), which have no anode active material, can exhibit extremely high energy density (≈1500 Wh L -1 ). However, there is a lack of understanding of the lithium plating/stripping mechanisms at initially lithium-free solid-state electrolyte (SSE) interfaces because excess lithium metal is often used. Here, it is demonstrated that commercially relevant quantities of lithium (>5 mAh cm -2 ) can be reliably plated at moderate current densities (1 mA cm -2 ) using the sulfide SSE Li 6 PS 5 Cl. Investigations of lithium plating/stripping mechanisms, in conjunction with cryo-ocused ion beam (FIB) imaging, synchrotron tomography, and phase-field modeling, reveal that the cycling stability of these cells is fundamentally limited by the nonuniform presence of lithium during stripping. Local lithium depletion causes isolated lithium regions toward the end of stripping, decreasing electrochemically active area and resulting in high local current densities and void formation. This accelerates subsequent filament growth and short circuiting compared to lithium-excess cells. Despite this degradation mode, here it is shown that anode-free cells exhibit comparable Coulombic efficiency to lithium-excess cells, and improved resistance to short circuiting is achieved by avoiding local lithium depletion through retention of thicker lithium at the interface. These new insights provide a foundation for engineering future high-energy anode-free SSBs.

25 ENERGY STORAGE↗
DOE OSTI2019

Adsorption and thermal decomposition of electolytes on nanometer magnesium oxide: An in situ 13C MAS NMR study

Mg batteries have been proposed as potential alternatives to lithium ion batteries due to their lower cost, higher safety, and enhanced charge density. However, Mg metal readily oxidizes when exposed to an oxidizer to form a thin MgO passivation surface layer that blocks the transport of Mg2+ across the solid electrode-electrolyte interface (SEI). In this work, in situ high temperature 13C single pulse (SP) and surface sensitive 1H-13C cross polarization (CP) MAS NMR combined with quantum chemistry calculations were conducted on samples containing common electrolytes for Mg-batteries, i.e., diglyme (G2) + Magnesium(II) bis(trifluoromethane sulfonyl) imide (Mg(TFSI)2). At elevated temperatures, neat G2 decomposes to methoxy and adsorbs onto the MgO surface. G2 represent the major MgO adsorbed species or the 0.1 M Mg(TFSI)2 in G2 electrolyte while for 1.0 M Mg(TFSI)2 in G2, the major surface adsorbed species are G2-solvated Mg-TFSI contact ion pairs with the first shells containing 2 G2 molecules and the second shell containing either 0 or up to 6 G2. In particular, a desolvation of the Mg-TFSI contact ion pairs is evident on the MgO surface. These results show that the MgO surface species are directly related to the solvation structures in the electrolytes, offering fundamental insights into the formation mechanism of SEI.

magnesium battery, electrolytes, diglyme, Mg(TFSI)↗