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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Cathode Interface Compatibility of Amorphous LiMn 2 O 4 (LMO) and Li 7 La 3 Zr 2 O 12 (LLZO) Characterized with Thin-Film Solid-State Electrochemical Cells

Solid-state lithium-ion batteries are a hopeful successor to traditional Li-ion cells that use liquid electrolytes. While a growing body of work has characterized the interfaces between various solid electrolytes and the lithium metal, interfaces with common cathode intercalation compounds are comparatively less understood. In this contribution, the influence of polarization and temperature on interfacial stability between LiMn 2 O 4 (LMO) and Li 7 La 3 Zr 2 O 12 (LLZO) are investigated. Sputtered thin-film LMO electrodes are utilized to permit high-capacity cycling while retaining a large ratio of interfacial area to electrode bulk. Electrochemical impedance spectroscopy (EIS) is compared across a set of full (LMO|LLZO|Li) and symmetric (LMO|LLZO|LMO, Li|LLZO|Li, and Au|LLZO|Au) cells to delineate impedance features that are specific to the evolution of the cathode interface. Furthermore, additional X-ray photoelectron spectroscopy (XPS) provides evidence of a limited interfacial reaction between LMO and LLZO that coincides with an increase in the impedance of the LMO–LLZO interface.

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

Low Impedance Cathode/Electrolyte Interfaces for High Energy Density Solid-State Batteries

All-solid-state batteries (ASSBs) using a ceramic fast Li-ion conductor as a solid-state electrolyte (SSE) have been proposed as a promising strategy to significantly increase the energy density of lithium batteries. Due to their high ion conductivity and excellent stability, Li-stuffed garnets exhibit the most promising physical and chemical properties for SSEs. However, the typical microstructure, thick (>100 μm) bulk electrolyte and simple planar electrode/electrolyte interfaces, combined with poor electrode wetting of the garnet result in excessively high area specific resistances (ASRs) that severely limit achievable current density and cell energy density. In this project, the team is building on their demonstrated expertise with garnet electrolytes and ASSBs to accomplish the following: (1) engineer interfaces to overcome high NMC/LLZ interfacial impedance and interfacial degradation; (2) develop processing and fabrication techniques to achieve high loading NMC/LLZ composite cathodes with low resistance and high cyclability; and (3) integrate the NMC/LLZ cathodes into all-solid-state Li-metal/LLZ cells to achieve high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Doping effect of Al in LLZO

Lithium ion batteries have become a common use in most electronic devices and transportation. However, the use of liquid electrolytes poses a serious safe hazard due to their high flammability. The narrow operating temperature and voltage windows also limit further improvement of the energy density.Solid-state lithium batteries with the use of more stable and safer solid electrolyte have garnered much attention and could be the future choice for battery technology. A promising potential candidate for the solid electrolyte component is the garnet type Li 7 La 3 Zr 2 O 12 (LLZO) ceramic material since it possesses high ionic conductivity at room temperature and enables the use of high capacity lithium anode and high voltage/capacity cathodes.However, to form the stable cubic phase of LLZO and high densification,high sintering temperatures above 1100°C is typically required, which causes Lithium loss of the system.Many studieshave been taken to dop LLZO with various precursors such as Ga, Ta, and Al to stabilize the cubic structure and reduce calcination temperature, while the doping effect on sintering densification is still unclear. In this study Al doping along with ball milling were explored to stabilize the cubic phase of LLZO and improve densification, while reducing the amount of impurity phases. Samples were synthesized from the precursors Li 2 CO 3 , Al 2 O 3 , La 2 O 3 , and ZrO 2 by ball milling followed by heat treatment for 12 hours at 1000°C. XRD with Rietveld fitting was used to determine the two phases of LLZO (cubic, tetragonal) and other possible secondary phases. Furthermore,SEM with top and cross sectional views was conducted to investigate the morphology and microstructure of sintered pellets.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Physical and Mechano-Electrochemical Phenomena of Thin Film Lithium-Ceramic Electrolyte Constructs

While a small number of solid electrolytes exhibit high ionic conductivity (~1mS cm at 298K), few are stable against Li metal. The garnet-type solid electrolyte, based on the nominal formula Li 7 La 3 Zr 2 O 12 (LLZO), is unique in that it is a fast ion conductor and – as we demonstrated in our recent project (DE-EE-00006821) – is stable against Li. Moreover, our former project successfully demonstrated a decrease in Li-LLZO interface resistance from 12,000 to 2 Ohms cm 2 and stable cycling at 1 mA cm 2 for 100 cycles (+/- 15 µm Li per cycle). Although the past project (DE-EE-00006821) demonstrated LLZO is a viable solid electrolyte for enabling batteries using metallic Li, the studies used thick pellets (1mm) and thick anodes (~500 µm). We believe that to achieve a step increase in technology readiness level (TRL), the same performance characteristics previously shown should be demonstrated in technologically relevant cells, e.g. thin LLZO and thin Li. The goal of this project is to acquire a deep fundamental understanding of the physical and mechano-electrochemical phenomena that control the performance of cells consisting of thin LLZO (~10 µm), thin Li anodes (~20 µm) and thin solid-state composite cathodes. If successful, the knowledge gained in this project will guide closely related commercialization efforts to scale the production of LLZO-based solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO), argyrodite-type Li 6 PS 5 Cl (LPSC), and NASICON-type Li 1+x+y Al x (Ti,Ge) 2-x Si y P 3-y O 12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Safe, Low-Cost, High Energy-Density, Solid-State Li-Ion Batteries

We developed intrinsically safe, robust, low-cost, high-energy-density solid-state Li-ion batteries, by integrating high conductivity garnet-type solid Li ion electrolytes and several different cathodes in tailored microstructures, fabricated by low-cost supported thin-film ceramic techniques, to overcome the primary technological barriers to next generation battery technology. In this ARPA-E project we employed Li-garnet solid-state electrolytes pioneered by one of the co-investigators (Thangadurai) which has room temperature (RT) conductivity of ~10 -3 S cm -1 . The highly stable garnet SSE allowed the use of S, NMC, and other cathodes with Li metal anodes without stability or flammability concerns. We studied the garnet’s stability when exposed to CO 2 and humidity (with or without an ALD coating) and showed that the material can be processed in ambient air for most steps prior to battery assembly, significantly reducing production costs. We extensively studied and scaled up the synthesis of the powder and explored external suppliers of garnet to determine the best pathway for commercial success. We used low-cost and scalable tapecasting fabrication methods to create porous-dense-porous “trilayer” solid electrolyte microstructures with a ~20 μm separating dense layer, and >70% porosity porous layers to host the electrodes. These scalable multilayer ceramic fabrication techniques, without need for dry rooms or vacuum equipment, also provide for dramatically reduced manufacturing costs. The tailored microstructured electrode supports (scaffold) increased interfacial area ~50x, overcoming the high impedance typical of planar geometry SSLiBs, resulting in record-setting 10 mA/cm 2 lithium cycling in a symmetric cell. We expanded our tapecasting ability and showed tapes >25m in length by the end of the project. We demonstrated the ability to sinter garnet without the use of a garnet powderbed, which could have been a major obstacle and waste of material at scale. At the same time, we expanded the size of our trilayers from coin cells (0.7 cm 2 ) to the full format design (30 cm 2 ). To develop full cells, we demonstrated 250 Wh/kg at room temperature with commercial NMC electrode films in a bilayer configuration. Similarly, we demonstrated 280 Wh/kg trilayer Li-S cells at room temperature with >90% capacity retention over 300 cycles. At 90°C we demonstrated 350 Wh/kg with a Li-S trilayer. The high thermal stability of the garnet electrolyte also enabled extended cycling (400 cycles) of a Li-TiS 2 cell at 150 °C, showcasing the exceptional safety and nonflammability of the solid-state trilayer batteries. Ion Storage Systems has taken this technology and knowledge to produce trilayer garnet electrolytes and is building out facilities to commercialize high performance solid state batteries. ISS has hired a strong staff, identified and communicated with a large number of potential partners, and successfully secured follow-on funding.

25 ENERGY STORAGE↗
DOE OSTI2020

NMR Investigations of Crystalline and Glassy Solid Electrolytes for Lithium Batteries: A Brief Review

The widespread use of energy storage for commercial products and services have led to great advancements in the field of lithium-based battery research. In particular, solid state lithium batteries show great promise for future commercial use, as solid electrolytes safely allow for the use of lithium-metal anodes, which can significantly increase the total energy density. Of the solid electrolytes, inorganic glass-ceramics and Li-based garnet electrolytes have received much attention in the past few years due to the high ionic conductivity achieved compared to polymer-based electrolytes. This review covers recent work on novel glassy and crystalline electrolyte materials, with a particular focus on the use of solid-state nuclear magnetic resonance spectroscopy for structural characterization and transport measurements.

Morales, Daniel J. (ORCID:0000000271845727)↗
DOE OSTI2022

Grain-boundary fracture mechanisms in Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolytes: When phase transformation acts as a temperature-dependent toughening mechanism

Garnet-type, solid electrolytes, such as Li 7 La 3 Zr 2 O 12 (LLZO), are a promising alternative to liquid electrolytes for lithium-metal batteries. However, such solid-electrolyte materials frequently exhibit undesirable lithium (Li) metal plating and fracture along grain boundaries. In this work, we employ atomistic simulations to investigate the mechanisms and key fracture properties associated with intergranular fracture along one such boundary. Our results show that, in the case of a Σ5 (310) grain boundary, this boundary exhibits brittle fracture behavior, i.e. the absence of dislocation activity ahead of the propagating crack tip, accompanied with a decrease in work of separation, peak stress, and maximum stress intensity factor as the temperature increases from 300 K to 1500 K. As the crack propagates, we predict two temperature-dependent Li clustering regimes. For temperatures at or below 900 K, Li tends to cluster in the bulk region away from the crack plane driven by a void-coalescence mechanism concomitant a simultaneous cubic-to-tetragonal phase transition. The tetragonalization of LLZO in this temperature regime acts as an emerging toughening mechanism. At higher temperatures, this phase transition mechanism is suppressed leading to a more uniform distribution of Li throughout the grain-boundary system and lower fracture properties as compared to lower temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Functional properties of Yttrium Iron Garnett thin films on graphene-coated Gd 3 Ga 5 O 12 for remote epitaxial transfer

Remote epitaxial growth via a graphene interlayer and subsequent mechanical exfoliation of a free-standing membrane is a recently developed technique used to transfer complex oxide thin films onto non-native substrates to form heterogeneously integrated structures for various device applications. One such oxide is Yttrium Iron Garnet (YIG), a material of choice for a wide range of magnetoelectric and spintronic devices owing to its strong magnetic properties and low microwave losses. YIG is predominantly grown on lattice matched Gadolinium Gallium Garnet (GGG) substrates, but by utilizing the remote epitaxy technique, high quality YIG films can be transferred from GGG onto another substrate such as piezoelectric Lithium Niobate (LN). Mechanical strain coupling between the layers and magnetostrictive nature of YIG would allow for the investigation of the interplay in YIG/LN structures leading to the design of novel frequency agile magneto-acoustic devices. In this study functional properties of a YIG film grown using PLD on graphene-coated GGG substrate were investigated and compared to traditional YIG on GGG. Both materials were characterized in terms of crystal structure, surface morphology, FMR and Gilbert damping, and Raman and XAS spectroscopy. Further, it was found that YIG on graphene-coated GGG exhibits significantly higher microwave losses than standard YIG on GGG (FMR linewidth 30.9 vs 2.1 Oe at 10 GHz, and Gilbert damping coefficient 15.4x10 -4 vs 3.4x10 -4 respectively), which was attributed to increased concentration of Fe 2+ cations in YIG/Graphene/GGG. While the damping is higher in these studied films compared to YIG grown directly on GGG, the resulting properties are still very favorable compared to many other competing materials which can be grown without the need for lattice matched substrates, such as metallic ferromagnets.

36 MATERIALS SCIENCE↗
DOE OSTI2023

VTO FY23 Annual Progress Report on 3D Printing of All-Solid-State Lithium Batteries

All-solid-state lithium metal batteries (ASSLBs) have attracted attention due to their potential for mitigating safety issues and addressing energy density limitations of conventional lithium-ion batteries (LIBs). While solid state electrolytes (SSEs) with room-temperature ionic conductivities greater than that of their liquid electrolyte counterparts have been discovered, integration of the different solid components of ASSLBs is not trivial. Taking garnet Li 7 La 3 Zr 2 O 12 (LLZO) electrolyte as an example, problems for this SSE include brittleness, high temperature processing for densification, poor contact with electrodes, and lack of scalable manufacturing methods. These obstacles must be overcome before LLZO becomes commercially viable for ASSLB applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Fast lithium ion diffusion in brownmillerite Li x Sr 2 Co 2 O 5

Transition metal oxides not only exhibits novel magnetic properties but also provides outstanding ionic transports. Ionic conductors have great potential for interesting tunable physical properties via ionic liquid gating and novel energy storage applications such as all-solid-state lithium batteries. In particular, low migration barriers and high hopping attempt frequency are the keys to achieve fast ion diffusion in solids. Taking advantage of the oxygen-vacancy channel in Li x Sr 2 Co 2 O 5 , we show that migration barriers of lithium ion are as small as 0.28–0.17 eV depending on the lithium concentration rates. Our first-principles calculation also investigated hopping attempt frequency and concluded the room temperature ionic diffusivity and ion conductivity are high as 10 −7 –10 −6 cm 2 s −1 and 10 −3 –10 −2 Scm −1 , respectively, which outperform most of perovskite-type, garnet-type, and sulfide Li-ion solid-state electrolytes. This work proves Li x Sr 2 Co 2 O 5 as a promising super-ionic conductor.

Crystallographic defects↗
DOE OSTI2024

Li Stripping Behavior of Anode‐Free Solid‐State Batteries Under Intermittent‐Current Discharge Conditions

Anode‐free manufacturing holds promise to enable high energy densities and lower Lithium (Li)‐metal solid‐state batteries (LMSSBs). Nevertheless, in contrast to thick Li foil (>50 µm), the stripping capacity of in situ‐formed Li (10–30 µm) is limited due to diminished creep flow, resulting in reduced accessible capacity. This study explores the correlation between stripping capacity and surface roughness of garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. The results reveal that stripping capacity can be enhanced through the surface modification of solid electrolytes. Additionally, this study scrutinizes the stripping behavior of in situ Li under intermittent‐current discharge conditions, which are more relevant to the operational conditions of electric vehicles (EVs). It is demonstrated that, when compared to constant‐current stripping, intermittent‐current stripping effectively suppresses void formation and enhances the stripping capacity of in situ Li by 40%. It is considered that the intermittent current inhibits the accumulation of Li vacancies, thereby delaying the void formation. These findings provide valuable insights into the development of high‐performance anode‐free LMSSBs for EVs.

25 ENERGY STORAGE↗
DOE OSTI2025

X-ray Diffraction Studies of Single-Crystal Materials for Broad Battery Applications

Single-crystal materials have attracted growing interest in battery research due to their well-defined crystallographic orientation, absence of grain boundaries, and enhanced mechanical and electrochemical stability. This Review provides a comprehensive overview of recent advances in the synthesis, structural evolution, and performance optimization of single-crystal electrodes and solid electrolytes. Particular focus is placed on the application of advanced X-ray diffraction (XRD) techniques, including operando synchrotron diffraction, reciprocal space mapping, and Bragg coherent diffraction imaging, which have enabled in-depth investigations of lattice strain, cation disorder, phase transitions, and defect formation. Representative case studies across Ni-rich layered oxides, spinel-type cathodes, and garnet-based electrolytes are examined to highlight the structural features unique to single crystals. Additionally, the synergistic integration of XRD with machine learning, tomography, and spectroscopy is discussed as a powerful direction for real-time analysis and predictive modeling. Furthermore, these insights provide critical guidance for the rational design of high-performance single-crystal materials in lithium, sodium, and solid-state battery systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Exploring the relationship between solvent-assisted ball milling, particle size, and sintering temperature in garnet-type solid electrolytes

Garnet-type solid electrolytes, such as Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), are promising materials for solid-state batteries, but processing remains a challenge, in part due to the high sintering temperature required for densification. Additionally, this temperature can be lowered by decreasing the initial particle size via solvent-assisted ball milling, but the relationship between solvent choice, particle properties, sintering behavior, and ionic conductivity is not well understood. In this work, we systematically explore these parameters, showing that milling in commonly used protic solvents, such as alcohols, effectively decreases the particle size but results in lithium loss (through Li + /H + exchange) that leads to poor sintering. By contrast, milling in aprotic solvents with surfactant reduces the particle size to ~220 nm without lithium loss, enabling the fabrication of dense samples (5.1 g/cm 3 ) with good ionic conductivity (0.43 mS/cm at 25 °C) at a lower sintering temperature (1000 °C). We compare ionic conductivities and activation energies for samples prepared with different particle sizes and sintering temperatures and use multiphase-field simulations to identify the mass transport and microstructural mechanisms responsible for the observed sintering dependence on particle size. These results further clarify the relationship between processing parameters and performance and represent important progress toward overcoming fabrication challenges for these materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Uncovering the Network Modifier for Highly Disordered Amorphous Li‐Garnet Glass‐Ceramics

Abstract Highly disordered amorphous Li 7 La 3 Zr 2 O 12 (aLLZO) is a promising class of electrolyte separators and protective layers for hybrid or all‐solid‐state batteries due to its grain‐boundary‐free nature and wide electrochemical stability window. Unlike low‐entropy ionic glasses such as Li x PO y N z (LiPON), these medium‐entropy non‐Zachariasen aLLZO phases offer a higher number of stable structure arrangements over a wide range of tunable synthesis temperatures, providing the potential to tune the LBU‐Li + transport relation. It is revealed that lanthanum is the active “network modifier” for this new class of highly disordered Li + conductors, whereas zirconium and lithium serve as “network formers”. Specifically, within the solubility limit of La in aLLZO, increasing the La concentration can result in longer bond distances between the first nearest neighbors of Zr─O and La─O within the same local building unit (LBU) and the second nearest neighbors of Zr─La across two adjacent network‐former and network‐modifier LBUs, suggesting a more disordered medium‐ and long‐range order structure in LLZO. These findings open new avenues for future designs of amorphous Li + electrolytes and the selection of network‐modifier dopants. Moreover, the wide yet relatively low synthesis temperatures of these glass‐ceramics make them attractive candidates for low‐cost and more sustainable hybrid‐ or all‐solid‐state batteries for energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

The addition of filler particles to polymer electrolytes is known to increment their ionic conductivity (IC). A detailed understanding of how the interactions between the constituent materials are responsible for the enhancement remains to be developed. A significant contribution is ascribed to an increment of the polymer amorphous fraction, induced by the fillers, resulting in the formation of higher ionic conductivity channels in the polymer matrix. However, the dependence of IC on the particle weight load and its composition on the polymer morphology is not fully understood. This work investigates Li-ion transport in composite polymer electrolytes (CPE) comprising Bi-doped LLZO particles embedded in PEO:LiTFSI matrixes. We find that the IC optimizes for very low particle weight loads (5-10%) and that both its magnitude and the load are required, strongly dependent on the garnet particle composition. Based on structural characterization results and electrochemical impedance spectroscopy, a mechanism is proposed to explain these findings. It is suggested that the Li-molar content in the garnet particle controls its interactions with the polymer matrix, resulting at the optimum loads reported, in the formation of high ionic conductivity channels. We propose that filler particle chemical manipulation of the polymer morphology is a promising avenue for the further development of composite polymer electrolytes.

bismuth↗
DOE OSTI2025

Low damping (111) oriented lithium aluminum ferrite thin films for spin wave applications

Spin wave-based spintronics are an alternative to conventional electronics due to their potential for efficient energy consumption, improved processing speed, and smaller device dimensions. Low damping magnetic insulators provide the medium for efficient propagation of spin waves for information transfer. Here, we have synthesized by pulsed laser deposition epitaxial spinel structure ferrite thin films of Li 0.5 (Al 1.0 Fe 1.5 )O 4 (LAFO) on (111)-oriented MgAl 2 O 4 that support isotropic magnon propagation in the film plane. Our ferromagnetic resonance measurements show low magnetic damping with a typical Gilbert damping parameter of α = 0.006 and weak-spin–orbit coupling with g = 2.02. These films have low effective magnetization, μ o M eff = 20 mT, similar to that of yttrium iron garnet, the gold standard of low loss magnetic insulators. Our findings show that LAFO is a good candidate as a spin wave medium since it can be grown at low temperatures in different crystal orientations.

Takana, Lerato [Stanford Univ., CA (United States)↗