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At least 37 records · Page 2

Composite Solid Ion Conductor with Engineered Lithium Interface

Successful widespread commercialization of electric vehicles is contingent upon development of safe high energy density batteries capable of long cycle life. Lithium metal affords the highest theoretical capacity (3,860 mAh/g) and lowest electrochemical potential (-3.04V vs SHE), which offers the highest specific energy density of anode materials today. While Li-ion batteries are capable of delivering energy densities of 400-600 Wh/kg, the development of lithium metal batteries such as Li-S and Li-air may boost this number up to 650 and 950 Wh/kg, respectively. However, significant progress towards the passivation of lithium metal must occur before the energy density benefit can be realized. Issues with lithium dendrite formation, anode volume expansion, and continuous solid electrolyte interphase (SEI) build-up often result in significant safety concerns, high cell resistance, and poor cycle life. The intrinsic high reactivity between lithium metal with conventional lithium ion electrolytes (organic carbonate-based solvents) makes it extremely difficult to overcome these problems. In this project, Wildcat performed focused, fundamental research and development on composite polymer/ceramic electrolytes and protected lithium metal anodes to develop an all solid state lithium metal battery targeting the DOE requirements to enable commercialization. Wildcat successfully leveraged its high throughput battery platform and explored a broad composite electrolyte compositional space. Additionally, Wildcat screened large numbers of inorganic and organic coatings for lithium metal protection using in situ liquid methods and translated the best results to all solid cells. The proposed composite polymer/ceramic electrolyte and a protected lithium metal anode enabled a solid-state lithium metal battery. The ultimate targets from this effort will deliver a safe all solid-state lithium metal pouch cell with over 350 Wh/kg and over 1,000 cycles (C/3) with the cost estimate below $100/kWh. During the course of the project, we demonstrated stable cycling of 10’s of cycles with the composite SSE and our protected lithium. The work has continued after the conclusion of the DOE funding, demonstrating further improvements in catholyte composition and thinner composite solid electrolytes.

25 ENERGY STORAGE↗

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↗

Operando Optical Microscopy for Visualization of Dendrite Growth in an Argyrodite LPSCl–Polymer Composite Electrolyte

Herein, we demonstrate the utility of optical microscopy as an accessible technique for the in situ visualization of dendrite growth within polymer–sulfide composite solid-state electrolytes. The composite electrolyte features in situ polymerization and cross-linking of the polymer between ceramic particles, which opens up extensive opportunities for accelerated materials discovery, given the vast array of acrylate/methacrylate monomers available. Specifically, the cross-linked polymer poly(triethylene glycol dimethacrylate) (poly(TEGDMA)) was observed to effectively fill pores and inhibit dendrite growth at the lithium metal interface, attributed to its glassy state at room temperature. This work represents the first application of optical microscopy to illustrate that the incorporation of glassy, undoped polymers such as poly(TEGDMA) can serve as a viable strategy for dendrite suppression in solid-state composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Consolidation of composite cathodes with NCM and sulfide solid-state electrolytes by hot pressing for all-solid-state Li metal batteries

In this study, hot pressing was evaluated as a method of cell fabrication to increase the energy density of next-generation all-solid-state batteries with NCM active material and sulfide solid-state electrolyte. Hot pressing involves consolidating glassy sulfide electrolyte by the application of pressure at a temperature above the electrolyte’s glass transition temperature. Typically, cell stacks are formed at room temperature and retain 15–30% porosity that limits cell energy density. On the other hand, the porosity of hot-pressed cell stacks is reduced to less than 10%. The electrochemical function of hot-pressed cathode composites was assessed as a function of active material and solid-state electrolyte compositions. Specifically, LiNi 0.85 Co 0.10 Mn 0.05 O 2 and LiNi 0.6 Co 0.2 Mn 0.2 O 2 were studied in combination with either glassy Li 7 P 3 S 11 , glassy Li 3 PS 4 , or β-Li 3 PS 4 solid-state electrolytes. Cathode composites composed of LiNi 0.6 Co 0.2 Mn 0.2 O 2 and Li 3 PS 4 maintained the best function after hot pressing at 200 °C and 370 MPa for 10 min. It was found that LiNi 0.6 Co 0.2 Mn 0.2 O 2 ’s resistance to microcracking and the inherent stability of Li 3 PS 4 ’s fully de-networked local structure are critical to maintain good electrochemical function after hot pressing. Furthermore, the results of this study show that hot pressing reduces porosity in the cathode composite and confirms the feasibility of cathode support of consolidated, reinforced glass separators.

25 ENERGY STORAGE↗

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗

Solid-state rigid-rod polymer composite electrolytes with nanocrystalline lithium ion pathways

A critical challenge for next-generation lithium-based batteries lies in development of electrolytes that enable thermal safety along with use of high-energy-density electrodes. We describe molecular ionic composite (MIC) electrolytes based on an aligned liquid crystalline polymer combined with ionic liquids and concentrated Li salt. This high strength (200 MPa) and non-flammable solid electrolyte possesses outstanding Li + conductivity (1 mS cm -1 at 25 °C) and electrochemical stability (5.6 V vs Li|Li + ) while suppressing dendrite growth and exhibiting low interfacial resistance (32 Ω cm 2 ) and overpotentials (≤ 120 mV @ 1 mA cm -2 ) during Li symmetric cell cycling. A heterogeneous salt doping process modifies a locally ordered polymer-ion assembly to incorporate an inter-grain network filled with defective LiFSI & LiBF 4 nanocrystals, strongly enhancing Li + conduction. Furthermore, this modular material fabrication platform shows promise for safe and high-energy-density energy storage and conversion applications, incorporating the fast transport of ceramic-like conductors with the superior flexibility of polymer electrolytes.

25 ENERGY STORAGE↗

Identifying Bounds of Inorganic Content in Solventless Processing of Hybrid Solid Electrolytes

Solid-state lithium batteries require safe, robust electrolytes to enable higher energy densities and improved safety over conventional cells. Hybrid polymer–ceramic electrolytes are a promising solution, combining the processability of polymers with the high ionic conductivity and mechanical strength of inorganic fillers. In this work, we demonstrate a solventless, UV-curing method to produce hybrid solid electrolytes using a poly(ethylene glycol) dimethyl ether (PEGDME)-based photocurable matrix incorporating Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) or Li 7 La 3 Zr 2 O 12 (LLZO) ceramic electrolyte. Inorganic filler loadings up to ∼55 wt.% could be successfully incorporated via this process which was the highest inorganic content at which the slurry remains processable and cured into a uniform film. The resulting UV-cured composite electrolytes remain flexible and exhibit room-temperature ionic conductivities on the order of 10 −4 S·cm −1 , along with notably improved lithium-ion transference numbers compared to conventional polymer electrolytes. Similar performance and processing limits were observed for both LAGP and LLZO, indicating that ceramic filler chemistry does not significantly affect the UV-curing process or the electrolyte's ion transport properties in this regime. Eliminating solvents from fabrication not only simplifies processing and mitigates environmental concerns but also enables higher solid contents that enhance mechanical strength and help suppress lithium dendrite formation. In conclusion, this scalable approach thus paves the way for manufacturing robust composite solid electrolytes for next-generation solid-state batteries (SSBs).

Batteries↗

Differences in the Interfacial Mechanical Properties of Thiophosphate and Argyrodite Solid Electrolytes and Their Composites

Interfacial mechanics are a significant contributor to the performance and degradation of solid-state batteries. Spatially resolved measurements of interfacial properties are extremely important to effectively model and understand the electrochemical behavior. Herein, we report the interfacial properties of thiophosphate (Li 3 PS 4 )- and argyrodite (Li 6 PS 5 Cl)-type solid electrolytes. Using atomic force microscopy, we showcase the differences in the surface morphology as well as adhesion of these materials. Additionally we investigate solvent-less processing of hybrid electrolytes using UV-assisted curing. Physical, chemical, and structural characterizations of the materials highlight the differences in the surface morphology, chemical makeup, and distribution of the inorganic phases between the argyrodite and thiophosphate solid electrolytes.

36 MATERIALS SCIENCE↗

A room temperature rechargeable Li 2 O-based lithium-air battery enabled by a solid electrolyte

Lithium-air batteries have scope to compete with gasoline in terms of energy density. However, in most systems, the reaction pathways either involve one- or two-electron transfer, leading to lithium peroxide (Li 2 O 2 ) or lithium superoxide (LiO 2 ), respectively. Kondori et al. investigated a lithium-air battery that uses a ceramic-polyethylene oxide–based composite solid electrolyte and found that it can undergo a four-electron redox reaction through lithium oxide (Li 2 O) formation and decomposition (see the Perspective by Dong and Lu). The composite electrolyte embedded with Li 10 GeP 2 S 12 nanoparticles shows high ionic conductivity and stability and high cycle stability through a four-electron transfer process.

25 ENERGY STORAGE↗

Reaction Current Heterogeneity at the Interface between a Lithium Electrode and Polymer/Ceramic Composite Electrolytes

Although lithium metal anodes are expected to increase the energy density of next-generation batteries, dendrite growth during charge remains a major bottleneck preventing widespread implementation. Composite solid electrolytes with ceramic particles embedded in a polymer matrix have the potential to prevent dendrites owing to the higher mechanical stiffness while also possessing the flexibility to maintain contact with the electrode. However, microscopically, the different mechanical and electrochemical properties of the polymer and ceramic domains can cause inhomogeneous charge transfer at the Li/electrolyte interface, which can lead to nonuniform Li deposition and propagation of dendrites. Here, we computationally examine the coupled electrochemical, transport, and mechanical processes at the interface to determine the propensity for dendrite formation and possible approaches to mitigate this issue. Predictions of two possible microstructures at the interface, namely, (i) where both the polymer and ceramic come in contact with Li metal and (ii) when only the polymer comes in contact with Li metal, suggest that the former has a greater tendency for nonuniform plating. In addition, predictions suggest that minimizing the interfacial resistance between polymers and ceramics and incorporating interlayers between the electrode and electrolyte help mitigate current heterogeneity. In conclusion, these predictions provide guidance for experimental approaches to prevent dendrites in composite electrolytes.

25 ENERGY STORAGE↗

NASA Tech Briefs, November 2006

Topics include: Simulator for Testing Spacecraft Separation Devices; Apparatus for Hot Impact Testing of Material Specimens; Instrument for Aircraft-Icing and Cloud-Physics Measurements; Advances in Measurement of Skin Friction in Airflow; Improved Apparatus for Testing Monoball Bearings; High-Speed Laser Scanner Maps a Surface in Three Dimensions; Electro-Optical Imaging Fourier-Transform Spectrometer; Infrared Instrument for Detecting Hydrogen Fires; Modified Coaxial Probe Feeds for Layered Antennas; Detecting Negative Obstacles by Use of Radar; Cryogenic Pound Circuits for Cryogenic Sapphire Oscillators; PixelLearn; New Software for Predicting Charging of Spacecraft; Conversion Between Osculating and Mean Orbital Elements; Generating a 2D Representation of a Complex Data Structure; Making Activated Carbon by Wet Pressurized Pyrolysis; Composite Solid Electrolyte Containing Li+- Conducting Fibers; Electrically Conductive Anodized Aluminum Surfaces; Rapid-Chill Cryogenic Coaxial Direct-Acting Solenoid Valve; Variable-Tension-Cord Suspension/Vibration- Isolation System; Techniques for Connecting Superconducting Thin Films; Versatile Friction Stir Welding/Friction Plug Welding System; Thermal Spore Exposure Vessels; Enumerating Spore-Forming Bacteria Airborne with Particles; Miniature Oxidizer Ionizer for a Fuel Cell; Miniature Ion-Array Spectrometer; Promoted-Combustion Chamber with Induction Heating Coil; Miniature Ion-Mobility Spectrometer; Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells; Miniature Free-Space Electrostatic Ion Thrusters; Miniature Bipolar Electrostatic Ion Thruster; Holographic Plossl Retroreflectors; Miniature Electrostatic Ion Thruster With Magnet; Using Apex To Construct CPM-GOMS Models; Sequence Detection for PPM Optical Communication With ISI; Algorithm for Rapid Searching Among Star-Catalog Entries; Expectation-Based Control of Noise and Chaos; Radio Heating of Lunar Soil to Release Gases; Using Electrostriction to Manipulate Ullage in Microgravity; Equations for Scoring Rules When Data Are Missing; Insulating Material for Next-Generation Spacecraft; and Pseudorandom Switching for Adding Radar to the AFF Sensor.

Source record↗

Benchmarking Bayesian Optimization Frameworks and Acquisition Strategies for Materials Discovery and Autonomous Laboratories

Bayesian optimization (BO) can accelerate materials discovery by guiding expensive experiments toward the most promising processing conditions. We systematically compare five BO surrogate and framework combinations (Gaussian processes in Ax, Gaussian processes and Monte-Carlo neural networks in BayBE, random forests in Lolopy, and tree-structured Parzen (TPE) estimators in Hyperopt) on three benchmarks that mimic common materials design tasks (a discrete solid-electrolyte composition space, a hybrid discrete/continuous laminate-composite design problem solved with micromechanics modeling, and the continuous Ishigami analytic function which is a standard optimization benchmark). Each BO surrogate is paired with posterior mean, probability of improvement, and expected improvement acquisition functions and run for 100 trials from randomized initial samples with uniform random search providing a control. Across five random seeds per setting, BayBE’s Gaussian-process surrogate with expected improvement consistently reached ≥95 % of the known optimum in the fewest evaluations, while Lolopy’s random forest matched or exceeded GP performance on purely categorical or mixed spaces at a higher computational cost. Posterior mean alone often stagnated at local optima, underscoring the need for exploration, whereas probability and expected improvement balanced exploration and exploitation leading to better optimization in fewer trials. Execution times ranged from milliseconds for TPE to minutes for neural-network and random-forest surrogates. These results establish baseline expectations for BO in automated materials laboratories and highlight expected improvement with Gaussian processes as a reliable first choice, with random forests offering a strong alternative when categorical variables dominate. The benchmark suite and code are released to facilitate future surrogate, acquisition, and constraint-handling research in data-driven materials optimization.

Bayesian optimization↗

A review of composite solid-state electrolytes for lithium batteries: fundamentals, key materials and advanced structures

All-solid-state lithium ion batteries (ASSLBs) are considered next-generation devices for energy storage due to their advantages in safety and potentially high energy density. As the key component in ASSLBs, solid-state electrolytes (SSEs) with non-flammability and good adaptability to lithium metal anodes have attracted extensive attention in recent years. Among the current SSEs, composite solid-state electrolytes (CSSEs) with multiple phases have greater flexibility to customize and combine the advantages of single-phase electrolytes, which have been widely investigated recently and regarded as promising candidates for commercial ASSLBs. Based on existing investigations, herein, we present a comprehensive overview of the recent developments in CSSEs. Initially, we introduce the historical development from solid-state ionic conductors to CSSEs, and then summarize the fundamentals including mechanisms of lithium ion transport, key evaluation parameters, design principles, and key materials. Finally, four main types of advanced structures for CSSEs are classified and highlighted according to the recent progress. Moreover, advanced characterization and computational simulation techniques including machine learning are reviewed for the first time, and the main challenges and perspectives of CSSEs are also provided for their future development.

25 ENERGY STORAGE↗

In Situ Alloying Enabled by Active Liquid Metal Filler for Self‐Healing Composite Polymer Electrolytes

Abstract Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga 62.5 In 21.5 Sn 16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self‐healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li‐ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li‐LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid‐state Li/LiFePO 4 battery achieves promising full‐cell functionality with notable rate performance and stable cycle life. This active filler‐mediated self‐healing approach could bring new insights into the battery design in versatile solid‐state systems.

Wu, Kai↗

Polymer-ceramic composite electrolytes for all-solid-state lithium batteries: Ionic conductivity and chemical interaction enhanced by oxygen vacancy in ceramic nanofibers

Perovskite Li 3x La 2/3-x TiO3 (LLTO) nanofibers have been heat-treated in the hydrogen-containing atmosphere and then incorporated with the poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) polymer to form a composite electrolyte. Hydrogen treatment has created oxygen vacancies in the LLTO nanofibers, which has reduced the activation energy of Li ion transport along intra-grains and inter-grains, leading to improvement in the ion conductivity of LLTO nanofibers. Hydrogen treatment of the LLTO nanofibers has also enhanced the chemical interaction between the LLTO nanofibers and the polymer matrix in the composite electrolyte, and favored the Li ion transport at the nanofiber/polymer interface, improving the ion conductivity of the composite electrolyte to 3.4×10- 4 S/cm at room temperature. As a result, the Li|composite-electrolyte|Li half-cell exhibits good stability during lithium plating/stripping cycling at room temperature, showing an overpotential of ~91 mV at a constant current density of 0.5 mA/cm 2 . Finally, the full-cell battery with the composite electrolyte, lithium metal anode and lithium iron phosphate cathode shows excellent rate capacity and cycling performance.

25 ENERGY STORAGE↗