Electrochemical and Nanomechanical Properties of TiO[subscript 2] Ceramic Filler Li-Ion Composite Ge
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Pan, Xiaona↗
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Gel composite electrolyte – an effective way to utilize ceramic fillers in lithium batteries
Achieving synergy between ion-conducting polymers and ceramics in a composite electrolyte has been proven to be difficult as the complicated ceramic/polymer interface presents challenges to understand and control. In this work, we report a strategy to utilize discrete ceramic fillers to form a gel composite electrolyte with enhanced transport properties for lithium metal batteries. The matrix of the composite membrane is crosslinked poly(ethylene oxide) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). The membrane is plasticized with tetraethylene glycol dimethyl ether (TEGDME). The incorporation of doped-lithium aluminum titanium phosphate particles (LICGC™) into the membrane greatly improves the membrane's cycling characteristics against the lithium electrode, exhibiting lower interfacial impedance, lower overpotential and higher rate capability. The underpinnings of the superior performance of the gel composite electrolyte are discussed in depth. LICGC™ can immobilize the TFSI - anions in the polymer matrix and simultaneously promote Li+ transport by increasing the plasticizer to Li + ratio. Further, the transport enhancement is achieved without sacrificing mechanical properties. The composite membrane shows significantly improved handleability and processability. This work sheds light on the design strategy for a safe electrolyte towards stable Li metal batteries.
25 ENERGY STORAGE↗
Electric field assisted solid-state interfacial joining of TaC-HfC ceramics without filler
Not provided.
Materials Science↗
Heat-Shield Gap Filler
Ceramic cloth strips provide flexible, easily replaceable insulating filler. Filler prevents hot gas from flowing between heat-shield tiles while allowing space for thermal expansion and contraction. Strips easily replaced when necessary.
Leiser, D. B.↗
High-Temperature Insulating Gap Filler
New inorganic, ceramic filler for gaps between refractory ceramic tiles offers high resistance to heat and erosion. Consists of ceramic-fiber fabric precoated with silica and further coated with silica containing small amount of silicon carbide powder to increase thermal emittance. Developed as replacement for organic filler used on thermal-protection system of Space Shuttle. Promises to serve for many missions and to reduce cost and delay of refurbishing aerospace craft. Used as sealing material in furnaces or as heat shield for sensitive components in automobiles, aircraft, and home appliances.
Toombs, Gordon R.↗
Characterization of Solid Polymers, Ceramic Gap Filler, and Closed-Cell Polymer Foam Using Low-Load Test Methods
Various solid polymers, polymer-based composites, and closed-cell polymer foam are being characterized to determine their mechanical properties, using low-load test methods. The residual mechanical properties of these materials after environmental exposure or extreme usage conditions determines their value in aerospace structural applications. In this experimental study, four separate polymers were evaluated to measure their individual mechanical responses after thermal aging and moisture exposure by dynamic mechanical analysis. A ceramic gap filler, used in the gaps between the tiles on the Space Shuttle, was also tested, using dynamic mechanical analysis to determine material property limits during flight. Closed-cell polymer foam, used for the Space Shuttle External Tank insulation, was tested under low load levels to evaluate how the foam's mechanical properties are affected by various loading and unloading scenarios.
Herring, Helen M.↗
Effects of Plasticizer Content and Ceramic Addition on Electrochemical Properties of Cross-Linked Polymer Electrolyte
The development of a safe electrolyte is the key to improving energy density for next generation lithium batteries. In this work, UV-crosslinked poly(ethylene oxide) (PEO) -based polymer and composite electrolytes are systematically investigated on their ionic conductivity, mechanical and electrochemical properties. The polymer electrolytes are plasticized with non-flammable linear short-chain PEO. In the composite electrolytes, a doped lithium aluminum titanium phosphate (LATP) ceramic, LICGC™, is used as the ceramic filler. It is found that the addition of the plasticizer leads to a tradeoff between ion transport and mechanical properties. In contrast, the addition of ceramic fillers improves both the ionic conductivity and mechanical properties. The sample with 20 wt% of LICGC™ shows a conductivity of ~0.6 mS cm –1 at 50 °C. This sample also demonstrates much longer cycle life than the neat polymer electrolyte in Li platting/stripping test with a capacity of 1 mAh cm –2 . Further, a full cell made with this composite electrolyte against Li metal anode and high voltage LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode shows 94% capacity retention after 30 cycles, compared to 58% capacity retention with the neat polymer electrolyte. These results demonstrate that a hybrid of polymer/ceramic/non-flammable plasticizer is a promising path to high energy density, high voltage lithium batteries.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Particle‐Size‐Dependent Lithium‐Ion Transport in PEO/LLZO Composite Electrolytes
Lithium-metal batteries with solid electrolytes can deliver higher energy density and improved safety than conventional Li-ion batteries. Among solid electrolyte candidates, polymer/ceramic composite electrolytes are attractive because they combine polymer flexibility with the high ionic conductivity of ceramics. However, whether ceramic fillers synergistically reduce polarization losses in the polymer matrix remains unclear. A central unknown is the critical polymer/ceramic interfacial resistance (Rint,crit), below which adding ceramics lowers electrolyte overpotential. Here, we present the first macroscale model framework to quantify R int,crit for composite electrolytes based on polyethylene oxide (PEO) and Ta-doped Li 7 La 3 Zr 2 O 12 (LLZO). A 1D model for DC-polarization of tri-layer cells (PEO-LiTFSI/LLZO/PEO-LiTFSI) shows that LLZO surface functionalization reduces the PEO/LLZO interfacial resistance, consistent with electrochemical impedance measurements. Extending to a 2D composite model, we show notably that Rint,crit scales linearly with LLZO particle diameter and shifts toward experimentally accessible values (e.g., 28.8 Ωcm 2 ) as particle size increases. At fixed ceramic volume fraction, larger LLZO particles reduce the number of interfacial crossings, driving more current through the ceramic phase and lowering concentration polarization. In contrast, R int,crit is largely independent of ceramic volume fraction. These results demonstrate that ceramic filler-size engineering can enable synergistic, energy-efficient transport in polymer/ceramic composite electrolytes.
25 ENERGY STORAGE↗
NASA-GRC High Voltage Materials Development and Test Capabilities Portfolio
This presentation provides the background information on NASA-GRC high voltage (HV) materials team research efforts towards electrified propulsion systems since 2016 . Additionally, it covers polymer and ceramic filler materials development for HV electrical insulation composites, copper/ carbon nanotube hybrid conductors, modeling efforts, HV test capabilities, and future material processing capabilities.
Boron Nitride↗
Balancing Functionality and Printability: High-Loading Polymer Resins for Direct Ink Writing
Although direct ink writing (DIW) allows the rapid fabrication of unique 3D printed objects, the resins—or “inks”—available for this technique are in short supply and often offer little functionality, leading to the development of new, custom inks. However, when creating new inks, the ability of the ink to lead to a successful print, or the “printability,” must be considered. Thus, this work examined the effect of filler composition/concentration, printing parameters, and lattice structure on the printability of new polysiloxane inks incorporating high concentrations (50–70 wt%) of metallic and ceramic fillers as well as emulsions. Results suggest that strut diameter and spacing ratio have the most influence on the printability of DIW materials and that the printability of silica- and metal-filled inks is more predictable than ceramic-filled inks. Additionally, higher filler loadings and SC geometries led to stiffer printed parts than lower loadings and FCT geometries, and metal-filled inks were more thermally stable than ceramic-filled inks. The findings in this work provide important insights into the tradeoffs associated with the development of unique and/or multifunctional DIW inks, printability, and the final material’s performance.
36 MATERIALS SCIENCE↗
Tool Severs Hidden Adhesive Bonds
New tool enters narrow gap between fragile materials and removes adhesively bonded filler without damage to adjacent surfaces. Reaches deep into narrow crevices to reach hidden bond lines. Tool originally developed to remove ceramic filler from between Space Shuttle surface-insulation tiles.
Keir, A. R.↗
Enhanced Surface Interactions Enable Fast Li + Conduction in Oxide/Polymer Composite Electrolyte
Abstract Li + ‐conducting oxides are considered better ceramic fillers than Li + ‐insulating oxides for improving Li + conductivity in composite polymer electrolytes owing to their ability to conduct Li + through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li + ‐insulating oxides (fluorite Gd 0.1 Ce 0.9 O 1.95 and perovskite La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 2.55 ) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li + conductivity above 10 −4 S cm −1 at 30 °C. Li solid‐state NMR results show an increase in Li + ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O 2− of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li + transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.
Wu, Nan↗
A single-ion-conducting polymer and high-entropy Li-garnet composite electrolyte with simultaneous enhancement in ion transport and mechanical properties
Enabling the lithium metal anode has been the holy grail for improving the energy density for the next generation advanced batteries. Developing electrolytes that will suppress Li dendrite growth and provide sufficient ionic conductivity remains a major challenge in this field. In this study, we develop a polymer–ceramic composite electrolyte for lithium metal batteries. The polymer matrix is a vinyl ethylene carbonate (VEC) based single-ion-conducting polymer electrolyte. The ceramic filler is a Li 7 La 3 Zr 0.5 Nb 0.5 Ta 0.5 Hf 0.5 O 12 high-entropy Li-garnet (HE Li-garnet) ceramic, which is less prone to surface Li 2 CO 3 formation compared to Al-doped Li garnets. The addition of HE Li-garnet leads to a 7-fold increase in the ionic conductivity (8.6 × 10 −5 S cm −1 at 30 °C) compared to the pure polymer, while maintaining a high Li + transference of 0.73. Proton nuclear magnetic resonance and thermogravimetric analysis results suggest that the addition of HE Li-garnet results in a lower degree of polymerization of VEC, leaving more unpolymerized VEC monomers in the matrix, serving as the governing mechanism for conductivity enhancement. The favorable interactions between HE Li-garnet particles and the polymer matrix lead to a stable and well-mixed composite with 2-fold enhancement of storage modulus at 40 °C. The simultaneous ion transport and mechanical property enhancement significantly improves the composite electrolyte's dendrite resistance and cycle life in Li symmetric cells. This work highlights the positive role HE Li-garnet can play in improving polymer electrolytes to enable lithium metal anodes.
Ock, Ji-young [Oak Ridge National Laboratory (ORNL↗
Mechanistic insight into the effects of A-site doping in perovskite nanorods on interfacial Li-ion and Na-ion transport in polymer–perovskite composite electrolytes
Composite polymer electrolytes (CPEs) offer a promising pathway to safer and higher energy density electrochemical energy storage yet optimizing interfacial ion transport remains a critical challenge due to high resistances and a lack of understanding of the complex interfacial electrostatic interactions. This work investigates the mechanistic origins of the interfacial ion transport enhancement in single-ion conducting (SIC) polymer electrolytes filled with A-site disordered perovskite LaxMyTiOz (LMTO) (M = Li, Na, K) nanorods. By integrating Density Functional Theory (DFT) with broadband dielectric spectroscopy (BDS) and pulsed-field-gradient NMR (PFG-NMR), we analyze the ion transport behavior in Li-based and Na-based SIC systems containing compositionally distinct LMTO fillers (LMTO800 and LMTO900). Specifically, we introduce the site-to-site energy difference (ΔE) descriptor, which extends beyond single-site descriptors such as adsorption energy and ion binding energies. We demonstrate that ΔE together with ion binding energies provide a more comprehensive picture of the energy landscape at the polymer–ceramic interface. The combined DFT and experimental results show that A-site doping in the ceramic filler can effectively modulate ΔE and ion binding energies, creating a favorable potential energy landscape that promotes enhanced ion transport along the interface. This comprehensive study illustrates the impact of ceramic compositional tuning on interfacial ion transport and provides materials design rules towards real-world applications.
B shepard, Lauren [Pennsylvania State University]↗
A review of composite polymer-ceramic electrolytes for lithium batteries
All solid-state lithium batteries are garnering attention in both academia and industry. Lithium-ion conductive polymers and lithium-ion conductive ceramics are the two major classes of solid electrolytes that have prevalently been pursued for many years. However, each of them has its own advantages and disadvantages. One approach to overcome the disadvantages and get the best out of each of those materials is a solid composite electrolyte that combines the advantages of inorganic ceramic electrolytes and solid polymer electrolytes. Such composite electrolytes can offer acceptable ionic conductivity, high mechanical strength, and favorable interfacial contact with electrodes, which can greatly improve the electrochemical performance of all-solid-state batteries compared to cells based on a polymer electrolyte alone or a ceramic electrolyte alone. We present in this review the state-of-the-art composite polymer-ceramic electrolytes in view of their electrochemical and physical properties for the applications in lithium batteries. The review mainly encompasses the polymer matrices, various ceramic filler materials, and the polymer/ceramics composite systems. Specifically, the structures, ionic conductivities, electrochemical/chemical stabilities, and fabrications of solid composite electrolytes are discussed in-depth. On the basis of previous work, a perspective on future research directions is highlighted for developing high-performance composite polymer-ceramic electrolytes.
25 ENERGY STORAGE↗
Effect of the filler morphology on the crystallization behavior and dielectric properties of the polyvinylidene fluoride‐based composite
Abstract Ceramic/polymer composites can be chemically stable, mechanically strong, and flexible, which make them candidates for electric devices, such as pressure or temperature sensors, energy storage or harvesting devices, actuators, and so forth. Depending on the application, various electrical properties are of importance. Polymers usually have low dielectric permittivity, but increased dielectric permittivity can be achieved by the addition of the ceramic fillers with high dielectric constant. With the aim to enhance dielectric properties of the composite without loss of flexibility, 5 wt% of BaTiO 3 ‐Fe 2 O 3 powder was added into a polyvinylidene fluoride matrix. The powder was prepared by different synthesis conditions to produce core/shell structures. The effect of the phase composition and morphology of the BaTiO 3 ‐Fe 2 O 3 core/shell filler on the structure and lattice dynamics of the polymer composites was investigated. Based on the results of the thermal analysis, various parameters of ceramic/polymer composites were determined. Differences in the phase composition and morphology of the filler have an influence on the formation of various polyvinylidene fluoride allomorphs and the degree of crystallinity. Furthermore, the dielectric performances of pure polyvinylidene fluoride and the polymer/ceramic composites were measured.
Polymer Science↗
Li Morphology Evolution during Initial Cycles in a Gel Composite Polymer Electrolyte
Understanding and controlling lithium morphology evolution and lithium dendrite formation and growth during cycling is one of the key challenges for high-energy lithium metal batteries. This challenge applies to liquid electrolyte batteries as well as solid-state and semi-solid-state batteries. Our current knowledge about the evolution of the Li morphology is mostly obtained from liquid electrolyte-based studies in a Li–Li symmetrical cell configuration. The knowledge obtained in such conditions may not readily transfer into solid-state or semi-solid-state batteries. In this work, Li morphology evolution during initial cycling in a full cell configuration with the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC 622) cathode and a semi-solid-state gel composite electrolyte is monitored via post-mortem photographs and scanning electron microscopy at multiple length scales. The gel composite electrolyte contains a cross-linked poly(ethylene oxide)-based polymer electrolyte, ceramic fillers, and a liquid plasticizer. The results show that severe surface pitting occurs as early as the second stripping cycle. Pit formation and continuous dissolution during the stripping process are the main cause of the Li surface roughening and dendrite growth mechanism in the model gel composite electrolyte. Comparing Li dendrite growth mechanisms in liquid, polymer, and ceramic solid electrolytes, the dendrite growth mechanism observed in this model electrolyte resembles that of the liquid electrolyte the most. This study suggests that strategies to control Li morphology and prevent dendrite growth in a gel composite electrolyte should be similar to strategies applicable to liquid electrolytes.
25 ENERGY STORAGE↗
Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO
Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.
25 ENERGY STORAGE↗