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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Chemical interaction and enhanced interfacial ion transport in a ceramic nanofiber–polymer composite electrolyte for all-solid-state lithium metal batteries

This article reports the synergy between ceramic nanofibers and a polymer, and the enhanced interfacial Li-ion transport along the nanofiber/polymer interface in a solid-state ceramic/polymer composite electrolyte, in which a three-dimensional (3D) electrospun aluminum-doped Li 0.33 La 0.557 TiO 3 (LLTO) nanofiber network is embedded in a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) matrix. Strong chemical interaction occurs between the nanofibers and the polymer matrix. Addition of the ceramic nanofibers into the polymer matrix results in the dehydrofluorination of the PVDF chains, deprotonation of the –CH 2 moiety and amorphization of the polymer matrix. Solid-state nuclear magnetic resonance (NMR) spectra reveal that lithium ions transport via three pathways: (i) intra-polymer transport, (ii) intra-nanofiber transport, and (iii) interfacial polymer/nanofiber transport. In addition, lithium phosphate is coated on the LLTO nanofiber surface before the nanofibers are embedded into the polymer matrix. The presence of lithium phosphate at the LLTO/polymer interface further enhances the chemical interaction between the nanofibers and the polymer, which promotes the lithium ion transport along the polymer/nanofiber interface. This in turn improves the ionic conductivity and electrochemical cycling stability of the nanofiber/polymer composite. As a result, the flexible LLTO/Li 3 PO 4 /polymer composite electrolyte membrane exhibits an ionic conductivity of 5.1 × 10 -4 S cm -1 at room temperature and an electrochemical stability window of 5.0 V vs. Li/Li + . A symmetric Li|electrolyte|Li half-cell shows a low overpotential of 50 mV at a constant current density of 0.5 mA cm -2 for more than 800 h. In addition, a full cell is constructed by sandwiching the composite electrolyte between a lithium metal anode and a LiFePO 4 -based cathode. Such an all-solid-state lithium metal battery exhibits excellent cycling performance and rate capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tracking copper nanofiller evolution in polysiloxane during processing into SiOC ceramic

Polymer-derived ceramics (PDCs) remain at the forefront of research for a variety of applications including ultra-high-temperature ceramics, energy storage and functional coatings. Despite their wide use, questions remain about the complex structural transition from polymer to ceramic and how local structure influences the final microstructure and resulting properties. This is further complicated when nanofillers are introduced to tailor structural and functional properties, as nanoparticle surfaces can interact with the matrix and influence the resulting structure. The inclusion of crystalline nanofiller produces a mixed crystalline–amorphous composite, which poses characterization challenges. With this study, we aim to address these challenges with a local-scale structural study that probes changes in a polysiloxane matrix with incorporated copper nanofiller. Composites were processed at three unique temperatures to capture mixing, pyrolysis and initial crystallization stages for the pre-ceramic polymer. We observed the evolution of the nanofiller with electron microscopy and applied synchrotron X-ray diffraction with differential pair distribution function (d-PDF) analysis to monitor changes in the matrix's local structure and interactions with the nanofiller. The application of the d-PDF to PDC materials is novel and informs future studies to understand interfacial interactions between nanofiller and matrix throughout PDC processing.

Chemistry↗
DOE OSTI2022

High-performance piezoelectric composites via β phase programming

Polymer-ceramic piezoelectric composites, combining high piezoelectricity and mechanical flexibility, have attracted increasing interest in both academia and industry. However, their piezoelectric activity is largely limited by intrinsically low crystallinity and weak spontaneous polarization. Here, we propose a Ti 3 C 2 T x MXene anchoring method to manipulate the intermolecular interactions within the all-trans conformation of a polymer matrix. Employing phase-field simulation and molecular dynamics calculations, we show that OH surface terminations on the Ti 3 C 2 T x nanosheets offer hydrogen bonding with the fluoropolymer matrix, leading to dipole alignment and enhanced net spontaneous polarization of the polymer-ceramic composites. We then translated this interfacial bonding strategy into electrospinning to boost the piezoelectric response of samarium doped Pb (Mg1/3Nb 2/3 )O 3 -PbTiO 3 /polyvinylidene fluoride composite nanofibers by 160% via Ti 3 C 2 T x nanosheets inclusion. With excellent piezoelectric and mechanical attributes, the as-electrospun piezoelectric nanofibers can be easily integrated into the conventional shoe insoles to form a foot sensor network for all-around gait patterns monitoring, walking habits identification and Metatarsalgi prognosis. This work utilizes the interfacial coupling mechanism of intermolecular anchoring as a strategy to develop high-performance piezoelectric composites for wearable electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evaluating Iodine Immobilization Technologies: Cermets, Polycermets, and Polyhalmets

The work in this report documents the efforts conducted to assess the feasibility of some of the ideas documented in Pacific Northwest National Laboratory invention disclosure reports (IDRs) including: 1) Iodine capture in polyacrylonitrile (PAN)-containing composite sorbents (32451-E). In this work, the composites evaluated included Ag0, Bi0, Cu0, Bi2S3, and Cu2S embedded in PAN. 2) Metal iodide removal from these sorbents through dissolution in dimethyl sulfoxide (DMSO) (32729-E). In this work, PAN dissolution was evaluated for multiple types of sorbents including Ag-Pan, Bi-PAN, Cu-PAN, Bi2S3-PAN, and Cu2S-PAN. 3) Using metal-sulfide sorbents for iodine capture (32647-E). In this work, the composites evaluated under this IDR included Ag2S, Bi2S3, and Cu2S embedded in PAN. 4) Using low-melting metals to immobilize (encapsulate) iodine-loaded and polymer-containing sorbents into polymer-ceramic-metal (called polycermet) or polymer-halide-metal (called polyhalmet) composite waste forms (32625-E). In this work, the iodine-loaded PAN composites included AgI-PAN, BiI-PAN, and CuI-PAN. 5) Ceramic-metal composite waste form synthesis of polymer-containing materials using low-melting metals like bismuth, tin, or bismuth-tin alloys (32537-E). In this work, the metals evaluated included Bi, 58Bi-42Sn eutectic. 6) Cermets for immobilizing commercial sorbents loaded with radioiodine (32806-E). In this work, AgIX (iodine-loaded silver faujasite zeolite) was evaluated in cermet form.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Non-Conductive Polymers Enable Higher Ionic Conductivities and Suppress Reactivity in Hybrid Sulfide-Polymer Solid State Electrolytes

Hybrid ceramic-polymer solid state electrolytes are promising candidates to enable energy-dense lithium metal batteries by leveraging inorganic high ionic conductivity and flexible polymer mechanical properties. However, studies of hybrid electrolytes using sulfide-type inorganics such as Li3PS4 (LPS) have largely focused on combining the inorganic with commercial poly(ethylene oxide) (PEO). PEO has proven to be insufficient for use in hybrid systems because it reacts with LPS and provides a competing pathway for ion transport, therefore producing a hybrid with low conductivity. Our work shows that using nonconductive, nonpolar polyethylene (PE) in a hybrid electrolyte with LPS eliminates both polymer and inorganic degradation and remarkably exhibit higher conductivities than those containing PEO at different polymer and salt concentrations. Using tracer-exchange NMR, we observe that the nonconductive nature of PE allows for iontransport through the inorganic whereas PEO provides a separate, competing pathway for lithium transport. Furthermore, compared to pure LPS, these hybrids enable longer term lithium cycling at 60°C. Our work shows that the path to enabling conductive and stable sulfide hybrids for solid state lithium metal batteries may be through the use of nonconductive, nonreactive polymers.

batteries↗
DOE OSTI2025

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↗
DOE OSTI2026

Structural effects of composition tuning in A-site disordered perovskite La0.5Li0.5−xMxTiO3 (M = Na, K) nanorods for fast interfacial transport for solid composite electrolyte design

Polymer-ceramic composite electrolytes (CPE) have emerged as promising replacements for currently used liquid organic electrolytes, which pose as safety hazards, in Li-ion batteries. Limits in conductivity enhancement in CPEs is often attributed to a high resistance for Li-ion transport along the interface due to the incompatibility of the polymer and ceramic phases. A clear understanding of the interfacial structure and how this impacts interfacial Li-ion transport is needed in order to efficiently design a CPE with optimal ionic conductivity. In this study, density functional theory (DFT) calculations, in conjunction with scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS), are used to unveil the bulk and surface structure of La0.5Li0.5−xMxTiO3 (M = Na, K) (LMTO) nanorods, a newly-reported ceramic system with promising applications in CPEs, and the LMTO interactions with the poly(lithium sulfonyl (trifluoromethane sulfonyl)imide methacrylate) (p(MTFSILi)) polymerized ionic liquid. Substitution of lithium for sodium and potassium onto the A-site perovskite lattice is shown to increase the stability of the preferred pseudocubic perovskite phase because of their increased cation size which allows them to reduce the TiO6 octahedral rotations in the bulk and at the surface. STEM and EELS results show that LMTO nanorods with differing compositions have Ti-enriched (110)-oriented surfaces. Increased sodium and potassium compositions in LMTO is also shown using the DFT calculations to weaken the binding of the lithium atom to the MTFSI unit when LiMTFSI is adsorbed to the LMTO surface. This weakening of lithium binding to the polymer at the LMTO interface indicates that the lithium mobility is increased, correlating to an increase in interfacial Li-ion transport. Overall, this work provides insights into how to tune the interfacial interactions between the polymer (p(MTFSI)) and ceramic (LMTO) for optimal CPE design.

Shepard, Lauren B [Pennsylvania State University, ↗
DOE OSTI2024

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗
DOE OSTI2020

Development of lithium ion conducting interface between lithium metal and a lithium ion conducting ceramic using block polymers

The lithium-air (Li-air) technology developed by EDF uses an air electrode which works with an aqueous electrolyte, which prevent the use of unprotected lithium metal electrode. A Li+ ionic conductor glass ceramic is used to separate the aqueous electrolyte compartment from the negative lithium electrode. However, this glass-ceramic is not stable in contact with lithium, it is thus necessary to add a protective buffer layer. In another hand, this protection should ideally resist to lithium dendritic growth. It is in this context that this research project which has as goal the development of a protective buffer layer based on block copolymer electrolytes (BCE) between the lithium metal and the lithium ionic conductor ceramic, for lithium-air battery. In a first part, the BCE is studied in lithium-lithium symmetric cells, in order to determine their electrochemical properties such as ionic conductivity, steady state transference number, and finally their resistance to dendritic growth during cycling. Several characterization techniques were employed and especially hard X-ray micro-tomography to analyze the lithium morphology before and after cycling. For single-ion BCE, we expect to suppress dendritic growth, however, we report here for the first time, the visualization of a homogeneous growth of lithium but the formation of dense lithium objects. In another part, the composite BCE-ceramic is studied by electrochemical impedance spectroscopy (EIS). The cycling of lithium-composite-lithium symmetric cells and the analysis of the EIS measurement after each cycle permit to determine if the dendrites have cross the protective layer and are in contact with the ceramic. Besides, the quantification of the polarization loss at the interface polymer-ceramic is evaluated by polarization experiments. This contribution is found to be small.

36 MATERIALS SCIENCE↗
DOE OSTI2026

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↗