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Highly Porous Polyimide Gel for Use as Battery Separator with Room Temperature Ionic Liquid Electrolytes

Advanced aerospace vehicular concepts require advances in many existing technologies, including space power and energy storage systems. Batteries represent one of the major areas in need of improvement, both in terms of energy density and safety, with growing concerns over the fire safety of commercial lithium-ion batteries. This has prompted efforts to develop nonflammable battery components, namely the electrolyte and separator. Existing commercial lithium-ion batteries utilize polyolefin microporous membranes as separators with an electrolyte consisting of a lithium salt dissolved in a mixture of cyclic carbonate solvents. This separator/electrolyte combination has ionic conductivities in the range of 10 −2 to 10 −3 S/cm. However, the cyclic carbonate solvents are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative. They offer good ionic conductivities and are inherently nonvolatile and nonflammable, giving them a safety advantage. However, many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Alternative separator materials, such as polyimides, are non-flammable and are capable of accepting RTILs into their structure. Polyimide gels, with a composition of 4,4′-oxydianiline, 3,3′,4,4′-tetracarboxylic dianhydride and cross-linked with Desmodur N3300A, possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85% porosity) for lithium-ion transport and conduction, as well as good mechanical properties. Furthermore, these polyimide gels are compatible with selected imidazolium-based RTILs. Nonflammable separator/electrolyte systems with room-temperature conductivities in the range of 10 −3 S/cm have been evaluated. It has been demonstrated that 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was the most promising among six RTILs screened, in terms of both ionic conductivity and constant current cycling.

Polyimide

Diamond-Loaded Polyimide Aerogel Scattering Filters and Their Applications in Astrophysical and Planetary Science Observations

Infrared-blocking, aerogel-based scattering filters have a broad range of potential applications in astrophysics and planetary science instruments in the far-infrared, sub-millimeter, and microwave regimes. This paper demonstrates the ability of conductively-loaded, polyimide aerogel filters to meet the mechanical and science instrument requirements for several experiments, including the Cosmology Large Angular Scale Surveyor (CLASS), the Experiment for Cryogenic Large-Aperture Intensity Mapping (EXCLAIM), and the Sub-millimeter Solar Observation Lunar Volatiles Experiment (SSOLVE). Thermal multi-physics simulations of the filters predict their performance when integrated into a cryogenic receiver. Prototype filters have survived cryogenic cycling to 4 K with no degradation in mechanical properties. Measurement of total hemispherical reflectance and transmittance, as well as cryogenic tests of the aerogel filters in a full receiver context, allow estimates of the integrated infrared emissivity of the filters. Knowledge of the emissivity will help instrument designers incorporate the filters into future experiments in planetary science, astrophysics, and cosmology.

Kyle R Helson

Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation

Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have potential applications on large, deployable, ultra-light weight Gossamer spacecraft as thin film membranes on antennas, solar sails, thermal/optical coatings, multi-layer insulation blankets, etc.. The challenge has been to develop a method to impart robust electrical conductivity into these materials without increasing solar absorptivity (alpha ) or decreasing optical transparency or film flexibility. Since these spacecraft will require significant compaction prior to launch, the film portion of the spacecraft will require folding. The state-of-the-art clear, conductive coating (e.g. indium-tin-oxide, ITO) is brittle and cannot tolerate folding. In this report, doping a polymer with single-walled carbon nanotubes (SWNTs) using two different methods afforded materials with good flexibility and surface conductivities in the range sufficient for ESC mitigation. A coating method afforded materials with minimal effects on the mechanical, optical, and thermo-optical properties as compared to dispersal of SWNTs in the matrix. The chemistry and physical properties of these nanocomposites are discussed.

Smith, Joseph G., Jr.

Visualizing Crystallization Dynamics and Transformation Pathways of Disordered Rocksalt Oxides During Thermally Activated Sol–Gel Synthesis

Sol–gel synthesis is a wet-chemical processing route for fabricating functional materials with control over composition and microstructure at relatively low temperatures compared to conventional solid-state synthesis. While sol–gel process initiates with intermixed molecular precursors, the early-stage nucleation pathways are insufficiently understood. Here, in this study, the chemical and structural transformation of ion disordered rocksalt (DRX) Li 1.2 Mn 0.4 Ti 0.4 O 2 (LMTO), a promising cathode material for lithium batteries, is studied by multiscale characterizations. In situ heating transmission electron microscopy (TEM) using a liquid cell visualizes and identifies crystallization pathways at the nanoscale. While some regions follow a classical multi-step transition through thermodynamically stable intermediates, others exhibit a kinetic shortcut via a localized amorphous matrix to directly form the DRX structure. Macroscale Fourier transform infrared spectroscopy corroborates the findings and reveals that transition metal ions are more strongly incorporated into the acetate-coordinated network than lithium. Although in situ heating TEM captures diverse local transformation pathways, in situ synchrotron X-ray diffraction indicates that the macroscopic transformation proceeds predominantly through spinel LMTO and lithium titanates toward DRX-LMTO. The findings uncover the spatiotemporal chemical and structural transformations in sol–gel derived DRX-LMTO materials, and call for fine-tuning of such sol–gel chemistries to manipulate the crystallization pathways and achieve target material homogeneity more efficiently.

cathode material

Mechanically and Thermally Robust Gel Electrolytes Built from A Charged Double Helical Polymer

Polymer electrolytes have received tremendous interest in the development of solid-state batteries, but often fall short in one or more key properties required for practical applications. Herein, a rigid gel polymer electrolyte prepared by immobilizing a liquid mixture of a lithium salt and poly(ethylene glycol) dimethyl ether with only 8 wt% poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT) is reported. The high charge density and rigid double helical structure of PBDT lead to formation of a nanofibrillar structure that endows this electrolyte with stronger mechanical properties, wider temperature window, and higher battery rate capability compared to all other poly(ethylene oxide) (PEO)-based electrolytes. The ion transport mechanism in this rigid polymer electrolyte is systematically studied using multiple complementary techniques. Li/LiFePO 4 cells show excellent capacity retention over long-term cycling, with thermal cycling reversibility between ambient temperature and elevated temperatures, demonstrating compelling potential for solid-state batteries targeting fast charging at high temperatures and slower discharging at ambient temperature.

36 MATERIALS SCIENCE

High Sulfur Loading and Capacity Retention in Bilayer Garnet Sulfurized‐Polyacrylonitrile/Lithium‐Metal Batteries with Gel Polymer Electrolytes

The cubic‐garnet (Li 7 La 3 Zr 2 O 12 , LLZO) lithium–sulfur battery shows great promise in the pursuit of achieving high energy densities. The sulfur used in the cathodes is abundant, inexpensive, and possesses high specific capacity. In addition, LLZO displays excellent chemical stability with Li metal; however, the instabilities in the sulfur cathode/LLZO interface can lead to performance degradation that limits the development of these batteries. Therefore, it is critical to resolve these interfacial challenges to achieve stable cycling. Here, an innovative gel polymer buffer layer to stabilize the sulfur cathode/LLZO interface is created. Employing a thin bilayer LLZO (dense/porous) architecture as a solid electrolyte and significantly high sulfur loading of 5.2 mg cm −2 , stable cycling is achieved with a high initial discharge capacity of 1542 mAh g −1 (discharge current density of 0.87 mA cm −2 ) and an average discharge capacity of 1218 mAh g −1 (discharge current density of 1.74 mA cm −2 ) with 80% capacity retention over 265 cycles, at room temperature (22 °C) and without applied pressure. Achieving such stability with high sulfur loading is a major step in the development of potentially commercial garnet lithium–sulfur batteries.

25 ENERGY STORAGE

Egg yolk as a model for gelation: From rheometry to flow physics

Egg yolks are an excellent model for studying sol-gel transitions, particularly the power law viscoelasticity that defines the critical point of gelation. However, prior studies lack comprehensive datasets and fail to visualize flow behavior linked to temperature and time-dependent linear and nonlinear rheology. Here, we present a detailed dataset characterizing egg yolk viscoelasticity across temperature, time, and forcing amplitude using oscillatory shear, step strain, step stress, and constant high strain rate. Novel protorheology visualizations link rheological properties with observable flow behavior. Our findings highlight the nuanced determination of the critical gel point, emphasizing observation timescale dependencies. We compare methods to identify critical temperatures for gelation, including power law viscoelasticity, moduli crossover, diverging zero-shear viscosity, and emerging equilibrium elastic modulus, while visualizing flow consequences near these transitions. Egg yolk is an accessible, realistic, and nontoxic material relevant to the physicist and the chef alike, making it ideal for understanding the rheology of critical gels. By integrating protorheology photos and videos with rigorous rheometric data, we deepen the understanding of critical gels, with broader impacts for studying other materials with sol-gel transitions.

Marsh, Maxwell C. [Department of Mechanical Scienc

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Electrochemistry

Space Electrochemical Research and Technology

Individual papers presented at the conference address the following topics: development of a micro-fiber nickel electrode for nickel-hydrogen cell, high performance nickel electrodes for space power application, bending properties of nickel electrodes for nickel-hydrogen batteries, effect of KOH concentration and anions on the performance of a Ni-H2 battery positive plate, advanced dependent pressure vessel nickel hydrogen spacecraft cell and battery design, electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery design, a novel unitized regenerative proton exchange membrane fuel cell, fuel cell systems for first lunar outpost - reactant storage options, the TMI regenerable solid oxide fuel cell, engineering development program of a closed aluminum-oxygen semi-cell system for an unmanned underwater vehicle, SPE OBOGS on-board oxygen generating system, hermetically sealed aluminum electrolytic capacitor, sol-gel technology and advanced electrochemical energy storage materials, development of electrochemical supercapacitors for EMA applications, and high energy density electrolytic capacitor.

Richard M Wilson