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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 307 records · Page 17

Importance of High Valence Element Nb in Ni-Rich Layered Cathodes for High-Voltage Lithium-Metal Batteries

Ni-rich layered cathode materials have attracted extensive attention due to their higher energy density and technological maturity in commercialization. As the nickel content is raised, especially surpassing 80%, the increased energy density comes with the tradeoff of diminished thermal stability and increased electrochemical structural instability of the cathode. Compared with Co, Al, B, and Ta, the introduction of high valence element Nb significantly improved the electrochemical cycling, delivering a capacity of 202 mAh/g, corresponding to a capacity retention of 92% after 200 cycles tested at 45 °C. Further, the ex situ differential scanning calorimetry and in situ isothermal microcalorimetry demonstrate that the Nb-modified cathode has the potential to enhance the safety of ultrahigh nickel (Ni) NMCs and displays remarkable resilience to extensive cycling by inhibiting high-temperature decomposition reactions and exhibiting a lower heat flow during electrochemical cycling.

25 ENERGY STORAGE↗

Unprecedented Multifunctionality in 1D Nb 1- x Ta x S 3 Transition Metal Trichalcogenide Alloy

One-dimensional (1D) van der Waals materials, such as nanofibers or nanoribbons are considered as the future ultimate limit of downscaling for modern electrical and electrochemical devices. Here, for the first time, we successfully synthesize nanofibers of a solid solution transition metal trichalcogenide (TMTC), Nb 1-x Ta x S 3 , with outstanding electrical, thermal, and electrochemical characteristics rivaling the performance of the-state-of-the art materials for each application. This material shows nearly unchanged sheet resistance (≈740 Ω/sq -1 ) versus bending cycles tested up to 90 cycles, stable sheet resistance in ambient conditions tested up to 60 days, remarkably high electrical breakdown current density of ≈ 30 MA cm -2 , strong evidence of successive charge density wave (CDW) transitions, and outstanding thermal stability up to ≈900 K. Additionally, this material demonstrates excellent activity and selectivity for CO2 conversion to CO reaching ≈ 350 mA cm -2 at – 0.8 V vs RHE with an outstanding turnover frequency number of 25 for CO formation. It also exhibits an excellent performance in a high-rate Li-air battery with the specific capacity of 3000 mAhg -1 at a high current density of 0.3 mAcm -2 . This study uncovers the multifunctionality in 1D TMTC alloys for a wide range of high-impact applications and opens a new direction for the design of the next generation of low-dimensional materials with high performance.

36 MATERIALS SCIENCE↗

Contribution of the catalytic dyad of SARS-CoV-2 main protease to binding covalent and noncovalent inhibitors

The effect of mutations of the catalytic dyad residues of SARS-CoV-2 main protease (MPro WT ) on the thermodynamics of binding of covalent inhibitors comprising nitrile [nirmatrelvir (NMV), NBH2], aldehyde (GC373), and ketone (BBH1) warheads to MPro is examined together with room temperature X-ray crystallography. When lacking the nucleophilic C145, NMV binding is ~400-fold weaker corresponding to 3.5 kcal/mol and 13.3 °C decrease in free energy (ΔG) and thermal stability (T m ), respectively, relative to MPro WT . The H41A mutation results in a 20-fold increase in the dissociation constant (K d ), and 1.7 kcal/mol and 1.4 °C decreases in ΔG and T m , respectively. Increasing the pH from 7.2 to 8.2 enhances NMV binding to MPro H41A , whereas no significant change is observed in binding to MPro WT . Structures of the four inhibitor complexes with MPro 1-304/C145A show that the active site geometries of the complexes are nearly identical to that of MPro WT with the nucleophilic sulfur of C145 positioned to react with the nitrile or the carbonyl carbon. These results support a two-step mechanism for the formation of the covalent complex involving an initial non-covalent binding followed by a nucleophilic attack by the thiolate anion of C145 on the warhead carbon. Noncovalent inhibitor ensitrelvir (ESV) exhibits a binding affinity to MPro WT that is similar to NMV but differs in its thermodynamic signature from NMV. The binding of ESV to MPro C145A also results in a significant, but smaller, increase in K d and decrease in ΔG and T m , relative to NMV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Dimethylamino Functional Group Substitution on the Physical, Structural and Radiolytic Properties of Pyridinium Ionic Liquids

A diverse range of 4-dimethylaminopyridinium (DMAP) bis(trifluoromethylsulfonyl)-amide ionic liquids with specific functionalities (alkyl, alkoxy, hydroxyalkyl and benzyl) were designed, characterized and compared with their pyridinium analogs in terms of their physical and radiolytic properties. The influence of the dimethylamino group on ionic liquid structure was investigated by X-ray diffraction and molecular dynamics simulations. The influence of the electron-donating ability of the dimethylamino-substituted cation is evident in the differences in the electronic density of states between the DMAP and pyridinium ILs. This leads to substantial changes in the radical transients observed in pulse radiolysis of the neat ILs. It was found that the DMAP salts were higher melting, more viscous and less conducting than their pyridinium analogs. However, the DMAP salts exhibited higher thermal stabilities and could therefore be useful for high-temperature applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic layer deposition of nickel sulfide thin films and their thermal and electrochemical stability

Nickel sulfides (NiS x ) show promise for a range of energy and other applications, but their (in)stability under processing and operating conditions is scarcely studied. Herein, we have developed a new NiS x atomic layer deposition process using an easily synthesized NiCl 2 (TMPDA) precursor (TMPDA = N,N,N′,N′-tetramethyl-1,3-propanediamine) with H 2 S. Thin films deposited at 165–225 °C consist mostly of the β-NiS phase and display low resistivity (∼40–120 μΩ cm), high purity (<3 at% impurities), and a rough morphology. The thermal stability of the NiS x thin films is studied using high-temperature X-ray diffraction, revealing that structural and compositional changes occur in reducing, inert, and oxidizing atmospheres at approximately 300–400 °C. Under electrochemical water splitting conditions, the films are unstable in acid due to dissolution, especially at oxidizing potentials. In an alkaline electrolyte, we do not observe Ni dissolution, but β-NiS transforms to Ni 3 S 2 under HER conditions, possibly supplemented with Ni and/or Ni(OH) 2 species. Under alkaline OER, all sulfur is lost and NiOOH is formed. In addition to offering an attractive, scalable route to the synthesis of NiS x thin films, our work highlights the importance of thermal and electrochemical (in)stability of sulfides as a crucial step for understanding and engineering materials for energy and other applications.

Mattinen, Miika [Univ. of Helsinki (Finland); Stan↗

In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries

A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.

degradation mechanisms↗

Highly Loaded Sulfur Cathode, Coated Separator and Gel Electrolyte for High Rate Li-Sulfur Batteries

As one of DOE Battery 500 Seedling projects, Cornell University and EIC Labs investigated and developed i) highly loaded sulfur cathodes (> 3 mg/cm 2 ), ii) hybrid separators, and iii) gel ceramic electrolytes (GCE) to mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries. Scalable nanomanufacturing processes such as air-controlled electrospray (ACES) and gas-assisted electrospinning (GAES) have been utilized to develop directly deposited electrodes and polymer/ceramic hybrid separators. First, in the development of highly loaded cathodes, alternating layers of sulfur impregnated mesoporous carbon and graphene were fabricated via ACES and the resulting layered cathodes and coated separators exhibit higher capacity and capacity retention (about 1,000 mAh/g capacity with less than 0.02% fade/cycles) than single layer cathode or cathode prepared by conventional slurry cast. Alternating layer approach via ACES has been applied to high loading systems (3 - 5 mg S/cm 2 ), demonstrating the potential to increase sulfur utilization and capacity retention. We have also incorporated iron oxides (Fe 3 O 4 ) into S/mesoporous carbon/graphene cathodes to enhance sulfur utilization and mitigation of polysulfide shuttling. and the effect of Fe 3 O 4 in mesoporous carbon and Gr is highly pronounced at high C rates of 1C and 2C cycling performance. To further improve the cathodes at high rates, graphene nanoribbons (GNR) which can promote ion transport were incorporated in the cathode, resulting in 550 mAh/g at 5C/5C rates. Hybrid Li-ion/Li-S cathodes has also been explored to better engage unreacted polysulfides during charge/discharge. S/LFP hybrid cathodes offer higher sulfur utilization and enhanced rate capability, as well as higher areal loading. This study suggests inclusion of iron phosphide (Fe2P) which can chemically interact with polysulfides can further enhance sulfur utilization and mitigation of soluble polysulfides at high rates. Secondly, in the development of hybrid separators, we first employed graphene coating on the commercial polyolefin separators, which exhibits higher capability, better capacity retention and enhanced rate capability. To improve the rate capability with enhanced safety features such as thermal stability and nonflammability, we developed polymer/ceramic hybrids based on thermally stable polyimide (PI) and room temperature curable ceramic precursors such as organopolysilazane (OPSZ) or polysilsesquioxanes (PSSQ), which exhibit no shrinkages up to 300 ºC and non-flammability. To improve mechanical properties and electrochemical stability, polybenzimidazole (PBI) and alumina have been incorporated in polymer/ceramic hybrid separator, replacing PI and OPSZ/PSSQ, respectively. Finally, the gel ceramic electrolyte (GCE) based on ceramic cross linkers have been applied to make Li-S cells even safer and also to mitigate the polysulfide shuttling further. The resulting gel ceramic electrolyte offers improved capacity retention and rate capability, and also effectively mitigates polysulfide shuttling which was also confirmed by modeling. Inclusion of high ion conducting additives into GCE together with polymer/ceramic hybrid separators exhibit the higher ionic conductivity than liquid electrolyte with commercial polyolefin separator. We demonstrated that the developed highly loaded sulfur cathodes, polymer/ceramic hybrid separators and gel ceramic electrolyte can effectively mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries with improved safety.

25 ENERGY STORAGE↗

Foam Fracturing Fluid Half-life Experimental Data

Foam thermal stability was studies at Temple University in collaboration with Oak Ridge National Lab (ORNL). The goal of this project is to explore thermally stable foams as hydrofracking fluid media for potential applications in enhanced geothermal system (EGS). Data generated from this project will allow researchers to explore foam as potential fracturing fluid. More than 800 data points on the half-life of foams are recorded in Excel files in the included archive resource (Half-life of Foams with Different Surfactants and Stabilizing Agents). The Excel file within each surfactant folder contains half-life data of the respective surfactant with different stabilizing agents, pressure, and temperature. The respective folders also contains Word files describing the details of the data included in the respective Excel sheet.

15 GEOTHERMAL ENERGY↗

Electronic Structure and Safety Insights into Prussian Blue Analog Cathode Behavior at Elevated Temperatures in Sodium-Ion Batteries

Prussian blue analogs (PBAs) represent promising cathode materials for sodium-ion batteries (SIBs) due to their high theoretical capacity, open framework structure, and use of earth-abundant elements. However, the high-temperature structural evolution, water content effects, and thermal safety of PBAs, particularly in charged states, remain poorly understood, hindering their practical deployment. Here, we investigate Na 2 Fe[Fe(CN) 6 ]·2H 2 O using thermogravimetric analysis (TGA), ex situ and in situ temperature-dependent X-ray absorption spectroscopy (XAS), and accelerated rate calorimetry (ARC). TGA and ex situ XAS confirm water loss between 150 and 200 °C, resulting in Fe 2+ oxidation, enhanced local symmetry, and uniform redox behavior that improves electrochemical performance. In situ XAS reveals irreversible structural changes above 240 °C, including ligand loss, Fe site distortion, and increased disorder, while ARC on charged electrodes shows minimal self-heating rates (<0.1 °C/min) up to 300 °C, indicating exceptional thermal stability without lattice oxygen release. These insights elucidate PBA thermal dynamics, demonstrating improved electrochemical performance of water-deficient PBAs and informing future material design and safety assessment for SIB applications.

batteries↗

Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Preparing cellulose II nanocrystals (CNC II) requires a polymorph transformation of natural cellulose I feedstocks. The transformation is usually achieved via a process such as mercerization or dissolution–regeneration. This study demonstrated a new method to prepare CNC II directly from bleached kraft pulp (BKP, a commercially available cellulose I feedstock) in a mildly acidic lithium bromide trihydrate (MALBTH) system, a concentrated (~61 wt%) solution of LiBr in water with a very low concentration (2.5 mM) of sulfuric acid. First, the BKP was treated in the MALBTH system to generate a cellulose II hydrolysis solid residue (CHR) with a yield of 64–86%, during which the selective hydrolysis of disordered cellulose and the polymorph transformation were completed simultaneously. Then, subsequent oxidation of the CHR by ammonium persulfate (APS, 0.1–0.6 M) resulted in the CNC II with high yield (up to 62%), high crystallinity (over 90%), rich surface carboxyl group (0.3–1.2 mmol g-1 cellulose), excellent colloidal stability (up to -59 mV zeta potential), and high thermal stability. The CNC II had a tunable length (26–57 nm), determined by the conditions of the MALBTH hydrolysis and the APS oxidation, but similar lateral dimension (8–10 nm). The characterization of the CHR by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy verified the polymorphic transformation from cellulose I to II during the MALBTH treatment. The swelling of the BKP in the MALBTH enabled cellulose crystallites to slide and reassemble, which completed the rearrangement of cellulose chains from parallel to anti-parallel conformation (polymorph transformation from cellulose I to II). This study provided an efficient and green method to produce cellulose II nanocrystals with controllable aspect ratios via the simultaneous hydrolysis and polymorph transformation of cellulose I feedstocks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Aerosol jet printed 3 omega sensors for thermal conductivity measurement

The 3 omega (3ω) method is a trusted technique for measuring thermal conductivity—a fundamental material property of critical importance in a broad range of applications. However, traditional 3ω sensor processing requires some form of physical vapor deposition, such as metal evaporation or sputtering. These 3ω sensor deposition techniques limit the materials and sample sizes applicable to the 3ω method. This work demonstrates an aerosol jet printing method to directly print silver 3ω sensors that yield accurate temperature-dependent measurement up to 300 °C on materials with thermal conductivity ranging from 1 to 150 W/m K. The interrelationship between printed sensor geometry, sensor thermal stability, and applicability to the 3ω method is examined. Thermal conductivity measurement with 3ω sensors conventionally sintered at 300 °C agrees to independent laser flash measurement within 4% from room temperature to 150 °C. An unconventional rapid high-temperature sintering method is shown to produce sensors that agree within 3% of the laser flash measurements from room temperature to 300 °C. The rapid sintering profiles also reduced the sensor–substrate thermal boundary resistance of the printed sensors by as much as 88%. The direct printing of 3ω sensors creates opportunities for measurement of thermal transport properties in applications previously inapplicable to the 3ω method.

47 OTHER INSTRUMENTATION↗

Corrosion evaluation of metal foams in eutectic molten salts for high temperature latent heat energy storage application

High-temperature Thermal Energy Storage (TES) has drawn great attention as a technology that can increase the role and profitability of micro nuclear reactors in the decentralized clean energy market. Various research needs have been proposed by Idaho National Laboratory (INL) in "the Integrated Energy Systems: 2020 Roadmap" with the goal of utilizing the high temperature of 550 degrees or more generated in the 4th generation reactor to industrial purposes from the standpoint of integrated energy systems [1]. With the recent development of the 4th generation nuclear power plant, including micro nuclear reactor, there is a great deal of interest in researching how to efficiently couple a heat source to an industrial process through thermal processing. Texas A&M University (TAMU) and INL are currently collaborating to develop a novel latent heat storage design called HITB (Heat pipe-Integrated Thermal Battery). As part of the small-scale experimental demonstration research for HITB, a study for storage medium selection was conducted at TAMU. Eutectic salts have attracted interest as high-temperature heat storage medium for HITB. Especially, chloride molten salts and fluoride molten salts are considered promising candidates due to their high melting temperature, thermal stability, and high latent heat of fusion. Since eutectic salts have poor thermal conductivity in general, it is critical to distribute materials with high thermal conductivity evenly to facilitate the charging and discharging of heat. In this study, metal foam was considered in the HITB system to overcome the poor heat transfer characteristics of eutectic salts. In order to improve heat transfer, it is necessary to study materials with high thermal conductivity, corrosion resistant to molten salts, such as fins, extended surfaces, particles, microcapsulation, or foam structure. Porous structure of copper or aluminum can increase heat transfer area, form a thermal transfer network, and increase the effective thermal conductivity of thermal storage medium [2]. Since the melting temperature is required to be at least 450? in the current HITB design, various eutectic salts are being considered. FLiNaK and FLiBe, which are famous for fluoride salts, are good candidates, but due to the sharp rise in the price of LiF recently, they are excluded for economic reasons to be applied to large-capacity thermal energy storage. On the other hand, chloride salts are very cheap and easy to obtain, have a high melting temperature, and have a high latent heat of fusion, so they are recently in the spotlight as a phase change material. However, because of the hygroscopic nature of chloride salts, HCl gas due to impurity is easy to be released and is particularly vulnerable to corrosion. Chloride eutectic salts have been tested and suggested for metal alloys that are particularly resistant to corrosion, such as SS304, SS316, Hastelloy, Inconel 625, Incoloy 800H, which has low thermal conductivity, and is very expensive [3-6]. Porous materials with high thermal conductivity such as copper and aluminum have been tested for stability in fluids such as paraffin or water as metal foam or metal fin structures, but high temperature corrosion tests were not performed on various eutectic salts yet. Therefore, this study investigated the high temperature corrosion characteristics of metal alloys, such as C10100 foam, C10100 plate, 6101 alloy foam, and SS316 plate, while immersed in the candidate eutectic salts. A total of 20 tests for SS316 coupons and 10 tests for C10100 coupons were performed to ensure the repeatability of the present measurements. Since it is difficult to completely remove the salt inside metal foam due to the complex inner structure of the metal foam, only the surface condition was observed with a microscopy and scanning electron microscopy (SEM) image, except for measuring the corrosion rate and average mass loss.

25 ENERGY STORAGE↗

Computational Design of Cost-Effective High-Entropy Thermal/Environmental Barrier Coatings

Developing cost-effective thermal/environmental barrier coatings (TEBC) requires balance among various properties including low thermal conductivity, matching coefficient of thermal expansion (CTE), high thermal stability, high fracture toughness, and high recession resistance while being affordable. Low oxygen diffusivity is desirable as it can slow down oxygen transport to reach the underlying bond coating and hence delay oxidation of the bond coating. This project aims to design low-cost high-performance TEBC based on high entropy rare earth disilicates to protect SiC-based ceramic matrix composites from chemical and thermal attack for better performance of components in the hot section of gas turbine engines. To accelerate the TEBC design, we utilize first-principles density functional theory to predict key properties including phase stability, CTE, lattice thermal conductivity, temperature-dependent elastic constants, and oxygen diffusivity. Alloying elements including Yb, Y, Er, Eu, Gd, Lu, La, and Ce are considered, and modeling prediction are compared with available experimental results.

coefficient of thermal expansion↗

Thermal and Radiation Stability in Nanocrystalline Cu

Nanocrystalline metals have presented intriguing possibilities for use in radiation environments due to their high grain boundary volume, serving as enhanced irradiation-induced defect sinks. Their promise has been lessened due to the propensity for nanocrystalline metals to suffer deleterious grain growth from combinations of irradiation and/or elevated homologous temperature. While approaches for stabilizing such materials against grain growth are the subject of current research, there is still a lack of central knowledge on the irradiation–grain boundary interactions in pure metals despite many studies on the same. Due to the breadth of available reports, we have critically reviewed studies on irradiation and thermal stability in pure, nanocrystalline copper (Cu) as a model FCC material, and on a few dilute Cu-based alloys. Our study has shown that, viewed collectively, there are large differences in interpretation of irradiation–grain boundary interactions, primarily due to a wide range of irradiation environments and variability in materials processing. We discuss the sources of these differences and analyses herein. Then, with the goal of gaining a more overarching mechanistic understanding of grain size stability in pure materials under irradiation, we provide several key recommendations for making meaningful evaluations across materials with different processing and under variable irradiation conditions.

36 MATERIALS SCIENCE↗

In situ formed catalysts for active, durable, and thermally stable ammonia protonic ceramic fuel cells at 550 °C

Ammonia protonic ceramic fuel cells (NH 3 -PCFCs) are promising and attractive energy-conversion devices owing to their high energy density, zero-carbon emission, and safety. The development of NH 3 -PCFCs, however, depends largely on the insufficient activity and poor durability of typical Ni-based anodes for ammonia decomposition, especially at low temperatures such as 550 °C. Herein, we report a self-assembled heterostructured Ru 0.95 Cu 0.05 Ni x (RCN) catalyst obtained through an in situ reaction between the surface-decorated Ru 0.95 Cu 0.05 nanoparticles and the Ni grain in the anode under typical processing conditions. At 550 °C, Ni–BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 anode-supported PCFCs with RCN catalysts exhibit a high peak power density of 0.732 W cm -2 and a significantly enhanced durability of 100 h in NH 3 . Moreover, the cells demonstrate improved thermal stability compared with the bare cell during a 31-cycle thermal cycling test in NH 3 between 550 and 700 °C. In conclusion, the enhanced performance is likely attributed to the synergistic effects of Ru and Cu in RCN for NH 3 decomposition, resulting in a more vital interaction of NH 3 than that of the bare anode surfaces, as confirmed by NH 3 thermal conversion, electrochemical performance, and theoretical simulations.

30 DIRECT ENERGY CONVERSION↗

High-temperature, spectrally-selective, scalable, and flexible thin-film Si absorber and emitter

Solar thermal technologies have great potential to provide low-cost storage for solar energy. However, their efficiencies are limited by a lack of scalable, mechanically flexible, durable, yet highly-efficient spectrally-selective solar absorbers suitable for high temperatures at low solar concentrations. Here, we overcome these challenges by fabricating a scalable free-standing spectrally-selective thin-film Si absorber and emitter (SSTFS) composite. Its high-temperature emittance shows strong spectral selectivity, even at 595 °C. Thermal stability is proven by measuring optical properties before and after thermal cycling equivalent to one day of concentrated sunlight. Despite the use of crystalline Si, the fabricated SSTFS composite exhibits exceptional mechanical flexibility to cover most surface geometries. The SSTFS composite demonstrates the potential of high-temperature, efficient and flexible solar absorbers and thermal emitters to advance renewable solar energy with storage.

36 MATERIALS SCIENCE↗

Reassembly of Peptide Nanofibrils on Live Cell Surfaces Promotes Cell–Cell Interactions

Nature regulates cellular interactions through the cell-surface molecules and plasma membranes. Despite advances in cell-surface engineering with diverse ligands and reactive groups, modulating cell–cell interactions through scaffolds of the cell-binding cues remains a challenging endeavor. Here, we assembled peptide nanofibrils on live cell surfaces to present the ligands that bind to the target cells. Surprisingly, with the same ligands, reducing the thermal stability of the nanofibrils promoted cellular interactions. Characterizations of the system revealed a thermally induced fibril disassembly and reassembly pathway that facilitated the complexation of the fibrils with the cells. Using the nanofibrils of varied stabilities, the cell–cell interaction was promoted to different extents with free-to-bound cell conversion ratios achieved at low (31%), medium (54%), and high (93%) levels. Further, this study expands the toolbox to generate desired cell behaviors for applications in many areas and highlights the merits of thermally less stable nanoassemblies in designing functional materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Bioinspired Artificial Injury Response System Based on a Robust Polymer Memristor to Mimic a Sense of Pain, Sign of Injury, and Healing

Abstract Flexible electronic skin with features that include sensing, processing, and responding to stimuli have transformed human–robot interactions. However, more advanced capabilities, such as human‐like self‐protection modalities with a sense of pain, sign of injury, and healing, are more challenging. Herein, a novel, flexible, and robust diffusive memristor based on a copolymer of chlorotrifluoroethylene and vinylidene fluoride (FK‐800) as an artificial nociceptor (pain sensor) is reported. Devices composed of Ag/FK‐800/Pt have outstanding switching endurance >10 6 cycles, orders of magnitude higher than any other two‐terminal polymer/organic memristors in literature (typically 10 2 –10 3 cycles). In situ conductive atomic force microscopy is employed to dynamically switch individual filaments, which demonstrates that conductive filaments correlate with polymer grain boundaries and FK‐800 has superior morphological stability under repeated switching cycles. It is hypothesized that the high thermal stability and high elasticity of FK‐800 contribute to the stability under local Joule heating associated with electrical switching. To mimic biological nociceptors, four signature nociceptive characteristics are demonstrated: threshold triggering, no adaptation, relaxation, and sensitization. Lastly, by integrating a triboelectric generator (artificial mechanoreceptor), memristor (artificial nociceptor), and light emitting diode (artificial bruise), the first bioinspired injury response system capable of sensing pain, showing signs of injury, and healing, is demonstrated.

36 MATERIALS SCIENCE↗