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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Stable operation of rechargeable lithium (Li)-based batteries at low temperatures is vital for cold-climate applications but is plagued with dendritic Li plating and unstable solid-electrolyte interphase (SEI). Here we report high-performance Li-metal batteries under low-temperature and high-rate-charging conditions. This is realized by utilizing a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of SEI and deposition morphology of Li metal anodes. A multilayer SEI containing a LiF-rich inner phase and amorphous outer layer effectively seals the Li surface in contrast to the conventional impassive SEI at low temperatures. As a result, galvanic Li corrosion and self-discharge were suppressed; stable Li deposition was realized from -60º to 45ºC; and a Li|LiCoO 2 cell with a capacity of 2.0 mAh cm -2 displayed a 200-cycle life at -15ºC with a recharge time of 45 minutes.

25 ENERGY STORAGE↗
NASA NTRS1989

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

High power density fuel cell systems for defense and civilian applications are being developed. Taking into consideration the main causes for efficiency losses (activation, mass transport and ohmic overpotentials) the only fuel cell systems capable of achieving high power densities are the ones with alkaline and solid polymer electrolyte. High power densities (0.8 W/sq cm at 0.8 V and 1 A/sq cm with H2 and O2 as reactants), were already used in NASA's Apollo and Space Shuttle flights as auxiliary power sources. Even higher power densities (4 W/sq cm - i.e., 8 A sq cm at 0.5 V) were reported by the USAF/International Fuel Cells in advanced versions of the alkaline system. High power densities (approximately 1 watt/sq cm) in solid polymer electrolyte fuel cells with ten times lower platinum loading in the electrodes (i.e., 0.4 mg/sq cm) were attained. It is now possible to reach a cell potential of 0.620 V at a current density of 2 A/sq cm and at a temperature of 95 C and pressure of 4/5 atm with H2/O2 as reactants. The slope of the linear region of the potential-current density plot for this case is 0.15 ohm-sq cm. With H2/air as reactants and under the same operating conditions, mass transport limitations are encountered at current densities above 1.4 A/sq cm. Thus, the cell potential at 1 A/sq cm with H2/air as reactants is less than that with H2/O2 as reactants by 40 mV, which is the expected value based on electrode kinetics of the oxygen reduction reaction, and at 2 A/sq cm with H2/air as reactant is less than the corresponding value with H2/O2 as reactants by 250 mV, which is due to the considerably greater mass transport limitations in the former case.

Srinivasan, Supramaniam↗
DOE OSTI2026

All‐Solid‐State Batteries With Mechanically Stable Interfaces Consisting of a Zero‐Strain Cation‐Disordered Rocksalt Cathode

Interface stabilization is critical to the development of working all‐solid‐state batteries. Rigid cathode/solid electrolyte interfaces often disintegrate due to anisotropic volume change of cathode‐active materials, resulting in irreversible capacity loss. Herein, we demonstrate that Li 1.211 Mo 0.467 Cr 0.3 O 2 (LMCO), a pioneering cation‐disordered rocksalt oxide (DRX) cathode that has intrinsically small volume change upon lithium intercalation, can be integrated with a thiophosphate‐based solid electrolyte for all‐solid‐state batteries. Interface stability of the all‐solid LMCO cell was investigated by electrochemical impedance spectroscopy, X‐ray micro‐computed tomography, and electron microscopy. Since LMCO was initially synthesized as a layered phase exhibiting a large volume change, interface disintegration can be observable in the early cycles. As layered LMCO phase‐transformed into DRX LMCO in subsequent cycles, reintegration of the interfaces occurs within a pressurized cell as a result of its zero‐stain behavior. Consequently, the DRX LMCO cathode maintains interface integrity, and thus electrical wiring, over an extended number of cycles, leading to improved capacity retention with small internal cell resistance.

DRX↗
DOE OSTI2021

Hosting Capacity Improvement Method Using MV–MV Solid-State-Transformer

As a large number of distributed generations are connected to the distribution system, research on the hosting capacity is actively being conducted. In particular, various methods, such as smart inverter functionality, co-located energy storage systems (ESS), and the use of on-load tap changers (OLTC), have been proposed to improve the hosting capacity. In this paper, a method to improve the hosting capacity by utilizing a solid-state transformer (SST) and its unique control capability is proposed. Lastly, the proposed method is verified in the distribution system of the Republic of Korea using the OpenDSS program.

24 POWER TRANSMISSION AND DISTRIBUTION↗
NASA NTRS2021

Pedestal Hazard Abatement and Soil Removal Construction Completion Report for Launch Complex 34, Solid Waste Management Unit CC054, Cape Canaveral Space Force Station, Florida

This Construction Completion Report summarizes the activities associated with implementation of an interim measure (IM) for hazard abatement of the Launch Pedestal and soil removal at Launch Complex 34 (LC34), Cape Canaveral Space Force Station, Florida. The purpose of the hazard abatement IM was to mitigate any continuing source of contamination associated with residual paint on the Launch Pedestal that contained polychlorinated biphenyls (PCBs). Sampling determined that residual PCB concerns were limited to the steel elements on the top-side of the Pedestal, which included the torus ring, feed pipe, down pipes, pipe straps and shields, remaining steel cover plates and bolts, and railing support steel. The IM also mitigated the potential spread of contamination to surrounding areas by removing fallen metal fragments from the concrete launch pad, as well as soil from trenches on the launch pad where PCB-containing paint chips may have accumulated prior to or during Pedestal hazard abatement activities.

Complex 34↗
NASA NTRS2019

Development of an Electrochemical Oxygen Compressor and Generator for Spacesuit Oxygen Resupply

The Electrochemistry Society is organizing a special session highlighting NASA applications and NASA technology development programs that use electrochemistry. NASA Johnson Space Center is sponsoring a technology development effort to use a solid oxide electrochemical cell stack to produce high pressure high purity oxygen capable of recharging spacesuit oxygen tanks between Extra-Vehicular Activities (EVAs). The attributes of the technology that are most important to NASA are the oxygen compatibility of the materials in the cell stack, and the solid state nature of the oxygen compression process. 2019 technical development work focuses on developing seals that connect individual wafers to for a cell stack.

Graf, John↗
DOE OSTI2023

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V 2 O 5 Double Layers

The 5/6s 2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V 2 O 5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s 2 cations situated in interlayer sites between condensed [V 4 O 10 ] n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered M x V 2 O 5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s 2 –O 2p-hybridized mid-gap states mediated by second-order Jahn–Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V–V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V–V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg 0.5 V 2 O 5 and δ-Tl 0.5 V 2 O 5 , respectively, as compared to 7 K for δ-Pb 0.5 V 2 O 5 . In δ-Pb 0.5 V 2 O 5 , the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V 4 O 10 ] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Geochemical Insights Into Volcanic and Lithospheric Evolution of Mars

Introduction: The Martian lithosphere plays a pivotal role in volcanic processes, altering surface features, climate shifts, and the planet's early habitability. Crucially, the rigid lithosphere significantly influences Mars' long-term thermal conditions. Studying various geological eons’ volcanic compositions unveils how the lithosphere has evolved, even though understanding the early Noachian volcanic chemistry remains challenging due to weathering and resurfacing. In this study, newly discovered Noachian volcanic terranes[1-2] along with Hesperian and Amazonian volcanic terranes[3] are considered(Figure 1), to infer the evolution of the Martian lithosphere. Figure 1:Mars topographic map derived from MOLA-HRSC data [4] highlights the study regions including the Noachian volcanic terranes, Arabia Terra (AT), Thaumasia Minor (TM), and the Southwest Margin of Icaria Planum (SWIP)[5].Additionally, the Hesperian volcanic terranes such as Syrtis Major (SM), Hesperia Planum (HP), and, the Amazonian volcanic terranes encompass Elysium Mons (EM), Alba Patera (AP), and Olympus Mons (OM) are marked. Methods and Datasets: We use the most recent elemental mass fraction maps derived from gamma spectroscopy data from the Mars Odyssey 2001mission [6]to ascertain the bulk composition of the Martian landscape. Utilizing the updated geochemical provinces dataset of Mars[7], we consider bulk chemistry variations within our study regions. The maps, at a resolution of 50×50, encompass elements like Al, Ca, Fe, Si, K, Th, H2O, Cl, and S, detected through Gamma-Ray Spectroscopy (GRS) with decimeter scale depth sensitivity[6].Additional major and minor elements like Mg, Na, Ti, P, and Mn, using mass balance methods [8]serve as inputs for melting and crystallization simulations. We employ the pMELTS model with FMQ-3to FMQ oxygen fugacity to estimate the Pressure(P)and melting degree(F)in various eons of volcanic terranes. We have also used conventional thermobarometric calculations to determine their formation P-T conditions, using silica activity and olivine-melt Mg-exchange thermometry[9-10]. Results: Chemical Composition of Studied Volcanic Terranes: To assess formation conditions, we have investigated if GRS-measured compositions signify primary igneous processes by evaluating weathering through the Chemical Index of Alteration (CIA), K/Th ratios, and ternary plots for aqueous alteration. Consistent K/Th ratios and low CIA (<50) across volcanic regions suggest minimal large-scale weathering, affirming well-preserved igneous material extending at decimeter depths. In addition, the calculated bulk compositions align with Martian mantle equilibrium, confirming studied volcanic terranes-Arabia Terra, Thaumasia Minor, and SWIP -as primary or less altered compositions, reinforcing their representativeness at a regional GRS scale on Mars. We have also estimated the bulk compositions of Hesperian and Amazonian volcanic terranes shown in Figure 1. All volcanic terranes represent the primary or minimally altered composition. Temporal Evolution of Martian Volcanic Terranes: Our results show P-T conditions ranging from 1.3-1.6 GPa and 1350-1390°C for Noachian terranes, while Hesperian volcanic terranes vary from 1.6-1.7 GPa and 1370-1395°C, and Amazonian volcanic terranes range between 1.9-2.8 GPa and 1380-1415°C. Our analyses correspond to lithospheric thicknesses/ depth of melting for Noachian which ranges from110-135 km, 120-235 km for Hesperian terranes, and 160-235 km for Amazonian terranes. Partial melting percentages (F) range from 8-12% for Noachian, 10-11% for Hesperian, and 10-12% for Amazonian. We have also calculated mantle potential temperatures (Tp) to show variations across epochs(Figure 2). Heat flux estimation shows variations from 51-65 mW/m2 for Noachian, 38-45 mW/m2for Hesperian, and 27-39 mW/m2for Amazonian terranes, implying temporal changes in lithospheric thickness and heat flow. Comparison of Noachian volcanic terranes with Hesperian and Amazonian reveals variations in lithospheric thickness and heat flux, indicating potential implications for Martian surface conditions, including volcanic activity, climate evolution, and early habitability. Figure 2: P-T diagram displays formation conditions of studied Martian volcanic regions using GRS data, alongside Noachian-age surface basalt samples from Gusev, Gale, and Jezero. Dashed lines represent Martian mantle potential temperatures, calculated by adding the latent heat of fusion to the equilibrium temperature at which melt and solid mantle coexist and subtracting the Martian adiabatic gradient corresponding to the depth of melt. The solid line shows the Martian mantle solidus [11].Discussion& Implication: The study explores Martian volcanic activity across eons. Uniform lithospheric thickness from the Noachian to Hesperian eons suggests persistent weak plumes until Hesperian, influencing heat flow variations. Noachian's high heat flux, likely due to concentrated radioactive elements, shows spatial heterogeneity, indicating early Mars' differentiated mantle. Volcanic outgassing plays avital role in the formation of the Martian climate, likely sustained water on the surface, influencing warm-wet or cold-dry conditions. Hesperian's favorable lithospheric heat flow (45 mW/m2) supports extended water existence, resembling Earth's conditions. Whereas, Amazonian's diminished heat flux (25 mW/m2) corresponds to water loss and arid climate. Hesperian's similar lithospheric thickness to mid-Noachian implies prolonged water retention, influencing climate and potential for astrobiological research, expanding perspectives for future Martian missions. Future work: As volcanism was active throughout its history. The emergence of Mars' extensive volcanic regions, known as large igneous provinces, which are linked to intermittent volcanic activity driven by mantle plumes, poses challenges to understanding the scale and persistence of these phenomena in Martian convection models. Therefore, understanding the regional-scale changes in eruptive processes within Martian volcanic provinces over time remains unclear and crucial for deciphering the evolution of the Martian interior without Earth-like plate tectonics. We will continue this work with petrological and thermoelastic analyses to study the compositional and spatiotemporal evolution of the Elysium Volcanic Province.

A Rani↗
DOE OSTI2025

Manipulating Aromaticity to Redirect Topochemical Polymerization Pathways

Topochemical polymerization (TCP) represents an essential route to create regio- and stereoregular polymers through solid-state transformations. Herein, we present an innovative strategy for controlling topochemical polymerization pathways by tailoring the terminal group aromaticity in the para-azaquinodimethane (AQM) ring system. Substituting phenyl groups with less aromatic furyl units extends significant spin density delocalization across the conjugated core upon thermal activation, inducing significant diradicaloid characters at furyl positions and enabling unconventional reactivities in both solution and solid states. Thermal treatment in toluene yields a unique cyclophane dimer formed via furyl-methine C-C coupling, confirmed by X-ray crystallography, while solid-state reactions produce polymers formed via both intercolumnar furyl-methine coupling and intracolumnar methine-methine coupling. The spin-center-directed mechanism underlying these transformations is validated through theoretical modeling and isotopic labeling experiments. This study highlights the prowess of aromaticity modulation in functional pro-aromatic systems, which enables the synthesis of polymers with main chain structures that are otherwise difficult to access.

Zhang, Qingsong↗
DOE OSTI2023

On the Impact of Mechanics on Electrochemistry of Lithium-Ion Battery Anodes

Abstract Models exploring electrochemistry-mechanics coupling in liquid electrolyte lithium-ion battery anodes have traditionally incorporated stress impact on thermodynamics, bulk diffusive transport, and fracture, while stress-kinetics coupling is more explored in the context of all solid-state batteries. Here, we showcase the existence of strong link between active particle surface pressure and reaction kinetics affecting performance even in liquid electrolyte systems. Traction-free and immobile particle surface mechanical boundary conditions are used to delineate the varying pressure magnitudes in graphite host during cycling. Both tensile and compressive stresses are generated in traction-free case, while a fixed surface subjects the entire particle to a compression state. Pressure magnitudes are nearly two to three orders of magnitude higher for the latter resulting in significant depression of open circuit potential and improvement of exchange current densities compared to stress-free state. The results demonstrate the need for incorporating stress-kinetics linkage in models and provide a rationale for putting battery electrodes under compression to improve kinetics.

25 ENERGY STORAGE↗
DOE OSTI2021

Synthesis, characterization, and thermodynamic study of selected K-based zeolites

Potassium-rich zeolites often occur in cementitious systems, as K{sup +} is widespread in various cementitious materials, such as Portland, blended and alkali-activated cements. The knowledge of their stability and of thermodynamic models for solid solutions with Na{sup +} and Ca{sup 2+} are critical to understand long-term development and durability in such cements. Completing previous studies on Na- and Ca-based zeolites, the current work aims to determine the thermodynamic data of 14 types of K-based zeolites, which could possibly form in cementitious systems. The zeolites were synthesized hydrothermally, exchanged with K{sup +}, and characterized thoroughly with respect to framework structures, elemental compositions, water contents, and bond variations. Their thermodynamic properties were derived from the experimental solubility data, which allowed establishing predominance diagrams in the K{sub 2}O-SiO{sub 2}-Al{sub 2}O{sub 3}-H{sub 2}O system. The K-based zeolites typically showed the lowest solubility between 0 and 100 °C, with the notable exception of Ca-gismondine and two Na-based zeolites: natrolite and Na-mordenite.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Metastable solubility and local structure of amorphous calcium carbonate (ACC)

The properties of amorphous calcium carbonate provide the foundation for understanding mineralization of calcified skeletons but inconsistencies between studies suggest the physical picture is incomplete. This study quantifies the metastable solubility and structure of ACC produced under a series of chemical conditions. Using complementary in situ methods that quantify ACC structure (in situ PDF analysis) in parallel with chemical composition (TGA, ICP-OES), we find two short-range structures are produced that also show distinct morphological differences. Conditions with high carbonate ion concentrations stabilize a Ca-rich ACC with short-range order that is independent of Mg content. In contrast, low carbonate solutions favor Mg-rich ACC with mixed Ca- and Mg-short range order. Measurements of solubility product determined from supersaturated and undersaturated conditions find the distinctive structures are related to solution carbonate activity while solubility is primarily determined by the magnesium content of the solid. Bulk solubility is a composite that concurs with established values. The findings demonstrate the type of ACC that forms is tuned by Mg2+ and CO3-2- concentration and suggest ACC structure, not bulk composition, is a reliable indicator of intermediate phase. This chemical framework also provides a basis for interpreting apparent differences between observations of ACC in synthetic and natural systems that reconciles previous structural studies.

Mergelsberg, Sebastian T.↗
DOE OSTI2022

Stabilization of Dinuclear Rhodium and Iridium Clusters on Layered Titanate and Niobate Supports

Atomically dispersed organometallic clusters can provide well-defined nuclearity of active sites for both fundamental studies as well as new regimes of activity and selectivity in chemical transformations. More recently, dinuclear clusters adsorbed onto solid surfaces have shown novel catalytic properties resulting from the synergistic effect of two metal centers to anchor different reactant species. Difficulty in synthesizing, stabilizing, and characterizing isolated atoms and clusters without agglomeration challenges allocating catalytic performance to atomic structure. Here, we explore the stability of dinuclear rhodium and iridium clusters adsorbed onto layered titanate and niobate supports using molecular precursors. Both systems maintain their nuclearity when Statistical analysis of HAADF-STEM images revealed that rhodium and iridium dimers had mean cluster-to-cluster distances very similar to what is expected from a random distribution of atoms over a large area, indicating that they are dispersed without aggregation. The stability of dinuclear rhodium clusters supported on titanate nanosheets was also investigated by X-ray absorption fine structure (EXAFS), DRIFTS, and first-principles calculations. Both X-ray absorption spectroscopy and HAADF-STEM simulations, guided by density functional theory (DFT)-optimized structure models, suggested that rhodium dimers adsorb onto the nanosheets in an end-on binding mode that is stable up to 100 degrees C under reducing conditions. Finally, this study highlights that crystalline nanosheets derived from layered metal oxides can be used as model supports to selectively stabilize dinuclear clusters, which could have implications for heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High-Performance Pt–Co Nanoframes for Fuel-Cell Electrocatalysis

Pt-based alloy catalysts are promising candidates for fuel-cell applications, especially for cathodic oxygen reduction reaction (ORR) and anodic methanol oxidation reaction (MOR). The rational design of composition and morphology is crucial to promoting catalytic performances. Here, we report the synthesis of Pt–Co nanoframes via chemical etching of Co from solid rhombic dodecahedra. The obtained Pt–Co nanoframes exhibit excellent ORR mass activity in acidic electrolyte, which is as high as 0.40 A mg Pt –1 initially and 0.34 A mg Pt –1 after 10 000 potential cycles at 0.95 V RHE . Furthermore, their MOR mass activity in alkaline media is up to 4.28 A mg Pt –1 and is 4-fold higher than that of commercial Pt/C catalyst. Furthermore, experimental studies indicate that the weakened binding of intermediate carbonaceous poison contributes to the enhanced MOR behavior. More impressively, the Pt–Co nanoframes also demonstrate remarkable stability under long-term testing, which could be attributed to the negligible electrochemical Co dissolution.

25 ENERGY STORAGE↗
DOE OSTI2020

LaCrO 3 -Coated La 0.6 Sr 0.4 Co 0.2 Fe0.8O3–δ Core–Shell Structured Cathode with Enhanced Cr Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells

La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) is a common cathode material for intermediate temperature solid oxide fuel cells due to its excellent oxygen reduction reaction catalytic activity. However, the Cr-poisoning effect is a severe issue causing its electrochemical performance degrada-tion. To develop a LSCF-based cathode with excellent Cr-tolerance, LaCrO 3 -coated LSCF core-shell structured (LCr@LSCF) cathode was prepared via solution infiltration method. After coated by LCr shell, the long-term stability and Cr-tolerance were obviously improved, at the price of sacrificing some electrochemical performance. As a result, the development of LCr@LSCF cathode with eye-catching Cr-tolerance is of great significance to the commercialization of LSCF.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Rate Enhancement of Acid-Catalyzed Alcohol Dehydration by Supramolecular Organic Capsules

The presence of a (sub)nanometric environment has been demonstrated to enhance the rate of homogeneous acid-catalyzed reactions. Conventionally, such catalysts are constructed by directly embedding a catalytically active acid site into the structure of a porous material, linking the acid properties with the properties of the embedding solid. Here, a holoenzyme mimicking approach was used, in which a self-assembled hexameric resorcinarene capsule (1.4 nm 3 cavity) acts like an apoenzyme that transforms into a catalytically active site by hosting hydrated HCl as a cofactor. This capsule binds the hydronium ion together with cyclohexanol (CyOH) and catalyzes the dehydration to cyclohexene with enhanced rates that are 2 orders of magnitude higher than those in the unconstrained environment. Kinetic analysis shows that cyclohexanol dehydration proceeds via an E2 mechanism on hydrated HCl in the unconstrained environment, while the constrained environment of the active capsule induces the stabilization of an ionic intermediate, allowing an E1 mechanism to dominate. By comparison with the reaction in zeolite environments, we show that the direct chemical environment of the capsule or a zeolite wall exerts only a minor direct influence. The volume constraint increases the reaction rate by inducing a larger activation entropy, indicating the stabilization of a later transition state in the E1 mechanism, as well as a higher reaction space of the carbenium ion constituting the transition state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Singlet Fission in a para -Azaquinodimethane-Based Quinoidal Conjugated Polymer

The exploitation of singlet fission (SF) in photovoltaic devices is restricted by the limited number of SF materials available and the conflicting requirement of intermolecular interactions to satisfy both efficient SF and subsequent triplet extraction. Intramolecular SF (iSF) represents an emerging alternative and may prove simpler to implement in devices. Here, on account of the excellent chemical structure tunability and solution processability, conjugated polymers have emerged as promising candidates for iSF materials despite being largely underexplored. It remains a significant challenge to develop SF-capable conjugated polymers and achieve efficient dissociation of the formed triplet pairs simultaneously. In this contribution, we present a new iSF material in a para-azaquinodimethane-based quinoidal conjugated polymer. Using transient optical techniques, we show that an ultrafast iSF process dominates the deactivation of the excited state in such polymer, featuring ultrafast population (<1 ps) and stepwise dissociation of triplet pairs. Notably, these multiexciton states could further diffuse apart to produce long-lived free triplets (tens of μs) in strongly coupled aggregates in solid thin film. Such findings not only introduce a new iSF-active conjugated polymer to the rare SF material family but also shed unique insight into interchain interaction-promoted triplet pair dissociation in aggregates of conjugated polymers, thus openning new avenues for developing next-generation SF-based photovoltaic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗