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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Synergy of carbonyl and azo chemistries for wide-temperature-range rechargeable aluminum organic batteries

Rechargeable aluminum organic batteries (RAOBs) are promising for developing cost-effective and sustainable energy storage devices due to the low cost, abundance, and high sustainability of aluminum and organic resources. In this study, we designed and synthesized a redox-active polymer bearing carbonyl and azo groups as a cathode material for RAOBs. The polymeric cathode exhibits a high reversible specific capacity, superior cyclic stability, fast charging capability, and a wide operation temperature range (₋40°C to 100°C). X-ray photoelectron spectroscopy (XPS), pair distribution function (PDF) analysis, and soft X-ray absorption near edge structure (XANES) were employed to gain fundamental insight into the carbonyl and azo chemistries in RAOBs, as well as the cathode electrolyte interphase (CEI) structure. We demonstrated a step-by-step alumination/de-alumination reaction for carbonyl and azo groups in the polymer cathode and unraveled a Al 2 O 3⁻ and AlN-rich CEI, which is critical for the impressive performance of RAOBs.

25 ENERGY STORAGE↗
DOE OSTI2020

High-Capacity P2-Type Na x Li 0.25 Mn 0.75 O 2 Cathode Enabled by Anionic Oxygen Redox

Sodium-ion battery technology has attracted significant attention due to its substantial cost advantage and similar operating mechanism to Li-ion batteries. P2-type sodium manganese oxide cathode is one of the most promising candidates, demonstrating both high capacity and good cycling stability. Here, we explore the lattice oxygen activity in layered sodium transition metal oxides. We synthesize a series of sodium lithium manganese oxides, NaxLi 0.25 Mn 0.75 O2 (x = 0.75 – 0.833), to optimize Na content. We further investigate the charge compensation mechanism for the best performing Na 0.75 Li 0.25 Mn 0.75 O 2 over an extensive electrochemical cycling window. The large charge and discharge capacity is enabled by reversible lattice oxygen redox in the high voltage region (≥2.5 V), along with Mn redox at the voltages below 2.5 V. Additionally, we reveal a small amount of oxygen gas evolution, 0.04% of the total oxygen in Na 0.25 Li 0.25 Mn 0.75 O 2 . This initial study will trigger an interest in the lattice oxygen activity in layered sodium metal oxide cathode, therefore, leading to better understanding of its correlation with crystal structure and electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2026

Anode-less Solid-State Li–S Batteries Enabled by Fe-Stabilized Polysulfides

Anode-less solid-state lithium-sulfur batteries (SSLSBs) with lithium sulfide (Li 2 S) as the cathode promise a high energy density and ease of manufacturing. However, Li 2 S is plagued by poor conductivity, sluggish activation kinetics, and a poor cycle life. Here, in this study, we report an FeCl 3 -activated Li 2 S (FLS) cathode with solid-state polysulfide intermediates generated through a redox reaction between FeCl 3 and Li 2 S. This strategy is shown to boost the electrical conductivity of Li 2 S by 7 orders of magnitude and lower the activation barrier. During cycling, Fe plays a significant role in stabilizing the highly active polysulfide species, contributing to the exceptional electrochemical performance. The FLS cathode achieves 80% capacity retention over 500 cycles with >99% Li 2 S utilization. Furthermore, a Li-metal-free (anode-less) full cell retained over 80% of its initial capacity after 240 cycles. This work underscores the promise of leveraging Fe-stabilized polysulfides in enabling high-energy, long-lasting, solid-state Li-S batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Hydroxypyridinone-based stabilization of Np(IV) enabling efficient U/Np/Pu separations in the Adapted PUREX process

The classical process to recover uranium (U) and plutonium (Pu) from used nuclear fuel using tributyl phosphate (TBP), namely the Plutonium Uranium Redox EXtraction (PUREX) process, is complicated by the persistent presence of neptunium (Np) and thus requires extra purification steps. The concept of Adapted PUREX seeks to achieve Np recovery by adjusting the valence of the metal more effectively, thereby controlling its behavior more precisely. This study introduces the use of an aqueous hydroxypyridinone chelator, 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO), to dictate the behavior of Np for recovery and meanwhile simplify cumbersome reprocessing steps. The interactions between Np and HOPO were probed mechanistically by way of absorption spectrophotometry, in conjunction with cyclic voltammetry. UV–Vis-NIR spectra illustrated the reduction of NpO 2 2+ to Np 4+ , with a fast reaction rate. Cyclic voltammetry revealed quasi-reversible processes between the oxidized and reduced forms of the ligand and its Np complexes. The corresponding heterogeneous rate constants (k 0 ) were estimated from the peak-to-peak separation potentials (ΔE p ), at ~ 4 – 35 μm/s for both HOPO and NpHOPO, with scan rates of 0.01 – 0.4 V/s. Meanwhile, the electromotive force (E MF ) as well as the change of Gibbs free energy (ΔG) were assessed from the half-wave potential (E 1/2 ), demonstrating the completeness of NpO 2 2+ reduction to Np 4+ by HOPO. The cumulative formation constant of the resulting NpHOPO complex (logβ 101 ) was determined by metal competition titration to be 42.0 ± 0.6, corroborating the extraordinarily high affinity of HOPO to tetravalent metal ions. Here, the prowess of valence control by HOPO and the high stability of the formed complex resulted in enhanced separations of Np from U and of Pu from U, with a maximum separation factor of ~7000 for both, nearly 90- and 10300-fold higher, respectively, than the values obtained using conventional PUREX formulae.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Evaluation of electrochemical performance and redox activity of Fe in Ti doped layered P2-Na0.67Mn0.5Fe0.5O2 cathode for sodium ion batteries

Here, we report a wet synthesis-based titanium doping strategy to improve the structural stability and electrochemical performances, such as cycling stability and rate capability, of P2-type Na 0.67 Fe 0.5 Mn 0.5 O 2 layered oxide cathodes. Through Ti 4+ doping aimed at replacing some of the Mn and Fe atoms in the crystal structure, effective mitigation of the Jahn Teller distortion caused by active Mn 3+ before charging and Fe 4+ after charging was achieved. X-ray diffraction (XRD), Raman spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Mössbauer spectroscopy were used to investigate the effects of the Ti 4+ dopant before and after cycling. It was observed that Ti 4+ doping increased the Na layer thickness, minimized the lattice volume strain, showed better structural stability, minimally decreased Fe migration to the Na layer, and lowered charge transfer resistance in these P2-type cathodes. Overall, our reported synthesis methodology and electrochemical characterizations highlight the feasibility of Ti doping in sodium layered oxide P2-type cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

A high-performance organic cathode customized for sulfide-based all-solid-state batteries

All-solid-state batteries (ASSBs) have become increasingly attractive recently due to their better safety and prospective long-term stability compared with conventional liquid batteries. However, obtaining a sustainable cathode candidate to match the solid electrolyte with regards to operating potential, chemical compatibility, and mechanical property is still an open challenge. In this work, the chemical incompatibility of quinone-based active materials and sulfide-based electrolyte were unveiled for the first time through a heteroconjugate addition reaction mechanism. To develop a quinone cathode customized for sulfide-based ASSBs, poly-(anthraquinonyl sulfide)-graphene (PAQS-G) nanocomposite was reported. The stable polymer framework of PAQS can protect the quinone redox center by preventing nucleophilic attack from sulfide-based solid electrolytes. The graphene additives can ameliorate redox kinetics and improve active material utilization. The PAQS-G cathode exhibited a specific capacity of ~178 mAh g -1 and a high material utilization of ~79%. Excellent cycling stability was achieved with 94 % capacity after 200 cycles in lithium batteries and 95.5 % capacity after 300 cycles in sodium batteries at 0.1C rate, respectively. A promising potential for energy storage applications was demonstrated.

25 ENERGY STORAGE↗
DOE OSTI2026

Oxidation of biogenic U(IV) mediated by iron-bearing clay minerals, iron-reducing bacteria, and organic ligands

Bioreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)) by dissimilatory metal-reducing bacteria (DMRB) is considered an effective strategy for uranium immobilization in contaminated environments. However, U(IV) can be reoxidized to U(VI) under fluctuating redox conditions and remobilized. This work investigates the oxidation behavior of biogenic U(IV) in the presence of bioreduced iron-bearing clay minerals (rNAu-2), iron-reducing bacteria (Shewanella putrefaciens CN32), and organic ligands (ethylenediaminetetraacetic acid (EDTA) and citrate). Results demonstrate that the presence of CN32 significantly inhibits U(IV) oxidation. rNAu-2 exerted a context-dependent influence on U(IV) oxidation: its effect was masked by bicarbonate-promoted U(VI) mobilization in the absence of active CN32, but became detectable when CN32-mediated microbial protection slowed U(IV) oxidation. EDTA and citrate markedly accelerate U(IV) oxidation via formation of soluble U(IV)-ligand complexes, changing U(IV) redox potentials, and by promoting clay mineral dissolution that enhances Fe(II)/Fe(III) redox cycling. Collectively, our findings constrain the roles that clay minerals, iron-reducing bacteria, and organic ligands play in governing U(IV) stability, emphasizing the need to account for these factors in developing robust bioremediation strategies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Low-nickel cathode chemistry for sustainable and high-energy lithium-ion batteries

The transition to sustainable energy storage demands lithium-ion batteries with high energy density and reduced reliance on critical metals such as nickel (Ni), yet current strategies to increase capacity have largely depended on raising Ni content, leading to escalating supply risks, rising costs and sustainability concerns. More critically, Ni-rich cathodes suffer from rapid electrochemical degradation driven by structural instability, creating an insurmountable trade-off between capacity and cycle life. Here, in this study, we introduce a low-Ni chemistry cathode, Li(Li 0.05 Ni 0.57 Mn 0.31 Co 0.07 )O 2 , with a radial phase integration design that overcomes these limitations, enabling a remarkable Ni usage reduction (Ni < 0.6) while demonstrating high capacity (215 mAh g −1 ) and markedly improved cyclability (~97% retention over 400 cycles) compared to conventional high-Ni cathodes (Ni = 0.8). Advanced X-ray and electron microscopy analyses reveal that the designed cathode exhibits a highly reversible oxygen anionic redox, benefiting from a structurally stable surface and minimizing irreversible phase transitions. Moreover, the integrated structure substantially mitigates lattice strain and improves mechanical stability even under harsh conditions. In conclusion, this advance offers a general design principle for developing next-generation cathodes that combine resource efficiency with long-term electrochemical reliability.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Anion selective membrane

Experimental anion permselective membranes were prepared and tested for their suitability as cell separators in a chemical redox power storage system being developed at NASA-Lewis Research Center. The goals of long-term (1000 hr) oxidative and thermal stability at 80 C in FeCl3 and CrCl3 electrolytes were met by most of the weak base and strong base amino exchange groups considered in the program. Good stability is exhibited by several of the membrane substrate resins. These are 'styrene' divinylbenzene copolymer and PVC film. At least four membrane systems produce strong flexible films with electrochemical properties (resistivity, cation transfer) superior to those of the 103QZL, the most promising commercial membrane. The physical and chemical properties of the resins are listed.

Alexander, S. S.↗
DOE OSTI2026

Evolution of size-selected Pt cluster catalysts on prototypical oxide supports

The current quest for new pathways into sustainable, efficient and durable energy conversion technologies makes the used for a fundamental understanding of the atomic-scale phenomena underlying catalytic processes ever more pressing. In this context, characterizing catalyst particles in situ provides valuable information about the evolution of their composition, structure, oxidation state and charge state during an ongoing process. To disentangle the influence of individual parameters – temperature, pressure, gas composition, cluster size, as well as support acidity, redox state and defect density – it is crucial to control them precisely and separately in experiments. At the example of size-selected Pt n clusters – i.e. sub-nm particles defined to the exact number of atoms – on flat oxide supports, we follow their rich evolution phenomena via (synchrotron-based) X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM) during temperature ramps and in various gas environments. Here, we present our experience with these highly defined, yet complicated-to-create samples in ultra-high vacuum (UHV) and at mbar pressures. We discuss their stability during transport to synchrotrons and under reaction conditions on three prototypical oxide supports and show the various phenomena that can be disentangled. Ptn clusters on the non-reducible silicon dioxide, SiO 2 , remain size-selected and show remarkable stability. Doping strongly influences the size-dependent binding energy shifts and changes the Pt response to oxidative and reaction conditions, which we attribute to different cluster geometries: p-type doping leads to wetting, enhanced sinter resistance and a diminished response to oxidative environments, compared to clusters on n-type doped samples. We compare the system with our previous findings of a similar change in dimensionality for Pt 20 clusters on the reducible ceria, CeO 2 (111), support, induced by modulation of its O vacancy density. The Pt n /CeO 2 system is particularly interesting for strategies to stabilize and redisperse Pt clusters dynamically. Finally, we study the evolution of Pt n clusters on another reducible oxide support, magnetite, Fe 3 O 4 (001), in 0.1 mbar alternating redox conditions at RT and elevated temperature. In analogy to findings previously reported for Pt/TiO 2 (110), the clusters either become encapsulated by a thin oxide film via strong metal–support interaction (SMSI) or deeply buried in the magnetite. Overall, our approach of following the evolution of size-selected clusters on oxide supports leads to fundamental atomic-scale insights on nano-scale catalyst materials, on our path to sustainable, dynamic and self-repairing catalysts.

Falling, Lorenz J. [Technical Univ. of Munich (Ger↗
DOE OSTI2023

Sterically attenuated electronic communication in cobalt complexes of meridional isoquinoline-derived ligands for applications in electrocatalysis

The ability to synthetically tune the ligand frameworks of redox-active molecules is of critical importance to the economy of solar fuels because manipulating their redox properties can afford control over the operating potentials of sustained electrocatalytic or photoelectrocatalytic processes. The electronic and steric properties of 2,2′:6′,2″-terpyridine (Terpy) ligand frameworks can be tuned by functional group substitution on ligand backbones, and these correlate strongly to their Hammett parameters. The synthesis of a new series of tridentate meridional ligands of 2,4,6-trisubstituted pyridines that engineers the ability to finely tune the redox potentials of cobalt complexes to more positive potentials than that of their Terpy analogs is achieved by aryl-functionalizing at the four-position and by including isoquinoline at the two- and six-positions of pyridine (Aryl-DiQ). Their cobalt complex syntheses, their electronic properties, and their catalytic activity for carbon dioxide (CO2) reduction are reported and compared to their Terpy analogs. The cobalt derivatives generally experience a positive shift in their redox features relative to the Terpy-based analogs, covering a complementary potential range. Although those evaluated fail to produce any quantifiable products for the reduction of CO2 and suffer from long-term instability, these results suggest possible alternate strategies for stabilizing these compounds during catalysis. We speculate that lower equilibrium association constants to the cobalt center are intrinsic to these ligands, which originate from a steric interaction between protons on the pyridine and isoquinoline moieties. Nevertheless, the new Aryl-DiQ ligand framework has been engineered to selectively tune homoleptic cobalt complexes’ redox potentials.

Chemistry↗
DOE OSTI2020

Using nature’s blueprint to expand catalysis with Earth-abundant metals

Original title changed for publication from; " Using Nature's Blueprint to Enable Catalysis with Earth-Abundant Metals" A diverse array of redox transformations that are essential to life are catalyzed by metalloenzymes that feature an earth-abundant metal. In contrast, platinum-group metals have been the cornerstone of many industrial catalytic reactions for decades, providing high activity, thermal stability and tolerance to chemical poisons. We assert that Nature’s blueprint provides the fundamental principles for vastly expanding the use of abundant metals in catalysis. We highlight the key physical properties of abundant metals that distinguish them from precious metals, and we look to Nature to understand how the inherent attributes of abundant metals can be embraced, leading to unique, highly efficient catalysts, emphasizing reactions crucial to the sustainable production and transformation of fuels and chemicals.

Bullock, Ronald M.↗
DOE OSTI2021

Warming Stimulates Iron-Mediated Carbon and Nutrient Cycling in Mineral-Poor Peatlands

We know that iron (Fe) plays a key role in elemental cycling at terrestrial–aquatic interfaces by stabilizing carbon (C), phosphorus (P), and nutrient cations through physicochemical associations and by potentially releasing these elements following the reduction of Fe(III) to Fe(II). However, the ecosystem-scale importance of Fe redox cycling and its responses to climate change remain unclear in precipitation-fed peatlands (bogs), C-rich wetlands with very low mineral content. We tested impacts of Fe redox cycling on C and nutrient release in two bogs in northern Minnesota and in Spruce and Peatland Responses Under Changing Environments (SPRUCE), an ecosystem-scale warming experiment. Concentrations of Fe(III) declined from the peat surface to 50 cm depth (31 to 0.5 µmol g -1 ) and co-occurred with Fe(II) (10 to 30 µmol g -1 ). Chemical reduction of Fe(III) released C and P from variably saturated (0–30 cm) peat (106–1006 µmol C g -1 ; 0.6–5 µmol P g -1 ), and Fe-bound C was similar to previous measurements from upland mineral soils. Concentrations of Fe(II) and dissolved organic carbon (DOC) were strongly (R 2 = 0.56–0.78) and positively correlated in water samples measured at SPRUCE enclosure outlets and ambient near-surface porewater. Concentrations of Fe(II) also correlated positively with P at warmer SPRUCE temperature treatments and increased with experimental warming, but stabilized at the highest temperature treatments as water depth declined. Although bogs have low total mineral content, mass balance measurements indicated that atmospheric deposition could in principle sustain significant Fe cycling and hydrologic losses in these ecosystems. Overall, Fe redox cycling significantly impacted C and nutrient dynamics in these mineral-poor bogs, contributing to strong correlations between Fe(II) and DOC in water samples. Increased Fe(III) reduction with warmer temperatures will likely promote peatland C and nutrient release, impacting ecosystem C budgets both directly and indirectly by enhancing decomposition and productivity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Enhanced mobility of cations and anions in the redox state: The polaronium mechanism

Hugely enhanced slow-ion diffusivity has been widely observed under extreme redox conditions and for unclear reasons. Aided by first-principles calculations on model systems of ZrO 2 , CeO 2 , BaTiO 3 and Li 4/3 Mn 2/3 O 2 , here we successfully explained the intriguing phenomenon by a polaronium mechanism. We found a polaronium, defined as a transitory complex of a polaronic electron or hole and a migrating counterion, becomes highly mobile when the counterion comes from a d 0 or f 0 cation (e.g., Zr 4+ , Ti 4+ and Ce 4 ) or a p 6 anion (e.g., O 2- ) in the host compound. Upon a redox reaction, the complex attains a d 1 /f 1 or p 5 configuration, which spontaneously forms because it is favored by an electron-phonon interaction (manifest as the Jahn-Teller effect in high symmetry systems) that enables local relaxation and lowers the system energy. Here our calculations found such interaction reaching its peak at the saddle point where the local environment is softest, so soft that it allows a reorientation of the anisotropic d/f/p orbital to minimize the electron repulsion locally. Since the complex may dissolve after a successful ion-migration event, the redox electron/hole can be recycled to form another free-radical-like polaronium elsewhere, thereby enhancing ion migration repeatedly. The proposed polaronium mechanism, which also operates in ceramics doped with mixed-valence cations, is most relevant under dynamic and extreme thermal/field/irradiation conditions where extra electrons/holes are abundantly generated by non-equilibrium redox reactions. For such operations, some with emerging applications, our diffusion-enhancing mechanism may provide new theoretical insight to help understand their material/microstructure stability and performance.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Rational design of heterogeneous single-site catalysts via surface organometallic chemistry

Single-site heterogeneous catalysts offer an attractive route to unite the molecular precision of homogeneous catalysis with the durability and practical advantages of solids. Surface organometallic chemistry (SOMC) provides a particularly powerful strategy for this purpose by grafting molecular precursors onto tailored surfaces and converting support functionalities into ligand environments for isolated metal centers. As a result, SOMC brings the language and logic of coordination chemistry to heterogeneous catalysis, where the support becomes an integral part of the active site coordination sphere. This Review surveys recent progress in the rational design of SOMC-derived single-site catalysts, with emphasis on synthetic routes, post synthetic transformations, and the deliberate tuning of catalytic behavior through metal-support interactions. Discussions are made on how support identity, hydroxyl topology, acidity, and redox activity shape the geometry, electronic structure, and oxidation state of supported metal sites, as well as how these factors determine activity, selectivity, and stability. We also examine a central limitation of these systems: despite their molecularly informed design, supported single sites often exist as structurally distributed ensembles rather than uniform species, particularly on amorphous supports. This site heterogeneity, along with catalyst dynamics under operating conditions, remains a major barrier to definitive structure-activity relationships. Therefore, emerging approaches that combine advanced characterization, first-principles modeling, ensemble kinetics, and machine learning to resolve active-site structure and guide catalyst development are highlighted. Together, these advances position SOMC as a versatile coordination chemistry framework for the predictive design of heterogeneous catalysts with well-defined molecularly tailored active sites.

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

Formation of Zerovalent Iron in Iron-Reducing Cultures of Methanosarcina barkeri

Methanogenic archaea have been shown to reduce iron from ferric [Fe(III)] to ferrous [Fe(II)] state, but minerals that form during iron reduction by different methanogens remain to be characterized. Here, we show that zerovalent iron (ZVI) minerals, ferrite [α-Fe(0)] and austenite [γ-Fe(0)], appear in the X-ray diffraction spectra minutes after the addition of ferrihydrite to the cultures of a methanogenic archaeon, Methanosarcina barkeri (M. barkeri). M. barkeri cells and redox-active, nonenzymatic soluble organic compounds in organic-rich spent culture supernatants can promote the formation of ZVI; the latter compounds also likely stabilize ZVI. Methanogenic microbes that inhabit organic- and Fe(III)-rich anaerobic environments may similarly reduce Fe(III) to Fe(II) and ZVI, with implications for the preservation of paleomagnetic signals during sediment diagenesis and potential applications in the protection of iron metals against corrosion and in the green synthesis of ZVI.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Acetylene Semi-Hydrogenation on a Perovskite Oxyhydride Surface: Insights from First Principles and Microkinetic Modeling

Although perovskite oxyhydrides (POHs) have shown promise as a support for selective hydrogenation, it is unknown if they themselves can catalyze alkyne semi-hydrogenation. Here, we use first-principles density functional theory, coupled with microkinetic modeling, to investigate acetylene semi-hydrogenation on a prototypical POH, cubic BaTiO 2.5 H 0.5 (BTOH). Two different mechanisms are examined on a representative surface of BTOH under the reaction conditions: both are based on the Horiuti–Polanyi mechanism, but the way of H 2 dissociation is different. In mechanism 1, a lattice hydride H atom and then a surface adsorbed H atom sequentially hydrogenate the adsorbed acetylene. In mechanism 2, two lattice hydride H atoms from the BTOH sequentially hydrogenate the adsorbed acetylene. In both mechanisms, the H atoms are replenished from gas phase H 2 dissociation. Using density functional theory (DFT), we have calculated pathways for these two mechanisms in hydrogenation of acetylene to ethylene, as well as further to ethane. Microkinetic modeling based on the DFT energetics indicates that at 523 K, hydrogenation to ethylene and ethane via mechanism 1 occurs at a rate up to two orders of magnitude faster than via mechanism 2. A selectivity analysis for the temperature range of 373–673 K shows that the product observed is essentially only ethylene within the more active mechanism 1. This is because at the steady state, there is a significant amount of surface anion vacancies that facilitate heterolytic H 2 dissociation and help stabilize a vinyl intermediate. In conclusion, the present findings suggest that POHs are capable of selective hydrogenation, thanks to their rich hydrogen surface-redox chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

High-Energy, High-Power Sodium-Ion Batteries from a Layered Organic Cathode

Sodium-ion batteries (SIBs) attract significant attention due to their potential as an alternative energy storage solution, yet challenges persist due to the limited energy density of existing cathode materials. In principle, redox-active organic materials can tackle this challenge because of their high theoretical energy densities. However, electrode-level energy densities of organic electrodes are compromised due to their poor electron/ion transport and severe dissolution. Here, we report the use of a low-bandgap, conductive, and highly insoluble layered metal-free cathode material for SIBs. It exhibits a high theoretical capacity of 355 mAh g –1 per formula unit, enabled by a four-electron redox process, and achieves an electrode-level energy density of 606 Wh kg –1 electrode (90 wt % active material) along with excellent cycling stability. It allows for facile two-dimensional Na+ diffusion, which enables a high intrinsic rate capability. Growth of the active cathode material in the presence of as little as 2 wt % carboxyl-functionalized carbon nanotubes improves charge transport and charge transfer kinetics and further enhances the power performance. Altogether, these allow the construction of SIB cells built from an affordable, sustainable organic small molecule, which provide a cathode energy density of 472 Wh kg –1 electrode when charging/discharging in 90 s and a top specific power of 31.6 kW kg –1 electrode .

36 MATERIALS SCIENCE↗